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EP1555309B1 - Désémulsifiants pour des mélanges de distillats moyens et de combustibles d'origine animale ou végétale - Google Patents

Désémulsifiants pour des mélanges de distillats moyens et de combustibles d'origine animale ou végétale Download PDF

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Publication number
EP1555309B1
EP1555309B1 EP04030573.2A EP04030573A EP1555309B1 EP 1555309 B1 EP1555309 B1 EP 1555309B1 EP 04030573 A EP04030573 A EP 04030573A EP 1555309 B1 EP1555309 B1 EP 1555309B1
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EP
European Patent Office
Prior art keywords
oil
ether
fuel oil
acid
diglycidyl ether
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EP04030573.2A
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German (de)
English (en)
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EP1555309A1 (fr
Inventor
Bettine Dr. Siggelkow
Werner Dr. Reimann
Dirk Dr. Leinweber
Ulrike Neuhaus
Renate Braun
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Clariant Produkte Deutschland GmbH
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Clariant Produkte Deutschland GmbH
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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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/143—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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • C10L1/2387—Polyoxyalkyleneamines (poly)oxyalkylene amines and 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof 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 a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof 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 a carboxyl radical or of salts, anhydrides or esters thereof poly-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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—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
    • C10L1/1981—Condensation polymers of aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/28—Organic compounds containing silicon
    • C10L1/285—Organic compounds containing silicon macromolecular compounds

Definitions

  • the present invention relates to the use of an additive as a demulsifier for mixtures of middle distillates with vegetable or animal fuel oils and water.
  • Oils obtained from animal or vegetable material are mainly metabolites comprising triglycerides of monocarboxylic acids, eg acids having 10 to 25 carbon atoms, and the formula in which R is an aliphatic radical of 10 to 25 carbon atoms, which may be saturated or unsaturated.
  • oils include glycerides of a variety of acids, the number and variety of which varies with the source of the oil, and may additionally contain phosphoglycerides.
  • Such oils can be obtained by methods known in the art.
  • EP-B-0 665 873 discloses a fuel oil composition
  • a fuel oil composition comprising a biofuel, a petroleum-based fuel oil and an additive which comprises (a) an oil-soluble ethylene copolymer or (b) a comb polymer or (c) a polar nitrogen compound or (d) a compound in which at least one substantially linear alkyl group having from 10 to 30 carbon atoms is bonded to a non-polymeric organic radical to provide at least one linear chain of atoms which includes the carbon atoms of the alkyl groups and one or more non-terminal oxygen atoms, or (e) one or more of the components ( a), (b), (c) and (d).
  • WO-A-00/31216 discloses a fuel composition comprising a diesel fuel, ethanol and a stabilizer additive.
  • the object of this invention was thus to find a suitable demulsifier for mixtures of middle distillates, biofuel oils and water.
  • Another object of the invention is the use of the block copolymer defined under C) as a demulsifier in mixtures of middle distillate fuel oils with biofuel oils and water.
  • Another object of the invention is a process for the demulsification of water from mixtures of middle distillate fuel oils with biofuel oils by adding to the mixtures the above-defined block copolymer.
  • middle distillate fuel oils are used. This refers in particular to those mineral oils which are obtained by distillation of crude oil and boiling in the range of 120 to 450 ° C, for example kerosene, jet fuel, diesel and fuel oil.
  • middle distillates are used which contain less than 350 ppm sulfur, more preferably less than 200 ppm sulfur, in particular less than 50 ppm sulfur and in special cases less than 10 ppm sulfur.
  • middle 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.degree. C., in particular 350.degree. C. and in special cases below 330.degree.
  • the middle distillates preferably have aromatics contents of less than 28% by weight, in particular less than 20% by weight.
  • biofuel oils are used as component B.
  • the biofuel oil which is often referred to as “biodiesel” or “biofuel” to fatty acid alkyl esters of fatty acids having 14 to 24 carbon atoms and alcohols having 1 to 4 carbon atoms.
  • fatty acids having 14 to 24 carbon atoms and alcohols having 1 to 4 carbon atoms.
  • a major part of the fatty acids contains one, two or three double bonds.
  • Rapsölkladremethylester and especially mixtures containing rapeseed, sunflower and / or soybean oil fatty acid methyl ester.
  • oils derived from animal or vegetable material which can be used in the composition of the present invention are rapeseed oil, coriander oil, soybean oil, cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, corn oil, almond oil, palm kernel oil, coconut oil, soybean oil, Mustard seed oil, beef tallow, bone oil and fish oils.
  • oils derived from wheat, jute, sesame, shea nut, arachis oil, and linseed oil and may be derived therefrom by methods known in the art.
  • oils can be used, which were obtained from used waste oils, such as cooking oil.
  • Rapeseed oil which is a mixture of glycerol partially esterified fatty acids, is preferred because it is available in large quantities and is readily available by squeezing rapeseed. Furthermore, the also widespread oils of sunflower and soybeans and their mixtures with rapeseed oil are preferred.
  • lower alkyl esters of fatty acids the following are suitable, for example as commercial mixtures: The ethyl, propyl, butyl and especially methyl esters of fatty acids having 12 to 22 carbon atoms, for example of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, Elaidic acid, petroselinic acid, ricinoleic acid, elaeostearic acid, linoleic acid, linolenic acid, eicosanoic acid, gadoleic acid, docosanoic acid or erucic acid, which preferably have an iodine value of 50 to 150, in particular 90 to 125.
  • Mixtures with particularly advantageous properties are those which are mainly, i. at least 50 wt .-%, contain methyl esters of fatty acids having 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, linoleic, linolenic and erucic acids.
  • Component C) is a crosslinked block copolymer prepared by crosslinking from a block copolymer of at least 2 different C 2 to C 4 alkylene oxides.
  • the block copolymer may consist of 2, 3, 4 or more blocks.
  • the block copolymers used are prepared by sequential polymerization of alkylene oxides (ethylene oxide, propylene oxide, butylene oxide), preferably under alkaline catalysis, as known in the art.
  • alkylene oxides ethylene oxide, propylene oxide, butylene oxide
  • the base polymer used to prepare the block copolymer C) generally has a molecular weight of 500 to 100,000 g / mol, preferably 1,000 to 60,000, especially 4,000 to 50,000 g / mol. These molecular weights are the molecular weights before crosslinking.
  • crosslinking of the block copolymers used is as known in the art by alkaline or acid catalyzed ring opening of di-, tri- or tetraglycidyl ethers, by esterification with polybasic carboxylic acids or Carboxylic anhydrides or by reaction with polyfunctional isocyanates.
  • Suitable crosslinkers are those compounds which can bind to the block polymer with at least 2 binding sites.
  • the following crosslinking agents may be mentioned: Bisphenol A diglycidyl ether, butane-1,4-diol diglycidyl ether, hexane-1,6-diol diglycidyl ether, ethylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, resorcinol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, Glycerinpropoxylattriglycidylether, polyglycerol polyglycidyl ether, p-Aminophenoltriglycidylether, polypropylene glycol diglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol polyglycidyl ether, trimethyl
  • the crosslinked block copolymers C) generally have a molecular weight of 1000-200,000 g / mol, preferably 2000-100,000, in particular 4000-50,000 g / mol, measured by gel permeation chromatography (GPC) against polystyrene standards in THF.
  • GPC gel permeation chromatography
  • WZ water number
  • DIN EN 12836, to which reference is hereby made To a solvent mixture consisting of a specific volume of 97: 3 dioxane and toluene, in which the block copolymer sample is a clear solution, add water at a temperature of (25 ⁇ 1) ° C until a permanent haze occurs. The number of water is given in milliliters of water needed to maintain the permanent turbidity.
  • the water number in the crosslinked block copolymer C) is preferably between 6 ml and 25 ml, in particular between 6 ml and 17 ml.
  • the crosslinked block copolymers C) are added to the mixtures containing A) and B) in amounts of 0.001 to 5% by weight, preferably 0.005 to 1% by weight and especially 0.01 to 0.05% by weight. They may be dissolved as such or dissolved or dispersed in solvents, such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures such as toluene, xylene, ethylbenzene, decane, pentadecane, gasoline fractions, kerosene, naphtha, diesel, fuel oil, isoparaffins or commercial solvent mixtures such as Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol, ® Isopar and ® Shellsol D types are used. Preferably, they are dissolved in fuel oil of animal or vegetable origin based on fatty acid alkyl esters.
  • the additives according to the invention preferably contain 1 to
  • the crosslinked block copolymers C) may be added to the oil to be treated according to methods known in the art. If more than one copolymer component is to be used, such components may be incorporated into the oil together or separately in any combination.
  • the crosslinked block copolymers C) can also be used together with one or more oil-soluble co-additives, which on their own improve the properties of crude oils, lubricating oils or fuel oils.
  • oil-soluble co-additives are polar compounds which cause paraffin dispersion (paraffin dispersants), alkylphenol-aldehyde resins, polymeric cold flow improvers and oil-soluble amphiphiles.
  • mixtures of the crosslinked block copolymers C) have proven outstandingly well with copolymers which contain from 10 to 40% by weight of vinyl acetate and from 60 to 90% by weight of ethylene.
  • the additives according to the invention are mixed with ethylene / vinyl acetate / vinyl 2-ethylhexanoate terpolymers, ethylene / vinyl acetate / vinyl neononanoate terpolymers and / or ethylene / vinyl acetate / vinyl neodecanoate terpolymers to simultaneously improve flowability and lubricity of mineral oils or mineral oil distillates.
  • the terpolymers of vinyl 2-ethylhexanoate, Vinyl neononanoate or vinyl neodecanoate contains, in addition to ethylene, 8 to 40% by weight of vinyl acetate and 1 to 40% by weight of the respective long-chain vinyl ester.
  • Further preferred copolymers contain, in addition to ethylene, 10 to 40% by weight of vinyl acetate and optionally 1 to 40% by weight of vinyl esters with C 3 to C 12 -alkyl groups in the ester radical and optionally from 0.5 to 20% by weight of olefins with 3 to 10 C atoms such as isobutylene, diisobutylene, propylene, methylpentene or norbornene.
  • paraffin dispersants are preferably low molecular weight or polymeric, oil-soluble compounds having ionic or polar groups, for example amine salts, imides and / or amides.
  • Particularly preferred paraffin dispersants contain reaction products of primary and / or secondary fatty amines having 8 to 36 carbon atoms, in particular dicocosamine, ditallow fatty amine and distearylamine.
  • Paraffin dispersants which have been obtained by reaction of aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their anhydrides have proven particularly suitable (cf. US 4 211 534 ).
  • paraffin dispersants are copolymers of maleic, fumaric and / or itaconic acid or of maleic anhydride and further ⁇ , ⁇ -unsaturated compounds which can optionally be reacted with primary and / or secondary monoalkylamines and / or aliphatic alcohols (cf. EP-A-0 154 177 ), the reaction products of Alkenylspirobislactonen with amines (see.
  • esters are suitable as co-additives which bring about a paraffin dispersion.
  • These esters are derived from polyols having 3 or more OH groups, in particular glycerol, trimethylolpropane, pentaerythritol and the oligomers having 2 to 10 monomer units, such as polyglycerol, obtainable therefrom by condensation.
  • the polyols are generally reacted with 1 to 100 mol of alkylene oxide, preferably 3 to 70, in particular 5 to 50 mol of alkylene oxide per mole of polyol.
  • Preferred alkylene oxides are ethylene oxide, propylene oxide and butylene oxide.
  • the alkoxylation is carried out by known methods.
  • the fatty acids suitable for the esterification of the alkoxylated polyols preferably have 8 to 50, in particular 12 to 30, especially 16 to 26 C-atoms.
  • Suitable fatty acids are, for example, lauric, tridecane, myristic, pentadecane, palmitic, margarine, stearic, isostearic, arachic and behenic, oleic and erucic acid, palmitoleic, myristolein, ricinoleic acid, as well as natural fats and Oils derived fatty acid mixtures.
  • Preferred fatty acid mixtures contain more than 50% fatty acids with at least 20 C atoms.
  • fatty acids used for esterification contain double bonds, in particular less than 10%; specifically, they are largely saturated. Under largely saturated here is an iodine value of the fatty acid used of up to 5 g of I per 100 g of fatty acid are understood.
  • Esterification may also be carried out starting from reactive derivatives of the fatty acids such as esters with lower alcohols (e.g., methyl or ethyl esters) or anhydrides.
  • polybasic carboxylic acids dimer fatty acids, alkenylsuccinic acids and aromatic polycarboxylic acids and derivatives thereof such as anhydrides and C 1 - to C 5 -esters.
  • Alkenylsuccinic acids and their derivatives with alkyl radicals having 8 to 200, in particular 10 to 50, carbon atoms are preferred. Examples are dodecenyl, octadecenyl and poly (isobutenyl) succinic anhydride.
  • the polybasic carboxylic acids are preferably used to lower levels of up to 30 mol%, preferably 1 to 20 mol%, in particular 2 to 10 mol%.
  • Ester and fatty acid are used for the esterification based on the content of hydroxyl groups on the one hand and carboxyl groups on the other hand in the ratio of 1.5: 1 to 1: 1.5, preferably 1.1: 1 to 1: 1.1, in particular equimolar.
  • the paraffin-dispersing effect is particularly pronounced when working with an acid excess of up to 20 mol%, especially up to 10 mol%, in particular up to 5 mol%.
  • the esterification is carried out by conventional methods.
  • the separation the reaction water can be carried out by distillation by direct condensation or preferably by azeotropic distillation in the presence of organic solvents, in particular aromatic solvents such as toluene, xylene or higher boiling mixtures such as ® Shellsol A, Shellsol B, Shellsol AB or Solvent Naphtha.
  • the esterification is preferably carried out completely, ie for the esterification 1.0 to 1.5 moles of fatty acid are used per mole of hydroxyl groups.
  • the acid number of the esters is generally below 15 mg KOH / g, preferably below 10 mg KOH / g, especially below 5 mg KOH / g.
  • paraffin dispersants are prepared by reacting compounds containing an acyl group with an amine.
  • This amine is a compound of the formula NR 6 R 7 R 8 , in which R 6 , R 7 and R 8 may be identical or different, and at least one of these groups is C 8 -C 36 -alkyl, C 6 - C 36 -cycloalkyl, C 8 -C 36 -alkenyl, in particular C 12 -C 24 -alkyl, C 12 -C 24 -alkenyl or cyclohexyl, and the other groups are either hydrogen, C 1 -C 36 -alkyl, C 2 -C 36 alkenyl, cyclohexyl, or a group of the formulas - (AO) x -E or - (CH 2 ) n -NYZ, where A is an ethylene or propylene group, x is a number from 1 to 50, E Is H, C 1 -C 30 -alkyl
  • the paraffin dispersants can be added to the crosslinked block copolymer C) or added separately to the middle distillate to be added.
  • alkylphenol-aldehyde resins are also suitable as paraffin dispersants.
  • Alkylphenol-aldehyde resins are known in principle and, for example in the Rompp Chemie Lexikon, 9th edition, Thieme Verlag 1988-92, Volume 4, p 3351ff , described.
  • the alkyl or alkenyl radicals of the alkylphenol have 6-24, preferably 8-22, in particular 9-18, carbon atoms. They may be linear or preferably branched, wherein the branch may contain secondary as well as tertiary structural elements.
  • alkylphenol-aldehyde resin may also contain up to 20 mole% of phenol units and / or alkylphenols with short alkyl chains, such as e.g. B. butylphenol.
  • alkylphenol-aldehyde resin the same or different alkylphenols may be used.
  • the aldehyde in the alkylphenol-aldehyde resin has 1 to 10, preferably 1 to 4, carbon atoms and may carry further functional groups. It is preferably an aliphatic aldehyde, more preferably it is formaldehyde.
  • the molecular weight of the alkylphenol-aldehyde resins is preferably 350 to 10,000, in particular 400 to 5000, g / mol. This preferably corresponds to a condensation degree n of from 3 to 40, in particular from 4 to 20.
  • the prerequisite here is that the resins are oil-soluble.
  • the preparation of the alkylphenol-aldehyde resins is carried out in a known manner by basic catalysis, resulting in resol-type condensation products, or by acid catalysis to form novolac-type condensation products.
  • the condensates obtained according to both types are suitable for the compositions according to the invention.
  • the condensation is in the presence of acidic catalysts.
  • an alkylphenol having 6-24, preferably 8-22, in particular 9-18, carbon atoms per alkyl group, or mixtures thereof and at least one aldehyde are reacted with each other, wherein about 0.5 mol per mol of alkylphenol compound. 2 mol, preferably 0.7 to 1.3 mol and in particular equimolar amounts of aldehyde are used.
  • Suitable alkylphenols are in particular n- and iso-hexylphenol, n- and iso-octylphenol, n- and iso-nonylphenol, n- and iso-decylphenol, n- and iso-dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, tripropenylphenol, tetrapropenylphenol and poly (isobutenyl) phenol -C 24th
  • the alkylphenols are preferably para-substituted.
  • the alkylphenols may carry one or more alkyl radicals. Preferably, they are substituted at most 5 mol%, especially at most 20 mol% and especially at most 40 mol% with more than one alkyl group. Preferably, at most 40 mol%, in particular at most 20 mol% of the alkylphenols used in the ortho position carry an alkyl radical. Specifically, the alkylphenols ortho to the hydroxyl group are not substituted with tertiary alkyl groups.
  • the aldehyde can be a mono- or dialdehyde and carry other functional groups such as -COOH.
  • Particularly suitable aldehydes are formaldehyde, acetaldehyde, butyraldehyde, glutaric dialdehyde and glyoxylic acid, with formaldehyde being preferred.
  • the formaldehyde can be used in the form of paraformaldehyde or in the form of a preferably 20-40% strength by weight aqueous formalin solution.
  • Corresponding amounts of trioxane can also be used.
  • alkylphenol and aldehyde is usually carried out in the presence of alkaline catalysts, for example alkali metal hydroxides or alkylamines, or of acidic catalysts, for example inorganic or organic acids, hydrochloric acid, sulfuric acid, phosphoric acid, sulfonic acid, sulfamidic acids or haloacetic acids, and in the presence of an aqueous azeotrope-forming organic solvent, for example toluene, xylene, higher aromatics or mixtures thereof.
  • alkaline catalysts for example alkali metal hydroxides or alkylamines
  • acidic catalysts for example inorganic or organic acids, hydrochloric acid, sulfuric acid, phosphoric acid, sulfonic acid, sulfamidic acids or haloacetic acids
  • an aqueous azeotrope-forming organic solvent for example toluene, xylene, higher aromatics or mixtures thereof.
  • the reaction mixture is heated to a
  • Solvents that do not release protons under condensation conditions may remain in the products after the condensation reaction.
  • the resins can be used directly or after neutralization of the catalyst, optionally after further dilution of the solution with aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, eg gasoline fractions, kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or solvents such as ® Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200, ® Exxsol, ® ISOPAR and ® Shellsol D types.
  • the crosslinked block copolymers C) are used together with comb polymers.
  • This term refers to polymers in which hydrocarbon radicals having at least 8, in particular at least 10, carbon atoms are bonded to a polymer backbone.
  • they are homopolymers whose alkyl side chains contain at least 8 and in particular at least 10 carbon atoms.
  • at least 20%, preferably at least 30% of the monomers have side chains (cf. Comb-like Polymers-Structure and Properties; NA Plate and VP Shibaev, J. Polym. Sci. Macromolecular Revs. 1974, 8, 117 ff ).
  • Suitable comb polymers are, for example, fumarate / vinyl acetate copolymers (cf. EP 0 153 176 A1 ), Copolymers of a C 6 -C 24 - ⁇ -olefin and a NC 6 -C 22 -alkylmaleimide (cf. EP-A-0 320 766 Further, esterified olefin / maleic anhydride copolymers, polymers and copolymers of ⁇ -olefins and esterified copolymers of styrene and maleic anhydride.
  • the mixing ratio (in parts by weight) of the crosslinked block copolymers C) with polymeric cold flow improvers, paraffin dispersants, comb polymers or resins is in each case 1: 1000 to 1: 1, preferably 1:10 to 1:50.
  • the crosslinked block copolymers C) can be used alone or together with other additives, for.
  • additives for.
  • pour point depressants or dewaxing aids with corrosion inhibitors, antioxidants, lubricity additives, sludge inhibitors, dehazers, and cloud point depressant additives.
  • the CFPP value is determined according to EN 116, the boiling characteristics according to ASTM D-86 and the determination of the cloud point according to ISO 3015.
  • Table 1 Analysis of the biodiesel used Oil no. CP CFPP E 1 Rapeseed acid methyl ester (RME) -2.3 -14 ° C E 2 90% rapeseed-oleic acid methyl ester (RME) + 10% soya-oleic acid methyl ester (sojaME) -2.0 -8 ° C C 16 C 16 ' C 18 C 18 ' C 18 " C 18 "' C 20 C 20 ' C 22 ⁇ saturated RME 4.4 0.4 1.6 57.8 21.6 8.8 1.5 0.7 0.2 7.7 SojaME 10.4 0.1 4.1 24.8 51.3 6.9 0.5 0.4 0.4 15.4 F1 F2 F3 F4 Sulfur content, ppm 7.9 4.9 32.0 900 Density, g / cm 3 .8436 0.8306 .8348 .8487 Initial
  • the testing of the emulsification of additives is carried out according to ASTM D 1094-85.

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Claims (10)

  1. Huile combustible, contenant une grande proportion d'un mélange de
    A) une huile combustible de distillat moyen et
    B) une huile combustible biologique,
    en un rapport de mélange A:B = 99:1 à 1:99, ainsi que
    C) 0,001 à 5 % en poids d'un copolymère séquencé réticulé d'oxydes d'alkylène en C2 à C4 soluble dans les huiles.
  2. Huile combustible selon la revendication 1, dans laquelle le poids moléculaire du constituant C) réticulé est compris entre 1 000 et 200 000 g/mol, mesuré par chromatographie par perméation de gel contre un étalon de polystyrène dans du THF.
  3. Huile combustible selon la revendication 1 et/ou 2, dans laquelle le copolymère séquencé C) présente un indice d'eau de 6 à 17 ml, déterminé selon DIN EN 12836.
  4. Huile combustible selon une ou plusieurs des revendications 1 à 3, dans laquelle l'agent de réticulation est choisi parmi l'éther diglycidylique de bisphénol A, l'éther diglycidylique de butane-1,4-diol, l'éther diglycidylique d'hexane-1,6-diol, l'éther diglycidylique d'éthylène glycol, l'éther diglycidylique de cyclohexane-diméthanol, l'éther diglycidylique de résorcinol, l'éther diglycidylique de
    glycérine, l'éther triglycidylique de glycérine, l'éther triglycidylique de propoxylate de glycérine, l'éther polyglycidylique de polyglycérine, l'éther triglycidylique de p-aminophénol, l'éther diglycidylique de polypropylène glycol, l'éther tétraglycidylique de pentaérythritol, l'éther polyglycidylique de sorbitol, l'éther triglycidylique de triméthylolpropane, l'éther triglycidylique d'huile de ricin, l'éther tétraglycidylique de diaminobiphényle, l'époxyde d'huile de soja, l'acide adipique, l'acide maléique, l'acide phtalique, l'anhydride de l'acide maléique, l'anhydride de l'acide succinique, l'anhydride de l'acide dodécylsuccinique, l'anhydride de l'acide phtalique, l'anhydride de l'acide triméllitique, l'anhydride de l'acide pyroméllitique, le diméthoxydiméthylsilane, le diéthoxydiméthylsilane, le diisocyanate de toluène et le diisocyanate de diphénylméthane.
  5. Huiles combustibles selon une ou plusieurs des revendications 1 à 4, qui contiennent en plus des constituants A), B) et C) également au moins une résine d'alkylphénol-formaldéhyde de formule
    Figure imgb0009
     dans laquelle RA représente alkyle ou alcényle en C4-C30, RB représente OH ou O-(A-O)x-H avec A = alkylène en C2-C4 et x = 1 à 50, et n représente un nombre de 2 à 50.
  6. Huiles combustibles selon une ou plusieurs des revendications 1 à 5, qui contiennent en plus des constituants A), B) et C) également au moins un copolymère qui contient, outre de l'éthylène, 10 à 40 % en poids d'acétate de vinyle et éventuellement 1 à 40 %
    en poids d'esters de vinyle contenant des groupes alkyle en C3 à C12 dans le radical ester et éventuellement 0,5 à 20 % en poids d'oléfines contenant 3 à 10 atomes C.
  7. Huiles combustibles selon une ou plusieurs des revendications 1 à 6, qui contiennent en plus des constituants A), B) et C) également au moins un sel d'amine, un imide ou un amide d'une amine grasse primaire et/ou secondaire contenant 8 à 36 atomes de carbone.
  8. Huiles combustibles selon une ou plusieurs des revendications 1 à 7, qui contiennent en plus des constituants A), B) et C) également au moins un copolymère dérivé d'amides, d'imides et/ou d'esters de l'acide maléique, de l'acide fumarique et/ou de l'acide itaconique.
  9. Huiles combustibles selon une ou plusieurs des revendications 1 à 8, qui contiennent en plus des constituants A), B) et C) également un polymère en peigne de formule
    Figure imgb0010
     dans laquelle
    A signifie R', COOR', OCOR', R"-COOR' ou OR' ;
    D signifie H, CH3, A ou R ;
    E signifie H ou A ;
    G signifie H, R" , R"-COOR', un radical aryle ou un radical hétérocyclique ;
    M signifie H, COOR", OCOR", OR" ou COOH ;
    N signifie H, R", COOR'', OCOR, COOH ou un radical aryle ;
    R' signifie une chaîne hydrocarbonée de 8 à 150 atomes de carbone ;
    R" signifie une chaîne hydrocarbonée de 1 à 10 atomes de carbone ;
    m signifie un nombre compris entre 0,4 et 1,0 ; et
    n signifie un nombre compris entre 0 et 0,6.
  10. Utilisation d'un copolymère séquencé C) tel que défini dans la revendication 1 pour la désémulsification de mélanges d'huiles combustibles de distillat moyen, d'huiles combustibles biologiques et d'eau.
EP04030573.2A 2004-01-15 2004-12-23 Désémulsifiants pour des mélanges de distillats moyens et de combustibles d'origine animale ou végétale Expired - Lifetime EP1555309B1 (fr)

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CA2493178A1 (fr) 2005-07-15
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