TW418249B - Middle distillate fuel with acid amide and cold flow improver - Google Patents

Abstract

This invention relates to low sulfur fuel compositions which exhibit improved lubricity compared to the low sulfur fuels alone. The low sulfur fuel compositions contain a middle distillate fuel having a sulfur content of 0.2% by weight or less, a carboxylic acid amide and at least one member selected from the group consisting of cold flow improvers, ashless dispersants, and mixtures thereof.

Description

Printed by the Central Bureau of Standards of the Ministry of Economic Affairs-Industrial and Consumer Cooperatives 4 1824 9 A7 B7 V. Description of the Invention (') The present invention includes the use of an additive to improve the slip properties of low-sulfur components, fuels, and the concentration of additives including the compound Thing. Sulfur contained in fuels, such as middle distillate fuels, such as diesel fuel and jet fuel, is said to be a serious environmental hazard. Therefore, strict regulations have been established to limit the amount of sulfur contained in such fuels. Unfortunately, fuels with low sulfur content have poor inherent lubricity, and this causes problems during fuel use. For example, the use of low-sulfur fuels in diesel engines often causes damage to the fuel injector, which is caused by the natural lubricating properties of the fuel to prevent damage. Therefore, it is necessary to improve the lubricating properties of low-sulfur fuels so as to avoid mechanical damage (fuel injector damage) caused by insufficient fuel lubricity, while retaining the environmental benefits of low-sulfur fuels. According to the present invention, the lubricating properties of the low-sulfur fuel can be improved by utilizing the additives described below. Surprisingly, the composition of the additives of the present invention has a synergistic effect. Therefore, in order to improve the lubricity of low-sulfur fuels, the present invention uses an additive including: A) ammonium carboxylate; and further comprising: B) a cold flow improver and / or C) an ashless dispersant. It has been found that when the additives include components A and B or a combination of A and C, they have a synergistic effect on fuel lubricity. However, the multiplication effect is distinct when the components A, B, and C are combined. The additive ingredients can be provided in combination, such as a single additive group -3-(Please read the precautions on the back before filling this page)

-" / Urine-This paper size applies to China National Standard (CNS) A4 (210X297 mm) 418249 A7 __B7_ 5. Description of the invention (>). However, when it is not easy to add 剤 in combination, of course, other methods can be used ^ For example, the individual ingredients 坷 are provided separately and incorporated into the fuel, and the fuel may already contain one or more additives. In this context, "low sulfur content" means a fuel whose sulfur content is typically 0.2 wtS! Or less, such as 0.05 wtJS or less, or 0.005 wtX or less. Examples of fuels that can be used include: Low Sulfur fuels such as diesel and jet engines and bio-diesel fuels. The latter are derived from petroleum or plants or mixtures thereof, and typically contain vegetable oils or their derivatives, if saponified, The esters produced by transesterification or re-esterification. Medium-thickness fuels usually have a boiling viscosity of 100-500 TC, and more typically 150-4001C :.

As the component A, carboxylic acid amines, amines and the like are commercially available, and they can also be produced by the application of known techniques. The carboxylic acids from which aldimines A are derived typically contain up to 60® fluorene atoms and may be mono- or polycarboxylic acids or dimerized acids. It may be saturated or unsaturated, branched or branched, and optionally may contain a ring. The acid backbone of the acid may contain hydroxyl substitution. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs {Please read the notes on the back before filling this page) When monocarboxylic acids are used, they typically have 10-40 傧 硪 atoms, more specifically 10-30 锢 and more Especially 12-24 atomic. Examples thereof include aliphatic fatty acids such as lauric acid, myristic acid, heptaic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, undecanoic acid, eicosanoic acid, or behenic acid. Rhenium oleate is preferred. When using a polycarboxylic acid (such as di- or tri-acids), it typically contains 340 硪 — ^ This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm) Employees of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the cooperative 4 1824 9 A7 B7 V. Description of the invention (4) Atoms, more specifically 3-30, and more particularly 3-24 fluorene atoms. Examples of such polyphosphonic acids include: dicarboxylic acids , Such as succinic acid, glutaric acid and tricarboxylic acids, such as 1,3,5-cyclohexane tricarboxylic acid and tetracarboxylic acids, such as 1,2,3,4-butanetetracarboxylic acid. Examples of hydroxy-substituted fatty acids include: M-maleic acid, maleic acid, dihydroxysuccinic acid, and citric acid. Optionally, hydroxy-substituted "dimerized" acids can also be used. Herein Such compounds are referred to as "dimer" or "trimer" acids. When used, "dimerized" acids typically contain 10-60%, preferably 20-60, and most preferably The ground is 30-60 値 硪 atoms. This kind of acid 僳 is prepared by dimerization of unsaturated acids, and is typically composed of acid monomers, dimers and trimers. Examples of dimer fatty acids are the dimerized products of oleic acid and linoleic acid. This "dimer" is typically a mixture containing 2 monomers, an 83vt3i dimer, and a terpolymer of 15wU and possibly more Pyrene acid. This "dimerized" acid and other aforementioned acids are commercially available or can be synthesized by known techniques. Phenylamine can be obtained from carboxylic acids and ammonia or the nitrogen compounds of formula (II). The reaction is formed:

R 2 [H (R 2) R 1] q Y Where: R1 is an alkyl group containing 2-10 fluorene atoms; q is 0-1 0; H-substituted hexahydropyridyl is pseudo-optional , Where the substituent is R2 or-[R1 H (R2)] q R2 (R1 and q are as above), -5-This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) (please (Read the notes on the back before filling out this page)

Order 418249 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (4) -H (R2) 2 or 4-pyridyl; and each substituent R2 can be selected from hydrogen and 1-6. Alkyl groups of fluorene atoms and groups of the following formula: 〇- (R 3 0) r R 4 where r is 0-15: R3 is an alkylene group of 2-6 sulfonic atoms; and R4 is 2-6 fluorene Atomic hydroxyalkyl, but at least one R2 group is hydrogen. When the compound of formula (I) contains more than one R1 group, it may be the same or different. The same applies when there is more than one R2 group, more than one R3 group, and more than one R4 group. q is preferably 0-5. r is preferably 0-10. R1 preferably contains 2-3 fluorene atoms. When R2 is alkyl, the moiety preferably contains 2-4 fluorene atoms. R3 is preferably an alkylene group containing 2 to 4 fluorene atoms. R4 is preferably a hydroxyalkyl group containing 21 镝 硪 atoms. The hydroxyalkyl group preferably contains 1 to 4 hydroxyl groups. When r is greater than 0, R4 is preferably a monohydroxyalkyl group, such as hydroxyethyl or hydroxypropyl. When r is zero, R4 is preferably a mono- or polyhydroxyalkyl group having at most 4 hydroxyl groups, such as hydroxyethyl, hydroxypropyl or hydroxy-2,2- (hydroxymethyl) ethyl. The number of atoms and the value of q in R * are independently interesting. This representation (for example): when q is greater than 0, R1 in the first repeat unit can be different. Similarly, the number of atoms and the value of r in R3 are independently selected. That is, for example, when r is greater than 0, R3 in each repeating unit may be the same or different. According to a preferred embodiment, in the nitrogen-containing compound of the formula (I), Y is -N (R 2) 2, R 2 is ethylene and 0-3. Examples of such compounds -6-(Please read the notes on the back before filling this page)

Revision-year This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 4 ί824 9 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. The description of the invention (Γ) contains ethanolamine and diethanolamine , Tris (hydroxymethyl) aminomethane, tris (ethylenetetramine), or bis (ethyltriamine) (substituted by two hydroxypropyl, as appropriate). In another embodiment, the nitrogen-containing compound of formula (I) is 4-morpholinyl or optionally N-substituted 1-hexahydropyridyl, and R1 is an alkylene containing 2-6 fluorene atoms. Group, q is 0 or 1 and R 2 is hydrogen. Examples of such compounds include ammonium hexahydrogen sulfide, bis- (aminoethyl hexamethylene) hexahydrogen, and morpholine. Nitrogen compounds of formula (I), either commercially available or produced by the application of known techniques. For example, the compound of formula (I) wherein r is 1 or more (i.e., an ether or polyether bond). It may be prepared by reacting a suitable amine, morpholine or hexahydropyridine compound with one or more alkoxides. When only one alkylene oxide is used, R3 and R4 contain the same alkylene moiety. When different alkylene groups are used, the alkylene groups of R3 and R4 are the same or different. According to an embodiment of the present invention, amidine A) contains a free carboxyl group of at least one acetic acid-derived moiety. Such compounds can be formed using a polycarboxylic acid as a starting acid, such as a dicarboxylic acid or a dimer or trimer acid. The mole number of the reactants is appropriately controlled so that the finished amidine contains at least one carboxyl functional group in the acid-derived moiety. For example, if an acid with a dicarboxyl group is used (such as a dicarboxylic acid or a dimer acid), the molecular ratio can be 1: 1. If amidine contains at least one carboxyl group in the acid-derived half, it can be used in its original form or derivatized to further enhance its properties. These compounds, which are based on further derived amines, usually depend on the size of the paper that was originally used. The Chinese National Standard (CNS) A4 specification (210X2.97 mm) is applied. (Please read the precautions on the back before filling out this page. ) Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Consumer Cooperatives, printed 41824 9 A7 B7 V. Description of the invention U) to form the type of amidine acid and the properties of amidine®. Example m, by introducing fuel-soluble species into enzyme molecules, fuel solubility can be increased. Examples can be long alkyl or alkylene. The number of fluorene atoms in the alkyl or alkylene group may depend on the number of sulfon atoms in the fluorene amine itself. These compounds react with the free carboxyl group of amidine to form an ester or further amidine chain. Examples of specific enzymes and aldols that can be used include oleyl alcohol and oleylamine. Dimer and trimer acid aldamines tend to easily contain alkyl groups or alkylene groups on the acid long main chain in an amount sufficient to generate fuel solubility. Alternatively, amidine can be further derivatized to produce one or more polar head groups. This causes an increase in the lubricity-improving effect of amidine. Generally, this is because the polar head group increases the affinity of amidine to the surface of the gold ring. Compounds that can be used to form one or more amphoteric head groups, including multiple limbs (such as ethylenediamine and triethylenediamine), the aforementioned alkanolamines, and multiple enzymes (such as ethylene glycol, diethylene glycol) , Triethylene glycol, Dipropylene glycol, Glycerol, Alcohol, Sorbitol, Mannase, Pentaerythritol, Sorbitol, 1,2-Butanediol, 2,3-hexanediase , 2,4-hexanediase, tetramethylethanedioxane, and 1,2-chenhexanediol). Although the former is a further derivative of amidine, it is very likely that the free carboxyl functional group of a polycarboxylic acid is used to introduce an oil-soluble or hibiscus head group, and then the finished product is reacted with the atmosphere or with the formula (II) The nitrogen-containing compounds mentioned above generate amidine, thus forming the same final compound. Of course, this assumes that the product generated after derivatization contains at least one free carboxyl group tilted into the acid-derived portion, so that the formation of aldehyde Possibly. The further derivative is sold in a pseudo-commercial manner, or can be borrowed from a known technology. -8-This paper size applies to the Chinese national standard (CNS > A4 size (210X297 mm)) ΙΊ --- ^ ---- ------- Order ^ ------, (Please read the notes on the back before filling out this page) Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs «ΓΒ24 9 A7 __B7_ V. Description of the invention (7) Manufactured by application. The preferred amines are oleylethanolamine and oleyldiethanolamine. Component B) In the practice of the present invention, a variety of cold-flow feeding improvers can be used. Examples are; ethylene services Saturated ester copolymers, bee sting polymers, polarized with nitrogen Compounds, hydrocarbon polymers and linear compounds, and mixtures of the foregoing. Cold fluid modifiers are well known in the art and there are many commercial suppliers. In this context, "cold stream modifiers" also include pour point drops. _, 蟠 crystal modifiers, 蟠 anti-stability additives, etc. are usually added to middle distillate fuels to improve low temperature properties. Such materials are well known to those skilled in the art and are commercially available. Available ingredients B) Examples of ethylenically unsaturated ester copolymers typically include those consisting of units of the following formula: -CR 5 R 6 -CHR 7-where R s is hydrogen or methyl;!? 8 is (: 001 ^, Where r8 is an alkyl group having 30 fluorene atoms, such as 1-9 fluorene, or 〇CR9, where rs is or η; and R7 is the aforementioned fluorene or C00R8. This includes ethylene and ethylene fluorene unsaturated esters A copolymer of a derivative thereof or a derivative thereof. Therefore, the copolymer may be an ester-former of ethylene and a saturated alcohol and an unsaturated carboxylic ester, or an ester formed of an unsaturated enzyme and a saturated carboxylic acid. Ethylene-ethylene is preferred Ester copolymers, more specifically ethylene-vinyl acetate, ethyl acetate Ethylene-propionate, Ethylene-hexanoate, Ethyl-octanoic acid This paper is again applicable to the China Touch Standard (CNS) A4 specification (2i0x297) (please read the precautions on the back before filling this page)

4 1824 9 A7 B7 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (<?) Ethylene. The copolymer usually contains 1-40 ^ 55 vinyl ester, preferably 5-35 wt%, and more preferably 10-35 wtS; Mixtures of two or more copolymers can also be used (see USP 3,961 · 916). The number average molecular weight of the copolymer obtained as a vapor phase permeation chamber is typically 1,000 to 10,000, and preferably 1,000 to 5,000. If desired, the copolymer may contain a derivative derived from an additional comonomer, that is, a terpolymer, a tetramer, or a higher copolymer, such as those in which the additional copolymer is isobutylene or diisobutylene. Copolymers: ethylene, unsaturated ester copolymers, direct copolymerization of comonomers, sugar exchange or hydrogenolysis, and re-esterification to provide different ethylene stripe unsaturated ester copolymers. Honeycomb polymers are polymers with branched hydrocarbon groups on the backbone of the polymer (see " Hive polymers. Structure and Properties, KAPlate et al. Poly-Sci. Macroaolecular Revs. · 8, pp. 117-253 ( 1974)) Hydrocarbyl typically has 10-30 A atoms and is directly or indirectly linked to the backbone. Examples of non-direct linking include the interposition of atoms or base states. This includes covalent and / or electronic valences (such as those in salts). Honeycomb polymers are typically homopolymers or copolymers with at least 20% of its ears having side branches with at least 6 plutonium atoms (at least 10 distillates compared to sodium chloride), preferably at least 40noU, and more preferably at least 5〇ΒΙ! Ϊβ honeycomb polymer can contain units derived from other monomers. -10 " This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) ΙΊ! ----- II (Please read the precautions on the back before filling this page) Order 41824 9 A7 B7 V. Description of the invention (9) _ Examples of bee m-type polymers to be used, including (e.g. > homopolymers of fumaric and iconic acid, maleic anhydride, fumaric or iconic acid, and other ethylene 糸 unsaturated 箪Copolymers such as alpha-hydrocarbons, such as 1-decanoic acid, butadiene, 1-tetradecene, hexadecene, and octadecene. Or unsaturated esters, such as vinyl acetate. The substance can be esterified in accordance with the degree of alcohol. Examples of alcohols are η_dec_bufer, η_twelve " bufer, η-tetradecanol, β-hexadec-1-ol, η -Eighteen_1 ~ leaven, 1_methylfifteen_1_leaven, 2-methyltridec-1-ol. Mixtures of leaves can also be used, but they are blunt leaveners rather than commercially sold. Fermentation mixture. Preferred honeycomb polymers are polymers and copolymers of fumarate and econate, such as EP-A-1 5 3 17 6, EP-A -1 5 3 1 7 7, Ε Ρ-A-2 2 5 6 8 8, WO 91/16407, tf〇95 / 03377 and WO 95 / 33805. The preferred fumarate polymer is a copolymer of (C02-20 alkyl) fumarate and vinyl acetate, especially those whose alkyl group is 14 fluorene atoms, or alkyl C μ / C interviewers. These can be made by known techniques. Other suitable bee-type polymers that can be used include polymers and copolymers of oleum, esterified copolymers of styrene and maleic anhydride, and styrene. Ester copolymer of fumaric acid. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). The spider polymers used in the present invention are usually 1,000. The number average molecular weight to 100,000 (as measured by a vapor phase osmometer), more specifically 1,000 to 30,000. It can be used as a cold flow improvement. The nitrogenous compounds are known in the art, and usually contain a Or more similar or different fluorene-bonded hydrocarbon groups, which can be in the form of cations. -11- The standard of this paper is applicable to China National Standard (CNS) A4 (210 × 297 mm)] 824 9 A7 B7 Central Bureau of Standards, Ministry of Economic Affairs Printed by employee consumer cooperatives ) Hydrocarbyl groups usually have up to 40 fluorene atoms. Examples of hydrocarbyl groups include: aliphatic groups (such as alkyl or alkenyl), alicyclic groups (such as cycloalkyl or cycloalkenyl), aryl, aliphatic substituted aryl Radicals, alicyclic substituted alicyclic radicals and aliphatic radicals. Aliphatic radicals usually contain from 12 to 24 锢 硪 atomic densities which are advantageously saturated. Hydrocarbyl radicals may contain non-hydrocarbon substituents, but they must not alter the nature of the radical Hydrocarbon special emblems, such as fluorene, halogen, hydroxyl, nitro, proyl, alkane and acyl. If the hydrocarbyl group is substituted, a single substituent 傜 is preferred. Examples of substituted S groups are: 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-fluorenyl, ethylethyl and propanepropyl. The hydroxyl group can also / or contain other atoms in the chain not composed of erbium atoms or in chen. A suitable atom is rhenium, and endosulfan is preferably gas. The hydroxyl group is bonded to one or more nitrogen atoms through an indirect linking group, such as -C0-, -C02 (-), -S03 (-) or an alkylene group. When the polar nitrogen compound is used for a nitrogen bonding substituent, the bonding group of each substituent may be the same or different. The polar nitride may contain an amine substituent such as a long-chain Cl2-C40 (preferably Cu-C 24) first-, second-, third-, or quaternary amine substituent. Preferably, the amine substituent is a dialkylamino substituent, which may be in the form of an amine salt (only tertiary and quaternary amines can form amine salts). Alkyl groups can be the same or similar. Examples of the secondary amine substituent include dodecylamine, tetradecylamine, coconut amine, and tritiated tallow amine. Examples of secondary amine substituents include bis (octadecylamino) and methyl behenylamine. Mixtures of amine substituents may also be used, such as those derived from naturally occurring amines. The preferred amine substituent is a secondary hydrogenated tallow amine substituent, and its alkyl group is said to be derived from the deuterated beef -12. This paper size is applicable to China National Standard (CNS) 8-4 (210X297 mm) JJ —.----- ^ 装 — 丨 (Please read the precautions on the back before filling this page) Order A7 4 ^ 8249 B7 V. Description of the invention () Oil and fat. It is typically composed of 4% (: 14, 31% (: 1 ^, and 59% (: 13 n-alkyl). The polar halide may contain an imine substituent, such as Changpu CU-C40, preferably Cw -C 24 alkyl substituent. The substituent may be a monomer (Chen or acyclic) or a polymer < ^ When acyclic, the substituent may be obtained from a precursor (such as an anhydride). The ring precursor includes: homogeneous Rings, heterocyclic rings or mixed polycyclic ring assemblies, or two or more of these same or different hydrazone assemblies combined. In the case of two or more such ring assemblies, the substituent may be It is located on the interphase or dissimilar assembly, preferably on the same assembly. The ring assembly is more aromatic than fluorene, and more preferably a benzene ring. Most preferably, the ring system is a single ring. In this case, the substituent is preferably ortho or meta. The benzene ring may be further substituted according to the circumstances. The atomic image in the formation or ring assembly is preferably a scorpion, but may contain, for example, one or more N, S or 0. Examples of polycyclic assemblies include: U) condensed benzene structures, such as naphthalene, phenanthrene, phenanthrene, and (b) condensed fluorene structures, such as molybdenum, indene, hydroindene, fluorene, and biphenyl vapors; (C) Combined Chen, such as Satoshi Benzene; (d) Heterocyclic compounds, such as pyrene, indene, 2, 3-dihydroindole, benzofuran, doped acetophenone, isoheterophthalene acetopyrene, benzophenone, Wazole And phenylthioamines; (e) partially saturated or non-aromatic cyclic rings, such as decalin (dehydrohydro), alpha dilute, cardinene, and borneol hoof; and (Π three-dimensional spatial structure, such as the original moraine Ethylene, Dicycloheptane (orthobornane) The paper size applies to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) IJ--; ------- (Please read the precautions on the back before filling in this Page), printed by 1T Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 418249 Printed by the Consumer Standards of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 5 ', Invention Description (A), Dichen Octane and Dichen Octene. Further / For specific examples of polar nitrides that can be used in the present invention, see: (ISP 4, 2 11, 5 3 4, IIS P 4, 1 4 7, S 2 0, USP 4, 6 3 1, 0 7 1, USP 4.639,256, DE-A-3,9 16,366, DE-A-41 3,279, DE-A-0,261,957, DE-A-272 t889, DE-A-316,108. GB-A-2,121,807, FR-A- 2,592,3S7, DE-A-941,56 1, EP-A-283,292, and E PA-353,981. Examples of cold polymer modification of hydrocarbon polymers can be found in WO 91/11488, 95/03377, and WO 95/33805. Hydrocarbon polymers can be made directly from monovinyl unsaturated monomers, or indirectly. It is made from the hydrogenation of polymers consisting of polyunsaturated monofluorene. Examples of such monomers are isoprene and butadiene. The preferred is an ethylene alpha-olefin copolymer having a number average molecular weight of at least 30,00 00 (box-condensed nickel translucent layer analysis picture (GPC), as measured relative to polystyrene standards), and more preferably At least 60,000 0, and more particularly at least 80,000. When the molecular weight is higher than 150,000, the difficulty of viscosity mixing increases. Alpha-olefins have fortunately up to 30 mega atoms. Examples include: propylene, 1-butene, isobutylene, η-octene-1, isooctene-1, η-decene-1, dodecene-1. The copolymers also contain small amounts (i.e., up to 10%) of other copolymerizable military garrisons, such as olefins other than a-olefins, and non-co-diene. The preferred copolymer is an ethylene-propylene copolymer. The copolymer usually has an ethylene content of 50-85bo1X, preferably 60-75%, and most preferably 65-70%. This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

Printed by 418249 A7 _; _ B7_ by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs of the 1T. V. Description of the Invention (β) When ethylene ot-olefin copolymer is used, it is preferably an ethylene propylene copolymer having a number average molecular weight of 60,000-120,000, which is more than隹 is 80,000 -100,000. Hydrocarbon polymers can be prepared by any method known to those skilled in the art, such as using Ziegler catalysts. Polymer rhenium is essentially amorphous because ionic polymers are less soluble in fuel at low temperatures. Other suitable hydrocarbon polymers include low molecular weight ethylene-Ot-olefin copolymers, which typically have a number average molecular weight of up to 7,500, preferably 1000-6000, and more preferably 2000-5000 (by steam phase doping Lande). "-Olefin" is the former. Likewise, propylene is preferred. Styrene can also be used. Linear cold-fluid modified compounds typically include a compound in which at least one substantially linear alkyl group having 10-30 値 硪 atoms, and optionally a non-polymer residual bond (such as Inorganic residues), thus providing at least one linear atomic bond containing an alkyl fluorene atom or one or more single terminal gas, sulfur and / or nitrogen atoms. The bonding group may be a polymer. Polygas alkylene compounds are usually used. By "substantially linear" you mean that although alkyl groups with a small degree of branching (such as methyl) can also be used, alkyl groups are preferably linear. If there is a fluorene atom, it is preferably inserted between fluorene atoms and can be in the form of a single or multiple gas-extended alkyl group in the bonding group. The gas-extended alkyl group preferably has 2-4 fluorene atoms. Examples thereof include phytoethyl and phytopropyl. The linear compound may be an ester whose alkyl fluorene is derived from an acid and the rest is derived from a polyol and vice versa. Alternatively, the linear compound can be ether or mixed ester-1 5-This paper size is applicable to China National Standard (CNS) A4 (2 丨 OX297 mm) (Please read the precautions on the back before filling this page) Order A7 B7 418249 V. Description of the invention (K) / ether. It may contain different ether groups. Examples of usable linear compounds include multi-airline alkyl fluorenes, fluorenes, esters / ethers, and mixtures thereof, specifically those containing one fluorene (preferably two) CiD-30 linear alkyl groups and a number average number of molecules most A linear compound of poly-arsenic alkylenediase of 5000 (measured by GPC), wherein the number average molecular weight is preferably 200 to 5000 (see EP-A-61895 and USP 4,491,455). , Diethers, ethers and their compounds are also suitable for cold fluid improvement. It is preferably a stearic acid or behenic acid ester of polyoxanthion, polymalonate, or a mixture of polyethylidene / propylidene. As mentioned previously, mixtures of some cold flow modifiers can be used, such as mixtures of ethylene stripe unsaturated copolymers and honeycomb polymers, such as ethylene-vinyl acetate copolymers and fumarate beetle type. The mixture of polymers (C) can be used as the ashless dispersant (as component C) in the present invention, which is well known to those skilled in the art. Examples include ashless dispersants of carboxylic acids, such as polyamine succinimide and polyamine succinimine; Mannich disperse thinner 1 (including reaction products of alkylphenols with aliphatic anhydrides and polyamines) And polyamine and hydrocarbyl polyamine dispersant. These dispersants are described in more detail in EP-A-0531000. The use of polyamine succinimide and Manny's dispersant 傜 is preferred. Succinimide dispersants can be prepared by reacting a substituted ammonium succinate with an amine / alcohol or an amine alcohol mixture. Succinic acid hydration_ can be derived from polyenes, such as polyiso-1 with a number average molecular weight (GPC tide) of 500-8000-6-This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) --- ------ (Please read the notes on the back before filling out this page)-Order printed by the Central Standards Bureau of the Ministry of Economic Affairs, Zhengong Consumer Cooperative, 418249 Five 'Invention Note (A) Butadiene, the molecular weight can be 900- 2100 and more specifically 950-1300. Examples of usable amines include polyamines having at least one primary amine group and an average of at least two other nitrogen atoms in the molecule. Examples are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and mixtures thereof. The reaction ratio of the succinic acid aldolizing agent and the amine is generally from 1 ·· 1 to 2.0: 1, preferably from 1.3: 1 to 1,8 ·· 1, such as about 1.6: 1. The present invention further provides a low-sulfur fuel including component A and further including components B and C. This type of fuel is obtained by mixing base fuel and additive components in the desired proportion. The base fuel can be a middle distillate fuel or a bio-diesel fuel (as described above). Ingredient A in the fuel is usually 500 PPDI, preferably 15-350 ppm, and most preferably 50-150 PPB. When used, usually, the amount of ingredient B is up to 100Θρρριη, preferably 100-500ppm, and most preferably 200-400PPH. When used, usually, the amount of ingredient C is up to 400ppm, preferably 25-200PPI », and the best is 50-150PPB. The number of children's capacity is related to volume, so it represents the concentration in milliliters per liter of fuel. For the sake of the present invention, the additives of the present invention can be provided in a concentrated form, diluted with fuel. Such concentrated materials are part of the present invention, and typically include 99 to 1 «1 ^ additives and l-99 \ »T! K is a solvent or diluent for additives, which is pseudo-miscible and / or soluble in the fuel in which the concentrate is used. Of course, the solvent or dilution itself may be a low sulfur component. However, other solvents or diluents include petroleum spirit (vhite spirit), kerosene, alcohols (such as 2-ethylhexanol, isopropanol, and isodecanol), and high boiling point aromatic solvents (such as toluene and xylene). ) And hexadecane modifiers (such as 2-ethylhexyl nitrite). Of course, they can be used alone or in combination. The concentrate or fuel may also contain other suitable proportions of fuel additives, thus providing a multifunctional fuel additive combination. Examples of customary fuel additives that can be used include: stabilizers, detergents, anti-foaming agents, cetane number -17- This paper size applies to China National Standard (CNS) A4 specifications (210X297 metric whole) (please open first Read the notes on the back and fill in this page) h.; Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives printed 41824 9 A7 B7 V. Description of the invention (4) Improvers, antioxidants, corrosion inhibitors, antistatic additives, sterilization Agent, dye, smoke reducing agent, catalyst life increasing agent and de-emulsifier. The total application ratio of the multifunctional formula containing lubricity enhancer is typically 2 5-2 0 0 pp in, more specifically 6 0-1 2 0 0 pp in β The present invention also provides a method for reducing the wear of fuel pumps of low-sulfur fuel engines by using low-sulfur fuels. The fuel can be used to reduce rotary and on-line fuels. Pump wear, which can be seen in, for example, diesel engines, or reduce wear on fuel transfer pumps. The latter is located between the fuel tank and the high-pressure fuel pump. This fuel is particularly suitable for reducing wear on the fuel injector pump. Fuel can also be used to reduce the wear of the final fuel injector in combination with the fuel pump and injector mechanism. The present invention is not suitable for the operation of diesel engines and jet engines. The present invention will be illustrated by the following examples The employees of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperative (please read the precautions on the back before filling out this page) The moisturizing strength of several diesel fuels is measured in accordance with the high frequency reciprocating rack (HFKR) test of CEC F-06-T-94. In the test, an electromagnetically driven small copper ball hit a fixed steel disk. Both the disk and the ball were immersed in an electronic heating bath containing the test fuel. It was obtained by measuring the average wear mark diameter (HWSD) on the ball caused by the vibration contacting the plate Wear, so it is measured that the fuel has lubricity. The lower the average wear trace obtained, the greater the lubricity of the fuel. The base fuel used is a secondary Scandinavian diesel fuel. This is the sulfur component Q.OOSwtX: of Diesel fuel. The composition and distillation characteristics of this fuel are as follows. —1 8 — This paper size applies to China National Standard (CNS) A4 (210X297 mm) y 4 2 B 11 4

AB 5. Description of the invention (π) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs at 15 t CCP16 0), g / »1 0.8160 Chain Academy®, SI v 〇1 89.6 Alkenes, Sivo 1 0.7 Aromatic, 3ίνο 1 9.7 Distillation characteristics (IP 123) Starting B.P., Ό 184 5% 200 10% 204 2096 212 30% 217 40¾ 223 50% 228 60% 235 70% 243 80% 251 90¾ 263 95% 269 Final boiling point, υ 290 Recycled,% 99 Residual,% 1 Loss,% 0 -19- (Please read the precautions on the back before filling this page)

Subscriber-This paper size applies Chinese National Standard (CMS) A4 specification (210 X 297 mm) 41824 9 A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention () The table below shows the HFRR of several diesel fuels test results. Table 1 Composition and quantity (ppm / vv) _ HFRR @ 60t3) Test number AB c MWSD (um) 1 0 0 0 650 2 25 0 0 680 3 0 200 0 645 4 0 0 100 650 5 0 200 100 630 6 25 200 0 525 7 25 0 100 555 8 25 200 100 415 -20- ^^ 1-1 ^ 1 ^^ 1--is- --- IC ϋ /.ς (Please read the notes on the back before filling this page ) The paper size of the edition applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 418249 A7 _____ B7 V. Description of the invention (19) In this table: Ingredient A is oleyldiacetaldehyde: cold fluid Modifier component B is a commercially available ethylene-vinyl acetate copolymer generally used in medium-thorium fuel. The fuel has a wide range of boiling points (20-90% is steamed in the range of 1 00 -1 20 t :), and finally boils. The temperature is 360-38010. Ingredient C (ashless dispersion) 傺 polyisobutylene-derived polyisobutylene succinimide, with an average molecular weight of 950. The amine used in the preparation of bupropionimine is tetraethylenepentamine β. The crystal obtained clearly confirms that the fuel of the present invention has improved lubricity. The base fuel of Test No. 1 had a very low inherent lubricity, which caused a relatively large average blind mark diameter & 50 «· in the HFRR test. Similarly, bad results were observed in Test No. 2. In Nos. 2-4, the tested fuel contained only components A, B, or C. In No. 5, the fuel contains components B and C, but no component A. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the note on the back before filling this page) " In contrast, No. 6-8 (especially No. 8), there are very small average wear marks , Indicates that the lubricity is significantly improved. 鼷 Note that the numbers of components A, B, and C of 6-8 are pseudo-same as the previous ones. From the observation, the slipping force has increased significantly. I learned that there is a synergistic effect between the components. Between A and B, 7 between A and C of sickle, and between A, B, and C of δ. This multiplication effect makes the number of components A, B, and / or C be the most reduced without being obvious. The lubricity of ground-breaking fuel. This results in material savings. The synergistic effect between ingredients A and B can be confirmed from other tests (such as Table 2-6). -21-This paper size applies Chinese national standards (CNS ) A4 specification (210X297 mm) 4 1824 9 A7 B7 V. Description of the invention (> Table 2 Composition and quantity (ppm / vv) HFRR) Test number k C MWSD (un) Θ 0 200 645 10 25 200 525 ( Please read the notes on the back before filling out this page) Ingredients A and B are the same as those in Table 1 Composition and quantity (ppm / vv) HFRR 060¾) Test number AC MWSD (um) 11 0 200 670 12 25 200 360 Component A is the same as above, cold fluid modifier B is a wide melting point range (20-90 volume% at 100-120 its distillative distillation). Commercially sold ethylene-vinyl acetate copolymer, the fuel has a final boiling point of about 360-380 ¾ 〇 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) Order _ Staff Consumption, Central Bureau of Standards Cooperative printed by the Central Bureau of Standards of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Central Government Bureau 418249 A7 __B7 V. Description of the invention (-f) Table 4 Composition and quantity (ppm / vv) HFRR @ 6012 > Test number AC HWSD (u ά) 13 0 200 675 14 25 200 485 Ingredient A is as above. The cold-boiler modifier B is a commercially available ethylene-vinyl acetate copolymer for middle-range fuels with a wide melt viscosity range (20-90% by volume at 100-120¾ radiant distillation). The final boiling point of the fuel is about 360-380¾. Table 5 Composition and quantity (ppm / vv) HFRR @ 60O) Test number AC MUSD (// m) 15 0 200 645 16 25 200 400 -23- This paper; ^ Applicable to China National Standard (CNS) A4 specification (210X 297 Mm) (Please read the notes on the back before filling out this page)

4 18249 A7 B7 V. Description of the invention (") Component A is fluorenyldiethyl. Cold fluid improver component B Pseudo-wide melting point Fan Yuan (20-90 vol% distillation at 100-120Ό), a commercially available ethylene-ethyl acetate copolymer for use in fuels with a final boiling point of 360-380 ¾. Table 6 Composition and quantity (ppm / vv) HFRR @ 601C) Test number AC MVSD (um) 17 0 200 685 18 25 200 350 (Please read the notes on the back before filling this page) Industrial and consumer cooperatives printed copies of A 傜 the aforementioned. Cold fluid improver component B Song wide-melting range (20-90% by volume distilled at a temperature of 120C or higher) Commercially available ethylene-vinyl acetate copolymers for middle distillate fuels with a high final boiling point of at least For 390 υ. The cold fluid modifiers in Tables 1 and 2 are commercially available. The cold fluid modifiers of Tables 3 and 4 were purchased from different suppliers and are the same as the suppliers of the cold fluid modifiers of Tables 5 and 6. The results in Table 2-6 confirm the synergistic effect between components A and B. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

No. 8 6 1 0 7 5 1 7 "Patent Case for Middle Distillate Fuel with Ammonium Amide and Cold Fluid Improver (Amended in October 88) Application of Patent Scope 1.—A Fuel Composition Including (A) A middle distillate fuel with a low sulfur content of 0.2wtS; S, (B) a carboxylic acid amine with a content of at most 500 PPm and (C) at least one member selected from the group consisting of: a cold fluid with a maximum of 1000 PPi « Modifiers, ashless dispersants and mixtures thereof up to 400PPI. 2. The fuel composition according to item 1 of the patent application, wherein (C) includes a mixture of at least one cold fluid improver and at least one ashless dispersant. 3. The fuel composition according to item 1 of the scope of the patent application, in which the ammonium carboxylate (B) is oleyl diethylammonium amine. 4. A method for improving the lubricity of low-sulfur fuels, including adding (B ) Ammonium carboxylate with a maximum of 500PPH1 and (C) at least one member is selected from the group consisting of: a cold fluid modifier of up to 1Θ00PPII, a mixture of ashless dispersant and its mixture up to 400ppm to (A) Medium distillate fuel with low sulfur content of 0.2wU or less. Please read first CAUTIONS then fill in the back of this page I. Ministry of Economic Affairs i. Member of the Property Bureau X-Consumer Cooperative Co., Ltd. This paper is printed in accordance with China National Standard (CNS) A4 (210 X 297 public love) Announcement application date, 〆Γ '. Case No. 0 It η Category CAP %-. Heart (The above blocks are filled by this Council) # 鋈 Patent Specification ^ Revised in October of the year of the invention w. I. New name Middle Distillate Fuel with Acid Amide and Cold Flow Improver English name Middle Distillate Fuel with Acid Amide and Cold Flow Improver Robert Quigley Gareth Charles Jeffrey National Invention / Creation / 1. United Kingdom 2. British housing, residence 1. Lease RG12 7WF Berkshire Breck Neil Fenmel 6 2. Lease RG12 5DZ Berkshire Breck No. 8 Angel Square, Neil Binfield Name (Name) Ethyl PetroleuK Additives Limited _ Ethyl PetroleuK Additives Limited Central Standards Bureau of the Ministry of Economic Affairs Shellfish Consumer Cooperatives Printed Lines Nationality's Residence (Office) Representative Name UK UK Berkshire RG12 2UM Blakenell London Road Dennis H. Rainier Dennis HR ain ea r This paper size applies to Chinese national standards (CNS > A4 ^ grid (210X297 mm) 418249 Five 'invention description (A) D Diene, the molecular weight may be 900-2100 and more specifically 950-1300. Examples of amines that may be used include those having at least one Polyamines and polyamines with an average of at least two other nitrogen atoms in the molecule. Examples are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and mixtures thereof. Succinic acid aldehyde modifiers The reaction ratio between amine and amine is usually 1 ·· 1 to 2.0: 1, preferably 1.3: 1 to 1,8 ·· 1, such as about 1.6: 1. The present invention further provides a low sulfur fuel, including Ingredient A and further, including ingredients B and C. This type of fuel is obtained by mixing base fuel and additive components in the desired proportion. The base fuel can be middle-distillate fuel or bio-diesel fuel (as above). Ingredient A In the fuel, it is usually 500 PPDI, preferably 15-350 ppm, and most preferably 50-150 PPB. When used, usually, the amount of component B is up to 100Θρρρη, preferably 100-500ppm, and, best 200-400PPH0 When used, usually, the amount of component C is up to 400ppm, preferably 25-200PPI », and most preferably 50-150PPB. This number is related to volume, so it represents every撖 mL concentration of fuel per liter. Because of the present invention, the additives of the present invention can be concentrated It is provided in the form of a diluent diluted with fuel. This type of concentrated substance is part of the present invention, and it typically includes 99 to 1 «1 ^ additives and l-99 \» t! K additives for solvents or diluents, The solvent or dilution is pseudo-miscible and / or soluble in the fuel in which the concentrate is used. Of course, the solvent or dilution itself may be a low sulfur component. However, other solvents or diluents include petroleum spirit (vhite spirit), kerosene, alcohols (such as 2-ethylhexanol, isopropanol, and isodecanol), and high boiling point aromatic solvents (such as toluene and xylene). ) And hexadecane modifiers (such as 2-ethylhexyl nitrite). Of course, they can be used alone or in combination. The concentrate or fuel may also contain other suitable proportions of fuel additives, thus providing a multifunctional fuel additive combination. Examples of customary fuel additives that can be used include: stabilizers, detergents, anti-foaming agents, cetane number -17- This paper size applies to China National Standard (CNS) A4 specifications (210X297 metric whole) (please open first (Please read the notes on the back and fill in this page) h.; Order printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Summary of the Invention (Invention claims that the acid fuel amine and the cold fluid modifier are medium fuel. The present invention is a low sulfur fuel with improved lubricity (compared to a fuel with a low content). The low sulfur fuel composition contains The sulphur content is 0.2wtX or less. Zhonghuan fuel, ketoamine, and at least one of them are composed of the following groups: cold stream tincture improver, ashless dispersant, and mixtures thereof. Abstract of the Invention ( Name of the invention: Middle Distillate Fuel with Acid Amide and Cold Flow Improver ----------'-- ^-Installation I "-ί (Please read the notes on the back before filling in this page 櫊) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs This invention relates to low sulfur fuel compositions which exhibit improved lubricity compared to the low sulfur fuels alone. The low sulfur fuel compositions contains a middle distillate fuel having a sulfur content of 0.2% by weight or less, a carboxylic acid amide and at least one member selected from the group consisting of cold flow improvers, ashless dispersants, and mixture s thereof. Line Λ. This paper music is again applicable to China National Standard (CNS) M specifications (2) 〇297 thin No. 8 6 1 0 7 5 1 7 "Patent Case for Middle Distillate Fuel with Ammonium Amide and Cold Fluid Improver (Amended in October 88) Application of Patent Scope 1.—A Fuel Composition Including (A) A middle distillate fuel with a low sulfur content of 0.2wtS; S, (B) a carboxylic acid amine with a content of at most 500 PPm and (C) at least one member selected from the group consisting of: a cold fluid with a maximum of 1000 PPi « Modifiers, ashless dispersants and mixtures thereof up to 400PPI. 2. The fuel composition according to item 1 of the patent application, wherein (C) includes a mixture of at least one cold fluid improver and at least one ashless dispersant. 3. The fuel composition according to item 1 of the scope of the patent application, in which the ammonium carboxylate (B) is oleyl diethylammonium amine. 4. A method for improving the lubricity of low-sulfur fuels, including adding (B ) Ammonium carboxylate with a maximum of 500PPH1 and (C) at least one member is selected from the group consisting of: a cold fluid modifier of up to 1Θ00PPII, a mixture of ashless dispersant and its mixture up to 400ppm to (A) Medium distillate fuel with low sulfur content of 0.2wU or less. Please read first CAUTIONS then fill in the back of this page Printed by the Ministry of Economic Affairs i. Member of the Property Bureau X-Consumer Cooperatives This paper is sized for China National Standard (CNS) A4 (210 X 297 public love)