WO2012117004A2 - Alcanols à chaîne moyenne dans des concentrés d'additif servant à améliorer la réduction de mousse dans les huiles combustibles - Google Patents

Alcanols à chaîne moyenne dans des concentrés d'additif servant à améliorer la réduction de mousse dans les huiles combustibles Download PDF

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WO2012117004A2
WO2012117004A2 PCT/EP2012/053392 EP2012053392W WO2012117004A2 WO 2012117004 A2 WO2012117004 A2 WO 2012117004A2 EP 2012053392 W EP2012053392 W EP 2012053392W WO 2012117004 A2 WO2012117004 A2 WO 2012117004A2
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additive
silicon
weight
antifoam agent
amount
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PCT/EP2012/053392
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German (de)
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WO2012117004A3 (fr
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Harald BÖHNKE
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Basf Se
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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
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • 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
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • 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
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
    • 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
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - 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
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
    • C10L1/231—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites nitro compounds; nitrates; nitrites
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—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)
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C10L2200/0476—Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel
    • 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
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/08—Inhibitors
    • C10L2230/082—Inhibitors for anti-foaming
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to the use of medium-chain alkanols for improving the defoaming action of a silicon-containing antifoam in fuel oils containing at least one detergent-effect additive. Furthermore, the present invention relates to an additive concentrate and its use for improving the foam reduction in fuel oils containing medium-chain alkanols, aromatic hydrocarbons or hydrocarbon mixtures and / or alkyl nitrates, silicon-containing antifoams and detergent-effect additives.
  • the subject of the present application is also a corresponding additive fuel oil.
  • Fuel oils usually contain antifoaming agents which are intended to prevent foaming of the fuel oil during movement or mechanical stress, for example when decanting or filling into storage tanks or tanks, or to reduce it to a tolerable degree.
  • antifoam agents also called defoamers
  • silicon-containing antifoam agents based on organosilicon chemistry such as polysiloxanes or silicone oils, are customary in this case.
  • the weight ratio of 2-ethylhexyl nitrate to 2-ethylhexanol never exceeds 3: 1.
  • a diesel fuel additive package is known, which according to Table 1 there as an additive with detergent effect 42 mg / kg of the reaction product of polyisobutenylsuccinanhydrid with tetraethylenepentamine in the molar ratio 1: 1, 20 mg / kg 2-ethylhexyl nitrate as a solvent, 132 mg / kg of an aromatic hydrocarbon mixture as a further solvent and 8 mg / kg of a conventional siloxane antifoam agent.
  • EP 0 681 023 A1 (3) describes fuel oils such as diesel fuels, kerosene, turbine fuels, heating oils and, inter alia, biofuel oils which comprise vegetable oils, which contain metal-containing detergents such as alkali or alkaline earth metal salts of acids or phenols, antifoams such as water-soluble polyethers Polysiloxane copolymers and ashless dispersants such as polyisobutenyl succinimides and, optionally, other components such as solvents, for example aromatic hydrocarbons, oil-soluble alcohols. demulsifiers, corrosion inhibitors, carrier liquids, antioxidants, metal deactivators, cold flow improvers or wax inhibitors.
  • fuel oils such as diesel fuels, kerosene, turbine fuels, heating oils and, inter alia, biofuel oils which comprise vegetable oils, which contain metal-containing detergents such as alkali or alkaline earth metal salts of acids or phenols, antifoams such as water-soluble polyethers Polysiloxane
  • the object underlying the present invention was to improve the defoaming action of the known antifoams, in particular the silicon-containing antifoams, and to provide a corresponding additive concentrate for use as an additive package in fuel oils, which improves the foam reduction in fuel oils.
  • At least one commercial dehazer wherein the sum of components (A) to (E) in each case is 100 wt .-%, and provided that in addition at least one of the following criteria is met: ( ⁇ ) the amount of the detergent-additive additive of component (D) is at least 10 times, more preferably at least 15 times, the amount of the silicon-containing antifoam agent of component (C);
  • the amount of the silicon-containing antifoam agent of component (C) Preferably, both criteria (.gamma.) And (.delta.) are met.
  • the improved effect of the present invention is due to the use of certain medium-cetane alkanols and above all the exactly matched ratio of the components (A), (B), (C) and (D).
  • the use according to the invention of said medium-chain alkanols has an advantageous effect on the foaming behavior, especially in fuel oils which contain or consist of biofuel oils.
  • Medium-chain alkanols which are component (A) in the additive concentrate according to the invention are C5- to cis-alkanols, in particular CQ- to C3-alkanols, especially C10-C10-alkanols, which are linear or preferably branched.
  • n-octanol, 2-ethylhexanol, n-nonanol, 2-propylheptanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol or isotridecanol are used in both aspects of the present invention. It is also possible to use a mixture of said alkanols. Very particular preference is given to 2-ethylhexanol.
  • Silica-containing antifoams of component (C) are to be understood as meaning all known antifoams of organic structure which are customary in the mineral oil sector and which contain one or more silicon atoms incorporated in the molecule. These may be, for example, polysiloxanes or silicone oils. In a preferred embodiment, polyether-modified polysiloxanes are used in both aspects of the present invention. These may, for example, have the structure of a polyether-polysiloxane copolymer.
  • additives having a detergent action of component (D) are compounds whose action in an internal combustion engine, in particular a diesel engine, consists predominantly or at least essentially in eliminating and / or increasing deposits prevent.
  • the detergents are preferably amphiphilic substances which have at least one hydrophobic hydrocarbon radical having a number-average molecular weight (M n ) of from 85 to 20,000, in particular from 300 to 5,000, in particular from 500 to 2,500, and at least one polar group ,
  • M n number-average molecular weight
  • the detergent-effect additives are selected hereunder:
  • derivatives with aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine.
  • the groups having hydroxyl and / or amino and / or amido and / or imido groups are, for example, carboxylic acid groups, acid amides, acid amides of di- or polyamines which, in addition to the amide function, still have free amine groups, succinic acid derivatives with an acid group. and an amide function, carboximides with monoamines, carbonic acid imides with di- or polyamines which, in addition to the imide function, still have free amine groups, and diimides which are formed by the reaction of di- or polyamines with two succinic acid derivatives.
  • Such fuel additives are described in particular in US Pat. No. 4,849,572.
  • Acid-free quaternized nitrogen compounds according to the above group (ii) obtained by addition of a compound containing at least one anhydride-reactive oxygen or nitrogen-containing group and additionally at least one quaternizable amino group to a polycarboxylic anhydride compound and subsequent quaternization, in particular with a Epoxy in the absence of free acid, are described in EP patent application Az. 10 168 622.8.
  • Suitable compounds having at least one anhydride-reactive oxygen or nitrogen-containing group and additionally at least one quaternizable amino group are in particular polyamines having at least one primary or secondary amino group and at least one tertiary amino group.
  • Particularly suitable polycarboxylic acid anhydrides are dicarboxylic acids such as succinic acid having a longer-chain hydrocarbyl substituent, preferably having a number-average molecular weight M n for the hydrocarbyl substituent of from 200 to 10,000, especially from 350 to 5,000.
  • a quaternized nitrogen compound is For example, the obtained at 40 ° C reaction product of polyisobutenylsuccinic anhydride in which the polyisobutenyl typically has a M n of 1000, with 3- (dimethyl-amino) - propylamine, which is a polyisobutenylsuccinic and then with styrene oxide in the absence of free acid at 70 ° C is quaternized.
  • Polytetrahydrobenzoxazines and bistetrahydrobenzoxazines according to group (iii) above are described in EP patent application Az. 10 194 307.4.
  • Such Polytetrahydrobenzoxazi- ne and Bistetrahydrobenzoxazine are obtainable by successive in a first reaction step a d- to C2o-alkylenediamine with two primary amino functions, for example 1, 2-ethylenediamine, with a d- to Ci2-aldehyde, eg formaldehyde, and a d- to Ce-alkanol at a temperature of 20 to 80 ° C with elimination and removal of water, wherein both the aldehyde and the alcohol in each case in more than twice the molar amount, in each case in the 4-fold molar amount, are used opposite the diamine, in a second reaction step, the condensation product thus obtained with a phenol having at least one long-chain substituent having 6 to 3000 carbon atoms,
  • At least one detergent-effect additive in both aspects of the present invention are compounds having succinic anhydride-derived moieties having hydroxy and / or amino and / or amido and / or imido groups, but especially a compound from the group (i) which is a polyisobutenyl-substituted succinimide.
  • fuel oils are to be understood as meaning in particular middle distillate fuels, especially diesel fuels. But also an application of the present invention in fuel oil or kerosene is possible.
  • Diesel fuels or middle distillate fuels are usually petroleum raffinates, which generally have a boiling range of 100 to 400. These are mostly distillates with a 95% point up to 360 ° C or even beyond. However, these may also be so-called "ultra low sulfur diesel” or "city diesel", characterized by a 95% point of, for example, a maximum of 345 ° C and a maximum sulfur content of 0.005 wt .-% or by a 95% point of example 285 ° C and a maximum sulfur content of 0.001 wt .-%.
  • diesel fuels whose major components are longer chain paraffins
  • those obtainable by coal gasification or gas liquefaction [GTL] fuels are also suitable.
  • mixtures of the abovementioned diesel fuels with regenerative fuels (biofuel oils) such as biodiesel or bioethanol.
  • biofuel oils biodiesel or bioethanol.
  • low sulfur diesel fuels that is having a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, more preferably less than 0.005% by weight, and especially of fewer than 0.02% by weight, in particular less than 0.005% by weight and especially less than 0.001% by weight of sulfur.
  • Diesel fuels can also contain water, for example in an amount of up to 20% by weight, for example in the form of diesel-water microemulsions or as so-called "white diesel".
  • the C5- to cis-alkanols or the inventive additive concentrate according to the present invention are used in fuel oils which are (a) from 0.1 to 100% by weight, preferably from 0.1 to less than 100 Wt .-%, in particular to 10 to 95 wt .-%, especially to 30 to 90 wt .-%, of at least
  • a biofuel based on fatty acid esters and at 0 to 99.9 wt .-%, preferably to more than 0 to 99.9 wt .-%, in particular to 5 to 90 wt .-%, especially to 10 to 70 Wt .-%, of middle distillates of fossil origin and / or of vegetable and / or animal origin, which are substantially hydrocarbon mixtures and are free of fatty acid esters exist.
  • the fuel oils may also consist of at least 100% by weight of at least one biofuel (a) based on fatty acid esters.
  • the fuel oil component (a) is usually referred to as "biodiesel".
  • biodiesel are preferably substantially alkyl esters of fatty acids derived from vegetable and / or animal oils and / or fats.
  • Alkyl esters are usually lower alkyl esters, especially C 4 to C 4 alkyl esters, understood by transesterification of occurring in vegetable and / or animal oils and / or fats glycerides, especially triglycerides, by means of lower alcohols, such as ethanol, n-propanol, iso-propanol, n-
  • Butanol, iso-butanol, sec-butanol, tert-butanol or especially methanol (“FAME”) are available.
  • Examples of vegetable oils which are converted into corresponding alkyl esters and thus can serve as a basis for biodiesel are castor oil, olive oil, peanut oil, palm kernel oil, coconut oil, mustard oil, cottonseed oil, and in particular sunflower oil, palm oil, soybean oil and rapeseed oil.
  • Other examples include oils that can be extracted from wheat, jute, sesame and the shea nut; furthermore, arachis oil, jatropha oil and linseed oil are also usable. The recovery of these oils and their conversion to the alkyl esters are known in the art or may be derived therefrom.
  • animal fats and oils that are converted into corresponding alkyl esters and thus can serve as the basis for biodiesel are fish oil, beef tallow, pig tallow and similar fats and oils that are produced as waste in the slaughtering or recycling of farm animals or wild animals.
  • saturated or unsaturated fatty acids which usually have 12 to 22 carbon atoms and may carry additional functional group such as hydroxyl groups, occur in the alkyl esters in particular lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, Linoleic acid, linolenic acid, elaidic acid, erucic acid and / or ricinoleic acid.
  • Typical lower alkyl esters based on vegetable and / or animal oils and / or fats which are used as biodiesel or biodiesel components are, for example, sunflower methyl ester, palm oil methyl ester ("PME”), soybean oil methyl ester (“SME”) and in particular rapeseed oil methyl ester (" RME ").
  • the fuel oil component (b) should be understood to mean the abovementioned middle distillate fuels, especially diesel fuels, in particular those which boil in the range from 120 to 450.degree.
  • the C5 to Cis alkanols or additive concentrate according to the present invention are used to improve the defoamer action of the silicon-containing antifoam agent in fuel oils such that the improvement is to the extent that at least one of the following criteria is met :
  • the BNPe NF-M 07-075 foam test is a common measurement method for determining the foam volume and foam decay time of fuel oil samples.
  • a measuring apparatus standardized according to this standard is used.
  • the additive concentrate according to the invention contains as component (B) in the function of a substantially non-polar solvent, which in interaction with the component (A) as the polar solvent the desired defoaming action, as a first alternative (i) one or more aromatic hydrocarbons, e.g. Toluene, xylenes or homologous mono- or dialkylbenzenes as well as from aromatic hydrocarbons existing or aromatic hydrocarbons as main components containing technical solvent mixtures of the names Shellsol® (manufacturer: Royal Dutch / Shell Group), Exxol® or Solvesso® (manufacturer: ExxonMobil) or solvent Naphtha.
  • aromatic hydrocarbons e.g. Toluene, xylenes or homologous mono- or dialkylbenzenes
  • aromatic hydrocarbons e.g. Toluene, xylenes or homologous mono- or dialkylbenzenes
  • aromatic hydrocarbons e.g. To
  • Ci2-Alkylnitrate As a second alternative (ii) for the component (B) are C5 to Ci2-Alkylnitrate into consideration, which are to function in the fuel oil as Cetaniereverêter or ignition accelerator.
  • alkyl nitrates are in particular nitrate esters of unsubstituted or substituted aliphatic or cycloaliphatic alcohols, usually having 5 to 10 carbon atoms.
  • the alkyl group in these nitrate esters may be linear or branched, saturated or unsaturated.
  • nitrate esters are n-amyl nitrate, isoamyl nitrate, 2-amyl nitrate, 3-amyl nitrate, tert-amyl nitrate, n-hexyl nitrate, n-heptyl nitrate, sec-heptyl nitrate, n-octyl nitrate, 2-ethylhexyl nitrate, sec-octyl nitrate, n-nonyl nitrate, n-decyl nitrate, cyclopentyl nitrate, cyclohexyl nitrate, methylcyclohexyl nitrate and isopropylcyclohexyl nitrate and branched decyl nitrates having an n-propyl or isopropyl radical in the 2-position of the alkyl chain, as described in
  • nitrate esters of alkoxy-substituted aliphatic alcohols such as 2-ethoxyethyl nitrate, 2- (2-ethoxyethoxy) ethyl nitrate, 1-methoxypropyl nitrate or 4-ethoxybutyl nitrate are also suitable, for example.
  • diol nitrates such as 1,6-hexamethylene dinitrate.
  • 2-ethylhexyl nitrate is the most common cetane number improver and is also preferred for the present invention.
  • mixtures of (i) and (iii) are also suitable, for example mixtures of 1 to 99 parts by weight of (i) and 99 to 1 part by weight of (ii) , in particular from 10 to 90 parts by weight of (i) and 90 to 10 parts by weight of (ii), especially of 25 to 75 parts by weight of (i) and 75 to 25 parts by weight of (ii), wherein the aromatic hydrocarbon (i) and the alkyl nitrates (ii) together account for the said amounts in the additive concentrate according to the invention.
  • Suitable co-additives of component (E) are suitable dehazers, for example alkoxylated phenol-formaldehyde condensates.
  • the additive concentrate according to the invention is usually added to the fuel oil in such an amount that the detergent-effect additive of component (D) or a mixture of several such detergent-effecting additives in the fuel oil in an amount of from 10 to 2000% by weight. ppm, in particular from 20 to 1000 ppm by weight, especially from 30 to 500 ppm by weight, is present.
  • the additive concentrate according to the invention or the fuel oil additized therewith can furthermore contain other customary co-additives, in particular cold flow improvers, corrosion inhibitors, demulsifiers, antioxidants and stabilizers, metal deactivators , Antistatic agents, lubricity improvers, dyes (markers) and / or other diluents and solvents.
  • suitable cold flow improvers are, for example, copolymers of ethylene with at least one further unsaturated monomer, especially ethylene-vinyl acetate copolymers.
  • Corrosion inhibitors suitable as further co-additives are, for example, succinic esters, especially with polyols, fatty acid derivatives, e.g. Olechreester, oligomerized fatty acids and substituted ethanolamines.
  • Demulsifiers suitable as further co-additives are, for example, the alkali and alkaline earth metal salts of alkyl-substituted phenol and naphthalenesulfonates and the alkali and alkaline earth metal salts of fatty acid, furthermore alcohol alkoxylates, e.g. Alcohol ethoxylates, phenol alkoxylates, e.g. tertiary butyl phenol ethoxylates or tertiary pentyl phenol ethoxylates, fatty acid, alkyl phenols, condensation products of ethylene oxide and propylene oxide, e.g. Ethylene oxide-propylene oxide block copolymers, polyethyleneimines and polysiloxanes.
  • alcohol alkoxylates e.g. Alcohol ethoxylates, phenol alkoxylates, e.g. tertiary butyl phenol ethoxylates or tertiary
  • suitable antioxidants are, for example, substituted phenols, e.g. 2,6-di-tert-butylphenol and 2,6-di-tert-butyl-3-methylphenol, as well as phenylenediamines, e.g. N, N'-di-sec-butyl-p-phenylenediamine.
  • Metal deactivators useful as further co-additives include, for example, salicylic acid derivatives, e.g. N, N'-disalicylidene-1,2-propanediamine.
  • a lubricity improver suitable as a further coadditive is, for example, glycerol monooleate. If the said co-additives and / or further diluents or solvents are used, they are used in the quantities customary for this purpose.
  • the subject of the present invention is also an additive fuel oil which contains a larger amount of basic fuel oil
  • AF A An additive formulation (AF A", for comparison) of the composition 25 wt .-% of a commercially available polyisobutenyl-substituted succinimide (Kerocom® PIBSI Fa. BASF SE) as an additive with detergent effect, 72 wt .-% Solvesso® 150 as aromatic hydrocarbon mixture, 1 wt .-% of a commercially available silicon-containing antifoaming agent and 2 wt .-% of a commercial Dehazers was added in a dosage of 200 mg / kg of the above-identified fuel DK 1. The foam volume and foam decay time of AFA additized fuel were determined.
  • AF B Another additive formulation (AF B", according to the present invention) of the composition 25 wt .-% of a commercial polyisobutenyl-substituted succinimide (Kerocom® PIBSI Fa. BASF SE) as an additive with detergent effect, 67 wt. % Solvesso® 150 as an aromatic hydrocarbon mixture, 5% by weight of 2-ethylhexanol, 1% by weight of a commercially available silicon-containing antifoam and 2% by weight of a commercial dehazer was added to the above-identified fuel at a dosage of 200 mg / kg DK 1 added.
  • the foam volume and foam decay time of AFA additized fuel were determined.
  • the following table shows the results of the determinations: Fuel Foam volume Foam disintegration time of unadditized DK 1 95 ml 35 sec

Abstract

L'invention concerne des alcanols à chaîne moyenne dans des concentrés d'additif servant à améliorer la réduction de mousse dans les huiles combustibles. Les alcanols en C5 à C15 conviennent pour améliorer dans les huiles combustibles l'effet antimousse d'un antimousse contenant du silicium, en particulier dans les huiles combustibles biologiques, lesquelles contiennent au moins un additif à effet détergent. De tels alcanols sont utilisés dans des concentrés d'additifs qui contiennent par ailleurs des hydrocarbures ou des mélanges d'hydrocarbures aromatiques présentant un point d'ébullition compris entre 100 et 250 C, ou des nitrates d'alkyle en C5 à C12 ainsi que des antimousses contenant du silicium, des additifs à effet détergent et, le cas échéant, des « dehazers » du commerce.
PCT/EP2012/053392 2011-03-01 2012-02-29 Alcanols à chaîne moyenne dans des concentrés d'additif servant à améliorer la réduction de mousse dans les huiles combustibles WO2012117004A2 (fr)

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EP3399013A1 (fr) 2017-05-05 2018-11-07 The Procter & Gamble Company Compositions de détergent à lessive présentant une meilleure élimination de graisse
EP3399012A1 (fr) 2017-05-05 2018-11-07 The Procter & Gamble Company Compositions détergentes liquides à rhéologie améliorée

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WO2000039254A1 (fr) 1998-12-23 2000-07-06 Shell Internationale Research Maatschappij B.V. Composition de fuel-oil
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US4849572A (en) 1987-12-22 1989-07-18 Exxon Chemical Patents Inc. Process for preparing polybutenes having enhanced reactivity using boron trifluoride catalysts (PT-647)
EP0681023A1 (fr) 1994-05-04 1995-11-08 Ethyl Petroleum Additives Limited Concentrés additifs pour combustible, compatibles
WO2000039254A1 (fr) 1998-12-23 2000-07-06 Shell Internationale Research Maatschappij B.V. Composition de fuel-oil
WO2008092809A1 (fr) 2007-01-29 2008-08-07 Basf Se Nitrates de décyle ramifiés et leur utilisation en tant qu'améliorateurs de combustion et/ou améliorateurs d'indice de cétane dans des carburants
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Publication number Priority date Publication date Assignee Title
EP3399013A1 (fr) 2017-05-05 2018-11-07 The Procter & Gamble Company Compositions de détergent à lessive présentant une meilleure élimination de graisse
EP3399012A1 (fr) 2017-05-05 2018-11-07 The Procter & Gamble Company Compositions détergentes liquides à rhéologie améliorée
WO2018204559A1 (fr) 2017-05-05 2018-11-08 The Procter & Gamble Company Compositions de détergent à lessive à élimination améliorée de graisse
WO2018204560A1 (fr) 2017-05-05 2018-11-08 The Procter & Gamble Company Compositions détergentes liquides à rhéologie améliorée
US11634662B2 (en) 2017-05-05 2023-04-25 The Procter & Gamble Company Liquid detergent compositions with improved rheology
US11634661B2 (en) 2017-05-05 2023-04-25 The Procter & Gamble Company Laundry detergent compositions with improved grease removal

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