Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
  • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/02—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
  • 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
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/188—Carboxylic acids; metal salts thereof
  • C10L1/189—Carboxylic acids; metal salts thereof having at least one carboxyl group bound to an aromatic carbon atom
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/188—Carboxylic acids; metal salts thereof
  • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—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
  • C10L1/196—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
  • C10L1/1963—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 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
  • C10L1/18—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
  • C10L1/222—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
  • C10L1/236—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
• • 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 invention relates to additives for low-sulfur mineral oil distillates with improved cold flowability and paraffin dispersancy, comprising an additive based on hydroxyl-methoxyphenylcarboxylic acid, to fuel oils additized therewith and to the use of the additive.
• Crude oils and middle distillates such as gas oil, diesel oil or heating oil, obtained by distillation of crude oils contain, depending on the origin of the crude oils, different amounts of n-paraffins which crystallize out as platelet-shaped crystals when the temperature is reduced and sometimes agglomerate with the inclusion of oil.
• This crystallization and agglomeration causes a deterioration in the flow properties of these oils or distillates, which may result in disruption in the course of extraction, transport, storage and/or use of the mineral oils and mineral oil distillates.
• the crystallization phenomenon can, especially in winter, lead to deposits on the pipe walls, and in individual cases, for example in the event of stoppage of a pipeline, even to its complete blockage.
• Typical flow improvers for crude oils and middle distillates are co- and terpolymers of ethylene with carboxylic esters of vinyl alcohol.
• a further task of flow improvers is the dispersion of the paraffin crystals, i.e. the retardation or prevention of the sedimentation of the paraffin crystals and therefore the formation of a paraffin-rich layer at the bottom of storage vessels.
• EP-A-0 061 895 discloses cold flow improvers for mineral oil distillates, which comprise esters, ethers or mixtures thereof.
• the esters/ethers contain two linear saturated C 10 - to C 30 -alkyl groups and a polyoxyalkylene group with from 200 to 5000 g/mol.
• EP-0 973 848 and EP-0 973 850 disclose mixtures of esters alkoxylated alcohols with more than 10 carbon atoms and fatty acids with 10-40 carbon atoms in combination with ethylene copolymers as flow improvers.
• EP-A-0 935 645 discloses alkylphenol-aldehyde resins as a lubricity-improving additive in low-sulfur middle distillates.
• EP-A-0 857 776 and EP-A-1 088 045 disclose processes for improving the flowability of paraffin-containing mineral oils and mineral oil distillates by addition of ethylene copolymers and alkylphenol-aldehyde resins, and also optionally further nitrogen-containing paraffin dispersants.
• WO-99/62973 discloses the use of copolymers of dialkylphenyl fumarate and a comonomer selected from vinyl acetate, styrene, C 3 - to C 30 - ⁇ -olefins, ethylene and carbon monoxide as a cold additive for oils.
• aromatic compounds which contain hydroxyl, methoxy and carboxyl groups are highly suitable for paraffin dispersancy in mineral oils and mineral oil distillates.
• the invention thus provides an additive for fuel oils, comprising at least one copolymer of ethylene and an unsaturated ester, at least one oil-soluble polar nitrogen compound which is a reaction product of amines of the formula NR 6 R 7 R 8 in which R 6 , R 7 and R 8 may be the same 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, especially C 12 -C 24 -alkyl, C 12 -C 24 -alkenyl or cyclohexyl, and the remaining groups are hydrogen, C 1 -C 36 -alkyl, C 2 -C 36 -alkenyl, cyclohexyl or a group of the formulae -(A-O) x -E or —(CH 2 ) n —NYZ in which A is an ethyl or propyl group, x is from 1 to
• the invention further provides for the use of the inventive additives in amounts of from 5 to 10 000 ppm as a paraffin dispersent in fuel oils, preferably in middle distillates.
• the invention further provides a process for improving the cold flow properties of fuel oils, comprising the addition of from 5 to 10 000 ppm of the inventive additives to the fuel oil.
• aromatic additives Particular preference is given to 4-hydroxy-3-methoxyphenylpropionic acid or 4-hydroxy-3-methoxycinnamic acid.
• the aromatic additives are added to middle distillates, irrespective of their content of copolymers of ethylene and an unsaturated ester, preferably in amounts of from 10 to 1000 ppm, in particular from 20 to 500 ppm.
• inventive additive for fuel oils is referred to hereinbelow as inventive additive.
• the inventive additives also comprise one or more copolymers of ethylene and unsaturated esters and optionally further olefinically unsaturated compounds.
• Suitable ethylene copolymers are in particular those which, in addition to ethylene, contain from 6 to 21 mol %, in particular from 10 to 18 mol % of unsaturated esters.
• These copolymers preferably have melt viscosities at 140° C. of from 20 to 10 000 mPas, in particular from 30 to 5000 mPas, especially from 50 to 2000 mPas.
• the unsaturated esters are preferably vinyl esters, acrylic esters and/or methacrylic esters.
• the further olefinically unsaturated compounds are preferably alkyl vinyl ethers and/or alkenes, which may be substituted by hydroxyl groups.
• one or more comonomers may be present in the copolymer.
• the vinyl esters are preferably those of the formula 2 CH 2 ⁇ CH—OCOR 1 (2) where R 1 is C 1 - to C 30 -alkyl, preferably C 4 - to C 16 -alkyl, especially C 6 - to C 12 -alkyl.
• R 1 is C 1 - to C 30 -alkyl, preferably C 4 - to C 16 -alkyl, especially C 6 - to C 12 -alkyl.
• the alkyl groups mentioned may be substituted by one or more hydroxyl groups.
• R 1 is a branched alkyl radical or a neoalkyl radical having from 7 to 11 carbon atoms, in particular having 8, 9 or 10 carbon atoms.
• Particularly preferred vinyl esters derive from secondary and especially tertiary carboxylic acids whose branch is in the alpha-position to the carbonyl group.
• Suitable vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl hexanoate, vinyl heptanoate, vinyl octanoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl laurate, vinyl stearate and Versatic esters such as vinyl neononanoate, vinyl neodecanoate, vinyl neoundecanoate.
• these ethylene copolymers contain vinyl acetate and at least one further vinyl ester of the formula 4 where R 1 is C 4 - to C 30 -alkyl, preferably C 4 - to C 16 -alkyl, especially C 6 - to C 12 -alkyl.
• the (meth)acrylic esters are preferably those of the formula 3 CH 2 ⁇ CR 2 —COOR 3 (3) where R 2 is hydrogen or methyl and R 3 is C 1 - to C 30 -alkyl, preferably C 4 - to C 16 -alkyl, especially C 6 - to C 12 -alkyl.
• Suitable acrylic esters include, for example, methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, n- and isobutyl(meth)acrylate, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl(meth)acrylate and mixtures of these comonomers.
• the alkyl groups mentioned may be substituted by one or more hydroxyl groups.
• An example of such an acrylic ester is hydroxyethyl methacrylate.
• the alkyl vinyl ethers are preferably compounds of the formula 4 CH 2 ⁇ CH—OR 4 (4) where R 4 is C 1 - to C 30 -alkyl, preferably C 4 - to C 16 -alkyl, especially C 6 - to C 12 -alkyl. Examples include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether. In a further embodiment, the alkyl groups mentioned may be substituted by one or more hydroxyl groups.
• the alkenes are preferably monounsaturated hydrocarbons having from 3 to 30 carbon atoms, in particular from 4 to 16 carbon atoms and especially from 5 to 12 carbon atoms.
• Suitable alkenes include propene, butene, isobutylene, pentene, hexene, 4-methylpentene, octene, diisobutylene and norbornene and derivatives thereof such as methylnorbornene and vinylnorbornene.
• the alkyl groups mentioned may be substituted by one or more hydroxyl groups.
• particularly preferred terpolymers contain from 0.1 to 12 mol %, in particular from 0.2 to 5 mol %, of vinyl neononanoate or of vinyl neodecanoate, and from 3.5 to 20 mol %, in particular from 8 to 15 mol %, of vinyl acetate, the total comonomer content being between 6 and 21 mol %, preferably between 12 and 18 mol %.
• copolymers contain, in addition to ethylene and from 8 to 18 mol % of vinyl esters, also from 0.5 to 15 mol % of alkenes as described above.
• the polymers on which the mixtures are based more preferably differ in at least one feature.
• they may contain different comonomers, or different comonomer contents, molecular weights and/or degrees of branching.
• the mixing ratio between the aromatic additives, the ethylene copolymers and the oil-soluble polar nitrogen compounds may, depending on the application, vary within wide limits, the ethylene copolymers and the oil-soluble polar nitrogen compounds often constituting the major proportion.
• the inventive additives preferably contain from 2 to 70% by weight, preferably from 5 to 50% by weight of the aromatic additive, and also from 30 to 98% by weight, preferably from 50 to 95% by weight of ethylene copolymers, and also the oil-soluble polar nitrogen compounds.
• concentrations are from 0.1 to 100 ppm, preferably from 1 to 50 ppm, in particular from 5 to 50 ppm of aromatic additive, from 20 to 500 ppm, preferably from 50 to 400 ppm, in particular from 75 to 350 ppm of ethylene copolymer and from 20 to 500 ppm, preferably from 50 to 400 ppm, in particular from 75 to 350 ppm of oil-soluble polar nitrogen compounds.
• the suitable oil-soluble polar nitrogen compounds are reaction products of fatty amines with compounds which contain an acyl group.
• the alkyl and alkenyl radicals may each be linear or branched and contain up to two double bonds. They are preferably linear and substantially saturated, i.e. they have iodine numbers of less than 75 g of I 2 /g, preferably less than 60 g of I 2 /g and in particular between 1 and 10 g of I 2 /g.
• R 6 , R 7 and R 8 groups are each 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.
• Suitable fatty amines are, for example, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosylamine, behenylamine, didecylamine, didodecylamine, ditetradecylamine, dihexadecylamine, dioctadecylamine, dieicosylamine, dibehenylamine and mixtures thereof.
• the amines especially contain chain cuts based on natural raw materials, for example coconut fatty amine, tallow fatty amine, hydrogenated tallow fatty amine, dicoconut fatty amine, ditallow fatty amine and di(hydrogenated tallow fatty amine).
• Particularly preferred amine derivatives are amine salts, imides and/or amides, for example amide-ammonium salts of secondary fatty amines, in particular of dicoconut fatty amine, ditallow fatty amine and distearylamine.
• Acyl group refers here to a functional group of the following formula: >C ⁇ O
• Carbonyl compounds suitable for the reaction with amines are either low molecular weight or polymeric compounds having one or more carboxyl groups. Preference is given to those low molecular weight carbonyl compounds having 2, 3 or 4 carbonyl groups. They may also contain heteroatoms such as oxygen, sulfur and nitrogen.
• Suitable carboxylic acids are, for example, maleic acid, fumaric acid, crotonic acid, itaconic acid, succinic acid, C 1 -C 40 -alkenylsuccinic acid, adipic acid, glutaric acid, sebacic acid and malonic acid, and also benzoic acid, phthalic acid, trimellitic acid and pyromellitic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid and their reactive derivatives, for example esters, anhydrides and acid halides.
• Useful polymeric carbonyl compounds have been found to be in particular copolymers of ethylenically unsaturated acids, for example acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid; particular preference is given to copolymers of maleic anhydride.
• Suitable comonomers are those which confer oil solubility on the copolymer. Oil-soluble means here that the copolymer, after reaction with the fatty amine, dissolves without residue in the middle distillate to be additized in practically relevant dosages.
• Suitable comonomers are, for example, olefins, alkyl esters of acrylic acid and methacrylic acid, alkyl vinyl esters, alkyl vinyl ethers having from 2 to 75, preferably from 4 to 40 and in particular from 8 to 20, carbon atoms in the alkyl radical.
• the alkyl radical attached to the double bond is equivalent here.
• the molecular weights of the polymeric carbonyl compounds are preferably between 400 and 20 000, more preferably between 500 and 10 000, for example between 1000 and 5000.
• oil-soluble polar nitrogen compounds which are 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 are particularly useful (cf. U.S. Pat. No. 4,211,534).
• Equally suitable as oil-soluble polar nitrogen compounds are amides and ammonium salts of aminoalkylenepolycarboxylic acids such as nitrilotriacetic acid or ethylenediaminetetraacetic acid with secondary amines (cf. EP 0 398 101).
• oil-soluble polar nitrogen compounds are copolymers of maleic anhydride and ⁇ , ⁇ -unsaturated compounds which may optionally be reacted with primary monoalkylamines and/or aliphatic alcohols (cf. EP-A-0 154 177, EP 0 777 712), the reaction products of alkenyl-spiro-bislactones with amines (cf. EP-A-0 413 279 B1) and, according to EP-A-0 606 055 A2, reaction products of terpolymers based on ⁇ , ⁇ -unsaturated dicarboxylic anhydrides, ⁇ , ⁇ -unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols.
• the mixing ratio between the inventive additives and oil-soluble polar nitrogen compounds as constituent II may vary depending upon the application.
• Such additive mixtures preferably contain from 5 to 95% by weight, preferably from 10 to 90% by weight of the inventive additive, and also from 5 to 95% by weight, preferably from 10 to 90% by weight of oil-soluble polar nitrogen compounds.
• ethylene copolymers and the oil-soluble polar nitrogen compounds may be present as coadditives in the fuel oils or in the inventive additive.
• olefin copolymers may be used as a coadditive in the inventive additives.
• Suitable olefin copolymers as a coadditive for the inventive additive may derive directly from monoethylenically unsaturated monomers, or may be prepared indirectly by hydrogenation of polymers which derive from polyunsaturated monomers such as isoprene or butadiene.
• Preferred copolymers contain, in addition to ethylene, structural units which derive from ⁇ -olefins having from 3 to 24 carbon atoms and have molecular weights of up to 120 000 g/mol.
• Preferred ⁇ -olefins are propylene, butene, isobutene, n-hexene, isohexene, n-octene, isooctene, n-decene, isodecene.
• the comonomer content of olefins is preferably between 15 and 50 mol %, more preferably between 20 and 35 mol % and especially between 30 and 45 mol %.
• These copolymers may also contain small amounts, for example up to 10 mol %, of further comonomers, for example nonterminal olefins or nonconjugated olefins. Preference is given to ethylene-propylene copolymers.
• the olefin copolymers may be prepared by known methods, for example by means of Ziegler or metallocene catalysts.
• olefin copolymers are block copolymers which contain blocks composed of olefinically unsaturated aromatic monomers A and blocks composed of hydrogenated polyolefins B.
• Particularly suitable block copolymers have the structure (AB) n A and (AB) m , where n is from 1 to 10 and m is from 2 to 10.
• the mixing ratio between the inventive additive and constituent III is generally in each case between 1:20 and 20:1, preferably in each case between 1:10 and 10:1 by weight.
• comb polymers may also be used as a coadditive.
• Suitable comb polymers as a coadditive for the inventive additive may be described, for example, by the formula 5
• A is R′, COOR′, OCOR′, R′′—COOR′, OR′;
• D is H, CH 3 , A or R′′;
• E is H, A;
• G is H, R′′, R′′—COOR′, an aryl radical or a heterocyclic radical
• M is H, COOR′′, OCOR′′, OR′′, COOH;
• N is H, R′′, COOR′′, OCOR′′, an aryl radical
• R′ is a hydrocarbon chain having from 8 to 50 carbon atoms
• R′′ is a hydrocarbon chain having from 1 to 10 carbon atoms
• alkylphenol-aldehyde resins are used as further constituents in the inventive additives (constituent V).
• Alkylphenol-aldehyde resins are known in principle and are described, for example, in Römpp Chemie Lexikon, 9th edition, Thieme Verlag 1988-92, volume 4, p. 3351 ff. Suitable in accordance with the invention are in particular those alkylphenol-aldehyde resins which derive from alkylphenols having one or two alkyl radicals in the ortho- and/or para-position to the OH group.
• alkylphenols which bear, on the aromatic ring, at least two hydrogen atoms capable of condensation with aldehydes, and especially monoalkylated phenols whose alkyl radical is in the para-position.
• the alkyl radicals may be the same or different in the alkylphenol-aldehyde resins usable in the process according to the invention, they may be saturated or unsaturated and have 1-200, preferably 1-20, in particular 4-12 carbon atoms; they are preferably n-, iso- and tert-butyl, n- and isopentyl, n- and isohexyl, n- and isooctyl, n- and isononyl, n- and isodecyl, n- and isododecyl, tetradecyl, hexadecyl, octadecyl,
• Suitable aldehydes for the alkylphenol-aldehyde resins are those having from 1 to 12 carbon atoms and preferably those having from 1 to 4 carbon atoms, for example formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 2-ethylhexanal, benzaldehyde, glyoxalic acid and reactive equivalents thereof, such as paraformaldehyde and trioxane. Particular preference is given to formaldehyde in the form of paraformaldehyde and especially formalin.
• molecular weights are always measured by means of gel permeation chromatography (GPC) against polystyrene standards in THF.
• the molecular weight of the alkylphenol-aldehyde resins is preferably 400-20 000 g/mol, especially 400-5000 g/mol.
• a prerequisite in this context is that the alkylphenol-aldehyde resins are oil-soluble at least in concentrations relevant to the application of from 0.001 to 1% by weight.
• the alkylphenol-formaldehyde resins contain oligo- or polymers having a repeat structural unit of the formula 3 where R 5 is C 1 -C 200 -alkyl or -alkenyl and n is from 2 to 100.
• R 5 is preferably C 4 -C 20 -alkyl or -alkenyl and especially C 6 -C 16 -alkyl or -alkenyl.
• n is preferably from 2 to 50 and especially from 3 to 25, for example from 5 to 15.
• alkylphenol-aldehyde resins having C 2 -C 40 -alkyl radicals of the alkylphenol, preferably having C 4 -C 20 -alkyl radicals, for example C 6 -C 12 -alkyl radicals.
• the alkyl radicals may be linear or branched; they are preferably linear.
• Particularly suitable alkylphenol-aldehyde resins derive from linear alkyl radicals having 8 and 9 carbon atoms.
• the average molecular weight, determined by means of GPC, is preferably between 700 and 20 000 g/mol, in particular between 800 and 10 000 g/mol, for example between 1000 and 2500 g/mol.
• alkylphenol-aldehyde resins are obtainable by known processes, for example by condensation of the appropriate alkylphenols with formaldehyde, i.e. with from 0.5 to 1.5 mol, preferably from 0.8 to 1.2 mol of formaldehyde per mole of alkylphenol.
• the condensation may be effected without solvent, but is preferably effected in the presence of a water-immiscible or only partly water-miscible inert organic solvent such as mineral oils, alcohols, ethers and the like. Particular preference is given to solvents which can form azeotropes with water.
• Useful such solvents are in particular aromatics such as toluene, xylene, diethylbenzene and relatively high-boiling commercial solvent mixtures such as ®Shellsol AB and Solvent Naphtha.
• the condensation is effected preferably between 70 and 200° C., for example between 90 and 160° C. It is catalyzed typically by from 0.05 to 5% by weight of bases or acids.
• bases or acids for example, the condensation catalyzed by amines, preferably tertiary amines, for example triethylamine, with subsequent neutralization by means of organic sulfonic acid leads to the suitable products.
• Preference is given in accordance with the invention to catalysis by organic sulfonic acids which, on completion of the condensation with amines, are converted to the oil-soluble ammonium sulfonates.
• the mixing ratio of the alkylphenol-aldehyde resins as a coadditive to the inventive additive is generally between 20:1 and 1:20, preferably between 1:10 and 10:1.
• polyoxyalkylene compounds may also be used as coadditives.
• Suitable polyoxyalkylene compounds as a coadditive for the inventive additive are, for example, esters, ethers and ether/esters which bear at least one alkyl radical having from 12 to 30 carbon atoms.
• the alkyl groups stem from an acid, the remainder stems from a polyhydric alcohol; when the alkyl radicals come from a fatty alcohol, the remainder of the compound stems from a polyacid.
• Suitable polyols are polyethylene glycols, polypropylene glycols, polybutylene glycols and copolymers thereof having a molecular weight of from approx. 100 to approx. 5000 g/mol, preferably from 200 to 2000 g/mol.
• alkoxylates of polyols for example of glycerol, trimethylolpropane, pentaerythritol, neopentyl glycol, and the oligomers which are obtainable therefrom by condensation and have from 2 to 10 monomer units, for example polyglycerol.
• Preferred alkoxylates are those having from 1 to 100 mol, in particular from 5 to 50 mol, of ethylene oxide, propylene oxide and/or butylene oxide per mole of polyol. Esters are particularly preferred.
• Fatty acids having from 12 to 26 carbon atoms are preferred for the reaction with the polyols to form the ester additives, and particular preference is given to using C 18 - to C 24 -fatty acids, especially stearic and behenic acid.
• the esters may also be prepared by esterifying polyoxyalkylated alcohols. Preference is given to fully esterified polyoxyalkylated polyols having molecular weights of from 150 to 2000, preferably from 200 to 600. Particularly suitable are PEG-600 dibehenate and glycerol ethylene glycol tribehenate.
• the mixing ratio between the inventive additive and the further constituent VI is generally between 1:10 and 10:1, preferably in each case between 1:5 and 5:1.
• inventive additive may be used alone or in a mixture with one or more of constituent(s) II, III, IV, V or VI.
• inventive additives may be used alone or else together with other additives, for example with other pour point depressants or dewaxing assistants, with antioxidants, flow improvers, cetane number improvers, dehazers, demulsifiers, detergents, lubricity additives, dispersants, antifoams, dyes, corrosion inhibitors, sludge inhibitors, odorants and/or additives for lowering the cloud point.
• the other additives may be added directly to the fuel oil mixture or be introduced into the mixture by mixing different fuel oil components which have already been additized individually with one or more of the additives mentioned.
• the inventive additives are suitable for improving the cold flow properties of fuel oils of animal, vegetable or mineral origin.
• they disperse the paraffins which precipitate out below the cloud point in middle distillates.
• they are superior to the prior art additives in problematic oils having a low aromatics content of less than 25% by weight, in particular less than 22% by weight, for example less than 20% by weight, of aromatics, and thus lower solubility for n-paraffins.
• Middle distillates refer in particular to those mineral oils which are obtained by distillation of crude oil and boil in the range from 120 to 450° C., for example kerosene, jet fuel, diesel and heating oil.
• Aromatic compounds refer to the totality of mono-, di- and polycyclic aromatic compounds, as can be determined by means of HPLC to DIN EN 12916 (2001 edition).
• the inventive additives are particularly advantageous in those middle distillates which contain less than 350 ppm of sulfur, more preferably less than 100 ppm of sulfur, in particular less than 50 ppm of sulfur and in special cases less than 10 ppm of sulfur. They are generally those middle distillates which have been subjected to refining under hydrogenating conditions and therefore contain only small fractions of polyaromatic and polar compounds. They are preferably those middle distillates which have 90% distillation points below 360° C., in particular 350° C. and in special cases below 340° C.
• Oils obtained from animal or vegetable material are mainly metabolism products which include triglycerides of monocarboxylic acids, for example acids having from 10 to 25 carbon atoms, and corresponding to the formula where R is an aliphatic radical which has from 10 to 25 carbon atoms and may be saturated or unsaturated.
• oils contain glycerides from a series of acids whose number and type vary with the source of the oil, and they may additionally contain phosphoglycerides.
• Such oils can be obtained by processes known from the prior art.
• the biofuel oil which is frequently also referred to as biodiesel or biofuel, comprises fatty acid alkyl esters composed of fatty acids having from 12 to 24 carbon atoms and alcohols having from 1 to 4 carbon atoms. Typically, a relatively large portion of the fatty acids contains one, two or three double bonds.
• the biofuel is more preferably, for example, rapeseed oil methyl ester and especially mixtures which comprise rapeseed oil fatty acid methyl ester, sunflower oil fatty acid methyl ester, palm oil fatty acid methyl ester, used oil fatty acid methyl ester and/or soya oil fatty acid methyl ester.
• oils which are derived from animal or vegetable material and which can be used in the inventive fuel oils are rapeseed oil, coriander oil, soya oil, cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, maize oil, almond oil, palm kernel oil, coconut oil, mustardseed oil, bovine tallow, bone oil and fish oils.
• rapeseed oil which is a mixture of fatty acids partially esterified with glycerol, since it is obtainable in large amounts and is obtainable in a simple manner by extractive pressing of rapeseeds.
• preference is given to the likewise widely available oils of sunflowers and soya, and also to their mixtures with rapeseed oil.
• Useful lower alkyl esters of fatty acids are the following, for example as commercial mixtures: the ethyl, propyl, butyl and in particular methyl esters of fatty acids having from 12 to 22 carbon atoms, for example of lauric acid, myristic acid, palmitic acid, palmitolic acid, stearic acid, oleic acid, elaidic acid, petroselic acid, ricinolic acid, elaeostearic acid, linoleic acid, linolenic acid, eicosanoic acid, gadoleic acid, docosanoic acid or erucic acid, each of which preferably has an iodine number of from 50 to 150, in particular from 90 to 125.
• Mixtures having particularly advantageous properties are those which comprise mainly, i.e. comprise at least 50% by weight of, methyl esters of fatty acids having from 16 to 22 carbon atoms, and 1, 2 or 3 double bonds.
• the preferred lower alkyl esters of fatty acids are the methyl esters of oleic acid, linoleic acid, linolenic acid and erucic acid.
• mixtures of synthetic fuels as are obtainable, for example, from the Fischer-Tropsch process, and a middle distillate of mineral origin A and/or a biofuel B as the fuel oil composition.
• test oils employed were current oils from European refineries.
• the CFPP value was determined to EN 116 and the cloud point to ISO 3015.
• the aromatic hydrocarbon groups were determined to DIN EN 12916 (November 2001 edition) Test oil 1
• Test oil 2 Test oil 3
• Test oil 4 Test oil 5 Distillation IBP [° C.] 166.3° C. 173.8° C. 240.7 173.8 166.6 90%-20% cut [° C.] 147° C. 117° C. 64.4 116.6 102.5 FBP [° C.] 377.9° C. 345.7° C.
• the ethylene copolymers used were commercial products having the properties reported in Table 2. The products were used in the form of 65% and 50% dilutions in kerosene.
• Polar polymeric nitrogen compound consisting of a comb polymer prepared from 1.3 mol % of 1-tetradecene, 1.3 mol % of hexadecene, 2.6 mol % of maleic anhydride and 0.2 mol % of allyl methyl polyglycol ether.
• the resulting polymer has a K value of 15 and is reacted with 2.6 mol % each of distearylamine and dicoconut fatty amine to give the amide ammonium salt.
• the titratable base nitrogen content of the 50% polymer solution is 0.69%.
• the lower 20% by volume is isolated and the cloud point is determined to ISO 3015. Only a slight deviation of the cloud point of the lower phase (CP cc ) from the blank value of the oil shows good paraffin dispersancy.
• the aromatic additives reported are used in an amount of 50-150 ppm.
• a dispersant is used generally in the presence of a cold flow improver.
• appropriate cold flow improvers were therefore used.
• the CFPP effectiveness and dispersing action of the inventive additives were determined in a composition of (by parts by weight) 50 ppm of the aromatic additive with 100 ppm of B1 and 400 ppm of A2.
• Aromatic CFPP CP cc Example additive [° C.] [° C.]
• Visual assessment 1 1 ⁇ 26 ⁇ 7.6 Homogeneously opaque, no sediment 2 2 ⁇ 27 ⁇ 7.9 Homogeneously opaque, no sediment 3 (C) 3 (C) ⁇ 22 ⁇ 5.2 5 ml of sediment, homogeneously opaque Results in Test Oil 2
• CFPP effectiveness and dispersing action of the inventive additives were determined in a composition of (by parts by weight) 100 ppm of the aromatic additive with 150 ppm of B1 and 300 ppm of A2.
• CFPP CP cc Example Aromatic additive [° C.] [° C.]
• Visual assessment 4 1 ⁇ 27 ⁇ 6.1 Homogeneously opaque, no sediment 5 2 ⁇ 28 ⁇ 6.5 Homogeneously opaque, no sediment 6 (C) 3 (C) ⁇ 21 ⁇ 4.7 8 ml of sediment Results in Test Oil 3
• CFPP effectiveness and dispersing action of the inventive additives were determined in a composition of (by parts by weight) 50 ppm of the aromatic additive with 100 ppm of B1 and 200 ppm of A3.
• CFPP CP cc Example Aromatic additive [° C.] [° C.]
• Visual assessment 7 1 ⁇ 23 ⁇ 7.9 1 ml of sediment, homogeneously opaque 8 2 ⁇ 24 ⁇ 8.1 Homogeneously opaque, no sediment 9 (C) 3 (C) ⁇ 19 ⁇ 6.8 12 ml of sediment, homogeneously opaque Results in Test Oil 4
• CFPP effectiveness and dispersing action of the inventive additives were determined in a composition of (by parts by weight) 50 ppm of the aromatic additive with 200 ppm of B1 and 300 ppm of A3.
• Aromatic CFPP CP cc Example additive [° C.] [° C.]
• Visual assessment 10 1 ⁇ 29 ⁇ 3.2 Homogeneously opaque, no sediment 11 2 ⁇ 28 ⁇ 3.5 Homogeneously opaque, no sediment 12 (C) 3 (C) ⁇ 23 ⁇ 1.2 11 ml of sediment, homogeneously opaque Results in Test Oil 5
• CFPP effectiveness and dispersing action of the inventive additives were determined in a composition of (by parts by weight) 100 ppm of the aromatic additive with 200 ppm of B1 and 300 ppm of A1.
• Aromatic CFPP Example additive [° C.] CP cc [° C.]
• Visual assessment 13 1 ⁇ 25 ⁇ 7.5 Homogeneously opaque, no sediment 14 2 ⁇ 27 ⁇ 7.1 Homogeneously opaque, no sediment 15 (C) 3 (C) ⁇ 22 ⁇ 4.9 15 ml of sediment, homogeneously opaque

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• 2005
  • 2005-04-30 DE DE102005020264A patent/DE102005020264B4/de not_active Expired - Fee Related
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