EP1173530B1 - Compositions de fuel-oil - Google Patents

Compositions de fuel-oil Download PDF

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Publication number
EP1173530B1
EP1173530B1 EP00920552A EP00920552A EP1173530B1 EP 1173530 B1 EP1173530 B1 EP 1173530B1 EP 00920552 A EP00920552 A EP 00920552A EP 00920552 A EP00920552 A EP 00920552A EP 1173530 B1 EP1173530 B1 EP 1173530B1
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Prior art keywords
fuel
fuel oil
ppm
metal
mass
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German (de)
English (en)
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EP1173530A1 (fr
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Rinaldo Caprotti
Brid Dilworth
Carlo S. Fava
Philip Infineum UK Ltd. COLLIER
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Infineum International Ltd
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Infineum International Ltd
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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
    • 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
    • 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
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • 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
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1828—Salts thereof
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/189—Carboxylic acids; metal salts thereof having at least one carboxyl group bound to an aromatic carbon atom
    • 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
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2406—Organic compounds containing sulfur, selenium and/or tellurium mercaptans; hydrocarbon sulfides
    • C10L1/2412—Organic compounds containing sulfur, selenium and/or tellurium mercaptans; hydrocarbon sulfides sulfur bond to an aromatic radical
    • 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
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
    • C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
    • 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
    • C10L1/30—Organic compounds compounds not mentioned before (complexes)
    • C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)

Definitions

  • This invention relates to fuel oil, especially middle distillate fuel oil, compositions of improved performance.
  • Combustors such as heating units, fueled by liquid fuels are also prone to emission of unburned or partially unburned substances especially when operated on a frequent start-stop programme or when the burner parts are inadequately maintained. As energy regulations become more stringent the emissions by such units need also to be minimised.
  • additives including metallic additives
  • Certain organometallic compounds are known to be effective combustion improvers for distillate fuels such as home heating oils.
  • US-A-3,112,789 describes the use of cyclopentadienyl manganese tricarbonyls for this purpose.
  • GB-A-1,090,289 and US-A-3,637,356 describe the use of calcium compounds for reducing smoke.
  • EP-B-0 476 196 describes an additive composition for hydrocarbonaceous fuel comprising
  • Canadian Patent No. 1,188,891 describes an additive comprising at least one oil-soluble and/or dispersible compound of a transition metal and/or alkaline earth metal as well as one of several inhibitors against polymerisation and oxidation of hydrocarbons which inhibits the formation of soot.
  • Examples 1 and 2 disclose compositions containing overbased (carbonated) barium sulfonate.
  • GB-A-2 248 068 discloses an additive for reducing smoke and particulate emissions during combustion of a fuel oil which comprises:
  • GB-A-2 321 906 discloses a fuel additive comprising (a) a calcium salt and (b) an alkali and/or alkaline earth metal salt other than one of calcium.
  • WO 96/34074, WO 96/34075 and WO 97/40122 disclose fuel additives for reducing the emission of particulates.
  • GB-A-2 091 291 discloses an additive for a diesel fuel oil, which comprises a fuel oil soluble or dispersible calcium compound and a fuel oil soluble or dispersible iron compound, for smoke suppression.
  • WO 94/11467 and WO 97/04045 disclose fuel additives containing platinum group metals such as platinum and palladium. These are used to improve the operation of diesel traps.
  • WO 99/03953 discloses fuel oil compositions with improved combustion performance and reduced particulate and smoke emissions, the compositions being free of transition metals and containing at least one fuel-soluble calcium or magnesium salt.
  • WO 99/36488 discloses the use of mixtures of iron compounds and either strontium or calcium compounds as additives for fuels. For low sulphur content fuels, the mixtures should be rich in iron.
  • a first aspect of the present invention is a process for improving the regenerative ability of a particulate trap of a fuel oil combustion device which process comprises supplying directly to the trap an additive composition, and/or adding to the fuel oil combustion device a fuel oil composition incorporating an additive composition wherein the additive composition comprises (a) at least one fuel-soluble or fuel-dispersible alkaline earth metal compound selected from calcium sulfonate and calcium salicylate, and (b) at least one fuel-soluble or fuel-dispersible transition metal compound wherein the or each transition metal is selected from the group consisting of iron, copper, cerium, chromium, cobalt and molybdenum characterised in that the fuel oil composition contains at most 0.05 mass % of sulfur, the total metal content derived from (a) and (b) in the fuel oil composition is at most 50 ppm by mass, the mass proportion of (a) to (b), based on metal content, is in the range of from 60:40 to 95:5, the or each metal compound (a) has a
  • a second aspect of the present invention is the use of an additive composition or a fuel oil composition incorporating an additive composition to reduce particulate matter emissions by improving the regenerative ability of a particulate trap of a fuel oil combustion device wherein the additive composition is as defined in the first aspect.
  • the advantages of this invention may be achieved in any distilled or distillable liquid hydrocarbonaceous fuel derived from petroleum, coal, shale and/or tar sands and bio-fuel.
  • the base fuels will be derived primarily, if not exclusively, from petroleum.
  • the invention is thus applicable to such fuels as gasoline, kerosine, jet fuel, aviation fuel, diesel fuel, home heating oil, light cycle oil, heavy cycle oil, light gas oil, heavy gas oil, and in general, any liquid hydrocarbonaceous product suitable for combustion in either an engine or in a burner apparatus.
  • Middle distillate fuel oils as a class of fuels, generally boil within the range of about 100°C to about 500°C, e.g. 150° to about 400°C, for example, those having a relatively high Final Boiling Point of above 360°C (ASTM D-86).
  • Middle distillates contain a spread of hydrocarbons boiling over a temperature range, including n-alkanes which precipitate as wax as the fuel cools. They may be characterised by the temperatures at which various %'s of fuel have vaporised, e.g. 10% to 90%, being the interim temperatures at which a certain volume % of initial fuel has distilled. The difference between say 90% and 20% distillation temperature may be significant.
  • the petroleum fuel oil can comprise atmospheric distillate or vacuum distillate, or cracked gas oil or a blend in any proportion of straight run and thermally and/or catalytically cracked distillates.
  • the most common middle distillate fuels are jet fuels, diesel fuels and heating oils.
  • the heating oil may be a straight atmospheric distillate, or it may contain minor amounts, e.g. up to 35 mass %, of vacuum gas oil or cracked gas oils or of both. Heating oils may be made of a blend of virgin distillate, e.g. gas oil, naphtha, etc. and cracked distillates, e.g. catalytic cycle shock.
  • a representative specification for a diesel fuel includes a minimum flash point of 38°C and a 90% distillation point between 282 and 380°C (see ASTM Designations D-396 and D-975).
  • the fuel oil may also be an animal or vegetable oil, or a mineral oil as described above in combination with an animal or vegetable oil.
  • Fuels from animal or vegetable sources are known as biofuels and are believed to be less damaging to the environment on combustion, and are obtained from a renewable source. It has been reported that on combustion less carbon dioxide is formed than is formed by the equivalent quantity of petroleum distillate fuel, e.g. diesel fuel, and very little sulfur dioxide is formed.
  • Certain derivatives of vegetable oil for example rapeseed oil, e.g. those obtained by saponification and reesterification with a monohydric alcohol, may be used as a substitute for diesel fuel.
  • mixtures of a rapeseed ester for example, rapeseed methyl ester (RME). with petroleum distillate fuels in ratios of, for example, 10:90 by volume are likely to be commercially available in the near future.
  • RME rapeseed methyl ester
  • a biofuel is a vegetable or animal oil or both or a derivative thereof, particularly an oil comprising fatty acid and/or fatty acid esters.
  • Vegetable oils are mainly triglycerides of monocarboxylic acids, e.g. acids containing 10-25 carbon atoms and listed below where R is an aliphatic radical of 10-25 carbon atoms which may be saturated or unsaturated.
  • oils contain glycerides of a number of acids, the number and kind varying with the source vegetable of the oil.
  • oils examples include rapeseed oil, coriander oil, soyabean oil, cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, maize oil, almond oil, palm kernel oil, coconut oil, mustard seed oil, beef tallow and fish oils.
  • Rapeseed oil which is a mixture of fatty acids partially esterified with glycerol, is preferred as it is available in large quantities and can be obtained in a simple way by pressing from rapeseed.
  • esters such as methyl esters, of fatty acids of the vegetable or animal oils.
  • esters can be made by transesterification.
  • lower alkyl esters of fatty acids consideration may be given to the following, for example as commercial mixtures: the ethyl, propyl, butyl and especially methyl esters of fatty acids with 12 to 22 carbon atoms, for example of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroselic acid, ricinoleic acid, elaeostearic acid, linoleic acid, linolenic acid, eicosanoic acid, gadoleic acid, docosanoic acid or erucic acid, which have an iodine number from 50 to 150, especially 90 to 125.
  • Mixtures with particularly advantageous properties are those which contain mainly, i.e. to at least 50 mass % methyl esters of fatty acids with 16 to 22 carbon atoms and 1, 2 or 3 double bonds.
  • the preferred lower alkyl esters of fatty acids are the methyl esters of oleic acid. linoleic acid, linolenic acid and erucic acid.
  • the biofuel is present in an amount of up to 50 mass % based on the mass of the middle distillate fuel oil, more preferably of up to 10 mass %, especially up to 5 mass %.
  • the fuel oil composition for example, diesel fuel oil, generally has a sulfur level of 0.2 mass % or less (as measured by X-ray Fluorescence according to ASTM D2622-94) based on the mass of the fuel oil composition.
  • the fuel oil composition contains at most 0.1 mass % of sulfur; more preferably at most 0.05 mass %; advantageously at most 0.04 mass %; more advantageously at most 0.03 mass %; especially at most 0.02 mass %; such as less than 0.01 mass % of sulfur.
  • Fuels oil compositions containing even lower sulfur levels, for example 75 ppm by mass or less, 50 ppm or less and 25 ppm or less, are also within the scope of the present invention.
  • the heating oil compositions of the present invention contain a sulfur level of at most 0.2 mass % (as measured by X-ray Fluorescence according to ASTM D2622-94) based on the mass of the heating oil composition.
  • the heating oil composition contains at most 0.1 mass % of sulfur; more preferably at most 0.05 mass %; advantageously at most 0.04 mass %.
  • the art describes methods for reducing the sulfur concentration of hydrocarbon middle distillate fuels, such methods including solvent extraction, sulfuric acid treatment, and hydrodesulfurisation.
  • Fuel oils having such low sulfur levels show good response to the additive compositions of the present invention despite the reduced tendency of such fuel oils to produce particulate emissions.
  • Hydrocarbon middle distillate fuel oils refers to middle distillate fuel oils which are substantially free, and preferably free, of ethers and/or alcohols.
  • substantially free' with reference to ethers and/or alcohols in fuel oil refers to an amount of up to 20 mass % based on the mass of the middle distillate fuel oil, preferably up to 10 mass %, more preferably up to 5 mass %.
  • the fuel oil is middle distillate fuel, such as a hydrocarbon middle distillate fuel oil; more preferably, the fuel oil is diesel fuel oil or heating oil.
  • the fuel oil compositions can be used in combustion devices operated by compression ignition mechanisms, as well as those operated by non-compression mechanisms.
  • An example of a combustion device operated by compression ignition mechanism is the internal combustion engine which is used to power mobile vehicles. While an example of a non-compression combustion device is a stationary burner.
  • the alkaline earth metal particularly suitable in the present invention is selected from calcium, sulfonate and calcium salicylate.
  • the metal salts of the present invention include predominantly neutral salts where minor amounts of non-organic anions, for example carbonate and/or hydroxide anions, may also be present provided their presence does not alter the predominantly neutral character of the metal salt.
  • non-organic anions for example carbonate and/or hydroxide anions
  • metal salts of the present invention preferably have a metal ratio of less than 2, more preferably less than 1.95, especially less than 1.9, advantageously less than 1.8, more especially less than 1.6, for example less than 1.5, such as less than 1.4 or less than 1.35.
  • the metal ratio is preferably at least about 1.0.
  • the metal ratio is the ratio of total metal to the metal associated with the organic anion. So metal salts having a metal ratio of less than 2 have greater than 50% of the metal associated with the organic anion.
  • the metal ratio can be calculated by
  • Suitable methods for measuring the total metal content include X-ray fluorescence and atomic absorption spectrometry.
  • Suitable methods for determining the amount of metal associated with the organic acid include potentiometric acid titration of the metal salt to determine the relative proportions of the different basic constituents (for example, metal carbonate and metal salt of organic acid); hydrolysis of a known amount of metal salt and then the potentiometric base titration of the organic acid to determine the equivalent moles of organic acid; and determination of the non-organic anions, such as carbonate, by measuring the CO, content.
  • ASTM D3712 may be used to determine the metal associated with the sulfonate.
  • a composition comprises one or more neutral metal salts and one or more co-additives
  • the neutral metal salt(s) may be separated from the co-additives, for example, by using dialysis techniques and then the neutral metal salt may be analysed as described above to determine the metal ratio.
  • suitable dialysis techniques is given by Amos, R. and Albaugh, E. W. in "Chromatography in Petroleum Analysis” Altgelt, K. H. and Gouw, T. H., Eds., pages 417 to 421, Marcel Dekker Inc., New York and Basel, 1979.
  • organic acids include surfactant molecules, examples of which are hydrocarbyl sulfonic acids, and hydrocarbyl substituted salicylic acids.
  • the neutral metal salts of the present invention may be salts of one type of surfactant or salts of more than one type of surfactant. Preferably, they are salts of one type of surfactant.
  • Sulfonic acids used in accordance with this aspect of the invention are typically obtained by sulfonation of hydrocarbyl-substituted, especially alkyl-substituted, aromatic hydrocarbons, for example, those obtained from the fractionation of petroleum by distillation and/or extraction, or by the alkylation of aromatic hydrocarbons.
  • alkyl-substituted aromatic hydrocarbons for example, those obtained from the fractionation of petroleum by distillation and/or extraction, or by the alkylation of aromatic hydrocarbons.
  • alkylating benzene, toluene, xylene, naphthalene, biphenyl or their halogen derivatives for example, chlorobenzene, chlorotoluene or chloronaphthalene.
  • Alkylation of aromatic hydrocarbons may be carried out in the presence of a catalyst with alkylating agents having from about 3 to more than 100 carbon atoms, such as, for example, haloparaffins, olefins that may be obtained by dehydrogenation of paraffins, and polyolefins, for example, polymers of ethylene, propylene, and/or butene.
  • alkylaryl sulfonic acids usually contain from about 22 to about 100 or more carbon atoms; preferably the alkylaryl sulfonic acids contain at least 26 carbon atoms, especially at least 28, such as at least 30, carbon atoms.
  • the sulfonic acids may be substituted by more than one alkyl group on the aromatic moiety, for example they may be dialkylaryl sulfonic acids.
  • the alkyl group preferably contains from about 16 to about 80 carbon atoms, with an average number of carbon atoms in the range of from 36-40, or an average carbon number of 24, depending on the source from which the alkyl group is obtained.
  • the sulfonic acid has a number average molecular weight of 350 or greater, more preferably 400 or greater, especially 500 or greater, such as 600 or greater. Number average molecular weight may be determined by ASTM D3712.
  • hydrocarbon solvents and/or diluent oils may also be included in the reaction mixture, as well as promoters.
  • Sulfonic acids suitable for use in accordance with the invention also include alkyl sulfonic acids.
  • the sulfonic acid suitably contains 22 to 100 carbon atoms, advantageously 25 to 80 carbon atoms, especially 30 to 60 carbon atoms.
  • the sulfonic acid is hydrocarbyl-substituted aromatic sulfonic acid, more preferably alkyl aryl sulfonic acid.
  • Salicylic acids used in accordance with the invention may be non-sulphurized or sulphurized, and may be chemically modified and/or contain additional substituents, for example, as discussed above for phenols. Processes similar to those for phenols may also be used for sulfurizing a hydrocarbyl-substituted salicylic acid, and are well known to those skilled in the art. Salicylic acids are typically prepared by the carboxylation, by the Kolbe-Schmitt process, of phenoxides, and in that case, will generally be obtained (normally in a diluent) in admixture with uncarboxylated phenol.
  • Preferred substituents in oil-soluble salicylic acids from which neutral calcium salts in accordance with the invention may be derived are the substituents represented by R in the above discussion of phenols.
  • the alkyl groups advantageously contain 5 to 100 carbon atoms, preferably 9 to 30 carbon atoms, especially 14 to 20 carbon atoms.
  • the proportion of any one type of surfactant to another is not critical provided the neutral character of the metal is not altered.
  • a single type of surfactant may contain a mixture of surfactants of the same type.
  • a sulfonic acid surfactant may contain a mixture of sulfonic acids of varying molecular weights.
  • Such a surfactant composition is considered as one type of surfactant.
  • hydrocarbyl refers to a group having a carbon atom directly attached to the rest of the molecule and having a hydrocarbon or predominantly hydrocarbon character.
  • hydrocarbon groups including aliphatic (e.g. alkyl or alkenyl), alicyclic (e.g. cycloalkyl or cycloalkenyl), aromatic, and alicyclic-substituted aromatic, and aromatic-substituted aliphatic and alicyclic groups.
  • Aliphatic groups are advantageously saturated. These groups may contain non-hydrocarbon substituents provided their presence does not alter the predominantly hydrocarbon character of the group. Examples include keto, halo, hydroxy, nitro, cyano, alkoxy and acyl. If the hydrocarbyl group is substituted, a single (mono) substituent is preferred.
  • substituted hydrocarbyl groups examples include 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-ketopropyl, ethoxyethyl, and propoxypropyl.
  • the groups may also or alternatively contain atoms other than carbon in a chain or ring otherwise composed of carbon atoms. Suitable hetero atoms include, for example, nitrogen, sulfur, and, preferably, oxygen.
  • the Total Base Number (TEN), as measured according to ASTM D2896, of the neutral alkaline earth metal compounds is at most 100, preferably at most 80, more preferably at most 70, advantageously at most 60, such as less than 50.
  • the alkaline earth metal compound is calcium sulfonate or calcium salicylate; especially preferred is a calcium sulfonate.
  • the combination of the compounds making up the additive composition of the present invention should be soluble or dispersible in the fuel oil in which it is to be used at the concentration in which it is to be used.
  • the transition metal is iron.
  • the compound of the transition metal is preferably selected from an organic acid salt of a transition metal; ferrocene (Fe[C 5 H 5 ] 2 ) or a derivative thereof.
  • the organic acids suitable for the transition metal are the same as those described above for the neutral alkaline earth metals.
  • Specific examples of preferred transition metal compounds of organic acids are iron naphthenate, iron oleate, copper naphthenate, copper oleate, copper dithiocarbamate, copper dithiophosphate, zinc dithiophosphate, zinc dithiocarbamate, molybdenum dithiocarbamate, molybdenum dithiophosphate, cobalt naphthenate, cobalt oleate, nickel oleate and nickel naphthenate.
  • alkenyl and alkyl succinate salts of iron, copper, cobalt and nickel are also suitable.
  • transition metal compounds are ⁇ -bonded ring compounds where the number of carbon atoms in the ring may be in the range of from 2 to 8, such as [C 5 H 5 ], [C 6 H 6 ], [C 8 H 8 ].
  • Examples include dibenzenechromium.
  • Transition metal compounds with one ⁇ -bonded ring and other ligands such as halogens, CO, RNC annd R 3 P (where R is a hydrocarbyl group and may be the same or different when there is more than one R group) are also within the scope of the invention.
  • the ⁇ -bonded ring may be heterocyclic such as [C 4 H 4 N], [C 4 H 4 P] and [C 4 H 4 S].
  • iron compounds include iron (II) and iron (III) compounds, and derivatives of ferrocene such as bis(alkyl substituted cyclopentadienyl) iron compounds, for example bis(methyl cyclopentadienyl) iron.
  • compounds such as cyclopentadienyl iron carbonyl compounds, for example, [C 5 H 5 ]Fe(CO) 3 and [C 5 H 5 ]Fe(CO) 2 Cl; [C 5 H 5 ][C 4 H 4 N]Fe; and [C 5 H 5 ][C 4 H 4 P]Fe are suitable in the present invention.
  • the fuel-soluble or fuel-dispersible transition metal compound is preferably ferrocene.
  • the compounds may be of the same or of different metals within the category.
  • the total amount of metal by mass, derived from the or each neutral alkaline earth metal compound in the fuel oil composition is at most 25 ppm; preferably the total amount of metal is at most 20 ppm, more preferably at most 15 ppm; advantageously at most 10 ppm; especially at most 7 ppm, such as at most 5 ppm, for example in the range of from 0.1 to 3 ppm or 0.5 to 3 ppm.
  • the total amount of metal by mass, derived from the or each transition metal compound, in the fuel oil composition is at most 25 ppm; preferably the total amount of metal is at most 20 ppm, more preferably at most 15 ppm; advantageously at most 10 ppm; especially at most 7 ppm, such as at most 5 ppm, for example in the range of from 0.1 to 3 ppm or 0.5 to 3 ppm.
  • the total amount of metal by mass, derived from the neutral alkaline earth metal compound and transition metal compound, in the fuel oil composition, in all aspects of the invention is preferably in the range of from 0.1 to 50 ppm; preferably from 0.1 to 40 ppm; more preferably from 0.1 to 30 ppm; advantageously from 0.1 to 20 ppm; more advantageously from 0.5 to 10 ppm; especially from 0.5 to 9 ppm; such as from 0.5 to 8 ppm.
  • fuel oil compositions wherein the total amount of metal by mass, derived from the neutral alkaline earth metal compound and transition metal compound, in the fuel oil composition is in the range of from 0.5 to 7 ppm, preferably from 0.75 to 6 ppm, advantageously from 1 to 5 ppm, such as from 1 to 4 ppm.
  • the amount of alkaline earth metal in the fuel oil composition is measured by atomic absorption and the amount of transition metal in the fuel oil composition is measured by atomic absorption.
  • a surprising feature of the present invention is that lower amounts of metal can be used in the fuel oil to achieve improved performance of the fuel oil.
  • the mass proportion, based on metal content, of (a) neutral alkaline earth metal compound to (b) transition metal compound is preferably in the range of from 70:30 to 95:5; such as in the range of from 80:20 to 95:5; for example in the range of from 80:20 to 90: 10.
  • the additive composition or concentrate comprising the metal compounds of the present invention may be in admixture with a carrier liquid (e.g. as a solution or a dispersion).
  • a carrier liquid e.g. as a solution or a dispersion
  • Such concentrates are convenient as a means for incorporating the metal compounds into bulk fuel oil such as distillate fuel oil, which incorporation may be done by methods known in the art.
  • the concentrates may also contain other fuel additives as required and preferably contain from 1 to 75 mass %, more preferably 2 to 60 mass %, most preferably 5 to 50 mass % of the additives, based on active ingredient, preferably in solution in the carrier liquid.
  • carrier liquids examples include organic solvents including hydrocarbon solvents, for example petroleum fractions such as naphtha, kerosene, lubricating oil, diesel fuel oil and heater oil; aromatic hydrocarbons such as aromatic fractions, e.g. those sold under the 'SOLVESSO' tradename; and paraffinic hydrocarbons such as hexane and pentane and isoparaffins.
  • hydrocarbon solvents for example petroleum fractions such as naphtha, kerosene, lubricating oil, diesel fuel oil and heater oil
  • aromatic hydrocarbons such as aromatic fractions, e.g. those sold under the 'SOLVESSO' tradename
  • paraffinic hydrocarbons such as hexane and pentane and isoparaffins.
  • the carrier liquid must, of course, be selected having regard to its compatibility with the additives and with the fuel oil.
  • the metal compounds of the present invention may be incorporated into the bulk fuel oil by other methods such as those known in the art. If co-additives are required, they may be incorporated into the bulk fuel oil at the same time as the metal compounds of the present invention or at a different time.
  • the present invention also provides a process for preparing a fuel oil composition as defined in the first aspect wherein the additive composition as defined in the first aspect is incorporated, preferably by blending or mixing, into a fuel oil, or the metal compounds of the present invention are incorporated , preferably by blending or mixing, into the fuel oil contemporaneously or sequentially.
  • the metal compounds of the present invention may be used in combination with one or more co-additives such as known in the art, for example the following: cold flow improvers, wax anti-settling agents, detergents, dispersants, antioxidants, corrosion inhibitors, dehazers, demulsifiers, metal deactivators, antifoaming agents, cetane improvers, cosolvents, package compatibilisers, other lubricity additives and antistatic additives.
  • a particularly preferred co-additive is a polyisobutenyl succinimide.
  • interaction may take place between any two or more of the metal compounds of the present invention after they have been incorporated into the fuel oil or additive composition, for example, between two different neutral alkaline earth metal compounds or between a neutral alkaline earth metal compound and a transition metal compound.
  • the interaction may take place in either the process of mixing or any subsequent condition to which the composition is exposed, including the use of the composition in its working environment.
  • Interactions may also take place when further auxiliary additives are added to the compositions of the invention or with components of fuel oil.
  • Such interaction may include interaction which alters the chemical constitution of the metal compounds.
  • the compositions of the invention include compositions in which interaction between any of the metal compounds has occurred, as well as compositions in which no interaction has occurred between the components mixed in the fuel oil.
  • fuel-soluble or “fuel-dispersible”, as used herein with respect to the metal compounds, does not mean that the metal compounds are soluble, dissolvable, miscible or capable of being suspended in the fuel oil in all proportions. They do mean, however, that the metal compounds of the present invention are, for instance, soluble or stable dispersible in the fuel oil to an extent sufficient to exert their intended effect in the environment in which the fuel oil composition is employed. Moreover, the additional incorporation of other additives such as those described above may affect the fuel solubility or dispersibility of the metal compounds of the invention.
  • neutral alkaline earth metal compound and transition metal compound in particular a neutral calcium compound and an iron compound
  • the neutral calcium compound is calcium sulfonate and preferably has a Total Base Number (TBN), as measured according to ASTM D2896, of at most 50, more preferably at most 30, such as at most 20; and the iron compound is preferably ferrocene.
  • TBN Total Base Number
  • An advantage of the present invention is that the use of expensive transition metal compounds in fuel oils can be minimised whilst still achieving effective performance, for example in the areas of particulate matter and/or smoke and lubricity.
  • Particulate matter emissions may be reduced by improved combustion of the fuel oil, which the metal compounds of the present invention play a role in promoting, and/or through after-treatment technologies of the exhaust gas, such as with a particulate trap.
  • a drawback of the particulate trap method is the need for periodic regeneration of the trap to burn-off the deposited soot to keep the back-pressure within acceptable limits. This procedure makes the system costly, hard to control, and reduces the durability of the trap.
  • the main problem in regenerating the trap is linked to the low exhaust gas temperature of diesel engines. The oxidation of diesel soot requires temperatures of about 600 °C which is difficult to attain.
  • organometallic additives to reduce the ignition temperature of the soot has been described in the SAE paper 922188 by B. Krutzsch and G. Wenninger.
  • the metal compounds of the present invention may be useful in improving the regenerative ability of a particulate matter trap.
  • Many types of the particulate traps are known to those skilled in the art including as non-limiting examples "cracked-wall” and “deep-bed” ceramic types and sintered metal types.
  • Treatment with the metal compounds of the present invention in such an amount that the total metal in the fuel oil composition is at most 50 ppm, such as 2 to 50 ppm, by mass based on metal may also prove to be effective in improving fuel lubricity, as measured in tests such as the HFRR (High Frequency Reciprocating Rig) test.
  • HFRR High Frequency Reciprocating Rig
  • the defined metal compounds of the present invention provide fuel oil, particularly diesel fuel oil and heating oil, compositions with improved low temperature flow performance compared to fuel oil compositions comprising the alkaline earth metal compounds alone, such as a neutral calcium compound.
  • This effect is particularly apparent in the Cold Filter Plugging Point (CFPP) test (according to IP 309/96) or the Simulated Filter Plugging Point (SFPP) test (according to IP 419/96).
  • CFPP Cold Filter Plugging Point
  • SFPP Simulated Filter Plugging Point
  • the defined metal compounds of the present invention when added to fuel oil, such as diesel fuel oil or heating oil, provide the resulting compositions with better stability against water, thereby minimising the formation of emulsions in the fuel oil compositions.
  • the haze forming tendencies of a fuel oil composition may be measured according to ASTM D 1094.

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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)
  • Lubricants (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Claims (9)

  1. Procédé pour améliorer l'aptitude à la régénération d'un piège à particules d'un dispositif de combustion de fuel-oil, procédé qui comprend l'alimentation directe du piège avec une composition d'additifs et/ou l'introduction dans le dispositif de combustion de fuel-oil d'une composition de fuel-oil renfermant une composition d'additifs, dans lequel la composition d'additifs comprend :
    (a) au moins un composé de métal alcalino-terreux, soluble dans les carburants ou dispersable dans les carburants, choisi entre le sulfonate de calcium et le salicylate de calcium, et (b) au moins un composé de métal de transition, soluble dans les carburants ou dispersable dans les carburants, dans lequel le ou chaque métal de transition est choisi dans le groupe consistant en fer, cuivre, cérium, chrome, cobalt et molybdène,
       caractérisé en ce que la composition de fuel-oil contient au plus 0,05 % en masse de soufre, la teneur totale en métaux provenant de (a) et (b) dans la composition de fuel-oil est d'au plus 50 ppm en masse, le rapport en masse de (a) à (b), sur la base de la teneur en métaux, est compris dans l'intervalle de 60:40 à 95:5, le ou chaque composé métallique (a) a un taux de métal inférieur à 2, et la composition de carburant ne comprend pas de composé de manganèse.
  2. Utilisation d'une composition d'additifs, ou d'une composition de fuel-oil renfermant une composition d'additifs, pour réduire les émissions de matières en particules en améliorant l'aptitude à la régénération d'un piège à particules d'un dispositif de combustion de fuel-oil, dans laquelle la composition d'additifs comprend :
    (a) au moins un composé de métal alcalino-terreux, soluble dans les carburants ou dispersable dans les carburants, choisi entre le sulfonate de calcium et le salicylate de calcium et (b) au moins un composé de métal de transition, soluble dans les carburants ou dispersable dans les carburants, dans lequel le ou chaque métal de transition est choisi dans le groupe consistant en fer, cuivre, cérium, chrome, cobalt et molybdène,
       caractérisée en ce que la composition de fuel-oil contient au plus 0,05 en masse de soufre, la teneur totale en métaux provenant de (a) et (b) dans la composition de fuel-oil est d'au plus 50 ppm en masse, le rapport en masse de (a) à (b) sur la base de la teneur en métaux est compris dans l'intervalle de 60:40 à 95:5, le ou chaque composé métallique (a) a un taux de métal inférieur à 2, et la composition de carburant ne comprend pas de composé de manganèse.
  3. Procédé/utilisation suivant l'une quelconque des revendications précédentes, dans lequel la composition d'additifs comprend au moins un sulfonate de calcium et un salicylate de calcium neutre, solubles dans les carburants ou dispersables dans les carburants, et au moins un composé de fer soluble dans les carburants ou dispersable dans les carburants.
  4. Procédé/utilisation suivant l'une quelconque des revendications précédentes, dans lequel le ou chaque composé de métal de transition est choisi dans le groupe consistant en un sel d'un acide organique et un ferrocène ou un de ses dérivés.
  5. Procédé/utilisation suivant la revendication 4, dans lequel l'acide organique est choisi dans le groupe consistant en un acide carboxylique ou un de ses anhydrides, un alcool, un phénol, un phénol sulfuré, l'acide salicylique et l'acide sulforüque.
  6. Procédé/utilisation suivant l'une quelconque des revendications précédentes, dans lequel le composé de métal de transition, soluble dans les carburants ou dispersable dans les carburants, est un ferrocène.
  7. Procédé/utilisation suivant l'une quelconque des revendications précédentes, dans lequel le rapport en masse, sur la base de la teneur en métal, de (a) à (b) est compris dans l'intervalle de 70:30 à 95:5, de préférence de 80:20 à 95:5.
  8. Procédé/utilisation suivant l'une quelconque des revendications précédentes, dans lequel la teneur totale en métaux, en masse, provenant de (a) et (b) est comprise dans l'intervalle de 0,1 à 50 ppm, avantageusement de 0,1 à 40 ppm, plus avantageusement de 0,1 à 30 ppm, mieux encore de 0,1 à 20 ppm, encore plus avantageusement de 0,5 à 10 ppm, notamment de 0,5 à 9 ppm.
  9. Procédé/utilisation suivant l'une quelconque des revendications précédentes, dans lequel sont également présents des additifs supplémentaires pour carburants.
EP00920552A 1999-03-26 2000-03-21 Compositions de fuel-oil Expired - Lifetime EP1173530B1 (fr)

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GB9907058 1999-03-26
GBGB9907058.3A GB9907058D0 (en) 1999-03-26 1999-03-26 Fuel oil compositions
PCT/EP2000/002574 WO2000058422A1 (fr) 1999-03-26 2000-03-21 Compositions de fuel-oil

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JP (1) JP2002540286A (fr)
KR (1) KR100902460B1 (fr)
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US8211190B2 (en) 1999-03-26 2012-07-03 Infineum International Limited Fuel oil compositions

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WO2004087846A1 (fr) * 2003-04-04 2004-10-14 Chandra Sharma Kailash Procede de preparation d'un additif pour carburant
KR100553548B1 (ko) * 2003-11-06 2006-02-20 한국동서발전(주) 가시 백연 제거용 연료 첨가제 및 이를 이용한 가시 백연 제거방법
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CA2367517C (fr) 2008-12-02
GB9907058D0 (en) 1999-05-19
JP2002540286A (ja) 2002-11-26
CA2367517A1 (fr) 2000-10-05
DE60015519D1 (de) 2004-12-09
KR20020010593A (ko) 2002-02-04
EP1173530A1 (fr) 2002-01-23
KR100902460B1 (ko) 2009-06-11
DE60015519T2 (de) 2005-10-20
WO2000058422A1 (fr) 2000-10-05

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