JPH09503530A - Additive and fuel composition - Google Patents

Abstract

  (57) [Summary] Dispersant, lubricity, cetane improver and / or defoamer additives are used in combination with the copolymer ethylene flow improver additives to enhance the low temperature fluidity of the fuel oil.

Description

Detailed Description of the Invention                         Additive and fuel composition   The present invention is directed to fuel oils, such as middle distillate fuel oils boiling in the range of 110 to 500 ° C. It relates to the use of additives to improve the cold flow properties of distillate petroleum fuels.   When the fuel oil is exposed to low ambient temperatures, wax separates from the fuel oil and May reduce the flow characteristics of the. For example, middle distillate fuel may precipitate at low temperatures. A wax that forms waxy crystals, the waxy crystals being a fuel fill. Tend to block small openings in the The problem is that the fuel is diesel oil. It is especially serious when Because in the fuel filter of the diesel engine The nominal aperture in is typically in the range of about 5-50 microns in diameter. the above Additives for overcoming the problems are known in the art and are referred to as rheological property improvers. I have.   Such additives, when blended with waxy mineral oils, are present in the Changing the shape and size of the wax crystals, and between the crystals and with the wax Low temperature, which reduces the adhesion between the oil and higher than in the absence of the additive Acts as a wax crystal modifier by maintaining the flow properties of the oil in You can   Many additives have been disclosed in the art to improve the cold flow properties of oils. , Which may be, for example, polymers or monomers, oil-soluble additive products or In the form of a condensate, for example US-A-3,048,479, UK-A-1,263,152, US-A-3,961, 961 and EP-A-0,261,957. Some of the above additives are cold flow modified. It is used industrially as a good agent (Cold Flow Improvers).   The cold flow improver can also be used in the art in combination with other additives. Is described. For example, UK-A-1,112,808 is a rust inhibitor, emulsifier, Food inhibitors, antioxidants, dispersants, dyes, dye stabilizers, turbidity inhibitors and antistatic agents Disclosed are ethylene-vinyl acetate copolymers in combination with antistatic additives.   In the present invention, surprisingly, the low temperature properties of the cold flow property improver as described above are low. Flow properties have previously been known in the art to have cold flow improvement properties. Seen to be further enhanced by using no co-additives. I put it out.   Accordingly, a first aspect of the invention is one or more of the following components:   (a) Hydrocarbyl-acylated with a carboxyacylating agent or hydrocarbyl Contains amines that are carbylated or hydrocarboxylated Having an oil-soluble, ash-free dispersant / detergent,   (b) Addition of oil-soluble and lubricity containing ester of carboxylic acid and alcohol An agent, wherein the acid has 2 to 50 carbon atoms and the alcohol is one or more Having carbon atoms in,   (c) oil-soluble nitrate or peroxycetane, and   (d) silicon-based composition or acylated with a carboxyl acylating agent Oil-soluble, containing a polyamine having at least a primary or secondary amino group Oil fuel defoamer, The use of an auxiliary additive selected from the component (A) containing Amount of Fuel Oil and Additives for Cold Flow Properties Improving Copolymer Ethylene Flow Modifier In a composition containing a small amount of component (B) containing Enhance the characteristics.   The enhancement of the cold flow properties of the component (B) by the component (A) of the present invention is due to addition of fuel oil and Applicable to blends with agents. Thus, the second aspect of the present invention is the fuel oil and additive. Regarding the blending method with   (i) Injecting the component (B) defined above into the fuel oil,   (ii) injecting component (A) as defined above into the fuel oil,   (iii) Measure the low temperature flow characteristics of the fuel oil after injection in the steps (i) and (ii) And   (iv) Relative injection of the components (A) and (B), taking into account the result of the step (iii). Ratios, or relative proportions thereof, can be adjusted to provide the fuel oil with desired cold flow characteristics. give, It is characterized by including various steps.   In the second aspect of the present invention, the fuel oil is preferably in a fluidized state, Wherein the step (i) is carried out at the first station and the second step (ii) is at the second station. However, the first and second stations are adjacent, The injection can be performed with a common injector. By automating this method, with sensors, for example By measuring the cold filter plugging point (CFPP) , Performing step (iii) and providing that information to one or both of the components (B) and (A). It can be delivered via a controller to control the person's infusion.   Surprisingly, the present invention uses a lower amount of component (B) to achieve a given cold flow characteristic. It is possible to achieve the performance improvement performance.   These features of the present invention will be described in more detail below.   The specification mentioned below is referred to as the present invention.   As used herein, the term "hydrocarbyl" refers to a direct bond to the rest of the molecule. A group having selected carbon atoms and having hydrocarbon or predominantly hydrocarbon character. Let's taste. Examples are aliphatic (eg alkyl or alkenyl), Alicyclic (eg, cycloalkyl or cycloalkenyl), aromatic and alicyclic Including hydrocarbon groups such as group-substituted aromatic, aromatic-substituted aliphatic and alicyclic groups . The aliphatic group is preferably a saturated aliphatic group. These groups are the predominant charcoal of the group Substituents other than hydrocarbons can be included as long as they do not change the hydrogenation properties. An example Includes keto, halo, hydroxy, nitro, cyano, alkoxy and acyl You. When the hydrocarbyl group is substituted, a single (mono) -substituted one is preferable.   Examples of substituted hydrocarbyl groups are 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-ketopropyl, ethoxyethyl and propoxypropyi Including a radical. These groups may also be linked to other sources in the chain or ring besides the carbon atom. It can also include children. Preferred heteroatoms are, for example, nitrogen, sulfur, and preferably Preferably, it includes an oxygen atom.Ingredient (A)   The components defined above by the lower case letters will be explained. (a) An ash-free dispersant is a dispersant for improving the detergency of fuel oil, Leaves little or no metal-containing distillates on combustion. These are numerous patent specifications And includes the following: -Hydrocarbyl polycarboxyacylating agents (e.g. hydrocarbyl dicarbohydrate) Acid anhydride) -acylated polyamines such as alkenylsuccinimide Liamines, where, for example, the alkenyl group is polyisobutylene. That Examples are described in EP-A-0,482,253. An example of such polyamines is Cyclization products, such as those described in EP-A-0,525,052. -Hydrocarbylated, for example by a polyolefin group such as polyisobutylene Polyamines. An example thereof is described in WO 91/12302. -Hydrocarbyl ether amines, such as hydrocarbyl groups 6-26 (eg , 8-10) carbon atoms, and preferably a methyl group such as an oxo-alcohol derivative. Alkyl ether monoamines, which are branched alkyl groups. This amine is like For example, it has 2 to 8 carbon atoms. Examples thereof are described in US-A-4,319,987. other Are examples of alkoxylated amines such as those described in US-A-4,409,000. It is. (b) the acids, alcohols and esters characterizing the lubricity additive are The details will be described. (i)acid   The acid derivatizing the ester may be a mono- or polycarboxylic acid, eg an aliphatic , Saturated or unsaturated, straight-chain or branched, mono- and dicarboxylic acids are preferred. Good For example, the acid can be represented by the general formula:                               R '(COOH)_x Here, x is an integer of 1 or more, for example, 1 to 4, and R'is a single value depending on the value of x. Or a polyvalent hydrocarbyl group having 2 to 50 carbon atoms, wherein the -COOH group is Are optionally substituted on different carbon atoms, if present more than once. May be.   The term "hydrocarbyl" includes carbon and hydrogen, the molecule being attached via a carbon atom. Means the group attached to the rest of It may be a straight chain or a branched chain, which chain is May be interspersed with one or more heteroatoms, eg O, S, N or P , Aroma that may be saturated or unsaturated and includes aliphatic, cycloaliphatic, or heterocyclic groups. It may be a group group and may be substituted or unsubstituted. Preferably, the acid is monocarboxylic When it is rubonic acid, the hydrocarbyl group has 10 (eg 12) to 30 carbons. An alkyl or alkenyl group having atoms, ie the acid is saturated or unsaturated It is. The alkenyl group may have one or more double bonds, for example 1, 2 or 3 double bonds. You can have a match. Examples of saturated carboxylic acids have 10 to 22 carbon atoms , For example, oleic acid, elaidic acid, palmitoleic acid, petroselinic acid, lyco Norein (riconoleic) acid, eleostrearic acid (eleostrearic) acid, linoleic acid, Linolenic acid, eicosanoic acid, galoliec acid, erucic acid and hypogine (hypogeic) acid. The acid is, for example, a polycarbocarbon having 2 to 4 carboxy groups. When it is an acid, the hydrocarbyl group is preferably a substituted or unsubstituted polymer. It is a thylene group. (ii)alcohol   The alcohol from which the ester is derived is a mono- or polyhydroxy alcohol, eg It can be, for example, trihydroxy alcohol. For example, the alcohol is It can be expressed as:                                 R²(OH) y Here, y represents an integer of 1 or more, and R²Is one or more carbon atoms, for example up to 10 charcoal Represents a hydrocarbyl group having an elementary atom, which is monovalent or polyvalent depending on the value of y. And, when two or more —OH groups are present, they may be carbons different from each other in some cases. It may be substituted on the atom.   The term "hydrocarbyl" has the same meaning as given above for the acid. Hold. For this alcohol, the hydrocarbyl group is preferably an alkyl A group or a substituted or unsubstituted polymethylene group. An example of monohydric alcohol is 1 Lower alkyl alcohols having up to 6 carbon atoms, eg methyl, ethyl, pro Pills and butyl alcohol.   Examples of polyhydric alcohols include aliphatic, saturated or unsaturated, straight chain or Is a branched, 2-10, preferably 2-6, more preferably 2-4 hydroxyl Having a group and having 2 to 90 carbon atoms, preferably 2 to 30, more preferably 2 to 12, Most preferably 2 to 5 alcohols. As a more specific example, the polyvalent alkane Cole is a glycol or diol, or a trihydric alcohol such as glycero It is (iii)Esters   These esters can be used alone or as a mixture of one or more esters. It may be composed of only carbon, hydrogen and oxygen. Preferably, the Esters have a molecular weight of 200 or higher, or at least 10 carbons Have atoms or have a molecular weight of 200 or more and at least 10 carbon atoms Hold.   Examples of esters that can be used are lower alkyl esters such as the saturated ones exemplified above. Alternatively, they are methyl esters of unsaturated monocarboxylic acids. For example, Stel is the saponification and esterification of natural fats and oils of plant or animal origin, or It can be obtained by a transesterification reaction with the lower aliphatic alcohol.   Examples of usable polyhydric alcohol esters are those in which all of the hydroxyl groups are Those which are tellurized, those where a part of the hydroxyl group is esterified, And mixtures thereof. Specific examples include trihydric alcohols and one or more of the above-mentioned saturated compounds. Or esters prepared with unsaturated carboxylic acids, eg glycerol mono Esters and glycerol diesters such as glycerol monooleate Glycerol, glycerol dioleate and glycerol monostearate. This Polyvalent esters such as can be prepared by esterification as is known in the art. Available or commercially available.   The ester can have one or more free hydroxyl groups. Examples of these are described in WO-PCT / EP 94/00148. (c) Examples of cetane modifiers are organic nitrates, such as those having up to 30 carbon atoms, preferably Preferably saturated, and preferably containing up to 12 carbon atoms, aliphatic or alicyclic groups. These are nitrate esters. Examples of such nitrates are methyl, ethyl, propyl , Isopropyl, butyl, amyl, hexyl, heptyl, octyl, isooctyl Tyl, 2-ethylhexyl, nonyl, decyl, allyl, cyclopentyl, cyclohexyl Xyl, methylcyclohexyl, cyclodecyl, 2-ethoxyethyl, and 2- (2 -Ethoxyethoxy) ethyl nitrates. Other examples are fuel soluble Oxides, hydroperoxides and peroxyesters. (d) Examples of defoamers include siloxane-polyoxyalkylene copolymers such as US No. 3,233,986 (which is referred to as a reference of the present invention) Yes, the formula: R₂SiO₀._{5 (4-b)} (Where R is a halogen atom or optionally halo At least two, which are genated hydrocarbon groups and b is 1 to 3) At least one siloxane block containing at least 2 siloxane groups, and At least one polyoxyalkylene block containing one oxyalkylene group It is a copolymer containing and. Generally, the alkylene group has 2 or 3 carbon atoms. Have a child and usually have both ethyleneoxy and propyleneoxy groups You. Advantageously, the copolymer is a polymethylsiloxane-polyoxyalkylene copolymer. A polymer, preferably a copolymer of the formula:               (CH_Three)_ThreeSiO [CH_Three(A) SiO]_m [(CH_Three)₂SiO]_n Si (CH_Three)_Three Where A is the following formula:                     -(CH₂)_p O (C₂H_FourO)_x (C_ThreeH₆O)_y Z Wherein Z is a hydrocarbyl group (OC: hydrocarbyl), or preferably Represents a hydrogen atom, the absolute values of m and n and their ratios, and p, x and y In each case, the ratio can be varied over a wide range, the total value of which is advantageously between 600 and 25000. It gives a range of molecular weights. The ratio of m: n is preferably in the range of 10: 1 to 1:20, and of n The value can be zero and the ratio of x: y is advantageously from 1: 100 to 100: 1, preferably from 20:80. Can be in the range 100: 1, or one of x or y (but not both) can be zero You. A preferred defoamer is Th.P. under the trademark TEGOPREN. Gold schmidt (Goldschmidt AG). Advantageously, this defoamer is 0.0001 to 0.2%, preferably 0.005 to 0.02% (by weight) in the fuel Exists in. Other antifoaming agents do not contain silicon atoms, for example those described in WO 94/06894. It can be made by acylating a polyamine as described.Ingredient (B)   Ethylene copolymer fluidity improvers, eg ethylene / unsaturated ester copolymers -Fluidity improver is a polymethyene segmented by oxyhydrocarbon chains. It has a len skeleton.   More specifically, the copolymer comprises, in addition to units derived from ethylene, the following formula:                               -CR^FiveR⁶-CHR⁷- (Where R⁶Represents hydrogen or a methyl group, R^FiveIs-OOCR⁸Or-COOR⁸(here, R⁸Is a hydrogen atom or C₁~ C₂₈ , Preferably C₁~ C₉, Straight or branched chain alkyl Represents a group, but R⁸Is R^Fiveが -COOR⁸Is represented by the condition that it is not a hydrogen atom And R again⁷Is a hydrogen atom or -COOR⁸Represents a unit) it can.   These are copolyesters of ethylene with ethylenically unsaturated esters or their derivatives. May include a mer. One example is an ester of ethylene and an unsaturated carboxylic acid This copolymer is preferably a copolymer of unsaturated alcohols and saturated esters. It is an ester with rubic acid. Ethylene-vinyl ester copolymers are preferred Ethylene-vinyl acetate, ethylene-vinyl propionate, ethylene-vinyl Hexanoate or ethylene-vinyl octanoate copolymers are preferred. Preferably, the copolymer is 1 to 25, for example 1 to 20 mol% of the vinyl ester, More preferably, it contains 3 to 17 mol% of vinyl ester. These are also two or more Mixtures of the copolymers described in US Pat. No. 3,961,916. It may be a mer mixture. Preferably, the vapor phase of this copolymer is The number average molecular weight measured by smometry is 1,000 to 10,000, more preferably It is 1,000 to 5,000. If necessary, this copolymer can be derived from ancillary comonomers For example, these are terpolymers or tetrapolymers May be more than one multicomponent polymer, where, for example, the additional comonomer is The mer is isobutylene or diisobutylene.   These copolymers can be prepared by direct polymerization of comonomers. Like this The polymer can also be transesterified with an ethylene-unsaturated ester copolymer. Rui or hydrolyzed or re-esterified to produce various ethylenically unsaturated ester copolymers. It can also be produced by producing a mer. For example, ethylene-vinyl Thus, the ruhexanoate and ethylene vinyl octanoate copolymers And can be produced, for example, from ethylene vinyl acetate copolymer.   Ingredient (B) is used with one or more of the following co-components: Can be used.Comb polymer   Comb-type polymers are "comb-like polymers, structures and properties (Comb-Like Polymers, S N.A.Plate and V.P.Shivaev (`` Tructure and Properties) '' Shivaev), J. Poly. Sci. Macromolecular Revs., 1974,8, Pp. Discussed in 117-253 Has been.   Generally, comb polymers have one or more long chain branches, for example 10 to 30 carbon atoms. However, hydrocarbyl components such as oxyhydrocarbyl branches suspended from the polymer skeleton Have branches, the branch (s) being directly or indirectly attached to the backbone . Examples of indirect bonds include bonds through inserted atoms or groups, which bond Includes covalent bonds and / or electrovalent bonds as in salts be able to.   Advantageously, the comb polymer is in the linear chain at least 25, preferably less than At least 40, more preferably at least 50 mol%, at least 6, preferably Contain at least 10 atoms, for example atoms selected from carbon, nitrogen and oxygen It is a homopolymer or copolymer containing units with side chains.   Examples of preferable comb polymers include those having units represented by the following general formula. You can list:                 -[C (D) (E) -CH (G)]_m -[C (J) (K) -CH (L)]_n - Where D = R¹¹， COOR¹¹， OCOR¹¹， R¹²COOR¹¹Or OR¹¹         E = H, CH_Three， D or R¹²         G = H or D         J = H, R¹²， R¹²COOR¹¹ Or aryl group or heterocyclic group         K = H, COOR¹²， OCOR¹²， OR¹² Or COOH         L = H, R¹²， COOR¹²， OCOR¹²Or aryl group         R¹¹ ≧ C_Ten Hydrocarbyl group         R¹² ≧ C₁Hydrocarbyl group m and n represent molar ratios, the sum of which is 1, m is finite, and up to 1 (1 And n is 0 to less than 1, preferably m is 1.0 to 0.4, and n is It is within the range of 0 to 0.6. R¹¹ Is preferably a hydrocarbyl having 10 to 30 carbon atoms. Represents a ruby group, also R¹² Is preferably a hydrocarbyl having 1 to 30 carbon atoms. Represents a radical.   This comb polymer may contain other monomers, if desired or necessary. The unit of origin can be included. It is also possible to include two or more different comb polymers It falls within the scope of the invention.   These comb polymers include maleic anhydride or fumaric acid and other ethylene. Unsaturated monomers such as α-olefins or unsaturated esters such as vinyl acetate It may be a copolymer with nil. Preference is given to using equimolar amounts of comonomer However, this is not essential and a molar ratio within the range of 2-1 and 1-2 is suitable. You. For example, examples of olefins that can be copolymerized with maleic anhydride include 1-decene, 1-dodecane. Includes decene, 1-tetradecene, 1-hexadecene and 1-octadecene.   The copolymer can be esterified by any suitable technique, and the Leic acid or fumaric acid is preferably at least 50% esterified But this is not essential. Examples of alcohols that can be used are n-decane-1- All, n-dodecane-1-ol, n-tetradecane-1-ol, n-hexadecane-1 -Includes oar and n-octadecane-1-ol. This alcohol is also It may contain up to 1 methyl branch per chain, for example 1-methyl pentade It can be can-1-ol and 2-methyltridecane-1-ol. This arco Is a mixture of straight chain alcohols and alcohols with a single methyl branch Good. Rather pure alcohol than commercially available alcohol mixtures It is preferred to use, but if a mixture is used, R¹² Is the carbon in the alkyl group When using an alcohol containing a branch at the 1- or 2-position, which means the average number of elementary atoms To R¹² Means a linear skeleton segment of the alcohol.   These comb polymers are especially fumarate or itaconate polymers, and And copolymers such as European Patent Applications 153 176, 153 177 and 225. 688 as well as those described in WO 91/16407.   A particularly preferred fumarate comb polymer is a combination of alkyl fumarate and vinyl acetate. A copolymer, wherein the alkyl group has 12 to 20 carbon atoms, More particular polymers have the alkyl group having 14 carbon atoms, or the alkyl group Ru group is C₁₄/ C₁₈ A mixture of alkyl groups, such as fumaric acid and vinyl acetate Solution copolymerization of a molar mixture and the resulting copolymer is an alcohol or a mixture thereof. Those produced by reacting with (preferably a linear alcohol) It is. If this mixture is used, it is advantageous to use a 1: 1 weight ratio of C.₁₄ And C₁₆ Al Cole mixture. Furthermore, C₁₄ Ester and the mixture C₁₄/ C₁₆ Mixture with ester Can be used advantageously. In such a mixture, C₁₄ And C₁₄/ C₁₆ The ratio with 1: 1 to 4: 1, preferably 2: 1 to 7: 2, most preferably about 3: 1 (by weight). is there. Particularly preferred fumarate comb copolymers include, for example, gas phase osmometry (V Number average molecular weight measured by PO), 1,000 to 100,000, preferably 1,000 to 30,000 You can have it.   Other suitable comb polymers are polymers or copolymers of α-olefins, Esterified copolymers of styrene and maleic anhydride, and ethers of styrene and fumaric acid Sterilized copolymer. Mixtures of two or more comb polymers are also used in the present invention. And, as noted above, such use may be useful.   Other examples of comb polymers are hydrocarbon polymers, such as ethylene and Have at least one α-olefin, preferably at most 20 carbon atoms. Α-olefins, specifically n-decene-1 and n-dodecene-1 It's Mar. Preferably, the number average molecular weight of such polymers is at least 30, It is 000. This hydrocarbon copolymer can be prepared by known methods, for example, Ziegler type. It can be prepared using the catalyst of.Linear group of compounds   This compound includes at least one substantially organic compound having 10 to 30 carbon atoms. Has a linear alkyl group attached to the non-polymeric organic residue, At least one linear atom chain having an elementary atom and one or more non-terminal oxygen atoms And a compound that provides   "Substantially straight chain" means that the alkyl group is preferably a straight chain. Tastes, but has a small degree of branching, such as a single methyl group, essentially A straight chain alkyl group may be used.   Preferably, the compound is such that the straight chain has more than one carbon atom in the alkyl group. When it may have a number, it has at least two kinds of the alkyl groups. Compound If the product has at least 3 of the above alkyl groups, the chains may overlap. There may be more than one linear chain. Straight chain (including multiple straight chains) Form part of the linking group between any two alkyl groups in the compound.   Oxygen atoms (including multiple oxygen atoms) must be inserted directly between the carbon atoms in the chain. And, for example, a mono- or polyoxyalkylene group (oxyalkylene group Preferably has 2 to 4 carbon atoms, for example oxyethylene and oxyproton. It is pyrene).   As mentioned above, the chain (including the chains) comprises carbon and oxygen atoms. That The chains may contain other heteroatoms such as nitrogen atoms.   The compound may be an ester, in which case the alkyl group is —O—C. Bonded to the rest of the compound as an On-alkyl group or -CO-On-alkyl group doing. In the case of the former group, the alkyl group is derived from an acid and the compound The rest of the is derived from polyhydric alcohols. In the latter case, the alkyl group is Derived from rucor, the rest of the compound being derived from polycarboxylic acids. Also, In the compound, the alcohol is bonded to the rest of the compound as an -O-n-alkyl group. It may be an ester. This compound is both an ester and an ether. They may be present or may have different ester groups.   For example, polyoxyalkylene ester, ether, ester / ether, and And mixtures thereof. In particular, EP-A-61 895 and US Pat. At least one, and preferably at least one, as described in 4,491,455. Also having two kinds of C10 to C30 linear alkyl groups, and having a molecular weight of 5,0. Up to 00, preferably 200 to 5,000 polyoxyalkylene glycol ( The alkylene group in the polyoxyalkylene glycol has 1 to 4 carbon atoms. Are included).   The preferred esters, ethers or esters / ethers used are of the formula Structurally shown.                             R^{twenty three}OBOR^{twenty four} (In the formula, R^{twenty three}And R^{twenty four}Are the same or different and are the following groups.           (A) n-alkyl-           (B) n-alkyl-CO-           (C) n-alkyl-OCO- (CH₂)_n −           (D) n-alkyl-OCO- (CH₂)_n -CO- n is specifically 1 to 34, the alkyl group is linear and has 10 to 30 carbon atoms. And B is a polyalkene of a glycol whose alkylene group has 1 to 4 carbon atoms. Len moieties, such as substantially straight chain polyoxymethylene, polyoxyethylene or Indicates a polyoxytrimethylene moiety, which has a lower alkyl side chain to some extent. Branches (such as polyoxypropylene glycol) are acceptable but glycol is It should preferably be qualitatively linear. B may include nitrogen. )   Suitable glycols generally have a molecular weight of about 100 to 5,000, preferably about 20. Substantially linear polyethylene glycol (PEG) having from 0 to 2,000 and Lipropylene glycol (PPG). Esters are preferred and have 10 carbon atoms. Fatty acids with ~ 30 are effective in reacting with glycol to form ester additives And C₁₈~ C_{twenty four}Preference is given to using fatty acids, especially behenic acid. ester Esterifies polyethoxylated fatty acids or polyethoxylated alcohols It is also prepared by   Polyoxyalkylene diesters, diethers, ethers / esters and their Mixtures are suitable as additives, diesters have narrow petroleum-based components Preferred when boiling point distillate, in which case a small amount of monoether and monoester May be present (usually produced during the manufacturing process). Especially polyethylene Recall, polypropylene glycol or polyethylene / polypropylene glycol The stearic acid or behenic acid diesters of the alcohol mixture are preferred.   Examples of other compounds of this general class include Japanese Patent Publication Nos. 2-51477 and 3- 34790 and European Patent Applications 117,108 and 326,356 And cyclic esterified ethers as described in European Patent Application No. 356,266. It is xylate.Hydrocarbon polymer   An example is represented by the following general formula. (Where T = H or R¹         U = H, T or aryl         R¹ = C_1-30Hydrocarbyl, and v and w represent molar ratios, v is in the range of 1.0 to 0.0, and w is 0.0 to 1.0. Within the range of. )   These polymers can be derived directly from ethylenically unsaturated monomers or from isoprene and By hydrogenating polymers made from monomers such as Manufactured indirectly.   Preferred hydrocarbon polymers have a number average molecular weight of at least 30,000 Is a copolymer of ethylene and at least one α-olefin. That α-o Preferably the reffin has at most 20 carbon atoms. Such me Examples of fins are propylene, 1-butene, isobutene, n-octene-1, iso Octene-1, n-decene-1 and n-dodecene-1. Copolymer is low Amount of another copolymerizable monomer, eg up to 10% by weight, eg α-olefin. Other olefins and non-conjugated dienes may be included. Preferred polymers are It is a ethylene-propylene copolymer. Two or more different ethylenes of this type It is within the scope of the invention to include alpha-olefin copolymers.   Gel permeation chromatography relative to polystyrene standards, as indicated above. The number average molecular weight of the ethylene-α-olefin copolymer measured by At least 30,000, advantageously at least 60,000, preferably at least It is 80,000. There is no functional upper limit, but a high viscosity of about 150,000 or more Mixing becomes difficult, and the preferred molecular weight range is 60,000 and 80,000. 120,000.   Advantageously, the copolymer has a molar ethylene content of 50 to 85%. So It is more advantageous that the ethylene content in the range of 57 to 80%, preferably 58 to 7%. 3%, more preferably 62 to 71%, most preferably 65 to 70% .   A preferred ethylene-α-olefin copolymer has a molar ethylene content of 62-7. Ethylene-propylene with 1% and number average molecular weight 60,000 to 120,000 Copolymers, and particularly preferred copolymers have ethylene contents of 62-71% and Ethylene-propylene copolymer having a molecular weight of 80,000 to 100,000 It is.   Copolymers can be prepared by methods known in the art, for example using Ziegler type catalysts. Is prepared in. Since highly crystalline polymers are relatively insoluble in cold fuel oil, Advantageously, the mer is substantially amorphous.   The additive composition further advantageously has a high number average molecular weight as measured by the vapor phase osmometry. At least 7500, advantageously 1,000 to 6,000, preferably 2,000 to 5,000 An ethylene-α-olefin copolymer having 00 may be included. Suitable α- The olefin is the one shown above or styrene, with propylene being preferred. Echi Advantageously, the len content is 60-77 mol%, but ethylene-propylene In the case of copolymers, up to 86% by weight are advantageously used.   Examples of hydrocarbon polymers are described in International Application No. 9 111 488.Polar compound   Such compounds have the formula: NR¹(R¹ Is hydrocarbi having 8 to 40 atoms Represents a radical. ) Oil-soluble nitrogen compounds having one or more, preferably two or more substituents A substituent or one or more substituents is in the form of a cation derived therefrom. You may. Oil-soluble polar nitrogen compounds are ionic or nonionic and Can act as a wax crystal growth inhibitor. For example, the compound At least one of (i) to (iii) is included. (I) at least 1 mole of hydrocarbyl-substituted amine and 1 mole of carbo To react with hydrocarbyl acid having 1 to 4 acid groups or its anhydride Amine salt and / or amide produced by the formula, NR¹ The substituent is of the formula --NR¹ R²  (R¹ Is defined as above and R² Is hydrogen or R¹ Represents However, R¹ as well as R² May be the same or different. And the substituent is an amine salt of a compound And / or form part of the amide group.   Ester / A having 30-300, preferably 50-150, total carbon atoms Mid is used. These nitrogen compounds are described in U.S. Pat. ing. Suitable amines are usually long chain C₁₂-C₄₀Primary, secondary, tertiary or quaternary amine Or a mixture thereof, but if the obtained nitrogen compound is oil-soluble, a short-chain amine is also used. Therefore, it usually has about 30 to 300 total carbon atoms. Nitrogen compounds are low At least one straight chain C₈~ C₄₀, Preferably C₁₄~ C_{twenty four}Having an alkyl moiety Is preferred.   Suitable amines include primary, secondary, tertiary or quaternary amines, but secondary Amine is preferred. Tertiary and quaternary amines are capable of forming amine salts. Only. Examples of secondary amines include dioctacedylamine and methylbehenyl. Examples include amines. Mixtures of amines derived from natural substances are also suitable. Preferred The new amine has the formula HNR¹ R²(R¹ And R² Is about 4% C₁₄, 31% C₁₆5, 9% C₁₈Is an alkyl group derived from hydrogenated animal fat. )of It is a secondary hydrogenated tallow amine.   Examples of suitable carboxylic acids and their anhydrides for the preparation of nitrogen compounds are: Chlorohexane 1,2-dicarboxylic acid, cyclohexene 1,2-dicarboxylic acid, cyclo Pentane 1,2-dicarboxylic acid and naphthalene dicarboxylic acid and dialkyl spiro An example is 1,4-dicarboxylic acid containing bislactone. Usually these acids are cyclic The portion has about 5 to 13 carbon atoms. Preferred acids useful in the present invention are phthalates Acids, benzenedicarboxylic acids such as isophthalic acid and terephthalic acid. lid Acid or its anhydride is particularly preferred. A particularly preferred compound is 1 mole of phthalic acid. Amine produced by reacting an anhydride with 2 moles of dihydrogenated tallow amine. It is a do-amine salt. Other preferred compounds dehydrate this amide-amine salt. The resulting diamide.   Other examples are long chain alkyl or alkylene substituted dicarboxylic acid derivatives such as The amine salt of the monoamide of modified succinic acid, examples of which are known in the art. See, for example, US Application No. 4 147 520. Suitable amines are listed above It is the one described.   Other examples are condensates as described in European Patent Application No. 327.423. (Ii) a chemical compound containing a cyclic ring system, which compound has the formula (I) It has at least two substituents.                             -A-NR¹ R2 (I) (In the formula, A is a linear or branched chain which may be optionally interrupted by one or more heteroatoms. R is an aliphatic hydrocarbyl group of¹ And R² Are the same or different, each independent And having 9 to 40 carbon atoms which may be interrupted by one or more heteroatoms. A dolocavir group, wherein the substituents are the same or different and the compound is optionally a salt thereof. It may be in the form of. )   A has 1 to 20 carbon atoms and is preferably a methylene or polymethylene group. Preferably.   As used herein, "hydrocarbyl" refers to a carbon directly attached to the residue of a molecule. It means a radical having elementary atoms and having hydrocarbon or predominantly hydrocarbon character. Examples include aliphatic groups (eg alkyl or alkenyl), alicyclic groups (eg , Cycloalkyl or cycloalkenyl), aromatic groups, and alicyclic substituted aromatic groups , And hydrocarbon groups including aromatic substituted aliphatic groups and alicyclic groups. Aliphatic The groups are advantageously saturated. These groups are based on the presence of non-hydrocarbon substituents. It may be included if it does not change the main properties of the hydrocarbon. As an example, Keto, Included are halo, hydroxy, nitro, cyano, alkoxy and acyl. Hide If the locarbyl group is substituted, a single (mono) substituent is preferred.   Examples of the substituted hydrocarbyl group include 2-hydroxyethyl and 3-hydroxy. Propyl, 4-hydroxybutyl, 2-ketopropyl, ethoxyethyl and pro Examples include poxypropyl. Also, those groups may be atoms or non-carbon atoms in the chain. May have a ring composed of carbon atoms. Examples of suitable heteroatoms include Examples include nitrogen, sulfur and preferred oxygen.   As the cyclic ring system, a homocyclic group, a heterocyclic group, a condensed polycyclic group or such Examples include systems in which two or more cyclic groups are bonded to each other and the cyclic groups may be the same or different. Can be When there are two or more such cyclic groups, are the substituents of general formula (I) the same? Or they are on different groups, preferably on the same group. The or each cyclic group is preferably Is aromatic, more preferably a benzene ring. More preferably, the cyclic ring system is a single When the substituent is preferably in the ortho or meta position, The benzene ring may be optionally further substituted.   The ring atom in the cyclic group is preferably a carbon atom, but is, for example, N, S or O. One or more ring atoms may be included, in which case the compound is a heterocyclic compound.   Examples of such polycyclic groups include: (A) Condensed benzene structure, for example, naphthalene, anthracene, phenanthrene And pyrene; (B) all rings or fused ring structures in which all of the rings are not benzene, such as azulene, Indene, hydroindene, fluorene and diphenylene oxide; (C) a "tip-forward" linked ring, eg, diphenyl; (D) Heterocyclic compounds such as quinoline, indole, 2,3-dihydroin Dole, benzofuran, coumarin, isocoumarin, benzothiophene, carbazo And thiodiphenylamine; (E) Non-aromatic or partially saturated ring systems such as decalin (ie decahi) Dronaphthalene), α-pinene, cardinene and bornylene; and (F) Three-dimensional structure, for example, norbornene, bicycloheptane (that is, norbornene Nan), bicyclooctane and bicyclooctene.   In the present invention, R¹ And R² Each hydrocarbyl group (formula I) that comprises For example, an alkyl group or an alkylene group or a mono- or polyalkoxyalkyl group is there. Each hydrocarbyl group is preferably a straight chain alkyl group. Each hydrocar The number of carbon atoms of the rubyl group is preferably 16 to 40, more preferably 16 to 24 is there.   Also, the cyclic system is substituted with only two substituents of general formula (I) and A is a methylene group. Preferably, there is.   Examples of salts of chemical compounds are acetate and hydrochloride.   The compound is prepared by reacting a secondary amine with the appropriate acid chloride. Conveniently it is prepared by reduction of the corresponding amide. (Iii) A condensate of a long-chain primary or secondary amine and a carboxylic acid-containing polymer.   Specific examples include UK application No. 2,121,807 and French application No. 2,592,387. And polymers as described in German Application No. 3,941,561; and US applications Of teremic acid and alkanolamines as described in 4,639,256. Ter; and branched chain carboxylic acid esters such as those described in U.S. Application No. 4,631,071. The reaction product of the amine and episode including the stele and the monocarboxylic acid polyester No.Carboxyl sulfide compound   An example is disclosed in EP 0261957. Fuel oil   The fuel oil is preferably middle distillate fuel oil. Such distilled fuel oils are generally Boiling in the range of about 110 to about 500 ° C, for example 150 to about 400 ° C. The fuel oil is atmospheric steam Distillation or vacuum distillation, or cracked gas oil or straight distillation and heat and / or catalyst cracking Mixtures of any proportion of the distilled distillate can be included. Most common petroleum distillate The output fuel is kerosene, jet fuel, diesel fuel, heating oil and And heavy fuel oil. The heater oil can be straight run atmospheric distillation, or Contains a small amount, for example 35% by weight or less of vacuum gas oil or cracked gas oil, or both can do.   The fuel oil can be animal, vegetable or mineral oils and is further synthesized Can be something. Similarly, additives other than the above may be contained.   The concentration of the additive combination in the oil is, for example, 1 additive per weight of fuel. ~ 5000ppm (active ingredient), for example 10 to 2000ppm (active ingredient) per fuel weight By weight, etc., preferably 25 to 500 ppm, more preferably 100 to 200 ppm. Yes.   The additive does not dissolve in the oil at room temperature in an amount of at least 1000 ppm based on the weight of the oil. I have to. However, in order to modify the shape of the wax crystals, the additive At least some of the oil may precipitate out of solution near the cloud point of the oil.   Concentrates are a means of adding the aforementioned additives to large quantities of oil such as distilled fuel. Conveniently, this addition can be done by methods known in the art. Wear. This concentrate may also contain other necessary additives, preferably oil. In the solution, preferably 3 to 75% by weight, more preferably 3 to 60% by weight of the additive, Most preferably, it can be contained at 10 to 50% by weight. Examples of liquid carriers are eg naphtha , Petroleum fractions such as kerosene and heater oil, hydrocarbon solvents; aromatic fractions (eg Aromatic hydrocarbons, including Solveso (trade name); and hexane and pentane And organic solvents containing paraffin hydrocarbons such as isoparaffin, and the above Including a mixture of. Of course, this liquid carrier must be compatible with the additive and the fuel. But To be selected.   The additives of the present invention can be added by other methods such as are known in the art. , Can be added to large amounts of oil. If others are needed, these are large amounts of oil Can be added at the same time as the additives of the present invention or at different times. Other additions Examples of agents include antioxidants, corrosion inhibitors, dehazars, metal deactivators, Cosolvents, package compatiblisers, fragrances, antistatic agents (conductivity enhancing Strong agents), biocides, dyes, smoke reducers, catalyst enhancers (catalyst life en hancers) powder boosters, additives for fuel economy, demulsifiers and injections It is reformation. Example   The following examples explain the invention in detail.Additive   The following additives as defined by the above reference code were used: B1: number average molecular weight measured by gel permeation chromatography (GPC) of 3,300 And an ethylene-vinyl acetate copolymer containing about 36% by weight vinyl acetate. B2: The number average molecular weight measured by GPC is 5,000 and vinyl acetate is about 13.5 weight. % Ethylene-vinyl acetate copolymer. B3: Mixture of additives B1 and B2 with a weight ratio (B1: B2) of 3: 1. A1: Pentaethylenehexamine [NH₂(CH₂)₂NH (CH₂)₂NH (CH₂)₂NH (CH₂)₂NH₂] Polyethylene amine and tetraethylene pentaamine are commercially available A mixture of anhydrous isobutylene substituted with polyisobutylene (MW 950) Polyisobutylene succinic anhydride acylated by humic acid-polyamine Producing product. A2: Acylation, as described in EP 525052, such that subsequent cyclization occurs. A polyisobutylene (MW 950) substituted no Water succinic acid and formula NH₂(CH₂)_ThreeNH (CH₂)₂NH (CH₂)_ThreeNH₂Obtained by reaction with Macrocycle. A3: Formula R-O- (CH, as disclosed in U.S. Patent Publication No. 4319987.₂)_ThreeNH₂ (Where R is 1 More than one iso-C_TenIt is an alkyl group. ) Is an ether amine. A4: octyl cetane nitrate improvement, known in the art and commercially available Agent. A5: Dilinoleic acid (C₃₆ Dimer acid) And ethylene glycol, as well as methanol and the group of neutralizing acids. The ester obtained by the reaction of. A6: Ethoxylated cocoamine commercially available as ARMAK 1282 . A7: NH disclosed in International Patent Publication No. WO94 / 06894₂(C₂H_Four) NH (C₂H_Four) 1 mole of OH , Slightly more than 2 moles of two linear alkanol acids with 12 and 14 carbon atoms respectively The product formed by the reaction with. C: 2-N¹, N¹-N, N-dialkylammonium salt of dialkylamidobenzoate So, this is the reaction between 1 mol of phthalic anhydride and 2 mol of dihydrogenated tallow amine The resulting half-amide / half-amine salt.fuel A fuel with the following characteristics was used: Key Point ・ All numbers are in ° C. Distillation characteristics are ASTM D-86 (IBP and FBP are the first and last boiling points, respectively) . ). -CP is the cloud point measured according to IP 219/82. ・ CFPP is a cold filter plugging point, and SFPP is a simulated filter. This is the plugging point (see "Test" below for details).test   Additives were dissolved in the above fuels and the following tests were performed on the fuels treated with the additives. Of the additives tested as filterability modifiers for distilled fuel. The following was measured to evaluate the effect. Simulated filter plugging point (SFPP)   This test is performed essentially by the method disclosed in EP-0404037. , This was a modification of the CFPP test. Cold filter plugging point test (or CFPP test)   This test details the “Petroleum Agency Journal”52 (510):173-285 (June) on (1966) By the method described, this is a cold stream of Nakadome in a car diesel. Designed to correlate with   Briefly, the oil sample tested (40 ml) was cooled in a bath maintained at about -34 ° C. Then, nonlinear cooling was performed at about 1 ° C./min. Intermittently (each temperature above the cloud point The cooled oil should be placed in the opposite direction, below the surface of the oil to be tested. Use a test device that is a pipette such that the Tested for ability to flow through paddle screen. The mouth of this funnel is Covered by a 350 mesh screen with an area such as a diameter of 12 mm You. Cyclic testing is performed by connecting the top of each pipette to a vacuum. Start, which allows the oil to pass through the screen until the mark indicating 20 ml of oil is reached. I was sucked by my pet. After success, the oil was quickly refluxed into a CFPP tube. This Test every 1 ° C until oil is unable to fill the pipette within 60 seconds The temperature that could not be satisfied was recorded as the CFPP temperature.result Key Point -△ SFPP and △ CFPP are the basic fuel SFPP (or CFPP) and that of the tested fuel. Represents the difference between. ・ The number below the component code is the treatment amount of ppm active ingredient per fuel weight. * Indicates the result of the combination of additives of the present invention. -Dash indicates that no value was obtained.   In the above results, the part in which the "B" component is replaced with the "A" component is the filtration of the fuel. It has been shown to either increase the severity or not to cause adverse effects. Further These provide the desired filtration rate and the "A" component itself provides beneficial properties. What to bring about by the combination of the present invention, which uses less and less "B" component I showed that you can.   The additive combination of the present invention also reduces the tendency of wax to settle in the fuel. Have a decreasing effect (ie they can be wax anti-sedimentation additives). Wear. ), And an extended programmed cooling test known in the art. (XPCT), which can be active in the slow cooling test.Another embodiment   Ingredients BX and BY were used, each having the following composition: BX: B2 (56ppm)     B1 (169ppm)     7 (75ppm)     C (75ppm) BY: B2 (50ppm)     3 (100ppm)     6 (100ppm)     C (199ppm)     5 (200ppm)   In the test described below, the concentrations of constituents of the components BX and BY in the fuel are The weight of the material is shown in parentheses. The structure defined in the above numbers 3 and 5, 6, and 7 The components are: 3: Ethylene having a number average molecular weight of 3300 by GPC and containing 36% vinyl acetate -Vinyl acetate copolymer. 5: Polymerization of monomers using cyclohexane as a solvent using a free radical catalyst Prepared by, the monomer containing a linear alkyl group having 18 carbon atoms, measured by GPC Itaconic acid polymer having a number average molecular weight of about 4000. 6: of styrene and fumaric acid having an esterified C14 alkyl group A copolymer having a number average molecular weight of 15,000 as measured by GPC, A ratio of len and esterified fumaric acid of 1: 1 (mol: mol). 7: Fumaric acid ester-acetic acid vinyl ester having a number average molecular weight of 20000 measured by GPC In a nyl copolymer, the fumaric acid ester has a linear alkyl group with 12-14 carbon atoms. What to do.   In addition, component AY was used containing: ・ Polyamine-modified polyisobutylene succinic anhydride detergent (200ppm) ・ Octyl cetane nitrate improver (240ppm) ・ Ethoxylated nonylphenol rust inhibitor (20ppm) ・ Silicon-containing defoamer (12.5ppm) ・ Fragrance (80ppm) ・ Isodecanol (47.5ppm) ・ "Solveso" 150 (385ppm) -Aromatic diluent ・ Primary demulsifier (5ppm) ・ Second demulsifier (10ppm)   In the test described below, the concentration of the constituents of the component AY in the fuel is the weight of the fuel. The amount is shown in parentheses. fuel The following fuels were used: Key Point ASTM D-86 FPB and IBP are fuel and initial boiling point. CP is measured according to IP 219/82.result   The results of the SFPP test are shown in the table below:   The SFPP difference is calculated using the component BX (or BY) alone, as well as the component BX (or BY) and And the SFPP obtained when component AY was used together. This result is Min AY was shown to enhance SFPP in 3 of 4 cases.

────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Lombardy Alessandro             UK O-X13 5 QUV               Oxfordshire Abingdon             Tabney Wood The Ride 2 (72) Inventor Goberdan Dansh Gordon             British O-X 26 Debbie               Oxford King Street               Guy Court 22

Claims (1)

[Claims] 1. Use of a co-additive selected from component (A) containing one or more of the following: (a) Hydrocarbyl-amine acylated with a carboxyacylating agent, or hydrocarbylated, or hydrocarboxylated Oil-soluble ashless dispersion cleaner containing: (b) a carboxylic acid having 2 to 50 carbon atoms and an ester of an alcohol having one or more carbon atoms, an oil-soluble lubricating additive An agent; (c) an oil-soluble nitric acid or cetane improver; and (d) a silicon-based composition or at least one primary or secondary amino group acylated with a carboxylic acylating agent. An oil-soluble petroleum fuel defoamer containing polyamines having a proportion of a large proportion of fuel oil and a small proportion of a cold flow improver including a copolymer ethylene flow improver. (B) The use in the composition having the ingredients to enhance the cold flow properties of the composition, the use of co-additives. 2. The use according to claim 1, wherein the component (A) contains a polyamine acylated with a hydrocarbyl polycarboxyacylating agent. 3. The use according to claim 2, wherein the component (A) contains an alkenylsuccinimide polyamine. 4. Use according to claim 3, wherein the alkenyl group is polyisobutylene. 5. The use according to any one of claims 1 to 4, wherein the component (A) contains at least one ester of a trihydric alcohol and a saturated or unsaturated carboxylic acid. 6. Use according to claim 5, wherein the ester is glycerol monooleate. 7. Use according to any one of claims 1 to 6, wherein the component (A) contains octyl nitrate. 8. Use according to any one of claims 1 to 7, wherein the component (B) contains an ethylene / unsaturated ester copolymer. 9. Use according to claim 8, wherein the unsaturated ester is an ester of an unsaturated alcohol with a saturated carboxylic acid. Ten. Furthermore, as a co-additive, an oil-soluble polar nitrogen compound having one or more substituents having the formula —NR ¹ — (wherein R ¹ represents a hydrocarbyl group having 8 to 40 carbon atoms) is contained. However, one or more of said substituents or substituents may optionally be in the form of cations derived therefrom, according to any one of claims 1-9. use. 11. Use according to any one of claims 1 to 10, wherein the fuel oil is middle distillate fuel oil. 12. The total concentration of components (A) and (B) in the fuel oil is in the range of 25 to 500 ppm of active ingredient per weight of fuel oil, according to any one of claims 1 to 11. use. 13. A method of adding an additive to a fuel oil, comprising the steps of: (i) injecting the component (B) according to claim 1 into the fuel oil; (ii) the component (A) according to claim 1. Injecting into the fuel oil; (iii) measuring the low temperature fluidity of the fuel oil after injecting the steps (i) and (ii); and (iv) the component (B) and the component (A). Adjusting the relative rates of injection of the, and thereby their relative properties, which are considered the result of step (iii), to provide the fuel oil with the desired low temperature fluidity. 14. 14. The method of claim 13, wherein the fuel oil has its flow such that step (i) is performed at a first location and step (ii) is performed at a second location. 15. 15. A method according to claims 13 and 14 wherein the sensor performs step (iii) and the information is provided to a controller for controlling the injection of both components (B) and (A).