EP0686182B1 - Compositions a base de petrole et adjuvants pour petrole - Google Patents

Compositions a base de petrole et adjuvants pour petrole Download PDF

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Publication number
EP0686182B1
EP0686182B1 EP94909061A EP94909061A EP0686182B1 EP 0686182 B1 EP0686182 B1 EP 0686182B1 EP 94909061 A EP94909061 A EP 94909061A EP 94909061 A EP94909061 A EP 94909061A EP 0686182 B1 EP0686182 B1 EP 0686182B1
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Prior art keywords
composition
fuel
weight
biofuel
fuel oil
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German (de)
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EP0686182A1 (fr
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Brian William Davies
Alessandro Lombardi
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Infineum USA LP
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Infineum USA LP
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    • 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
    • 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
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/224—Amides; Imides carboxylic acid amides, imides
    • 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
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
    • 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
    • C10L1/28—Organic compounds containing silicon
    • 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
    • C10L1/28—Organic compounds containing silicon
    • C10L1/285—Organic compounds containing silicon macromolecular 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1608—Well defined compounds, e.g. hexane, benzene
    • 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
    • C10L1/16—Hydrocarbons
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • 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
    • C10L1/1802—Organic compounds containing oxygen natural products, e.g. waxes, extracts, fatty oils
    • 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
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
    • 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
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/1915—Esters ester radical containing compounds; ester ethers; carbonic acid esters complex esters (at least 3 ester bonds)

Definitions

  • This invention relates to oil compositions, primarily to fuel oil compositions, and more especially to the control of foaming in such compositions.
  • foaming frequently occurs as the oil is passed from one vessel to another.
  • the foaming may interfere with the pumping of the oil, and may be such as to require a reduction in pumping rate to allow foam collapse to avoid oil spills. It is desirable to control foaming to permit higher rates of oil transfer.
  • oils such as liquid petroleum oils, especially fuel and lubricant oils.
  • oils typically pass through a distribution network, involving pumping through pipelines, or a series of storage tanks.
  • Fuel oils derived from vegetable or animal material are believed to be less damaging to the environment on combustion, and are obtained from a renewable resource. Certain biofuels may be used as complete substitutes for fuel oils such as diesel fuel oils. Similarly, certain biofuels may be used as partial substitutes for such fuel oils, being blended into the oils in suitable proportions.
  • Biofuels per se have lower foaming tendencies than typical fuel oils, such as diesel fuel oils.
  • blends of a biofuel with a diesel fuel oil have much higher foaming tendencies than the fuel oil per se. This finding is surprising since the minor components of fuel oils believed to be responsible for stabilisation of foam and surface-active in nature, differ from the constituents of these biofuels. Consequently, the addition of a quantity of biofuel to a fuel oil was not expected to increase the foaming tendency of the resulting blend.
  • foaming in a blend of petroleum-based fuel oil and a biofuel may be successfully controlled, in the sense that the initial foam height upon agitation is reduced, by an antifoam additive conventionally used to control foaming in petroleum distillate fuel oils (hereinafter referred to as a petroleum fuel antifoam).
  • an antifoam additive conventionally used to control foaming in petroleum distillate fuel oils
  • Such additives are themselves surface-active in nature, and are believed to interfere in some way with the foam-stabilising tendency of other components of the fuel blend.
  • US-A-2 862 885 describes the use of a silicon-containing antifoam for the prevention of foaming of petroleum oil substitutes.
  • FR-A-2 579 481 describes the use of siloxane-oxyalkylene block copolymers as antifoam agents for hydrocarbon fuel oils.
  • GB-A-658 494 describes antifoam compositions comprising a water-immiscible organic liquid.
  • the invention accordingly provides, in a first aspect, a fuel oil composition
  • a fuel oil composition comprising a major proportion of a blend of petroleum-based middle distillate fuel oil and a biofuel and a minor proportion of a petroleum fuel antifoam, wherein the antifoam is a silicon-containing composition and wherein the fuel oil has a sulphur concentration of 0.05% by weight or less, based on the weight of fuel.
  • the petroleum fuel antifoams useful in this first aspect of the invention are silicon-containing compositions. It has further been found that foaming in the blend of the first aspect may be successfully controlled, in the sense that foam collapse is accelerated, when the blend contains at most 65% by weight of a biofuel.
  • the invention accordingly provides, in a preferred embodiment of the first aspect, a fuel oil composition
  • a fuel oil composition comprising a major proportion of a blend of petroleum-based fuel oil and a biofuel and a minor proportion of a petroleum fuel antifoam being a silicon-containing composition, the fuel oil blend containing at most 65% by weight of a biofuel and at least 35% by weight of a petroleum-based fuel oil.
  • the invention also provides, in a second aspect, a concentrate comprising a petroleum fuel antifoam in admixture with a blend of a petroleum-based fuel oil and a biofuel; and in a third aspect, the use of a petroleum fuel antifoam to control foaming in a blend of petroleum-based fuel oil and a biofuel.
  • the Petroleum-Based Fuel Oil (of all aspects of the invention)
  • the petroleum-based fuel oil is suitably a middle distillate fuel oil, i.e. a fuel oil obtained in refining crude oil as the fraction between the lighter kerosene and jet fuels fraction and the heavier fuel oil fraction.
  • a middle distillate fuel oil i.e. a fuel oil obtained in refining crude oil as the fraction between the lighter kerosene and jet fuels fraction and the heavier fuel oil fraction.
  • Such distillate fuel oils generally boil within the range of about 100°C to about 500°C (ASTM D-86), e.g. 150°C to about 400°C, for example, those having a relatively high Final Boiling Point of above 360°C, such as 380°C.
  • the 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 petroleum distillate fuels are kerosene, jet fuels, diesel fuels, heating oils and heavy fuel oils.
  • the heating oil may be a straight atmospheric distillate, or it may contain minor amounts, e.g. up to 35 wt%, 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 stock.
  • a representative specification for a diesel fuel includes a minimum flash point of 38°C and a 90% distillation point of between 282 and 380°C (see ASTM Designations D-396 and D-975).
  • the fuel oil has a sulphur concentration of 0.05% by weight or less, and preferably 0.01% by weight or less.
  • the art describes methods for reducing the sulphur concentration of hydrocarbon middle distillate fuels, such methods including solvent extraction, sulphuric acid treatment, and hydrodesulphurisation.
  • the Biofuel (of all aspects of the invention)
  • the biofuel may be one or more oils derived from animal or vegetable material or both and capable of being utilised as a fuel.
  • Oils obtained from animal or vegetable material are mainly metabolites comprising trigylcerides of monocarboxylic acids, e.g. acids containing mainly 10-25 carbon atoms and of the form: where R represents an aliphatic radical of predominantly 10-25 carbon atoms which may be saturated or unsaturated. Preferably, R is an aliphatic radical of 10-25 carbons.
  • such oils contain glycerides of a number of acids, the number and kind varying with the source of the oil, and may additionally contain phosphoglycerides. Such oils may be obtained by methods known in the art.
  • esters such as methyl esters, of fatty acids of the vegetable or animal oils.
  • esters can be made by transesterification.
  • oils that are derived from animal or vegetable material therefore includes reference both to oils obtained from said animal or vegetable material or both, or to derivatives thereof.
  • oils derived from animal or vegetable material are rapeseed oil, coriander oil, soyabean oil, cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, maize oil, almond oil, palm kemel oil, coconut oil, mustard seed oil, beef tallow and fish oils. Further examples include oils derived from corn, jute, sesame, shea nut, ground nut and linseed and may be derived therefrom by methods known in the art. 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.
  • Rapeseed oil typically contains the esters of, in addition to some 11 to 19% C 16 to C 18 saturated acids, some 23 to 32% mono-, 40 to 50% di- and 4 to 12% tri-unsaturated C 18 to C 22 acids, primarily oleic, linoleic, linolenic and erucic acids.
  • 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 wt% 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.
  • oils may be used as biofuels, preferred are vegetable oils or derivatives thereof, of which particularly preferred biofuels are rapeseed oil, cottonseed oil, soyabean oil, sunflower oil, olive oil, palm oil, or alkyl ester derivatives thereof, rapeseed oil methyl ester being especially preferred.
  • the proportion of biofuel in the blend may range from 0.1% to 99.9%, preferably from 0.1% to 90% and more preferably from 0.5% to 85%, by weight.
  • the proportion by biofuel is advantageously at most 65%, and more advantageously at most 55%, by weight.
  • the blend may contain additives other than the petroleum fuel antifoam.
  • additives other than the petroleum fuel antifoam.
  • one or more co-additives such as low temperature flow improvers, stabilisers, dispersants, antioxidants, corrosion inhibitors, cetane improvers, emissions-reducing agents, reodorants, lubricity agents, antistatic additives or demulsifiers may be present in the blend.
  • co-additives may be added to the blend simultaneously with the petroleum fuel antifoam; for example, the antifoam and co-additives may comprise a single additive.
  • one or more co-additives may be added to the blend independent of the antifoam, or to the petroleum-based fuel oil or biofuel prior to blending.
  • the antifoam is advantageously insoluble in the fuel being treated but is dispersible therein to form a stable dispersion, if necessary with the aid of a suitable dispersant or solvent, either with or without the use of mechanical dispersing aids.
  • Such a composition advantageously comprises a siloxane polymer, for example a block copolymer containing siloxane blocks and oxyalkylene blocks.
  • siloxane polymers are those of general formula (i) wherein R represents a hydrocarbyl group, n represents an integer in the range of 1 to 3 and m represents a number ⁇ 2.
  • the hydrocarbyl group may be a relatively simple hydrocarbyl group of from 1 to 30 carbon atoms or may be a polymeric group.
  • the groups represented by R may be the same or different in any given siloxane group or throughout the siloxane polymer and the value of n in the various siloxane groups in the siloxane polymer may be the same or different.
  • the preferred polymers are block co-polymers comprising at least two blocks, one block comprising siloxane groups as represented by general formula (i) and the second block comprising oxyalkylene groups of general formula (ii) (R 1 -O)
  • each siloxane block and the oxyalkylene block may be linked to each other by means of a divalent hydrocarbylene group; this may be R in general formula (i).
  • each siloxane block contains at least one group represented by general formula (i) wherein at least one group represented by R is a divalent hydrocarbylene group.
  • the siloxane block has a ratio of hydrocarbyl groups to silicon atoms of 1:1 to 3:1.
  • the hydrocarbyl groups that are represented by R in general formula (i) may be alkenyl groups for example vinyl and allyl; cycloalkenyl groups, for example cyclohexenyl; alkyl groups, for example methyl, ethyl, isopropyl, octyl and dodecyl; aryl groups, for example phenyl and naphthyl; aralkyl groups, for example benzyl and phenylethyl; alkaryl groups, for example styryl, tolyl and n-hexylphenyl; or cycloalkyl groups, for example cyclohexyl.
  • the divalent hydrocarbylene groups represented by R in general formula (i) may be alkylene groups such as methylene, ethylene, propylene, butylene, 2,2-di-methyl-1,3-propylene and decylene, arylene groups such as phenylene and p,p'-diphenylene, or alkarylene groups such as phenylethylene.
  • the divalent hydrocarbylene group is an alkylene group containing from two to four successive carbon atoms.
  • divalent hydrocarbylene groups are linked to a silicon atom of the siloxane block by a silicon-to-carbon bond and to an oxygen atom of the oxyalkylene block by a carbon-to-oxygen bond.
  • the siloxane block in the copolymers may contain siloxane groups that are represented by general formula (i) wherein either the same hydrocarbyl groups are attached to the silicon atoms (e.g. the dimethylsiloxy, diphenylsiloxy and diethylsiloxy groups) or different hydrocarbyl groups are attached to the silicon atoms (e.g. the methylphenylsiloxy, phenylethylmethylsiloxy and ethylvinylsiloxy groups).
  • siloxane groups that are represented by general formula (i) wherein either the same hydrocarbyl groups are attached to the silicon atoms (e.g. the dimethylsiloxy, diphenylsiloxy and diethylsiloxy groups) or different hydrocarbyl groups are attached to the silicon atoms (e.g. the methylphenylsiloxy, phenylethylmethylsiloxy and ethylvinylsiloxy groups).
  • the siloxane block in the copolymers may contain one or more types of siloxane group that are represented by general formula (i) provided that at least one group has at least one divalent hydrocarbyl substituent.
  • ethylenemethylsiloxy groups can be present in the siloxane block or the siloxane block can contain more than one type of siloxane group, e.g. the block can contain both ethylenemethylsiloxy groups and diphenylsiloxy groups, or the block can contain ethylenemethylsiloxy groups, diphenylsiloxy groups and diethylsiloxy groups.
  • the siloxane block may contain trifunctional siloxane groups (e.g. monomethylsiloxane groups, CH 3 SiO 1.5 ), difunctional siloxane groups (e.g. dimethylsiloxane groups, (CH 3 ) 2 SiO, monofunctional siloxane groups (e.g. trimethylsiloxane groups, (CH 3 ) 3 SiO 0.5 ) or combinations of these types of siloxane groups having the same or different substituents. Due to the functionality of the siloxane groups, the siloxane block may be predominantly linear or cyclic or crosslinked, or it may have combinations of these structures.
  • trifunctional siloxane groups e.g. monomethylsiloxane groups, CH 3 SiO 1.5
  • difunctional siloxane groups e.g. dimethylsiloxane groups, (CH 3 ) 2 SiO
  • monofunctional siloxane groups e.g. trimethylsiloxane groups, (CH 3 ) 3 SiO 0.5
  • the siloxane block may contain organic end-blocking or chain-terminating organic groups in addition to the monofunctional siloxane chain-terminating groups encompassed by general formula (i).
  • Organic end-blocking groups may be hydroxyl groups, aryloxy groups such as phenoxy, alkoxy groups such as methoxy, ethoxy, propoxy and butoxy, and acyloxy groups such as acetoxy.
  • the siloxane blocks in the copolymers contain at least two siloxane groups that are represented by general formula (i) (so that m represents a number ⁇ 2).
  • the siloxane blocks contain a total of from five to twenty siloxane groups that are represented by general formula (i), with m representing a number in the range of 5 to 20. That part of the average molecular weight of the copolymer that is attributable to the siloxane blocks may be as high as 50000 but preferably it is from 220 to 20000.
  • the copolymers are usually not as useful, e.g. they may be too viscous for convenient use in the additives of this invention.
  • the oxyalkylene blocks in the copolymers each contain at least two oxyalkylene groups that are represented by the general formula (ii) wherein R 1 is an alkylene group.
  • R 1 is an alkylene group.
  • at least 60 per cent by weight of such groups represented by general formula (ii) are oxyethylene or oxypropylene groups.
  • oxyalkylene groups that are represented by general formula (ii) which can also be present in the oxyalkylene block, preferably in amounts not exceeding 40 per cent by weight are oxy-1,4-butylene, oxy-1,5-amylene, oxy-2,2-dimethyl-1,3-propylene, or oxy-1,10-decylene groups.
  • the oxyalkylene blocks in the copolymers may contain oxyethylene or oxypropylene groups alone or along with one or more of the various types of oxyalkylene groups represented by general formula (ii); the oxyalkylene blocks can contain only oxyethylene groups or only oxypropylene groups or both oxyethylene and oxypropylene groups, or other combinations of the various types of oxyalkylene groups represented by general formula (ii).
  • the oxyalkylene blocks in the copolymers may contain organic end-blocking or chain-terminating groups.
  • Such end-blocking groups may be hydroxy groups, aryloxy groups such as phenoxy, alkoxy groups such as methoxy, ethoxy, propoxy and butoxy, and alkenyloxy groups such as vinyloxy and allyloxy.
  • a single group can serve as an end-blocking group for more than one oxyalkylene block; for example, the glyceroxy group can serve as an end-blocking group for three oxyalkylene chains.
  • the oxyalkylene blocks in the copolymers contain at least two oxyalkylene groups that are represented by general formula (ii). Preferably, each block contains from four to thirty of such groups. That part of the average molecular weight of the copolymer that is attributable to the oxyalkylene blocks can vary from 176 (for (C 2 H 4 O) 4 ) to 200000, but preferably it is from 176 to 15000.
  • each oxyalkylene block contains at least two oxyalkylene groups represented by general formula (ii), the number of oxyalkylene groups and that part of the average molecular weight of the copolymer that is attributable to the oxyalkylene blocks is not critical, providing that the resulting copolymer is not rendered physically incompatible with oleaginous liquids.
  • those copolymers in which that part of the average molecular weight that is attributable to the oxyalkylene blocks exceeds 200000 or that contain more than fifty oxyalkylene groups per block prove less useful, e.g. they are too viscous for convenient use in the additives of this invention.
  • the copolymers may contain siloxane blocks and oxyalkylene blocks in any relative amounts.
  • the copolymer should contain from 5 parts by weight to 95 parts by weight of siloxane blocks and from 5 parts by weight to 95 parts by weight of oxyalkylene blocks per 100 parts by weight of the copolymer.
  • the copolymers contain 5 parts by weight to 50 parts by weight of the siloxane blocks and from 50 parts by weight to 95 parts by weight of the oxyalkylene blocks per 100 parts by weight of the copolymer.
  • the copolymers may contain more than one of each of the blocks and the blocks may be arranged in various configurations such as linear, cyclic or branched configurations.
  • the most preferred block co-polymers have the general formula (iii) wherein p represents an integer ⁇ 2 and preferably represents an integer in the range of 4 to 30, c represents an integer in the range of 0 to 2, m represents an integer ⁇ 2, R 2 represents a monovalent hydrocarbyl radical of 1 to 12 carbon atoms preferably a linear aliphatic radical for example a methyl or ethyl group, R 3 represents a divalent hydrocarbyl radical of 1 to 12 carbon atoms preferably an alkylene group of at least two carbon atoms for example ethylene, 1,3-propylene or 1,4-butylene, R 4 represents the same or different divalent hydrocarbyl radicals of 2 to 10 carbon atoms such as for example ethylene, 1,3-propylene or 1,6-hexylene, and R 5 represents a monovalent hydrocarbyl group of 1 to 12 carbon atoms or an end-group such as for example hydroxyl or hydrogen. It is preferred that R 4 represents different hydrocarbyl radical
  • block copolymers may be produced by an addition reaction between siloxanes containing silicon-bonded hydrogen atoms and oxyalkylene polymers containing alkenyl end-blocking groups in the presence of a platinum catalyst. These copolymers can also be prepared by a metathesis reaction between siloxanes containing silicon-bonded chloro-organo groups and an alkaline metal salt of a hydroxy end-blocked oxyalkylene polymer.
  • the concentration of the antifoam in the fuel oil composition may for example be in the range of 0.1 to 10,000 ppm, preferably 0.5 to 5000 ppm and most preferably 1 to 100 ppm (active ingredient) by weight per weight of fuel oil. Particularly advantageous concentrations are in the range of 1 to 20 ppm.
  • Concentrates are convenient as a means for incorporating the antifoam into the bulk fuel blend. Incorporation may be by methods known in the art.
  • the concentrates may also contain co-additives as required and as hereinbefore described and preferably contain from 3 to 75 wt%, more preferably 3 to 60 wt%, most preferably 10 to 50 wt% of the additives preferably in solution in oil.
  • carrier liquids are organic solvents including hydrocarbon solvents, for example petroleum fractions such as naphtha, kerosene, diesel and heater oil; aromatic hydrocarbons such as aromatic fractions, e.g. those sold under the 'SOLVESSO' trade name; and 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 blend.
  • suitable as such a carrier liquid is the fuel blend into the bulk of which the concentrate will be incorporated.
  • the antifoam may be incorporated into the bulk fuel blend by other methods such as those known in the art.
  • Co-additives may be incorporated into the bulk fuel blend at the same time as the antifoam or at a different time.
  • Antifoam A a proprietary block copolymer comprising siloxane blocks and oxyalkylene blocks, and of the general class hereinbefore described. Antifoam A is sold commercially for the treatment of middle distillate fuel oils.
  • the fuel oil compositions defined in Table 5 were prepared by a conventional laboratory blending technique, using a WARING blender.
  • the foaming tendency of each blend of biofuel and petroleum-based fuel oil was measured following addition of antifoam A, using a test procedure involving the agitation by hand of 100 ml of test fuel oil in a previously-cleaned and dried 4 oz bottle, the bottle then being placed in normal attitude on a stationary, flat surface.
  • the subsequent length of time (in seconds) over which the foam generated by shaking collapsed sufficiently to reveal a clear area of liquid surface was recorded as one measure of foaming tendency, longer foam collapse times indicating greater foam stability.
  • the silicon-containing antifoam significantly reduced foam collapse time in all blends comprising fuel oil A and at most 60% of biofuel (by wt.), and in all blends comprising fuel oil B and at most 70% of biofuel (by wt.) These results suggest the silicon-containing antifoam to be generally effective in fuel oil blends comprising at most about 65% biofuel (by wt.).
  • each blend in Table 5 was also measured in terms of the initial foam height obtained upon agitation.
  • the foam height of each antifoam-containing fuel oil composition is shown (in parentheses) as a percentage of the foam height of the corresponding untreated blend.
  • blend foam height results show that initial foam height is generally reduced upon addition of a petroleum fuel antifoam.

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Claims (23)

  1. Composition de fuel-oil, comprenant une proportion dominante d'un mélange d'un fuel-oil distillé moyen dérivé du pétrole et d'un biocarburant et une petite proportion d'un agent anti-mousse pour carburant dérivé du pétrole, dans laquelle l'agent anti-mousse est une composition contenant du silicium, et le fuel-oil a une concentration en soufre égale ou inférieure à 0,05 % en poids, sur la base du poids du carburant.
  2. Composition suivant la revendication 1, dans laquelle le mélange à base de fuel-oil contient au plus 65 % en poids de biocarburant et au moins 35 % en poids de fuel-oil dérivé du pétrole.
  3. Composition suivant la revendication 2, dans laquelle le mélange contient 0,1 % à 65 % en poids de biocarburant.
  4. Composition suivant la revendication 3, dans laquelle le mélange contient 0,5 % à 55 % en poids de biocarburant.
  5. Composition suivant l'une quelconque des revendications 1 à 4, dans laquelle le fuel-oil a une concentration en soufre égale ou inférieure à 0,01 % en poids, sur la base du poids du carburant.
  6. Composition suivant l'une quelconque des revendications 1 à 5, dans laquelle le fuel-oil distillé moyen consiste en huile de chauffe ou carburant diesel.
  7. Composition suivant la revendication 6, dans laquelle le fuel-oil consiste en carburant diesel.
  8. Composition suivant l'une quelconque des revendications 1 à 7, dans laquelle le fuel-oil distillé moyen a été soumis à une hydrodésulfuration.
  9. Composition suivant l'une quelconque des revendications 1 à 8, dans laquelle la composition contenant du silicium comprend un polymère de siloxane.
  10. Composition suivant la revendication 9, dans laquelle le polymère de siloxane est un copolymère séquencé contenant des séquences siloxane et des séquences oxyalkylène.
  11. Composition suivant la revendication 9 ou la revendication 10, dans laquelle le polymère de siloxane répond à la formule générale (i)
    Figure 00250001
    dans laquelle R représente un groupe hydrocarbyle ou hydrocarbylène, n représente un nombre entier de 1 à 3 et m représente un nombre égal ou supérieur à 2, et les groupes représentés par R peuvent être identiques ou différents dans n'importe quel groupe siloxane donné dans la totalité du polymère de siloxane, et n dans les divers groupes de siloxane dans le polymère de siloxane peut être avoir des valeurs identiques ou différentes.
  12. Composition suivant l'une quelconque des revendications 1 à 11, dans laquelle la biocarburant consiste en un ou plusieurs esters alkyliques d'acides gras d'huiles végétales ou animales.
  13. Composition suivant la revendication 12, dans laquelle les esters alkyliques sont des esters méthyliques, éthyliques, propyliques et butyliques d'acides gras ayant 12 à 22 atomes de carbone.
  14. Composition suivant la revendication 12 ou la revendication 13, dans laquelle les esters alkyliques sont des esters méthyliques d'acide oléique, d'acide linoléique, d'acide linolénique et d'acide érucique.
  15. Composition suivant l'une quelconque des revendications 12 à 14, dans laquelle le biocarburant consiste en un mélange contenant au moins 50 % en poids d'esters méthyliques d'acides gras ayant 16 à 22 atomes de carbone, et 1, 2 ou 3 doubles liaisons.
  16. Composition suivant l'une quelconque des revendications 12 à 15, dans laquelle le biocarburant est un ester méthylique de colza.
  17. Composition suivant l'une quelconque des revendications 1 à 16, qui comprend 0,1 à 10 000 ppm en poids d'agent anti-mousse.
  18. Composition suivant l'une quelconque des revendications précédentes, dans laquelle le mélange contient un ou plusieurs co-additifs.
  19. Composition suivant la revendication 18, dans laquelle le mélange contient, comme co-additifs, un ou plusieurs agents améliorant l'écoulement à basse température, stabilisants, dispersants, anti-oxydants, inhibiteurs de corrosion, agents améliorant l'indide de cétane, agents diminuant les émissions de polluants, désodorisants, agents d'onctuosité, additifs antistatiques ou désémulsionnants.
  20. Concentré comprenant un agent anti-mousse pour carburant dérivé du pétrole, dans lequel l'agent anti-mousse consiste en une composition contenant du silicium, en mélange avec un mélange d'un fuel-oil distillé moyen dérivé du pétrole ayant une concentration en soufre égale ou inférieure à 0,05 % en poids, sur la base du poids du carburant, et d'un biocarburant.
  21. Concentré suivant la revendication 20, contenant également un ou plusieurs co-additifs.
  22. Concentré suivant la revendication 21, contenant un ou plusieurs co-additifs répondant à la définition suivant la revendication 19.
  23. Utilisation d'un agent anti-mousse ou carburant du dérivé du pétrole, dans laquelle l'agent anti-mousse est une composition contenant du silicium, pour s'opposer au moussage dans un mélange d'un fuel-oil distillé moyen dérivé du pétrole ayant une concentration en soufre égale ou inférieure à 0,05 % en poids, sur la base du poids du carburant, et d'un bio-carburant.
EP94909061A 1993-02-26 1994-02-24 Compositions a base de petrole et adjuvants pour petrole Revoked EP0686182B1 (fr)

Applications Claiming Priority (3)

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GB9303924 1993-02-26
GB939303924A GB9303924D0 (en) 1993-02-26 1993-02-26 Oil additives and compositions
PCT/EP1994/000550 WO1994019430A1 (fr) 1993-02-26 1994-02-24 Compositions a base de petrole et adjuvants pour petrole

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EP0686182B1 true EP0686182B1 (fr) 1999-11-03

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CA (1) CA2157002C (fr)
DE (1) DE69421523T2 (fr)
GB (1) GB9303924D0 (fr)
MX (1) MX9401472A (fr)
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FR2750141B1 (fr) * 1996-06-19 2004-04-30 Total Raffinage Distribution Combustible pour chaudieres a base d'huile vegetale et a basse teneur en soufre
US6656977B2 (en) * 2001-07-20 2003-12-02 Air Products And Chemical, Inc. Alkyl glycidyl ether-capped polyamine foam control agents
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GR1006805B (el) * 2009-02-26 2010-06-16 Dorivale Holdings Limited, Βιοντιζελ που περιεχει μη φαινολικα προσθετα και ως εκ τουτου διαθετει αυξημενη οξειδωτικη σταθεροτητα και χαμηλο αριθμο οξυτητος
FR2985267B1 (fr) * 2011-12-28 2014-06-13 Total Raffinage Marketing Composition combustible comprenant un fioul lourd et un produit issu de la biomasse.
FR2985266B1 (fr) * 2011-12-28 2014-06-13 Total Raffinage Marketing Composition combustible comprenant un fioul lourd et un produit issu de la biomasse.
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JPH08506844A (ja) 1996-07-23
EP0686182A1 (fr) 1995-12-13
CA2157002A1 (fr) 1994-09-01
GB9303924D0 (en) 1993-04-14
DE69421523T2 (de) 2000-05-31
WO1994019430A1 (fr) 1994-09-01
KR100306334B1 (ko) 2001-11-30
DE69421523D1 (de) 1999-12-09
MX9401472A (es) 1994-08-31
CA2157002C (fr) 2004-07-27

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