EP2038380B1 - Mélange constitué de composés d'azote polaires oléosolubles et d'amides d'acides en tant que dispersant de paraffine pour des carburants - Google Patents

Mélange constitué de composés d'azote polaires oléosolubles et d'amides d'acides en tant que dispersant de paraffine pour des carburants Download PDF

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EP2038380B1
EP2038380B1 EP07730085A EP07730085A EP2038380B1 EP 2038380 B1 EP2038380 B1 EP 2038380B1 EP 07730085 A EP07730085 A EP 07730085A EP 07730085 A EP07730085 A EP 07730085A EP 2038380 B1 EP2038380 B1 EP 2038380B1
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oil
fuels
weight
acid
mixture
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EP2038380A2 (fr
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Ansgar Eisenbeis
Irene Trötsch-Schaller
Ulrich Annen
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BASF SE
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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
    • C10L1/10—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
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • 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
    • 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
    • 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
    • C10L10/16—Pour-point depressants
    • 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
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/1955—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by an alcohol, ether, aldehyde, ketonic, ketal, acetal 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
    • 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
    • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
    • 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
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • 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
    • C10L1/10—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

Definitions

  • the present invention relates to the use of this mixture as an additive to fuels, especially in the function as a paraffin dispersant, such fuels themselves and fuel additive concentrates containing this mixture dissolved in a hydrocarbon solvent.
  • the fuels mentioned have in particular a biodiesel component.
  • Middle distillate fuels of fossil origin especially gas oils, diesel oils or light fuel oils derived from petroleum, have different levels of paraffins depending on the source of the crude oil.
  • cloudy point or Cloud Point (“CP") precipitates solid paraffins.
  • the platy n-paraffin crystals form a kind of "house of cards structure” and the middle distillate fuel stagnates, although its predominant part is still liquid.
  • the precipitated n-paraffins in the temperature range between cloud point (cloud point) and pour point (pour point) the flowability of middle distillate fuels is significantly affected;
  • the paraffins clog filters and cause uneven or completely interrupted fuel supply to the combustion units. Similar disturbances occur with light fuel oils.
  • ethylene-vinyl carboxylate copolymers have long been used as cold flow improvers or Middle Distillate Flow Improvers ("MDFI").
  • MDFI Middle Distillate Flow Improvers
  • a disadvantage of these additives is that the precipitated paraffin crystals tend due to their relative to the liquid part higher density tend to settle more and more at the bottom of the container during storage. As a result, a homogeneous low-paraffin phase forms in the upper container part and a two-phase paraffin-rich layer at the bottom. Since the deduction of the fuel usually takes place slightly above the container bottom both in the vehicle tanks and in storage or delivery tanks of the mineral oil dealer, there is the risk that the high concentration of solid paraffins leads to blockages of filters and metering devices. This danger is greater the further the storage temperature falls below the excretion temperature of the paraffins, since the amount of paraffin precipitated increases with decreasing temperature. In particular, levels of biodiesel also enhance this undesirable tendency of the middle distillate fuel to paraffin sedimentation.
  • WO 00/23541 (1) is the use of a mixture of 5 to 95 wt .-% of at least one reaction product of a poly (C 2 - to C 20 carboxylic acid having at least one tertiary amino group) with secondary amines and 5 to 95 Wt .-% of at least one reaction product of maleic anhydride and a primary alkylamine as an additive for petroleum middle distillates, in particular as paraffin dispersant and lubricity additive described.
  • the GB-A 1 410 788 discloses a fuel additive composition consisting of a fatty acid amide of aliphatic polyamines and an alkanolamine ester of a fatty or naphthenic acid in the weight ratio of 1: 8 to 8: 1.
  • the GB-A 842 991 discloses a fuel additive composition consisting of a fatty acid amide of ethylene diamine with oleic acid and a diethylaminoethyl methacrylate based copolymer.
  • the object was to provide products which ensure improved fluidity behavior of fuels, in particular those fuels which have a proportion of biofuel (biodiesel) which is based on fatty acid esters, at low temperature, by exhibiting such a dispersing action in that settling of excreted paraffins is delayed or prevented.
  • biofuel biodiesel
  • the object is achieved by the above-mentioned mixture of components (a) to (c), which is all the more surprising, since the components (a) and (b) alone respectively no or only a small, not sufficient flow improving Effect in a mixture of a conventional middle distillate of fossil origin and a biofuel oil which is based on fatty acid esters have.
  • the component (c) is not necessarily necessary for achieving the intended flowability improvement, but usually significantly enhances this effect.
  • the polar, oil-soluble nitrogen compounds of component (a) which are capable of sufficiently dispersing paraffin crystals precipitated in fuels in the cold can be both ionic and nonionic and preferably have at least one, especially at least 2, substituents of the general formula > NR 22 , wherein R 22 is a C 8 - to C 40 hydrocarbon radical.
  • the Nitrogen substituents may also be quaternized, that is in cationic form. Examples of such nitrogen compounds are ammonium salts and / or amides obtainable by reacting at least one amine substituted with at least one hydrocarbon radical with a carboxylic acid having up to 4 carboxyl groups or with a suitable derivative thereof.
  • the amines preferably contain at least one linear C 8 - to C 40 -alkyl radical.
  • suitable primary amines are octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologues.
  • Suitable secondary amines are, for example, dioctadecylamine and methylbehenylamine.
  • amine mixtures in particular industrially available amine mixtures such as fatty amines or hydrogenated tallamines, as described for example in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, in the chapter "Amines, aliphatic".
  • suitable polar, oil-soluble nitrogen compounds are ring systems bearing at least two substituents of the formula -A'-NR 23 R 24 , wherein A 'represents a linear or branched aliphatic hydrocarbon group optionally substituted by one or more moieties selected is interrupted by O, S, NR 35 and CO, and R 23 and R 24 are a C 9 to C 40 hydrocarbon radical optionally substituted by one or more moieties selected from O, S, NR 35 and CO, interrupted and / or substituted by one or more substituents selected from OH, SH and NR 35 R 36 , wherein R 35 is C 1 - to C 40 -alkyl optionally substituted by one or more moieties are selected from CO, NR 35 , O and S, interrupted, and / or by one or more radicals selected from NR 37 R 38 , OR 37 , SR 37 , COR 37 , COLOR 37 , CONR 37 R 38 , aryl or heterocyclyl, s is substitute
  • the mixture according to the invention contains as component (a) at least one oil-soluble reaction product of at least one tertiary amino group-containing poly (C 2 - to C 20 -carboxylic acids) with primary or secondary amines.
  • the component (a) underlying at least one tertiary amino group-containing poly (C 2 - to C 20 carboxylic acids) preferably contain at least 3 carboxyl groups, especially 3 to 12, especially 3 to 5 carboxyl groups.
  • the carboxylic acid units in the polycarboxylic acids preferably have 2 to 10 carbon atoms, in particular they are acetic acid units.
  • the carboxylic acid units are suitably linked to the polycarboxylic acids, for example via one or more carbon and / or nitrogen atoms. Preferably, they are attached to tertiary nitrogen atoms, which are connected in the case of several nitrogen atoms via hydrocarbon chains.
  • the mixture according to the invention contains as component (a) at least one oil-soluble reaction product based on poly (C 2 - to C 20 -carboxylic acids) of general formula I or II containing at least one tertiary amino group in which the variable A is a straight-chain or branched C 2 - to C 6 -alkylene group or the grouping of the formula III and the variable B denotes a C 1 - to C 19 -alkylene group.
  • oil-soluble reaction product of component (a), in particular that of the general formula I or II, is an amide, an amide ammonium salt or an ammonium salt in which none, one or more carboxylic acid groups are converted into amide groups.
  • Straight-chain or branched C 2 -C 6 -alkylene groups of the variable A are, for example, 1,1-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4- Butylene, 2-methyl-1,3-propylene, 1,5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene (hexamethylene) and in particular 1,2-ethylene.
  • the variable A comprises 2 to 4, in particular 2 or 3 carbon atoms.
  • C 1 - to C 19 -alkylene groups of the variable B are, for example, 1,2-ethylene, 1,3-propylene, 1,4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene, nonadecamethylene and in particular methylene.
  • the variable B comprises 1 to 10, in particular 1 to 4, carbon atoms.
  • the primary and secondary amines as reaction partners for the polycarboxylic acids to form the component (a) are usually monoamines, in particular aliphatic monoamines. These primary and secondary amines can be from a variety be selected from amines carrying - optionally interconnected - hydrocarbon radicals.
  • These longer-chain alkyl radicals are preferably straight-chain or only slightly branched.
  • the abovementioned secondary amines are derived with regard to their longer-chain alkyl radicals from naturally occurring fatty acid or from its derivatives.
  • the two radicals R are the same.
  • the abovementioned secondary amines can be bound to the polycarboxylic acids by means of amide structures or in the form of the ammonium salts, and only one part can be present as amide structures and another part as ammonium salts. Preferably, only a few or no free acid groups are present.
  • the oil-soluble reaction products of component (a) are completely in the form of the amide structures.
  • components (a) are reaction products of nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1,2-diaminetetraacetic acid with in each case 0.5 to 1.5 mol per carboxyl group, in particular 0.8 to 1.2 mol per carboxyl group, dioleylamine, Dipalmitinamine, Dikokosfettamin, distearylamine, dibehenylamine or especially Ditalgfettamin.
  • a particularly preferred component (a) is the reaction product of 1 mole of ethylenediaminetetraacetic acid and 4 moles of hydrogenated ditallow fatty amine.
  • the polyamines on which the oil-soluble acid amides of component (b) are based can either be structurally clearly defined low molecular weight "oligo" amines or polymers having up to 1000, in particular up to 500, especially up to 100, nitrogen atoms in the macromolecule.
  • oligo low molecular weight
  • the latter are then usually polyalkyleneimines, for example polyethyleneimines, or polyvinylamines.
  • the polyamines mentioned are reacted with C 8 - to C 30 -fatty acids, in particular C 16 - to C 20 -fatty acids, to give the oil-soluble acid amides.
  • C 8 - to C 30 -fatty acids in particular C 16 - to C 20 -fatty acids
  • reactive fatty acid derivatives such as the corresponding esters, halides or anhydrides, for the reaction.
  • Suitable polyamines for the conversion to the acid amides of component (b) are, for example: ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenhexamine, polyethyleneimines of average degree of polymerization (corresponding to the number of nitrogen atoms) of e.g. , B. 10, 35, 50 or 100 and polyamines, which were obtained by reaction of oligoamines (with chain extension) with acrylonitrile and subsequent hydrogenation, for. N, N'-bis (3-aminopropyl) ethylenediamine.
  • Suitable fatty acids for the conversion to the acid amides of component (b) are pure fatty acids and technically customary fatty acid mixtures which comprise, for example, stearic acid, palmitic acid, lauric acid, oleic acid, linoleic acid and / or linolenic acid.
  • fatty acid mixtures for example tallow fatty acid, coconut oil fatty acid, trans fatty acid, coconut oil fatty acid, soybean oil fatty acid, rapeseed oil fatty acid, peanut oil fatty acid or palm oil fatty acid, which contain oleic acid and palmitic acid as main components.
  • the mixture according to the invention contains as component (b) at least one oil-soluble acid amide of aliphatic polyamines having 2 to 6 nitrogen atoms and C 16 - to C 20 -fatty acids, all primary and secondary amino functions of the polyamines being converted into acid amide functions.
  • a typical example of an oil-soluble acid amide of component (b) is the reaction product of 3 moles of oleic acid with 1 mole of diethylenetriamine.
  • the oil-soluble reaction products of component (c) underlying ⁇ , ⁇ -dicarboxylic acids having 4 to 300, especially 4 to 75, especially 4 to 12 carbon atoms are usually succinic acid, maleic acid, fumaric acid or derivatives thereof, at the bridging ethylene or Ethenylene group may have shorter or longer chain hydrocarbyl substituents which contain or may carry heteroatoms and / or functional groups.
  • succinic acid, maleic acid, fumaric acid or derivatives thereof at the bridging ethylene or Ethenylene group may have shorter or longer chain hydrocarbyl substituents which contain or may carry heteroatoms and / or functional groups.
  • these are generally used in the form of the free dicarboxylic acid or its reactive derivatives.
  • Carboxylic acid halides, carboxylic acid esters or, in particular, carboxylic acid anhydrides can be used here as reactive derivatives.
  • the mixture according to the invention contains as component (c) at least one oil-soluble reaction product of maleic anhydride and primary alkylamines.
  • the primary alkylamines underlying the oil-soluble reaction products of component (c) are usually medium-chain or long-chain alkyl monoamines preferably having 8 to 30, in particular 12 to 22 carbon atoms, and linear or branched, saturated or unsaturated alkyl chain, for example octyl, nonyl, iso-nonyl -, decyl, undecyl, tridecyl, iso-tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecylamine and mixtures of such amines.
  • alkyl monoamines preferably having 8 to 30, in particular 12 to 22 carbon atoms, and linear or branched, saturated or unsaturated alkyl chain, for example octyl, nonyl, iso-nonyl -, decyl, undecyl, tridecyl, iso-tride
  • reaction products of component (c) are usually - depending on the stoichiometry and reaction regime - as half or bisamides of maleic acid before; they may also contain minor amount of corresponding ammonium salts.
  • the preparation of the oil-soluble reaction products of component (c) from maleic anhydride and primary alkylamines is described in document (1).
  • a typical example of an oil-soluble reaction product of component (c) is the reaction product of 1 mol of maleic anhydride with 1 mol of iso-tridecylamine, which is present predominantly as a half-amide of maleic acid.
  • the mixture according to the invention can be prepared by simple mixing, optionally in a suitable solvent, of components (a) and (b) or (a) to (c) without heat input.
  • the mixture according to the invention is suitable as an additive to fuels, especially middle distillate fuels.
  • Middle distillate fuels which are used in particular as gas oils, petroleum, diesel oils (diesel fuels) or light fuel oils, are often referred to as fuel oils.
  • Such middle distillate fuels generally have boiling temperatures of 150 to 400 ° C.
  • the mixture according to the invention can be injected directly into the fuels, i. undiluted, but preferably as 10 to 70 wt .-%, in particular as 30 to 65 wt .-%, especially as 45 to 60 wt .-% solution (concentrate) in a suitable solvent, usually a hydrocarbon solvent be added.
  • a suitable solvent usually a hydrocarbon solvent be added.
  • Common solvents in this context are aliphatic or aromatic hydrocarbons, for example xylenes or mixtures of high-boiling aromatics such as solvent naphtha. Even middle distillate fuels themselves can be used as solvents for such concentrates.
  • the metering rate of the mixture in the fuels is generally 10 to 10,000 ppm by weight, in particular 50 to 5000 ppm by weight, especially 50 to 1000 ppm by weight, e.g. 150 to 400 ppm by weight, based in each case on the total amount of middle distillate fuel.
  • the fuel component (A) is usually referred to as "biodiesel".
  • the middle distillates of the fuel component (A) 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, in particular C 1 - 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, isoPropanol , n-butanol, iso-butanol, sec-butanol, tert-butanol, or especially methanol ("FAME").
  • FAME methanol
  • 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.
  • Vegetable fats are also useful in principle as a source of biodiesel, but play a minor role.
  • animal fats and oils that are converted into corresponding alkyl esters and thus can serve as a basis for biodiesel are fish oil, beef tallow, Pig tallow and similar fats and oils derived from the slaughtering or recycling of farmed or wild animals.
  • saturated or unsaturated fatty acids which usually have from 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, linolenic, elaidic, erucic and ricinolic acids, especially in the form of mixtures of such fatty acids.
  • 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 especially rapeseed oil methyl ester (“RME”). ).
  • fuel component (B) is to be understood to mean boiling middle distillate fuels in the range from 120 to 450 ° C.
  • middle distillate fuels are used in particular as diesel fuel, heating oil or kerosene, with diesel fuel and heating oil being particularly preferred.
  • Middle distillate fuels are fuels obtained by distillation of crude oil and boiling in the range of 120 to 450 ° C.
  • low sulfur middle distillates are used, i. those containing less than 350 ppm of sulfur, in particular less than 200 ppm of sulfur, especially less than 50 ppm of sulfur. In special cases they contain less than 10 ppm sulfur, these middle distillates are also called "sulfur-free".
  • These are generally crude oil distillates, which have been subjected to a hydrogenating refining, and therefore contain only small amounts of polyaromatic and polar compounds.
  • middle distillates which have 95% distillation points below 370 ° C., in particular below 350 ° C. and in special cases below 330 ° C.
  • Low-sulfur and sulfur-free middle distillates can also be obtained from heavier petroleum fractions, which can no longer be distilled under atmospheric pressure.
  • Hydrocarbon cracking, thermal cracking, catalytic cracking, coker processes and / or visbreaking may be mentioned as typical conversion processes for the preparation of middle distillates from heavy petroleum fractions. Depending on the procedure These middle distillates fall to low sulfur or sulfur-free or are subjected to a hydrogenating refining.
  • the middle distillates preferably have aromatics contents of less than 28% by weight, in particular less than 20% by weight.
  • the content of normal paraffins is between 5% and 50% by weight, preferably between 10 and 35% by weight.
  • middle distillates should also be understood here, which can be derived either indirectly from fossil sources such as crude oil or natural gas or else produced from biomass via gasification and subsequent hydrogenation.
  • a typical example of a middle distillate fuel derived indirectly from fossil sources is GTL (gas-to-liquid) diesel fuel produced by Fischer-Tropsch synthesis.
  • GTL gas-to-liquid diesel fuel produced by Fischer-Tropsch synthesis.
  • a middle distillate is produced via the BTL (“bio-to-liquid”) process, which can be used either alone or in admixture with other middle distillates as fuel component (B).
  • the middle distillates also include hydrocarbons obtained by hydrogenation of fats and fatty oils. They contain mostly n-paraffins.
  • the said middle distillate fuels have in common that they are essentially hydrocarbon mixtures and are free from fatty acid esters.
  • the mixture according to the invention is preferably used in the said fuels as a paraffin dispersant ("WASA").
  • WASA paraffin dispersant
  • the mixture according to the invention often unfolds its action as paraffin dispersant only particularly well together with the customary flow improvers.
  • flow improvers are to be understood as meaning all additives which improve the cold properties of middle distillate fuels.
  • MDFI actual cold flow improvers
  • nucleators see also Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A16, page 719 ff.).
  • the middle distillate fuels according to the invention contain in addition to the mixture according to the invention in the presence of cold flow improvers these in an amount of usually 1 to 2000 ppm by weight, preferably from 5 to 1000 ppm by weight, especially from 10 to 750 ppm by weight and especially from 50 to 500 ppm by weight, for example from 150 to 400 ppm by weight.
  • the monomer is preferably selected from alkenylcarboxylic esters, (meth) acrylic esters and olefins.
  • Suitable olefins are, for example, those having 3 to 10 carbon atoms and having 1 to 3, preferably 1 or 2, in particular having one carbon-carbon double bond.
  • the carbon-carbon double bond can be arranged both terminally ( ⁇ -olefins) and internally.
  • ⁇ -olefins particularly preferably ⁇ -olefins having 3 to 6 carbon atoms, for example propene, 1-butene, 1-pentene and 1-hexene.
  • Suitable (meth) acrylic esters are, for example, esters of (meth) acrylic acid with C 1 - to C 10 -alkanols, in particular with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol , Hexanol, heptanol, octanol, 2-ethylhexanol, nonanol and decanol.
  • esters of (meth) acrylic acid with C 1 - to C 10 -alkanols in particular with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol , Hexanol, heptanol, octanol, 2-ethylhe
  • Suitable alkenylcarboxylic esters are, for example, the vinyl and propenyl esters of carboxylic acids having 2 to 20 carbon atoms, the hydrocarbon radical of which may be linear or branched. Preferred among these are the vinyl esters.
  • carboxylic acids having a branched hydrocarbon radical preferred are those whose branch is in the ⁇ -position to the carboxyl group, the ⁇ -carbon atom being particularly preferably tertiary, ie. H. the carboxylic acid is a so-called neocarboxylic acid.
  • the hydrocarbon radical of the carboxylic acid is linear.
  • alkenylcarboxylic esters examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, with vinyl esters being preferred.
  • a particularly preferred alkenyl carboxylic acid ester is vinyl acetate; typical copolymers of group (d) resulting therefrom are ethylene-vinyl acetate copolymers ("EVA”), which are widely used in diesel fuels.
  • EVA ethylene-vinyl acetate copolymers
  • the ethylenically unsaturated monomer is selected from alkenylcarboxylic esters.
  • copolymers which contain two or more mutually different alkenylcarboxylic acid esters in copolymerized form, these differing in the alkenyl function and / or in the carboxylic acid group. Also suitable are copolymers which, in addition to the alkenylcarboxylic ester (s), contain at least one olefin and / or at least one (meth) acrylic acid ester in copolymerized form.
  • the ethylenically unsaturated monomer is in the copolymer of group (d) in an amount of preferably 1 to 50 mol .-%, in particular from 10 to 50 mol .-% and especially from 5 to 20 mol .-%, based on the total copolymer , copolymerized.
  • the copolymer of group (d) preferably has a number average molecular weight M n of from 1000 to 20,000, particularly preferably from 1000 to 10,000 and in particular from 1000 to 6000.
  • Preferred comb polymers are obtainable, for example, by the copolymerization of maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an ⁇ -olefin or an unsaturated ester such as vinyl acetate, and subsequent esterification of the anhydride or acid function with an alcohol having at least 10 carbon atoms.
  • Other preferred comb polymers are copolymers of ⁇ -olefins and esterified comonomers, for example, esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid.
  • mixtures of comb polymers are suitable.
  • Comb polymers may also be polyfumarates or polymaleinates.
  • homopolymers and copolymers of vinyl ethers are suitable comb polymers.
  • Preferred polyoxyalkylene compounds of the formula V in which both R 19 and R 20 are R 21 are polyethylene glycols and polypropylene glycols having a number average molecular weight of 100 to 5,000.
  • Preferred polyoxyalkylenes of the formula V in which one of the radicals R 19 is R 21 and the other is R 21 -CO- are polyoxyalkylene esters of fatty acids having 10 to 30 carbon atoms such as stearic acid or behenic acid.
  • Preferred polyoxyalkylene compounds in which both R 19 and R 20 are R 21 -CO- are diesters of fatty acids having 10 to 30 carbon atoms, preferably stearic or behenic acid.
  • Suitable poly (meth) acrylic esters of group (h) are both homo- and copolymers of acrylic and methacrylic acid esters. Preferred are copolymers of at least two mutually different (meth) acrylic acid esters, which differ with respect to the fused alcohol. Optionally, the copolymer contains a further, different of which olefinically unsaturated monomer copolymerized. The weight-average molecular weight of the polymer is preferably 50,000 to 500,000.
  • a particularly preferred polymer is a copolymer of methacrylic acid and methacrylic acid esters of saturated C 14 and C 15 alcohols wherein the acid groups are neutralized with hydrogenated tallamine.
  • Suitable poly (meth) acrylic esters are, for example, in WO 00/44857 which is incorporated herein by reference in its entirety.
  • the mixture according to the invention is an efficient one in its function as paraffin dispersant and versatile cold stabilization system for middle distillate fuels, especially those with a share of biodiesel.
  • the use of the mixture according to the invention in particular in combination with flow improvers, can contribute to an improvement in the lubricating effect.
  • the lubricating effect is determined, for example, in the so-called HFRR test according to ISO 12156.
  • the mixture according to the invention can be added both middle distillate fuels, which are completely fossil origin, that is, derived from petroleum, as well as fuels containing a proportion of biodiesel in addition to the petroleum-based portion, to improve their properties.
  • middle distillate fuels which are completely fossil origin, that is, derived from petroleum, as well as fuels containing a proportion of biodiesel in addition to the petroleum-based portion, to improve their properties.
  • a significant improvement in the cold flow behavior of the middle distillate fuel i. a reduction in CP values and / or CFPP values, regardless of the origin or composition of the fuel observed.
  • the precipitated paraffin crystals are effectively kept in suspension, so that there is no clogging of filters and lines by sedimented paraffin.
  • the mixture according to the invention has a good broad action and thus effects that the precipitated paraffin crystals are very well dispersed in the most varied middle distillate fuels.
  • the present invention also fuels, in particular those with a biodiesel content, which contain the mixture according to the invention.
  • the fuels mentioned or the fuel additive concentrates mentioned contain further additives in customary amounts of flow improver (as described above), further paraffin dispersants, conductivity improvers, corrosion protection additives, lubricity additives, antioxidants, metal deactivators, antifoams, demulsifiers, Detergents, cetane improvers, solvents or diluents, dyes or fragrances, or mixtures thereof.
  • RME rapeseed oil methyl ester
  • SME soybean oil methyl ester
  • PME palm oil methyl ester
  • FB1 and FB2 were selected for their CFPP performance in the diesel fuels used. It is very likely that other diesel fuels will require other MDFI. Thus, the blends of the invention are not limited to use in conjunction with FB1 and FB2.
  • the additives K1 to K3 and FB1 or FB2 were each added separately to the diesel fuels. It is also possible to use the concentrates First mix K1, K2 and K3 with the MDFI FB1 or FB2 and then mix them together in the diesel fuels DK1 to DK7.
  • the fuels DK1 to DK7 were admixed with the amounts of biodiesel additive specified in the table below, the concentrate K1, K2 or K3 and the flow improver FB1 or FB2, mixed with stirring at 40.degree. C. and then cooled to room temperature.
  • the CP was determined according to ISO 3015 and the CFPP according to EN 116. Thereafter, the additized fuel samples were cooled in 500 ml glass cylinders in a cold bath from room temperature at a cooling rate of about 14 ° C per hour to -13 ° C and stored for 16 hours at this temperature.
  • CP * (column 8) and CFPP * (column 11) indicate the values of the additized fuel samples before cooling.
  • CP # (column 9) and CFPP # (column 12) indicate the corresponding values of the 20% by volume soil phase each separated after cooling.
  • Column 10 is the absolute value of the difference from CP # to CP *.
  • Column 13 indicates the vol .-% sediment of paraffin after storage in a cold bath at -13 ° C. If the specified value moves in the lower range (in the case of the examples listed below 40% by volume), the lower the value given here, the better the paraffin dispersing behavior. However, very high values in column 13 (in the case of the examples listed above 60% by volume) are also an indication of good paraffin dispersion behavior. Paraffin sedimentation is usually critical of about 10 to 30% by volume, since then most of the precipitated paraffin crystals are in the 20% by volume soil phase used to characterize the effectiveness of the additives as described.

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Claims (13)

  1. Mélange contenant
    (a) 5 à 95% en poids d'au moins un composé azoté soluble dans l'huile, polaire, différent des composants (b) et (c), qui est en mesure de disperser suffisamment les cristaux de paraffine précipités au froid dans des carburants et qui est choisi parmi les produits de transformation d'au moins deux poly(acides carboxyliques en C2-C20) présentant au moins un groupe amino tertiaire avec des amines primaires ou secondaires,
    (b) 1 à 50% en poids d'au moins un amide d'acide soluble dans l'huile de polyamines comprenant 2 à 1000 atomes d'azote et d'acides gras en C8-C30 et
    (c) 0 à 50% en poids d'au moins un produit de transformation, soluble dans l'huile, d'acides α,β-dicarboxyliques comprenant 4 à 300 atomes de carbone ou leurs dérivés et d'alkylamines primaires,
    la somme de tous les composants du mélange de (a) à (c) étant de 100% en poids.
  2. Mélange selon la revendication 1, contenant comme composant (a) au moins un produit de transformation, soluble dans l'huile, à base de poly(acides carboxyliques en C2-C20) présentant au moins un groupe amino tertiaire de formule générale I ou II
    Figure imgb0012
    Figure imgb0013
     où la variable A représente un groupe C2-C6-alkylène linéaire ou ramifié ou le groupe de formule III
    Figure imgb0014
     et la variable B représente un groupe C1-C19-alkylène.
  3. Mélange selon la revendication 1 ou 2, caractérisé en ce que le produit de transformation, soluble dans l'huile, du composant (a) est un amide, un sel d'amidoammonium ou un sel d'ammonium dans lequel aucun, un ou plusieurs groupes acide carboxylique est/sont transformés en groupes amide.
  4. Mélange selon les revendications 1 à 3, caractérisé en ce que les amines à la base des produits de transformation, solubles dans l'huile, du composant (a) sont des amines secondaires et présentent la formule générale HNR2, dans laquelle les deux variables R signifient, indépendamment l'une de l'autre, à chaque fois des radicaux C10-C30-alkyle linéaires ou ramifiés.
  5. Mélange selon les revendications 1 à 4, contenant comme composant (b) au moins un amide d'acide, soluble dans l'huile, de polyamines aliphatiques comprenant 2 à 6 atomes d'azote et d'acides gras en C16-C20, où toutes les fonctions amino primaires et secondaires des polyamines sont transformées en fonctions amide d'acide.
  6. utilisation du mélange selon les revendications 1 à 5 comme additif pour carburants.
  7. Utilisation du mélange selon la revendication 6 comme additif pour des carburants, qui sont composés de
    (A) 0,1 à 75% en poids d'au moins un biocarburant qui est à base d'esters d'acides gras et
    (B) 25 à 99,9% en poids de distillats moyens d'origine fossile et/ou d'origine végétale et/ou d'origine animale, qui sont essentiellement des mélanges d'hydrocarbures et exempts d'esters d'acides gras.
  8. Utilisation selon la revendication 7, où il s'agit, pour le composant de carburant (A), essentiellement d'esters alkyliques d'acides gras qui sont dérivés d'huiles et/ou de graisses végétales et/ou animales.
  9. Utilisation selon les revendications 6, 7 ou 8 dans une fonction comme dispersant de paraffine.
  10. Carburants selon les revendications 6 à 8 contenant un mélange selon les revendications 1 à 5.
  11. Carburants selon la revendication 10, contenant comme autres additifs, en quantités usuelles pour ceux-ci, des agents d'amélioration de l'écoulement, d'autres dispersants de paraffines, des agents d'amélioration de la conductibilité, des additifs de protection contre la corrosion, des additifs de lubrification, des antioxydants, des désactivateurs de métaux, des antimousses, des désémulsifiants, des détergents, des agents d'amélioration de l'indice de cétane, des agents de solubilisation ou des diluants, des colorants ou des parfums ou leurs mélanges.
  12. Concentrat d'additif pour carburants, contenant 10 à 70% en poids, par rapport à la quantité totale du concentrat, d'un mélange selon les revendications 1 à 5, dissous dans un solvant hydrocarboné.
  13. Concentrat d'additif pour carburants selon la revendication 12, contenant comme autres additifs, en quantités usuelles pour ceux-ci, des agents d'amélioration de l'écoulement, d'autres dispersants de paraffines, des agents d'amélioration de la conductibilité, des additifs de protection contre la corrosion, des additifs de lubrification, des antioxydants, des désactivateurs de métaux, des antimousses, des désémulsifiants, des détergents, des agents d'amélioration de l'indice de cétane, des agents de solubilisation ou des diluants, des colorants ou des parfums ou leurs mélanges.
EP07730085A 2006-06-22 2007-06-12 Mélange constitué de composés d'azote polaires oléosolubles et d'amides d'acides en tant que dispersant de paraffine pour des carburants Active EP2038380B1 (fr)

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