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
  • C10L1/143—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
  • C10L1/146—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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/16—Hydrocarbons
  • C10L1/1625—Hydrocarbons macromolecular compounds
  • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
  • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
• • 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
  • C10L1/198—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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
  • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
  • C10L1/2406—Organic compounds containing sulfur, selenium and/or tellurium mercaptans; hydrocarbon sulfides
  • C10L1/2418—Organic compounds containing sulfur, selenium and/or tellurium mercaptans; hydrocarbon sulfides containing a carboxylic substituted; derivatives thereof, e.g. 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
  • 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
  • C10L2200/00—Components of fuel compositions
  • C10L2200/04—Organic compounds
  • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
  • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
  • C10L2200/0446—Diesel
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
  • C10L2230/14—Function and purpose of a components of a fuel or the composition as a whole for improving storage or transport of the fuel
• • 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
  • C10L2270/00—Specifically adapted fuels
  • C10L2270/02—Specifically adapted fuels for internal combustion engines
  • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine

Definitions

• the invention relates to novel compositions for reducing crystallization of paraffin crystals in fuels.
• Middle distillate fuels of fossil origin especially gas oils, diesel oils or light heating oils, which are obtained from mineral oil, have different contents of paraffins according to the origin of the crude oil.
• CP cloud point
• the platelet-shaped n-paraffin crystals form a kind of "house of cards structure” and the middle distillate fuel ceases to flow even though its predominant portion is still liquid.
• the precipitated n-paraffins in the temperature range between cloud point and pour point (“PP") considerably impair the flowability of the middle distillate fuels; the paraffins block filters and cause irregular or completely interrupted fuel supply to the combustion units. Similar disruptions occur in the case of light heating oils.
• MDFIs middle distillate flow improvers
• EVA ethylene-vinyl carboxylate copolymers
• EVA ethylene-vinyl acetate copolymers
• Alkylphenol-aldehyde resins in combination with other additives are known to improve the flow properties of paraffine containing mineral oils and mineral oil derivatives, see e.g. EP 857776 A1 .
• Another object of the invention is the use the mixtures according to the present invention for reducing crystallization of paraffin crystals in fuels and/or improving the cold flow properties of fuels.
• Another object of the invention are middle distillate fuels comprising these mixtures.
• Component (A) are reaction products of acetylene and p-alkylphenols which primarily comprise repeating units of formula (I) wherein, R 2 in formula I is a linear or branched, saturated or unsaturated aliphatic hydrocarbon group with 2 to 100 carbon atoms. In a particularly preferred embodiment of the invention R 2 in is a linear or branched, saturated aliphatic hydrocarbon group with 3 to 20, more preferably from 4 to 16 carbon atoms.
• R 2 is preferably substituted mainly in para position to the phenolic OH-group.
• R 2 are ethyl, n-propyl, iso -propyl, n-butyl, iso-butyl, sec-butyl and tert- butyl, n-pentyl, tert -pentyl, n-hexyl, 2-ethylhexyl, 2-propylheptyl, n-octyl, iso-octyl, n-nonyl, iso-nonyl, n-decyl, iso-decyl, n-undecyl, iso-undecyl, n-dodecyl, iso-dodecyl, n-tridecyl, iso-tridecyl, n-tetradecyl, iso-tetradecyl, n-hexadecyl, iso-hexadecyl, n-oct
• R 2 iso -propyl, iso-butyl, sec-butyl, tert -butyl, tert -pentyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, and n-hexadecyl.
• R 2 iso -propyl, tert-butyl, and tert -pentyl.
• substituents R 2 are preferably derived from oligomers or polymers of propene or iso-butene, e.g. trimers, tetramers, pentamers or hexamers of propene or dimers, trimers or tetramers of iso-butene or n-butene.
• R 2 can be derived from an iso -butene containing polymer, preferably a homopolymer of iso -butene, with a weight average molecular weight Mw of 225 to 1400 g/mol, preferably 350 to 1300, more preferably 500 to 1200, and most preferably 600 to 1100 g/mol.
• Components (A) may be obtained by reacting a phenolic compound of formula R 2 -C 6 H 4 -OH with acetylene.
• acetylene adds to a carbon atom of R 2 -C 6 H 4 -OH (usually the carbon atom in ortho position to the OH group) followed by reaction of the obtained vinyl group with further R 2 -C 6 H 4 -OH.
• the obtained resin may to some extent be crosslinked as further acetylene might add to the less reactive meta position.
• Koresin® a resin marketed by BASF, and which is obtainable by reacting acetylene and para tertiary butyl phenol.
• component (A) primarily comprises units of formula (I)
• acetylene in the reaction component (A) may further comprise (see e.g. A. O. Zoss et al., Industrial and Engineering Chemistry, 41, 1949, 73 - 77 ) units of formula (II) and/or terminal groups of formula (III)
• the resin may comprise further structural elements which are incorporated by using comonomers or reactive additives as further starting materials in the reaction.
• At least 80 %, more preferably at least 90%, even more preferably at least 95% by weight of the starting materials used for the preparation of the resin are R 2 -C 6 H 4 -OH and acetylene.
• the number average and weight average molecular weights Mn and Mw of components (A) are Mn from 500 to 2000 and Mw from 750 to 4100 g/mol.
• terminal vinylidene groups of formula (III) can be proven by infrared spectroscopy or iodine number according to EN 14111:2003. Typical are absorption bands at wavenumbers of 985 cm -1 and/or 900 cm -1 , each approximately ⁇ 20 cm -1 .
• the content of ingredients in component (A) being insoluble in cyclohexane at 20 °C is less than 1 wt%, preferably not more than 0.75 wt%, more preferably not more than 0.5 wt% and most preferably not more than 0.25 wt%.
• the solubility of component (A) in cyclohexane at 20 °C is usually at least 45% by weight, preferably at least 50%, more preferably at least 55%, and most preferably at least 60% by weight (measured after initial stirring and heating to 70 °C in a closed container and cooling down to 20 °C).
• the content of metals in component (A) is not more than 100 ppm by weight, preferably not more than 50 ppm by weight, more preferably not more than 25 ppm by weight, most preferably not more than 15 ppm by weight, and especially not more than 10 ppm by weight, calculated for each metal species.
• Sources of metals in component (A) are usually catalysts used or basic solutions of (earth) alkaline bases used during work up procedures. Metals are detrimental in fuels since they may lead to deposits in engines, such as combustion spaces, injectors or valves, or fuel pipes.
• Component (A) is added to the middle distillate fuel or diesel fuel in a total amount of preferably 1 to 1000 ppm by weight, more preferably of 2 to 500 ppm by weight, even more preferably of 3 to 350 ppm by weight and especially of 4 to 250 ppm by weight, for example of 5 to 100 ppm by weight.
• Component (B) is at least one cold flow improver which is selected from the group consisting of compounds (B1) to (B6) listed below.
• Suitable cold flow improvers are in principle all organic compounds which are capable of improving the flow performance of middle distillate fuels or diesel fuels under cold conditions. For the intended purpose, they must have sufficient oil solubility. More particularly, useful cold flow improvers for this purpose are the cold flow improvers (middle distillate flow improvers, MDFIs) typically used in the case of middle distillates of fossil origin, i.e. in the case of customary mineral diesel fuels. However, it is also possible to use organic compounds which partly or predominantly have the properties of a wax antisettling additive ("WASA”) when used in customary diesel fuels. They can also act partly or predominantly as nucleators. It is also possible to use mixtures of organic compounds effective as MDFIs and/or effective as WASAs and/or effective as nucleators.
• MDFIs middle distillate flow improvers
• WASA wax antisettling additive
• the cold flow improver is selected from:
• Suitable C 2 - to C 40 -olefin monomers for the copolymers of class (B1) are, for example, those having 2 to 20 and especially 2 to 10 carbon atoms, and 1 to 3 and preferably 1 or 2 carbon-carbon double bonds, especially having one carbon-carbon double bond.
• the carbon-carbon double bond may be arranged either terminally (a-olefins) or internally.
• preference is given to ⁇ -olefins particular preference to ⁇ -olefins having 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene, 1-hexene and in particular ethylene.
• the at least one further ethylenically unsaturated monomer is preferably selected from alkenyl carboxylates, (meth)acrylic esters and further olefins.
• further olefins are also copolymerized, they are preferably higher in molecular weight than the abovementioned C 2 - to C 40 -olefin base monomers.
• the olefin base monomer used is ethylene or propene
• suitable further olefins are especially C 10 - to C 40 - ⁇ -olefins. Further olefins are in most cases only additionally copolymerized when monomers with carboxylic ester functions are also used.
• Suitable (meth)acrylic esters are, for example, esters of (meth)acrylic acid with C 1 - to C 20 -alkanols, especially 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, and structural isomers thereof.
• Suitable alkenyl carboxylates are, for example, C 2 - to C 14 -alkenyl esters, for example the vinyl and propenyl esters, of carboxylic acids having 2 to 21 carbon atoms, whose hydrocarbyl radical may be linear or branched.
• preference is given to the vinyl esters.
• carboxylic acids with a branched hydrocarbyl radical preference is given to those whose branch is in the ⁇ position to the carboxyl group, and the ⁇ -carbon atom is more preferably tertiary, i.e. the carboxylic acid is what is called a neocarboxylic acid.
• the hydrocarbyl radical of the carboxylic acid is preferably linear.
• alkenyl carboxylates examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, preference being given to the vinyl esters.
• a particularly preferred alkenyl carboxylate is vinyl acetate; typical copolymers of group (B1) resulting therefrom are ethylene-vinyl acetate copolymers ("EVAs”), which are some of the most frequently used.
• Ethylene-vinyl acetate copolymers usable particularly advantageously and the preparation thereof are described in WO 99/29748 .
• Suitable copolymers of class (B1) are also those which comprise two or more different alkenyl carboxylates in copolymerized form, which differ in the alkenyl function and/or in the carboxylic acid group.
• copolymers which, as well as the alkenyl carboxylate(s), comprise at least one olefin and/or at least one (meth)acrylic ester in copolymerized form.
• Terpolymers of a C 2 - to C 40 - ⁇ -olefin, a C 1 - to C 20 -alkyl ester of an ethylenically unsaturated monocarboxylic acid having 3 to 15 carbon atoms and a C 2 - to C 14 -alkenyl ester of a saturated monocarboxylic acid having 2 to 21 carbon atoms are also suitable as copolymers of class (B1).
• Terpolymers of this kind are described in WO 2005/054314 .
• a typical terpolymer of this kind is formed from ethylene, 2-ethylhexyl acrylate or 2-propylheptyl acrylate and vinyl acetate.
• the at least one or the further ethylenically unsaturated monomer(s) are copolymerized in the copolymers of class (B1) in an amount of preferably 1 to 50% by weight, especially 10 to 45% by weight and in particular 20 to 40% by weight, based on the overall copolymer.
• the main proportion in terms of weight of the monomer units in the copolymers of class (B1) therefore originates generally from the C 2 - to C 40 base olefins.
• the copolymers of class (B1) preferably have a number-average molecular weight Mn of 1000 to 20 000, more preferably of 1000 to 10 000 and especially of 1000 to 8000.
• Typical comb polymers of component (B2) are, for example, obtainable 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.
• Further suitable 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.
• Suitable comb polymers may also be polyfumarates or polymaleates. Homo- and copolymers of vinyl ethers are also suitable comb polymers.
• Comb polymers suitable as components of class (B2) are, for example, also those described in WO 2004/035715 and in " Comb-Like Polymers, Structure and Properties", N. A. Plate and V. P. Shibaev, J. Poly. Sci. Macromolecular Revs. 8, pages 117 to 253 (1974 ). Mixtures of comb polymers are also suitable.
• Polyoxyalkylenes suitable as components of class (B3) are, for example, polyoxyalkylene esters, polyoxyalkylene ethers, mixed polyoxyalkylene ester/ethers and mixtures thereof. These polyoxyalkylene compounds preferably comprise at least one linear alkyl group, preferably at least two linear alkyl groups, each having 10 to 30 carbon atoms and a polyoxyalkylene group having a number-average molecular weight of up to 5000. Such polyoxyalkylene compounds are described, for example, in EP-A 061 895 and also in US 4 491 455 . Particular polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols having a number-average molecular weight of 100 to 5000. Additionally suitable are polyoxyalkylene mono- and diesters of fatty acids having 10 to 30 carbon atoms, such as stearic acid or behenic acid.
• Polar nitrogen compounds suitable as components of class (B4) may be either ionic or nonionic and preferably have at least one substituent, especially at least two substituents, in the form of a tertiary nitrogen atom of the general formula >NR 7 in which R 7 is a C 8 - to C 40 -hydrocarbyl radical.
• the nitrogen substituents may also be quaternized, i.e. be in cationic form. Examples of such nitrogen compounds are ammonium salts and/or amides which are obtainable by the reaction of at least one amine substituted by at least one hydrocarbyl radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof.
• the amines preferably comprise at least one linear C 8 - to C 40 -alkyl radical.
• Primary amines suitable for preparing the polar nitrogen compounds mentioned are, for example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologs; secondary amines suitable for this purpose are, for example, dioctadecylamine and methylbehenylamine.
• amine mixtures especially amine mixtures obtainable on the industrial scale, such as fatty amines or hydrogenated tallamines, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition, "Amines, aliphatic” chapter .
• Acids suitable for the reaction are, for example, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and succinic acids substituted by long-chain hydrocarbyl radicals.
• the component of class (B4) is an oil-soluble reaction product of poly(C 2 - to C 20 -carboxylic acids) having at least one tertiary amino group with primary or secondary amines.
• the poly(C 2 - to C 20 -carboxylic acids) which have at least one tertiary amino group and form the basis of this reaction product comprise preferably at least 3 carboxyl groups, especially 3 to 12 and in particular 3 to 5 carboxyl groups.
• the carboxylic acid units in the polycarboxylic acids have preferably 2 to 10 carbon atoms, and are especially acetic acid units.
• the carboxylic acid units are suitably bonded to the polycarboxylic acids, usually via one or more carbon and/or nitrogen atoms. They are preferably attached to tertiary nitrogen atoms which, in the case of a plurality of nitrogen atoms, are bonded via hydrocarbon chains.
• the component of class (B4) is preferably an oil-soluble reaction product based on poly(C 2 - to C 20 -carboxylic acids) which have at least one tertiary amino group and are of the general formula (IVa) or IVb in which the variable A is a straight-chain or branched C 2 - to C 6 -alkylene group or the moiety of the formula (V) and the variable B is a C 1 - to C 19 -alkylene group.
• the compounds of the general formulae (IVa) and (IVb) especially have the properties of a WASA.
• the preferred oil-soluble reaction product of component (B4) is an amide, an amide-ammonium salt or an ammonium salt in which no, one or more carboxylic acid groups have been converted to amide groups.
• Straight-chain or branched C 2 - to 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 especially 1,2-ethylene.
• the variable A comprises preferably 2 to 4 and especially 2 or 3 carbon atoms.
• C 1 - to C 19 -alkylene groups of the variable B are, for example, methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene, nonadecamethylene and especially methylene.
• the variable B comprises preferably 1 to 10 and especially 1 to 4 carbon atoms.
• the primary and secondary amines as a reaction partner for the polycarboxylic acids to form component (B4) are typically monoamines, especially aliphatic monoamines. These primary and secondary amines may be selected from a multitude of amines which bear hydrocarbyl radicals which may optionally be bonded to one another.
• These parent amines of the oil-soluble reaction products of component (B4) are usually secondary amines and have the general formula HN(R 8 ) 2 in which the two variables R 8 are each independently straight-chain or branched C 10 - to C 30 -alkyl radicals, especially C 14 - to C 24 -alkyl radicals. These relatively long-chain alkyl radicals are preferably straight-chain or only slightly branched.
• the secondary amines mentioned, with regard to their relatively long-chain alkyl radicals derive from naturally occurring fatty acids and from derivatives thereof.
• the two R 8 radicals are preferably identical.
• the secondary amines mentioned may be bonded to the polycarboxylic acids by means of amide structures or in the form of the ammonium salts; it is also possible for only a portion to be present as amide structures and another portion as ammonium salts. Preferably only few, if any, free acid groups are present.
• the oil-soluble reaction products of component (B4) are preferably present completely in the form of the amide structures.
• Typical examples of such components (B4) are reaction products of nitrilotriacetic acid, of ethylenediaminetetraacetic acid or of propylene-1,2-diaminetetraacetic acid with in each case 0.5 to 1.5 mol per carboxyl group, especially 0.8 to 1.2 mol per carboxyl group, of a di-C 10 - to C 24 -alkyl amine, preferably dioleylamine, dipalmitamine, dicocoamine, distearylamine, dibehenylamine or especially ditallamine.
• a particularly preferred component (B4) is the reaction product of 1 mol of ethylenediaminetetraacetic acid and 4 mol of hydrogenated ditallamine.
• component (B4) include the N,N-dialkylammonium salts of 2-N',N'-dialkylamidobenzoates, for example the reaction product of 1 mol of phthalic anhydride and 2 mol of ditallamine, the latter being hydrogenated or unhydrogenated, and the reaction product of 1 mol of an alkenylspirobislactone with 2 mol of a dialkylamine, for example ditallamine and/or tallamine, the latter two being hydrogenated or unhydrogenated.
• N,N-dialkylammonium salts of 2-N',N'-dialkylamidobenzoates for example the reaction product of 1 mol of phthalic anhydride and 2 mol of ditallamine, the latter being hydrogenated or unhydrogenated
• the reaction product of 1 mol of an alkenylspirobislactone with 2 mol of a dialkylamine for example ditallamine and/or tallamine, the latter two being hydrogenated or unhydrogenated.
• component of class (B4) are cyclic compounds with tertiary amino groups or condensates of long-chain primary or secondary amines with carboxylic acid-containing polymers, as described in WO 93/18115 .
• polar nitrogen-containing compounds are copolymers of alphaolefins with maleic anhydride and optionally further comonomers which are further reacted with primary or secondary amines.
• the polar nitrogen-containing compounds are copolymers of C 10 - to C 20 -alpha-olefins with maleic anhydride which are further reacted with primary or secondary C 8 -C 16 -alkyl amines which are bound via amide- and/or imide-groups.
• Examples are disclosed in EP 1526167 A designated as component B), especially those in Table 4 thereof, or in EP 1857529 designated as component B) which are incorporated by reference.
• copolymers are disclosed in WO 16/83130 which are incorporated by reference as copolymers of unsaturated dicarboxylic acids, C 6 - to C 20 -alpha olefins, C 6 - to C 20 -alkylesters of acrylic acid or methacrylic acid, and optionally further copolymerizable monomers which are further reacted with dialkylamines bearing C 17 - to C 30 -alkyl groups.
• Examples 1 to 10 in Table A of WO 16/83130 are Especially preferred. Examples 1 to 10 in Table A of WO 16/83130 .
• Further polar nitrogen-containing compounds are reaction products of phthalic anhydride with amines, especially dialkylamines, as described in US 4211534 .
• Sulfocarboxylic acids, sulfonic acids or derivatives thereof which are suitable as cold flow improvers of the component of class (B5) are, for example, the oil-soluble carboxamides and carboxylic esters of ortho-sulfobenzoic acid, in which the sulfonic acid function is present as a sulfonate with alkyl-substituted ammonium cations, as described in EP-A 261 957 .
• Poly(meth)acrylic esters suitable as cold flow improvers of the component of class (B6) are either homo- or copolymers of acrylic and methacrylic esters. Preference is given to copolymers of at least two different (meth)acrylic esters which differ with regard to the esterified alcohol.
• the copolymer optionally comprises another different olefinically unsaturated monomer in copolymerized form.
• 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 esters of saturated C 14 - and C 15 -alcohols, the acid groups having been neutralized with hydrogenated tallamine. Suitable poly(meth)acrylic esters are described, for example, in WO 00/44857 .
• the inventive mixtures can preferably be used in fuels in their function as a paraffin dispersant ("WASA").
• WASA paraffin dispersant
• the inventive mixtures often display their action as a paraffin dispersant particularly well only once together with the flow improvers.
• flow improvers shall be understood to mean all additives which improve the cold properties of middle distillate fuels.
• MDFI actual cold flow improvers
• nucleators cf. also Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, volume A16, p. 719 ff .
• inventive middle distillate fuels comprise these, in addition to component (A), in an amount of typically 1 to 2000 ppm by weight, preferably of 5 to 1000 ppm by weight, especially of 10 to 750 ppm by weight and in particular of 50 to 500 ppm by weight, for example of 150 to 400 ppm by weight.
• the inventive mixtures can be added either to middle distillate fuels entirely of fossil origin, i.e. those that have been obtained from mineral oil, or to fuels which, as well as the proportion based on mineral oil, comprise a proportion of biodiesel, in order to improve the properties thereof.
• a distinct improvement in the cold flow characteristics of the middle distillate fuel is observed, i.e. a lowering of the PP and/or CP values and/or CFPP values, irrespective of the origin or the composition of the fuel.
• the paraffin crystals which precipitate out are effectively kept suspended, and so there are no blockages of filters and lines by sedimented paraffin.
• the inventive mixtures have a good activity spectrum and thus achieve very good dispersion of the paraffin crystals which precipitate out in a wide variety of different middle distillate fuels.
• the present invention also provides fuels, especially those with a biodiesel content, comprising the inventive mixtures.
• the fuels or fuel additive concentrates also comprise, as further additives in amounts customary therefor, flow improvers (as described above), further paraffin dispersants, conductivity improvers, anticorrosion additives, lubricity additives, antioxidants, metal deactivators, antifoams, demulsifiers, detergents, cetane number improvers, solvents or diluents, dyes or fragrances or mixtures thereof.
• flow improvers as described above
• further paraffin dispersants as described above
• conductivity improvers for lubric acid
• anticorrosion additives lubricity additives
• lubricity additives antioxidants
• metal deactivators antifoams
• demulsifiers demulsifiers
• detergents cetane number improvers
• solvents or diluents dyes or fragrances or mixtures thereof.
• fuel oils shall be understood to mean middle distillate fuels of fossil, vegetable or animal origin, biofuel oils ("biodiesel”) and mixtures of such middle distillate fuels and biofuel oils.
• Middle distillate fuels are especially understood to mean fuels which are obtained by distilling crude oil as the first process step and boil within the range from 120 to 450°C.
• Such middle distillate fuels are used especially as diesel fuel, heating oil or kerosene, particular preference being given to diesel fuel and heating oil.
• They are generally crude oil distillates which have been subjected to refining under hydrogenating conditions and therefore comprise only small proportions of polyaromatic and polar compounds. They are preferably those middle distillates which have 90% distillation points below 370°C, especially below 360°C and in special cases below 330°C.
• Low-sulfur and sulfur-free middle distillates may also be obtained from relatively heavy mineral oil fractions which cannot be distilled under atmospheric pressure.
• Typical conversion processes for preparing middle distillates from heavy crude oil fractions include: hydrocracking, thermal cracking, catalytic cracking, coking processes and/or visbreaking. Depending on the process, these middle distillates are obtained in low-sulfur or sulfur-free form, or are subjected to refining under hydrogenating conditions.
• the middle distillates preferably have aromatics contents of below 35% by weight, preferably below 33% by weight, and especially below 30% by weight.
• the content of normal paraffins is between 5% by weight and 50% by weight, preferably between 10 and 35% by weight.
• the aromatics content of the middle distillates is more than 20% by weight, preferably more than 21%, more preferably at least 22% and most preferably at least 23% by weight.
• middle distillate fuels shall also be understood here to mean those fuels which can either be derived indirectly from fossil sources such as mineral oil or natural gas, or else are produced from biomass via gasification and subsequent hydrogenation.
• a typical example of a middle distillate fuel which is derived indirectly from fossil sources is the GTL ("gas-to-liquid”) diesel fuel obtained by means of Fischer-Tropsch synthesis.
• a middle distillate is prepared from biomass, for example, via the BTL ("biomass-to-liquid”) process, and can be used as fuel either alone or in a mixture with other middle distillates.
• the middle distillates also include hydrocarbons which are obtained by the hydrogenation of fats and fatty oils. They comprise predominantly n-paraffins.
• the inventive copolymer can also be used in biofuel oils and in mixtures of the middle distillates mentioned with biofuel oils, in order to improve cold flow characteristics.
• Mixtures of this kind are commercially available and usually comprise the biofuel oils in minor amounts, typically in amounts of 1% to 30% by weight, especially of 3% to 10% by weight, based on the total amount of middle distillate of fossil, vegetable or animal origin and biofuel oil.
• Biofuel oils are generally based on fatty acid esters, preferably essentially on alkyl esters of fatty acids which derive from vegetable and/or animal oils and/or fats.
• Alkyl esters are preferably understood to mean lower alkyl esters, especially C 1 - to C 4 -alkyl esters, which are obtainable by transesterifying the glycerides which occur in vegetable and/or animal oils and/or fats, especially triglycerides, by means of lower alcohols, for example ethanol or in particular methanol (“FAME").
• Typical lower alkyl esters which are based on vegetable and/or animal oils and/or fats and find use as a biofuel oil or components thereof are, for example, HVO (hydrogenated vegetable oil), sunflower methyl ester, palm oil methyl ester (“PME”), soya oil methyl ester (“SME”) and especially rapeseed oil methyl ester ("RME”).
• HVO hydrogenated vegetable oil
• PME palm oil methyl ester
• SME soya oil methyl ester
• RME rapeseed oil methyl ester
• the inventive copolymer brings about a reduction in the crystallization of paraffin crystals in fuels, especially those which comprise biofuel oils.
• a resin was prepared from p- tert -butylphenol and acetylene analogous to the experimental procedure as described in A. O. Zoss et al., Industrial and Engineering Chemistry, 41, 1949, 73 - 77 .
• the resin was used as a solution of 40 wt% in Solvesso 150.
• diesel fuels having the details of origin and indices reported in Table A were used.
• the cloud point (CP) to ISO 3015 and the CFPP to EN 116 of the additized fuel samples were determined. Thereafter, the additized fuel samples in 500 ml glass cylinders, in order to determine the delta CP, were cooled to -16°C in a cold bath and stored at this temperature for 16 hours. For each sample, the CP was again determined to ISO 3015 on the 20% by volume base phase separated off at -16°C. The smaller the deviation of the CP of the 20% by volume base phase from the original CP (delta CP) for the respective fuel sample, the better the dispersion of the paraffins.
• Table A Fuels Fuel Origin Cloud Point CP [°C] CFPP [°C] Density @15°C [kg/m3] 90 Vol% - 20 Vol% [°C] IBP [°C] FBP [°C] n-Paraffine [%] DF1 Eastern Europe -7.2 -8 835.1 103 179.4 354.4 18.02 DF2 Eastern Europe -7.5 -9 836 82 192.5 351.9 22.41 DF3 Eastern Europe -3.7 -6 839.9 93 183.5 364.4 17.37
• Table B Use Examples Fuel Wax AntiSettling Flow Improver (WAFI) ratio component (A) amount [ppm] CFPP Orginal CFPP bottom Delta CFPP DF1 WAFI1 without -23 -21 2.5 WAFI1 70/30 Example 2 600 -18 -19 1.9 WAFI1 70/30 Example 3 600 -22 -21 1.1 DF2 WAFI2
• component (A) based upon acetaldehyde yields better (i.e. lower) delta CP values than component (A) based upon formaldehyde (Example 2).

Landscapes

• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Liquid Carbonaceous Fuels (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=70779598

Family Applications (1)

Country Status (1)

Citations (15)

• 2021
  • 2021-05-10 EP EP21172949.6A patent/EP3913035A1/de active Pending

Patent Citations (15)

Non-Patent Citations (3)

Similar Documents

Legal Events