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 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
  • C10L1/16—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 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
  • C10L1/1963—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 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
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 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

Definitions

• the present invention relates to the use of nucleating agents to improve the cold flowability of mineral oil distillates containing detergent additives.
• paraffin-rich crude oils are extracted and processed, which consequently also lead to paraffin-rich fuel oils.
• the paraffins contained in particular in middle distillates can crystallize on lowering the temperature of the oil and partially agglomerate with the inclusion of oil. This crystallization and agglomeration can cause blockages of the filters in engines and firing systems, especially in winter, which prevents safe metering of the fuels and may possibly lead to a complete interruption of the fuel supply.
• the paraffin problem is also exacerbated by the environmental reasons to reduce the sulfur content increasing hydrodesulfurization of fuel oils, which leads to an increased proportion of cold-critical paraffins in the fuel oil.
• middle distillates are often added chemical additives, so-called cold flow improvers or flow improvers, modify the crystal structure and agglomeration tendency of the precipitated paraffins, so that the so-additive oils still pump or use at temperatures, often more than 20 ° C. lower than non-additized oils.
• cold flow improver oil-soluble copolymers of ethylene and unsaturated esters, oil-soluble polar nitrogen compounds and / or comb polymers are usually used. In addition, however, other additions have been proposed.
• detergent additives are being developed with ever increasing effectiveness. In addition, they are often used in very high dosage rates. It is reported that this reduces, for example, in diesel fuels, the specific consumption and the performance of the engines is increased.
• these additives often have negative effects on the cold flowability of middle distillates and in particular on the efficacy of known cold flow improvers. Especially with middle distillates with low boiling point and simultaneously low aromatic content, it is often difficult or even impossible to adjust in the presence of modern detergent additives using conventional flow improvers a satisfactory cold flow behavior. For example, the addition of detergent additives often results in an antagonistic effect on the effectiveness of the added cold flow improvers.
• the paraffin dispersion of the middle distillate, set by paraffin dispersants is impaired, without being able to be restored by increased dosage of paraffin dispersant.
• the CFPP measured filterability with cold flow improvers additive oils is significantly reduced in the cold and can be compensated only by greatly increased dosage of the flow improver.
• detergent additives which are derived from higher polyamines and those which are, for example, conditional have very high molecular weights by multiple alkylation and / or acylation of these polyamines.
• those detergent additives whose hydrophobic residue is derived from sterically hindered olefins and / or higher molecular weight and / or polyfunctionalized poly (olefins).
• the additives contain in a preferred embodiment in addition to the components A) and B) a different B) Mineralölaltf Strukturvercoster C).
• the improvement in the response of cold flow improvers C) according to the invention is understood to improve at least one cold property of middle distillates adjusted or adjustable by cold flow improver C) and impaired by the addition of a detergent additive A) by addition of a compound B) acting as a nucleating agent for the paraffin crystallization , Specifically, by adding the nucleating agent B), the cold property set or adjustable without the presence of the detergent additive A) by the cold flow improver C) is achieved.
• Cold properties are understood here individually or in combination as the pour point, the cold filter plugging point, the low-temperature flow, and the paraffin dispersion of middle distillates.
• Especially affected is the response of flow improvers in middle distillates containing more than 10 ppm of a nitrogen containing detergent additive A), in particular more than 20 ppm and especially more than 40 ppm such as 50 to 2,000 ppm of nitrogen-containing detergent additive A).
• the additives according to the invention preferably contain from 0.01 to 10 parts by weight, based on one part by weight of the nitrogen-containing detergent additive A, and in particular from 0.05 to 5 parts by weight, for example from 0.1 to 3 parts by weight of the oil-soluble compound B) acting as nucleator for the paraffin crystallization.
• Ashless means that the additives in question essentially consist only of elements which form gaseous reaction products during combustion.
• the additives consist essentially only of the elements carbon, hydrogen, oxygen and nitrogen.
• ashless additives are substantially free of metals and metal salts.
• Nucleators are understood to be compounds which initiate the crystallization of paraffins on cooling a paraffin-containing oil. They thus shift the beginning of the paraffin crystallization of the oil additized with them, which can be determined, for example, by measuring the cloud point or the Wax Appearance Temperature (WAT), to higher temperatures. These are compounds that are soluble in the oil above the cloud point and begin to crystallize just above the temperature of the paraffin saturation and then serve as seed for the crystallization of the paraffins. Thus, they prevent over-saturation of the oil with paraffins and lead to crystallization near the saturation concentration. This leads to the formation of a multiplicity of equally small paraffin crystals.
• WAT Wax Appearance Temperature
• paraffin crystallization thus begins at a higher temperature than in non-additized oil. This can be determined, for example, by measuring the WAT by means of differential scanning calorimetry (DSC) with a slow cooling of the oil at, for example, -2 K / min.
• DSC differential scanning calorimetry
• middle distillates 10 to 10,000 ppm and in particular 50 to 3,000 ppm of the nitrogen-containing detergent additives A) are added.
• the alkyl or alkenyl group imparts oil-solubility to the detergent additives.
• alkyl radical has 15 to 500 carbon atoms and in particular 20 to 350 carbon atoms, for example 50 to 200 carbon atoms.
• This alkyl radical can be linear or branched, in particular it is branched.
• the alkyl radical is derived from oligomers of lower olefins having 3 to 6 C atoms such as propene, butene, pentene or hexene and mixtures thereof.
• Preferred isomers of these olefins are isobutene, 2-butene, 1-butene, 2-methyl-2-butene, 2,3-dimethyl-2-butene, 1-pentene, 2-pentene and iso-pentene and mixtures thereof.
• Particular preference is given to propene, isobutene, 2-butene, 2-methyl-2-butene, 2,3-dimethyl-2-butene and mixtures thereof.
• Particularly suitable for the preparation of such detergent additives are highly reactive low molecular weight polyolefins having a proportion of terminal double bonds of at least 75 mol%, especially at least 85% and in particular at least 90% such as at least 95%.
• Particularly preferred low molecular weight polyolefins are poly (isobutylene), poly (2-butene), poly (2-methyl-2-butene), poly (2,3-dimethyl-2-butene), poly (ethylene-co-isobutylene) and atactic poly (propylene).
• the molecular weight of particularly preferred polyolefins is between 500 and 3000 g / mol.
• Such oligomers of lower olefins are accessible for example by polymerization by means of Lewis acids such as BF 3 and AlCl 3 , by means of Ziegler catalysts and in particular by means of metallocene catalysts.
• the polar component of the detergent additives which are particularly problematic for the response of known cold additives is derived from polyamines having 2 to 20 N atoms.
• polyamines correspond to the formula (R 9 ) 2 N- [AN (R 9 )] q - (R 9 ) wherein each R 9 is independently hydrogen, an alkyl or hydroxyalkyl radical of up to 24 carbon atoms, a polyoxyalkylene radical (AO) r or polyiminoalkylene radical - [AN (R 9 )] s - (R 9 ) but wherein at least one R 9 is hydrogen, q is an integer from 1 to 19, A is an alkylene radical having 1 to 6 C atoms, r and s independently of one another are from 1 to 50.
• polyamines usually these are mixtures of polyamines and in particular mixtures of poly (ethylene amines) and / or poly (propyleneamines).
• DETA dimethylaminopropylamine
• TETA triethylenetetramine
• TEPA tetraethylenepentamine
• PEHA pentaethylenehexamine
• PEHA pentapropylenehexamine
• heavy polyamines ethylenediamine, 1,2-propylenediamine, dimethylaminopropylamine, diethylenetriamine (DETA), dipropy
• Heavy polyamines are generally understood as meaning mixtures of polyalkylenepolyamines which, in addition to small amounts of TEPA and PEHA, mainly contain oligomers having 7 or more nitrogen atoms, of which two or more are in the form of primary amino groups. These polyamines often also contain branched structural elements via tertiary amino groups.
• Suitable amines include those which comprise cyclic structural units derived from piperazine.
• the piperazine units may preferably carry hydrogen at one or both nitrogen atoms, an alkyl or hydroxyalkyl radical having up to 24 carbon atoms or a polyiminoalkylene radical - [AN (R 9 )] s - (R 9 ), where A, R 9 and s have the meanings given above.
• Suitable amines include alicyclic diamines such as 1,4-di (aminomethyl) cyclohexane and heterocyclic nitrogen compounds such as imidazolines and N-aminoalkylpiperazines such as N- (2-aminoethyl) piperazine.
• detergent additives whose polar portion is derived from hydroxyl-bearing polyamines, heterocycle-substituted polyamines, and aromatic polyamines are problematic.
• Examples include: N- (2-hydroxyethyl) ethylenediamine, N, N 1 -bis (2-hydroxyethyl) ethylenediamine, N- (3-hydroxybutyl) tetra (methylene) diamine, N-2-aminoethylpiperazine, N-2 and N-3-aminopropylmorpholine, N-3- (dimethylamino ) propylpiperazine, 2-heptyl-3- (2-aminopropyl) imidazoline, 1,4-bis (2-aminoethyl) piperazine, 1- (2-hydroxyethyl) piperazine, various isomers of phenylenediamine and naphthalenediamine and mixtures of these amines.
• Detergent additives based on heavy polyamines in which R 9 is hydrogen in the above formula and q has values of at least 3, in particular at least 4, such as 5, 6 or 7, are particularly critical for the cold additization of middle distillates.
• R 9 is hydrogen in the above formula and q has values of at least 3, in particular at least 4, such as 5, 6 or 7, are particularly critical for the cold additization of middle distillates.
• a proportion of more than 10 wt .-%, in particular more than 20 wt .-% and especially of more than 50 wt .-% of amines having q-values of 4 or higher and especially with q Values of 5 or higher and in particular with q values of 6 or higher on the total amount of amines used have proven particularly critical.
• the oil-soluble alkyl moiety and the polar head group of the detergent additives may be linked together either directly via a C-N or through an ester, amide or imide bond.
• preferred detergent additives are alkylpolyamines, Mannich reaction products, hydrocarbyl-substituted succinic acid amides and imides, and mixtures of these classes of substances.
• the detergent additives linked via C-N bonds are preferably alkylpoly (amines) which are obtainable, for example, by reacting polyisobutylenes with polyamines, for example by hydroformylation and subsequent reductive amination with the abovementioned polyamines.
• one or more alkyl radicals may be bound to the polyamine.
• Detergent additives based on higher polyamines having more than 4 N atoms, for example those having 5, 6 or 7 N atoms, are particularly critical for the cold addition.
• Detergent additives containing amide or imide bonds are obtainable, for example, by reaction of alkenylsuccinic anhydrides with polyamines.
• Alkenylsuccinic anhydride and polyamine are preferably reacted in a molar ratio of about 1: 0.5 to about 1: 1.
• the preparation of the underlying Alkenylbernsteinklaanhydride is usually carried out by addition of ethylenically unsaturated polyolefins or chlorinated polyolefins to ethylenically unsaturated dicarboxylic acids.
• alkenyl succinic anhydrides can be prepared by reaction of chlorinated polyolefins with maleic anhydride.
• the preparation also succeeds by thermal addition of polyolefins to maleic anhydride in an "ene reaction".
• highly reactive olefins with a high content of, for example, more than 75% and especially more than 85 mol%, based on the total number of polyolefin molecules, of isomers having a terminal double bond are particularly suitable.
• the molar ratio of the two reactants in the reaction between maleic anhydride and polyolefin can vary within wide limits. Preferably, it may be between 10: 1 and 1: 5, with molar ratios of 6: 1 to 1: 1 being particularly preferred.
• Maleic anhydride is preferably used in stoichiometric excess, for example 1.1 to 3 moles of maleic anhydride per mole of polyolefin. Excess maleic anhydride can be removed from the reaction by, for example, distillation.
• the accessible reaction products have, based on the reacted with unsaturated carboxylic acids fractions of the poly (olefins) on average a Malein istsgrad of more than 1, preferably about 1.01 to 2.0 and in particular 1.1 to 1.8 dicarboxylic acid per alkyl radical.
• alkenyl succinic anhydrides with polyamines leads to products which can carry one or more amide and / or imide bonds per polyamine and depending on the Maleinleitersgrad one or two polyamines per alkyl radical.
• Alkenylsuccinic anhydride per mole of polyamine is preferably used for the reaction of 1.0 to 1.7 and in particular 1.1 to 1.5, so that free primary amino groups remain in the product.
• alkenyl succinic anhydride and polyamine are reacted equimolarly.
• Typical and particularly preferred acylated nitrogen compounds are obtained by reacting poly (isobutylene), poly (2-butenyl), poly (2-methyl-2-butenyl) -, poly (2,3-dimethyl-2-butenyl) - or Poly (propenyl) succinic anhydrides having an average of about 1.2 to 1.5 anhydride groups per alkyl radical whose alkylene radicals carry between 50 and 400 carbon atoms, with a mixture of poly (ethylene amines) having about 3 to 7 nitrogen atoms and about 1 to 6 ethylene units available.
• Mannich bases of this kind are prepared by known processes, for example by alkylating phenol and / or salicylic acid with the polyolefins described above, such as, for example, poly (isobutylene), poly (2-butene), poly (2-methyl-2-butene), poly ( 2,3-dimethyl-2-butene) or atactic poly (propylene) and subsequent condensation of the alkylphenol with aldehydes having 1 to 6 carbon atoms such as formaldehyde or its reactive equivalents such as formalin or paraformaldehyde and those described above Polyamines such as TEPA, PEHA or heavy polyamines produced.
• polyolefins described above such as, for example, poly (isobutylene), poly (2-butene), poly (2-methyl-2-butene), poly ( 2,3-dimethyl-2-butene) or atactic poly (propylene) and subsequent condensation of the alkylphenol with aldehydes having 1 to 6 carbon atoms such as formaldeh
• the average molecular weight determined by means of vapor pressure osmometry is particularly efficient, but at the same time also for the cold additization of middle distillates of particularly critical detergent additives is above 800 g / mol and in particular above 2,000 g / mol such as above 3,000 g / mol.
• the average molecular weight of the above-described detergent additives can also be increased via crosslinking reagents and adapted to the intended use.
• Suitable crosslinking reagents are, for example, dialdehydes such as glutaric dialdehyde, bisepoxides derived, for example, from bisphenol A, dicarboxylic acids and their reactive derivatives such as maleic anhydride and alkenylsuccinic anhydrides, and higher polybasic carboxylic acids and their derivatives such as trimellitic acid, trimellitic anhydride and pyromellitic dianhydride.
• dialdehydes such as glutaric dialdehyde
• bisepoxides derived, for example, from bisphenol A
• dicarboxylic acids and their reactive derivatives such as maleic anhydride and alkenylsuccinic anhydrides
• higher polybasic carboxylic acids and their derivatives such as trimellitic acid, trimellitic anhydride and pyromellitic dianhydride.
• Preferred copolymers of ethylene B) acting as nucleator for the paraffin crystallization contain preferably 5 to 10 mol%, particularly preferably 5 to 9 mol% and in particular 5 to 7.9 mol% of structural units derived from at least one ethylenically unsaturated carboxylic acid ester.
• Suitable ethylenically unsaturated carboxylic acid esters are, on the one hand, esters of vinyl alcohol with C 1 -C 20 -carboxylic acids. In addition to vinyl acetate in particular esters of vinyl alcohol with C 4 -C 14 carboxylic acids are preferred.
• Particularly preferred are esters of aliphatic carboxylic acids whose alkyl radicals or alkenyl radicals may be linear and in particular branched.
• branched alkyl radicals particular preference is given to those whose branching is in the ⁇ -position relative to the carboxyl group.
• vinyl esters examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pentanoate, vinyl pivalate, Vinylhexanoate, vinyl-n-octanoate, vinyl-2-ethylhexanoate, vinylneononanoate, vinylisodecanoate, vinylneodecanoate, vinylneoundecanoate and vinylisotridecylate.
• esters of unsaturated carboxylic acids such as acrylic acid and methacrylic acid with C 1 -C 20 -alcohols and in particular with C 4 -C 14 -alcohols.
• Preferred are saturated linear as well as branched fatty alcohols.
• Particularly suitable are esters of branched fatty alcohols, wherein the branch is preferably in the 2-position to the OH group.
• Suitable ethylenically unsaturated carboxylic acid esters are methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate and the corresponding esters of methacrylic acid.
• the copolymers B) acting as nucleator for the paraffin crystallization contain, in addition to structural units derived from ethylene, structural units derived from at least 2 different ethylenically unsaturated carboxylic acid esters.
• Copolymers which contain structural units derived from esters of the vinyl alcohol with a C 1 -C 4 -carboxylic acid and esters of the vinyl alcohol with a C 5 -C 16 -carboxylic acid have proved particularly suitable.
• the above-mentioned branched carboxylic acids having 5 to 16 carbon atoms are preferred.
• copolymers B) are terpolymers of ethylene, vinyl acetate and vinyl neononanoate, of ethylene, vinyl acetate and vinyl neodecanoate, of ethylene, vinyl acetate and vinyl neoanecanoate and of ethylene, vinyl acetate and 2-ethylhexyl vinyl ester. Furthermore, copolymers have proven useful in addition to derived from ethylene structural units of esters of vinyl alcohol with a C 1 -C 4 carboxylic acid and esters of acrylic acid or methacrylic acid with C 5 -C 20 alcohols derived structural units.
• Examples of such copolymers B) are terpolymers of ethylene, vinyl acetate and 2-ethylhexyl acrylate, of ethylene, vinyl acetate and octyl acrylate, of ethylene, vinyl acetate and iso-tridecyl acrylate and of ethylene, vinyl acetate and stearyl acrylate.
• the ratio of short-chain to long-chain ester can thereby vary widely. It is preferably in the ratio between 1:10 and 10: 1, especially between 1: 5 and 5: 1, for example between 1: 3 and 3: 1.
• the copolymers of ethylene and ethylenically unsaturated carboxylic acid esters may further contain minor amounts of structural units derived from lower olefins.
• Preferred olefins are, in particular, those having 3 to 8 C atoms, such as propene, n-butene, isobutylene, pentene, hexene, 4-methylpentene and diisobutylene.
• Such terpolymers or higher polymers may contain up to 3 mol% of lower olefins, with the proviso that the total comonomer content is not more than 10.5 mol%, preferably not more than 9.0 and in particular not more than 7.9 mol%.
• the melt viscosity of the solvent-free polymers measured at 140 ° C. is preferably between 100 and 5,000 mPas, in particular between 150 and 2,000 mPas, for example between 200 and 1,000 mPas.
• the quantitative ratio between detergent additive A) and nucleators B) in the additized oil can vary within wide limits. It has proven particularly useful to use from 0.01 to 10 parts by weight, in particular from 0.05 to 5 parts by weight, for example from 0.1 to 3 parts by weight of nucleator per part by weight of detergent additive, in each case based on the active ingredient.
• cold flow improvers C are oil-soluble polar nitrogen compounds (constituent IV). These are preferably reaction products of fatty amines with compounds containing an acyl group.
• the preferred amines are compounds 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 ethyl or propyl group, x is
• the alkyl and alkenyl radicals can be linear or branched and contain up to two double bonds. They are preferably linear and substantially saturated, ie they have iodine numbers of less than 75 gl 2 / g, preferably less than 60 gl 2 / g and in particular between 1 and 10 gl 2 / g. Particularly preferred are secondary fatty amines in which two of the groups R 6 , R 7 and R 8 are 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 contain chain cuts based on natural raw materials such.
• Particularly preferred amine derivatives are amine salts, imides and / or amides such as amide ammonium salts secondary fatty amines, especially dicocosfettamine, ditallow fatty amine and distearylamine.
• Suitable carbonyl compounds for the reaction with amines are both monomeric and polymeric compounds having one or more carboxyl groups. In the case of the monomeric carbonyl compounds, preference is given to those having 2, 3 or 4 carbonyl groups. They can also contain heteroatoms such as oxygen, sulfur and nitrogen.
• carboxylic acids examples include maleic, fumaric, crotonic, itaconic, succinic, C 1 -C 40 -alkenylsuccinic, adipic, glutaric, sebacic, and malonic acids and benzoic, phthalic, trimellitic and pyromellitic acid, nitrilotriacetic acid , Ethylenediaminetetraacetic acid and their reactive derivatives such as esters, anhydrides and acid halides.
• Copolymers of ethylenically unsaturated acids such as, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, have proven particularly suitable as polymeric carbonyl compounds, particular preference is given to copolymers of maleic anhydride.
• Suitable comonomers are those which impart oil solubility to the copolymer. Oil-soluble means here that the copolymer dissolves without residue in the middle distillate to be additive after reaction with the fatty amine in practice-relevant metering rates.
• Suitable comonomers are, for example, olefins, alkyl esters of acrylic acid and methacrylic acid, alkyl vinyl esters and alkyl vinyl ethers having 2 to 75, preferably 4 to 40 and in particular 8 to 20 carbon atoms in the alkyl radical.
• the carbon number refers to the alkyl radical attached to the double bond.
• 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 1,000 and 5,000.
• Oil-soluble polar nitrogen compounds 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 ).
• amides and ammonium salts of aminoalkylene polycarboxylic acids such as nitrilotriacetic acid or ethylenediaminetetraacetic acid with secondary amines are suitable as oil-soluble polar nitrogen compounds (cf. EP 0 398 101 ).
• oil-soluble polar nitrogen compounds are copolymers of maleic anhydride with ⁇ , ⁇ -unsaturated compounds, which can optionally be reacted with primary monoalkylamines and / or aliphatic alcohols (cf. EP-A-0 154 177 . EP-0 777 712 ), the reaction products of Alkenylspirobislactonen with amines (see. EP-A-0 413 279 B1) and after EP-A-0 606 055 A2 Reaction products of terpolymers based on ⁇ , ⁇ -unsaturated dicarboxylic acid anhydrides, ⁇ , ⁇ -unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols.
• the mixing ratio between the inventive ethylene copolymers III and oil-soluble polar nitrogen compounds as constituent IV may vary depending on the application.
• Such additive mixtures preferably contain 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, based on the active compounds, of at least one oil-soluble polar nitrogen compound per part by weight of the additive combination according to the invention.
• the additives preferably contain 15-80% by weight, preferably 20-70% by weight of detergent additive A), 2-40% by weight, preferably 5-25% by weight of nucleator B) and 15-80% by weight. %, preferably 20-70 wt.% cold flow improver C).
• the additives to be used according to the invention are preferably used as concentrates which contain from 10 to 95% by weight and preferably from 20 to 80% by weight, for example from 25 to 60% by weight of solvent.
• Preferred solvents are higher-boiling aliphatic, aromatic hydrocarbons, alcohols, esters, ethers and mixtures thereof.
• Such concentrates preferably contain from 0.01 to 10 parts by weight, preferably from 0.05 to 5 parts by weight, for example from 0.1 to 3 parts by weight of the nucleator compound B) per part by weight of detergent additive A).
• the Nucleatoren B improve the response of detergent additive-containing middle distillates such as kerosene, jet fuel, diesel and fuel oil for conventional flow improvers with regard to the lowering of pour point and CFPP value and the improvement of paraffin dispersion.
• Particularly preferred mineral oil distillates are middle distillates.
• the middle distillate is in particular those mineral oils which are obtained by distillation of crude oil, boiling in the range of about 150 to 450 ° C and in particular in the range of about 170 to 390 ° C, for example kerosene, jet fuel, diesel and fuel oil.
• middle distillates contain about 5 to 50 wt .-%, such as about 10 to 35 wt .-% n-paraffins, of which the longer-chain crystallize on cooling and can affect the flowability of the middle distillate.
• the compositions to be used according to the invention are particularly advantageous in middle aromatics with a low aromatic content of less than 21% by weight, for example less than 19% by weight.
• compositions are also particularly advantageous in low boiling point middle distillates, that is to say in middle distillates which have 90% distillation points below 360 ° C., in particular 350 ° C. and in special cases below 340 ° C. and further in such middle distillates, the boiling ranges between 20 and 90% distillation volume of less than 120 ° C and in particular of less than 110 ° C.
• aromatic compounds is meant the sum of mono-, di- and polycyclic aromatic compounds as determinable by HPLC according to DIN EN 12916 (2001 edition).
• the middle distillates may also contain minor amounts, for example up to 40% by volume, preferably 1 to 20% by volume, especially 2 to 15, for example 3 to 10% by volume of the oils of animal and / or vegetable origin described in more detail below such as fatty acid methyl esters.
• biofuels oils obtained from animal and preferably vegetable material or both, and derivatives thereof, which can be used as fuel and especially as diesel or fuel oil.
• biofuels oils obtained from animal and preferably vegetable material or both, and derivatives thereof, which can be used as fuel and especially as diesel or fuel oil.
• biofuels examples include 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, mustard seed oil, beef tallow, bone oil, fish oils and used edible oils.
• Other examples include oils derived from wheat, jute, sesame, shea nut, arachis oil and linseed oil.
• the fatty acid alkyl esters, also referred to as biodiesel can be derived from these oils by methods known in the art.
• Rapeseed oil which is a mixture of glycerol esterified fatty acids, is preferred because it is available in large quantities and is readily available by squeezing rapeseed.
• sunflower, palm and soybeans and their mixtures with rapeseed oil are preferred.
• esters of fatty acids are particularly suitable as biofuels.
• Preferred esters have an iodine value of from 50 to 150 and especially from 90 to 125.
• Mixtures with particularly advantageous properties are those which are predominantly, i. H. to contain at least 50 wt .-% of 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.
• the additives can be used alone or together with other additives, for.
• pour point depressants or dewaxing aids with other detergents, with antioxidants, cetane number improvers, dehazers, Demulsifiers, dispersants, defoamers, dyes, corrosion inhibitors, lubricity additives, sludge inhibitors, odorants and / or additives for lowering the cloud point.
• detergent additives (A) with different nucleators (B) and further flow improvers (C) with the characteristics given below were used.
• paraffin dispersion in middle distillates is determined in the short sediment test as follows: 150 ml of the middle distillates mixed with the additive components indicated in the table were cooled to -13 ° C. in a cold cabinet at -2 ° C./hour in 200 ml graduated cylinders and stored at this temperature for 16 hours. Subsequently, the volume and appearance of both the sedimented paraffin phase and the oil phase above are visually determined and assessed. A small amount of sediment and a cloudy oil phase show a good paraffin dispersion.
• detergent additives A various reaction products of alkenylsuccinic anhydrides (ASA) based on highly reactive polyolefins (proportion of terminal double bonds> 90%, degree of maleation about 1.2 to 1.3) listed in Table 2 with polyamines were used. Alkenyl succinic anhydride and polyamine were reacted thereto in a molar ratio of 1.0 to 1.5 moles alkenyl succinic anhydride per mole of polyamine (see Table 2). For better meterability, the detergent additives were used as 33% solutions in higher boiling aromatic solvent. The dosage rates given in Tables 2 to 4 for the detergent additives A) and nucleators B) relate to the active ingredients used.
• ASA alkenylsuccinic anhydrides
• test oil 1 The determination of the CFPP values in test oil 1 was carried out after adding the oil with 200 ppm C2 and 150 ppm C3.
• detergent additive A1 the reaction product of poly (isobutenyl) -succinic anhydride and pentaethylene-hexamine according to Table 2
• detergent additive A2 the reaction product of poly (isobutenyl) succinic anhydride and pentaethylenehexamine according to Table 2, Example 13 used.

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