RU2108368C1 - Composition and method of modifying growth of paraffin crystals - Google Patents

Abstract

FIELD: growing crystals. SUBSTANCE: one or more additives are used to modify properties of growth of paraffin crystals in oils originated from animal or vegetable material. EFFECT: enabled crystal structure control. 11 cl, 1 tbl

Description

 The invention relates to the use of additives that modify paraffin crystals in oils derived from animal or plant material, or from mixtures thereof, or their derivatives.

где
R обозначает алифатический радикал с 10-25 атомами углерода, который может быть насыщенным или ненасыщенным.Oils derived from animal or plant material are mainly metabolites, including triglycerides of monocarboxylic acids, for example, acids containing 10-25 carbon atoms and having the form:

Where
R denotes an aliphatic radical with 10-25 carbon atoms, which may be saturated or unsaturated.

 Typically, such oils contain glycerides of a number of acids, their number and type vary depending on the source of the oil, and they may additionally contain phosphoglycerides. Such oils can be obtained by methods known in the art.

 Examples of derivatives of such oils are alkyl esters, such as methyl esters of fatty acids of vegetable or animal oils. Such esters can be obtained by transesterification.

 A reference in this specification to oils that are derived from animal or plant material includes a reference to both oils derived from said animal or plant material, or from both of these materials, and their derivatives.

French Patent A-2492402 describes fuel compositions containing one or more animal and vegetable derived fatty acid esters described by the general formula
R ¹ -COO-R ² ,
in which R ¹ contains 5-23 carbon atoms and is an almost linear saturated or unsaturated aliphatic radical, and R ² contains 1-12 carbon atoms and is a linear or branched saturated or unsaturated aliphatic radical. Such fuel compositions are described as being particularly suitable for use in diesel engines, while having a range of cetane numbers substantially equivalent to the range of conventional diesel fuels made from mineral oils (petroleum products).

However, the usefulness of such fatty acid ester compositions as diesel fuels is limited by their properties at low temperatures. German patent A-4040317 describes that, at temperatures below -5 ^° C, such fuels can solidify in feed lines due to insufficient filterability, and it describes a method for improving filterability at low temperatures, including a mixture of methyl esters of fatty acids with short chain and selected polymeric materials, in particular polymers of esters or copolymers of esters of acrylic and / or methacrylic acids, derivatives of alcohols containing 1-22 carbon atoms.

 Properties at low temperature of oil-based petroleum products, i.e. mineral oils and their derivatives, such as crude oil, lubricating oil and fuel oil, for example, middle distillate fuel oil, are known in the art. It is known to use additives to modify the structure of paraffin crystals of these petroleum products and their derivatives. Examples of such additives and their use are described in US patents A-3048479, Great Britain A-1263152, USA A-3961916, USA A-4211534, in European patents A153176 and A-153177. They are sometimes called "Cold Flow Additives." A compilation of posts published by P.H. Ogden, Esq. Chemicals in the Oil Industry, which documents the proceedings of a symposium organized by the Royal Chemical Society and held at the University of Manchester on March 22-23, 1983, describes on page 112 how certain alkyl-containing regions of the molecular structure of such additives are believed to be similar on linear saturated hydrocarbon chains of heavier n-alkane molecules (paraffin), usually present as minor in the number of components of these oils. In addition, due to these structural similarities, such additives are believed to interfere with the crystallization of these n-alkanes into plate-like crystals, since they precipitate from a solution in oil at low temperatures. The additives thus modify the size and shape of the paraffin crystals and reduce the adhesion forces between the crystals and between the paraffin and the oil in such a way as to allow the oil to remain fluid at a lower temperature and pass through the coarse filters.

 In contrast to these petroleum products and their derivatives, the low temperature properties of the oils of the present invention, which are oils derived from animal and plant material, are mainly controlled by the precipitation of higher molecular weight fatty acid esters present as main components. Such fatty acid esters are often derived from mixtures of saturated and unsaturated fatty acids.

В общем такие ненасыщенные производные жирных кислот преобладают над их насыщенными аналогами, хотя точные пропорции отдельных компонентов в составе конкретного масла могут изменяться в результате сезонных колебаний жирных кислот в компоненте в составе материала-источника, или в результате конкретного способа, с помощью которого они получены.The main components of rapeseed oil methyl ester are:

In general, such unsaturated derivatives of fatty acids prevail over their saturated analogues, although the exact proportions of the individual components in a particular oil may vary as a result of seasonal fluctuations in the fatty acids in the component in the source material, or as a result of the specific method by which they are obtained.

 This predominance of ethylenically unsaturated esters of fatty acids provides the production of oils whose crystallization behavior differs from the behavior of the aforementioned oil products, and it is believed that the difference in the morphological structures of crystals between these two classes of oil is the result of different structural configurations of the hydrocarbon chains deposited n alkanes and esters of unsaturated fatty acids, respectively.

 It has been found that some additives acting as additives modifying paraffin crystals in petroleum products and their derivatives are also effective as additives modifying paraffin crystals in oils derived from animal or plant material, despite their apparent lack of structural similarity with respect to ethylene unsaturated hydrocarbon chains.

 The object of the invention is a composition containing, as a basis, animal or vegetable oil, which further comprises an additive that improves cold flow, selected from the group comprising one or more of the following substances: comb polymer; ester, ester / polyoxyalkylene ether or a mixture thereof; ethylene / unsaturated ester copolymer; a polar organic nitrogen-containing paraffin crystal growth inhibitor, a hydrocarbon polymer, sulfur-containing carboxyl compounds, an alkyl aromatic depressant, with the exception of mixtures of polymer esters or copolymers of esters of acrylic and / or methacrylic acid and alcohols containing 1-22 carbon atoms.

где
n = 1-30; алкильная группа является линейной и насыщенной и содержит 10-30 атомов углерода, A - обозначает сегмент полиоксиалкилена с мол. м. 100-5000, где алкиленовая группа имеет 1-4 атомов углерода.Moreover, the specified ester, ester / ether of polyoxyalkylene or a mixture thereof are characterized by the formula RO- (A) -OR ² , where R and R ^{2 are the} same or different and can mean:

Where
n is 1-30; the alkyl group is linear and saturated and contains 10-30 carbon atoms, A - denotes a polyoxyalkylene segment with a mol. m. 100-5000, where the alkylene group has 1-4 carbon atoms.

 It is advisable to use an amine salt and / or amide obtained by reacting at least one mole of a hydrocarbon-substituted amine with at least one mole of a hydrocarbonic acid or its anhydride having 1-4 carboxyl groups, preferably benzenedicarboxylic acid, as the indicated polar organic nitrogen-containing paraffin crystal growth inhibitor. or its anhydride. Moreover, it is preferable that the basis of the claimed composition is biofuel, which, in turn, is a vegetable oil or its derivative.

 The specified biofuel is selected from the group consisting of rapeseed oil, cottonseed oil, soybean oil, sunflower oil, olive oil, palm oil or their complex alkyl ether derivatives; for example, biofuel is a rapeseed oil methyl ester.

 Biofuels may contain a mixture of vegetable oils and / or a mixture of their copolymers.

 Another object of the invention is a method of modifying the growth of paraffin crystals in animal or vegetable oil, which consists in mixing the oil with an additive selected from the group comprising one or more of the above substances. In the inventive method, the oil is biofuel.

Thus, the present invention claims a composition containing a large part of the oil, consisting mainly of such oil, which is obtained from animal or plant material, in a mixture with a smaller part of the additive containing one or more of the following substances:
(I) comb polymer;
(Ii) a polyoxyalkylene ester, an ester / ether or a mixture thereof;
(Iii) an ethylene unsaturated ester copolymer;
(Iv) a polar organic nitrogen-containing paraffin crystal growth inhibitor;
(V) a hydrocarbon polymer, and
(VI) sulfur-containing carboxyl compounds;
(Vii) an alkyl aromatic depressant,
provided that the composition does not contain mixtures of polymeric esters or copolymers of esters of acrylic and / or methacrylic acid and alcohols having 1-22 carbon atoms.

 Oils. Examples of oils derived from animal or plant material are rapeseed oil, coriander oil, soybean oil, cottonseed oil, sunflower oil, castor oil, olive oil, peanut oil, corn oil, palm oil, coconut oil, mustard oil, beef animal oil and fish oil. Additional examples include oils made from cereal, jute, sesame, walnut, peanut and flaxseed, and they can be obtained from them using methods known in the art. Rapeseed oil, which is a mixture of fatty acids partially esterified with glycerin, is preferred because it is available in large quantities and can be obtained simply by squeezing from rapeseed.

 The following can be considered as lower alkyl fatty acid esters, for example, as commercially available mixtures: ethyl, propyl, butyl and, in particular, methyl esters of fatty acids with 12-22 carbon atoms, for example, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroselic acid, ricinoleic acid, eleostearic acid, linoleic acid, linolenic acid, eicosanoic acid, g adoleic acid, docosanoic acid or erucic acid, which have an iodine number of 50-150, in particular 90-125. Mixtures with particularly preferred properties are those which mainly contain, for example, at least 50 wt.% Methyl esters of fatty acids with 16-22 carbon atoms and 1, 2 or 3 double bonds. Preferred esters of lower fatty acid alkyls are methyl esters of oleic acid, linoleic acid, linolenic acid and erucic acid.

 Commercially available mixtures of this type of acid are obtained, for example, by cleavage and esterification of animal and vegetable fats and oils by transesterification with lower aliphatic alcohols. To obtain low-alkyl esters of fatty acids, it is advisable to start the process with fats and oils with a high iodine number, such as, for example, sunflower oil, castor oil, soybean oil, cottonseed oil, peanut oil or beef tallow. Low alkyl fatty acid esters based on a new variety of rapeseed oil, the fatty acid component of which is derived from more than 80% by weight of unsaturated fatty acids with 18 carbon atoms, are preferred.

 Oils suitable for use as biofuel are particularly preferred according to the invention. Biofuels, i.e. fuels made from animal and plant material are believed to be less harmful to the environment when burned, and are obtained from a renewable source. It is known that less carbon dioxide is formed during combustion than with the equivalent amount of distillate fuel from oil, for example diesel fuel, and very little sulfur dioxide is formed. Some derivatives of vegetable oil, for example, obtained by saponification and transesterification using monohydroxy alkyl alcohol, can be used as a substitute for diesel fuel. It is known that mixtures of rapeseed ester, for example rapeseed oil methyl ester (RME), with distillate fuels from oil in ratios of, for example, 10:90 by volume, are likely to be available for sale in the near future.

 Thus, biofuel is an oil obtained from plant or animal material, or from a mixture thereof, or is derived from it, suitable for use as fuel.

 While many of the above oils can be used as biotypes, vegetable oils or derivatives thereof are preferred, of which rapeseed oil, cottonseed oil, soybean oil, sunflower oil, olive oil, palm oil or derivatives thereof are particularly preferred. an alkyl ester form, with rapeseed oil methyl ester being most preferred.

 The concentration of the additive in oil can be, for example, in the range of 1-10000 per million additives (active ingredient) by weight of the fuel, for example, 10-5000 parts per million or 10-2000 parts per million (active ingredient) by weight by weight of fuel, preferably from 25-500 ppm, more preferably 100-200 ppm.

 The additive or additives must be soluble in oil to a level of at least 1000 ppm by weight of the weight of the oil at ambient temperature. However, at least some of the additive may leave the solution at a temperature near the cloud point of the oil in order to modify the resulting paraffin crystals.

 The additive may be included in the oil volume using methods known in the art. When more than one added component or additional additive component is to be used, such components may be added to the oil together or separately in any combination.

 A concentrate containing an additive dispersed in a carrier fluid (e.g., in solution) is a convenient means of administering the additive. The concentrates of the invention are a convenient means of introducing an additive into a volume of oil, such as a distillate fuel, which introduction can be carried out using methods known in the art. The concentrates may also contain other desired additives, and preferably contain 3-75 wt.%, More preferably 3-60 wt.%, Most preferably 10-50 wt.% Additives, preferably in an oil solution. Examples of a carrier fluid are organic solvents, including hydrocarbon solvents, for example, petroleum fractions such as heavy gasoline, kerosene, diesel fuel and fuel for heaters; aromatic hydrocarbons, such as aromatic fractions, for example, sold under the brand name "SOLVESSO"; and paraffin hydrocarbons such as hexane and pentane and isoparaffins. Naturally, the carrier fluid should be selected taking into account its compatibility with the additive and with the fuel.

 The additives of the invention can be introduced into the oil volume using other methods known in the art. If additional additives are required, they can be added to the oil at the same time as the additives of the invention or at other times.

 Preferred additives according to various embodiments of the present invention are described below.

 (I) Comb polymers.

 Comb polymers are polymers in which hydrocarbyl groups "hang" from the polymer backbone and are described in Comb-Like Polymers. Structure and Properties, N. A. Plate and V. P. Shhibaev, J. Poly. Sci. Macromolecular Revs., 8, p. 117 to 253 (1974).

 It is advisable that the comb polymer was a homopolymer having side chains containing at least 6 and preferably at least 10 carbon atoms, or a copolymer having at least 25, and preferably at least 40, more preferably at least 50 pier % of units having side chains containing at least 6 and preferably at least 10 carbon atoms.

где
D = R¹¹, COOR¹¹, OCOR¹¹, R¹²COOR¹¹ или OR¹¹,
E = H, CH₃, D или R¹²,
C = H или D,
J = H, R¹², R¹²COOR¹¹ или арильную или гетероциклическую группу,
K = H, COOR¹², OCOR¹², OR¹² или COOH,
L = H, R¹², COOR¹², OCOR¹² или арил,
R¹¹ ≥ гидрокарбил C₁₀,
R¹² ≥ гидрокарбил C₁,
m и n обозначают молярные концентрации, при этом m находится в диапазоне 1,0-0,4; n находится в диапазоне 0-0,6. Преимущественно R¹¹ обозначает гидрокарбильную группу с 10-30 атомами углерода, а R¹² - гидрокарбильную группу с 1-30 атомами углерода.As examples of preferred comb polymers, polymers of the general formula may be mentioned.

Where
D = R ¹¹ , COOR ¹¹ , OCOR ¹¹ , R ¹² COOR ¹¹ or OR ¹¹ ,
E = H, CH ₃ , D or R ¹² ,
C = H or D,
J = H, R ¹² , R ¹² COOR ¹¹ or an aryl or heterocyclic group,
K = H, COOR ¹² , OCOR ¹² , OR ¹² or COOH,
L = H, R ¹² , COOR ¹² , OCOR ¹² or aryl,
R ¹¹ ≥ hydrocarbyl C ₁₀ ,
R ¹² ≥ hydrocarbyl C ₁ ,
m and n denote molar concentrations, while m is in the range of 1.0-0.4; n is in the range 0-0.6. Advantageously, R ¹¹ is a hydrocarbyl group with 10-30 carbon atoms, and R ¹² is a hydrocarbyl group with 1-30 carbon atoms.

 The comb polymer may contain units derived from other monomers, if desired or is desired. The inclusion of two or more comb polymers is within the scope of this invention.

 These comb polymers can be copolymers of maleic anhydride or fumaric acid and another ethylenically unsaturated monomer, for example, an α-olefin or an unsaturated ester, for example vinyl acetate. It is preferred, but not necessary, to use equimolar amounts of comonomers, although molar proportions in the range of 2: 1 and 1: 2 are suitable. Examples of olefins that can be copolymerized, for example, with maleic anhydride, include 1-decene, 1-dodecene, 1 -tetradecene, 1-hexadecene and 1-octadecene.

This copolymer can be esterified using any suitable method and it is preferable, but not necessary, that maleic anhydride or fumaric acid is esterified by at least 50%. Examples of alcohols that can be used include n-decan-1-ol, n-dodecan-1-ol, n-tetradecan-1-ol, n-hexadecan-1-ol and n-octadecan-1-ol. These alcohols may also include up to one methyl branch per chain, for example 1-methylpentadecan-1-ol, 2-methyltridecan-1-ol. This alcohol may be a mixture of normal and unbranched methyl alcohols. Pure alcohols are preferred rather than alcohol mixtures available on the market, but if mixtures are used, then R ¹² is the average number of carbon atoms in the alkyl group; if alcohols that have a branching in 1 or 2 position are used, R ¹² denotes a straight chain segment of the main chain of the alcohol.

 These comb polymers can, in particular, be fumarate or itaconate polymers and such copolymers, such as, for example, those described in European Patent Applications 153176; 153177 and 225688, as well as in WO 91/16407.

The most preferred fumarate-based comb polymers are alkyl fumarate and vinyl acetate copolymers in which the alkyl groups have 12-20 carbon atoms, in particular polymers in which the alkyl groups have 14 carbon atoms or in which the alkyl groups are a mixture of C ₁₄ / c _16, obtained, e.g., by copolymerization in a solution of an equimolar mixture of fumaric acid and vinyl acetate and reacting the resulting copolymer with the alcohol or mixture of alcohols, which are the n edpochtitelno straight-chain alcohols. When using the mixture, it is advisable that it was a 1: 1 mixture by weight of normal alcohols C ₁₄ and alcohols C ₁₆ . Moreover, it is advisable to use mixtures of C ₁₄ ester with mixed C ₁₄ / C ₁₆ ester. In such mixtures, it is advisable to have a ratio of C ₁₄ to C ₁₄ / C ₁₆ in the range from 1: 1 to 4: 1, preferably from 2: 1 to 7: 2, and most preferably about 3: 1 by weight. The most preferred fumarate-based comb polymers may, for example, have a number average molecular weight in the range of 1000-100000, preferably 1000-30000, as measured by vapor phase osmometry (OPF).

 Other suitable comb polymers are polymers and copolymers of α-olefins and esterified copolymers of styrene and maleic anhydride, and esterified copolymers of styrene and fumaric acid; mixtures of two or more comb polymers can be used according to this invention, and, as indicated above, such use may be appropriate.

 (II) Polyoxyalkylene compounds.

Examples of polyoxyalkylene compounds are esters, esters / esters of polyoxyalkylene and mixtures thereof, in particular containing at least one, preferably at least two linear saturated alkyl groups C ₁₀ -C ₃₀ and a polyoxyalkylene glycol group per mol. m up to 5000, preferably 200-5000, while the alkyl group in the specified polyoxyalkylene glycol contains 1-4 carbon atoms. These materials are the subject of European Patent Publication 0 061 895 A2. Other such additives are described in US Pat. No. 4,491,455.

где
n обозначает, например, 1-30, при этом алкильная группа является линейной и насыщенной и содержит 10-30 атомов углерода, и A обозначает полиалкиленовый сегмент гликоля, в котором алкиленовая группа имеет 1-4 атомов углерода, такой как полиоксиметилен, полиоксиэтилен или полиокситриметиленовую часть, которая является практически линейной; может присутствовать некоторая степень разветвления с боковыми цепями низшего алкила (такими, как в полиоксипропиленгликоле), но предпочтительно, чтобы гликоль был практически линейным, а также может содержать азот.Preferred esters, ethers or ester / ethers that can be used can be structurally described by the formula
RO (A) -OR ²
wherein
R and R ^{2 are the} same or different and may be

Where
n denotes, for example, 1-30, wherein the alkyl group is linear and saturated and contains 10-30 carbon atoms, and A denotes the polyalkylene segment of the glycol, in which the alkylene group has 1-4 carbon atoms, such as polyoxymethylene, polyoxyethylene or polyoxytrimethylene a part that is almost linear; some degree of branching with lower alkyl side chains (such as in polyoxypropylene glycol) may be present, but it is preferred that the glycol is substantially linear and may also contain nitrogen.

Examples of suitable glycols are substantially linear polyethylene glycols (PEG) and polypropylene glycols (PPG) having a mol.m. from about 100-5000, preferably from about 200 to 2000. Esters are preferred, and fatty acids containing 10-30 carbon atoms are useful for reacting with glycols to form ester additives, with a C ₁₈ -C ₂₄ fatty acid being preferred, in particular behenic acid. These esters can also be prepared by esterifying polyethoxylated fatty acids or polyethoxylated alcohols.

 Polyoxyalkylene diesters, ethers / esters and mixtures thereof are suitable as additives, while diesters are preferred for use with a narrow boiling range distillate where small amounts of monoesters and monoesters (which often form in receiving process). For the quality of the additive, it is important that a larger amount of dialkyl compound is present. In particular, diesters of stearic or behenic acids of polyethylene glycol, propylene glycol or polyethylene / polypropylene glycol mixtures are preferred.

 Other examples of polyoxyalkylene compounds are described in Japanese Patent Publication Nos. 2-51477 and N 3-34790 (both from Sanyo), and esterified alkoxylated amines, described in European Patent A-117,108 and European Patent A-326356 (both from Nippon Oil and Fats )

 (III) Ethylene-unsaturated ester copolymers.

в которой
R¹ обозначает водород или метильную группу;
R² обозначает группу -OOCR⁴ или -COOR⁴, где R⁴ обозначает водород или алкильную группу с прямой или разветвленной цепью с C₁-C₂₈, предпочтительно C₁-C₁₆, более предпочтительно C₁-C₈, при условии, что R⁴ не обозначает водород, когда R² обозначает -COOR⁴; и
R³ обозначает водород или -COOR⁴.Additives to improve the flowability of the ethylene copolymer have a main chain in the form of polymethylene, divided into segments by the side chains of hydroxyhydrocarbon, i.e. flow improvers in the form of an ethylenically unsaturated ester copolymer. Unsaturated monomers copolymerizable with ethylene to produce these copolymers include unsaturated mono and diesters of the general formula:

wherein
R ¹ represents hydrogen or a methyl group;
R ² is a group —OOCR ⁴ or —COOR ⁴ , where R ⁴ is hydrogen or a straight or branched chain alkyl group with C ₁ -C ₂₈ , preferably C ₁ -C ₁₆ , more preferably C ₁ -C ₈ , provided that R ^{4 is} not hydrogen when R ² is —COOR ⁴ ; and
R ³ is hydrogen or —COOR ⁴ .

This monomer, when R ² and R ³ is hydrogen and R ¹ is OOCR ⁴ , includes vinyl alcohol esters of monobasic carboxylic acids with C ₁ -C ₂₉ , preferably C ₁ -C ₅ , and preferably monobasic carboxylic acids with C ₂ -C ₂₉ , more preferably monobasic carboxylic acids with C ₁ -C ₅ , most preferably monobasic carboxylic acids with C ₂ -C ₅ . Examples of vinyl esters that can be copolymerized with ethylene include vinyl acetate, vinyl propionate and vinyl butyrate or isobutyrate, with vinyl acetate and vinyl propionate being preferred. It is preferred that the copolymers contain 5-40 wt.% Vinyl ester, more preferably 10-35 wt.% Vinyl ester (replace with molar). They may also be in the form of mixtures of the two copolymers described in US Pat. No. 3,961,916. Preferably, the number average molecular weight of this copolymer when measured by vapor phase osmometry is 1000-10000, more preferably 1000-5000. If desired, the copolymers can be obtained from additional comonomers, for example, they can be terpolymers or tetrapolymers, or higher polymers, for example, when the additional comonomer is isobutylene or diisobutylene.

 Such copolymers can also be prepared by transesterification or hydrolysis and re-esterification of an ethylenically unsaturated ester copolymer to produce another ethylenically unsaturated ester copolymer. For example, ethylene vinyl hexanoate and ethylene vinyl octanoate copolymers can be prepared in this way, for example, from an ethylene vinyl acetate copolymer.

 (IV) Polar organic nitrogen-containing compounds.

The oil-soluble polar nitrogen compound is either ionic or non-ionic and can act as an inhibitor of the growth of paraffin crystals in fuels. It contains, for example, one or more of the compounds (a) to (c) below:
(a) An amine salt and / or amide obtained by reacting at least one molar fraction of a hydrocarbyl substituted amine with a molar fraction of hydroxycarboxylic acid having 1-4 carboxylic acid groups or its anhydride.

Ester / amides can be used when they contain 30-300, preferably 50-150 total carbon atoms. These nitrogen-containing compounds are described in US Pat. No. 4,211,534. Suitable amines are typically C ₁₂ -C ₄₀ long chain primary, secondary, tertiary or quaternary amines or mixtures thereof, but shorter chain amines may be used, provided that the resulting nitrogen-containing compound is soluble in oil and therefore, under normal conditions, contains approximately 30-300 total carbon atoms. The nitrogen-containing compound preferably contains at least one straight chain alkyl segment with a C ₈ -C ₄₀ , preferably a C ₁₄ -C ₂₄ .

Suitable amines include primary, secondary, tertiary or quaternary, but are preferably secondary. Tertiary and quaternary amines can only form amine salts. Examples of amines include tetradecylamine, cocoamine and hydrogenated animal fat amine. Examples of secondary amines include dioctadecylamine and methyl behenylamine. Mixtures of amines, such as mixtures derived from natural materials, are also suitable. A preferred amine is a secondary amine from hydrogenated animal fat of the formula HNR ¹ R ² in which R ¹ and R ² are alkyl groups derived from hydrogenated animal fat consisting of about 4% C ₁₄ , 31% C ₁₆ , 59% C ₁₈ .

 Examples of suitable carboxylic acids and their anhydrides for the preparation of nitrogen-containing compounds include cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid and naphthalenedicarboxylic acid, and 1,4-dicarboxylic acid, including dialkylspirobislactone. Typically, these acids have about 5-13 carbon atoms in the cyclic part. Preferred acids used according to the invention are benzo dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid. Most preferred is phthalic acid or its anhydride. The most preferred compound is an amide-amine salt formed by the reaction of 1 molar part of phthalic anhydride with 2 molar parts of an amine from dihydrogenated fat. Another preferred compound is diamide formed by the dehydration of this amido-amine salt.

 Other examples are long chain alkyl or alkylene substituted dicarboxylic acid derivatives, such as amine salts of substituted succinic acid monoamides, examples of which are known in the art and are described, for example, in US Pat. No. 4,147,520. Suitable amines may be as described above.

 Other examples are condensation products described in European Patent A-327423.

(b) A chemical compound containing or comprising a cyclic ring system, wherein the compound carries at least two substituents of the general formula I on the ring system
-A-NR ¹ R ²
in which A denotes an aliphatic hydrocarbyl group, which is optionally interrupted by one or more heteroatoms and which is straight-chain or branched, and R ¹ and R ^{2 are the} same or different and each of them independently represents a hydrocarbyl group containing 9-40 carbon atoms optionally interrupted by one or more heteroatoms, the substituents being the same or different, and the compound is optionally presented in the form of its salt.

 Preferably, A has 1-20 carbon atoms and is preferably a methylene or polymethylene group.

 Used the term "hydrocarbyl" refers to a group having a carbon atom directly attached to the remainder of the molecule, and having a hydrocarbon or predominant hydrocarbon character. Examples include hydrocarbon groups, including aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl or cycloalkenyl), aromatic and alicyclic-substituted aromatic and aromatic-substituted aliphatic and alicyclic groups. It is advisable that the aliphatic groups are saturated. These groups may contain non-hydrocarbon substituents provided that their presence does not substantially alter the hydrocarbon nature of the group. Examples include keto, halo, hydroxy, nitro, cyano, alkoxy and acyl groups. If the hydrocarbyl group is substituted, one (mono) substituent is preferred.

 Examples of substituted hydrocarbyl groups include 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-ketopropyl, ethoxyethyl and propoxypropyl. These groups can also, or alternatively, contain atoms other than carbon in a chain or ring with a different arrangement of carbon atoms. Suitable heteroatoms include, for example, nitrogen, sulfur, and, preferably, oxygen.

 A cyclic ring system may include homocyclic, heterocyclic or compactly “fused” polycyclic groups, or a system in which two or more of these cyclic groups are connected to one another, and in which the cyclic groups can be the same or different. Where there are two or more such cyclic associations, the substituents of the general formula (1) may be on the same or different associations, preferably on the same association. Preferably, this single or each cyclic combination is an aromatic, more preferably benzene ring. Most preferably, the cyclic ring system is a single benzene ring when it is preferred that the substituents are in the ortho or meta positions, and this benzene ring may optionally be further substituted.

 The ring atoms in this cyclic association or associations are preferably carbon atoms, but they can, for example, include one or more ring atoms of N, S or O, in this case or when the compound is a heterocyclic compound.

Examples of such polycyclic compounds include:
(I) condensed benzene structures such as naphthalene, anthracene, phenanthrene and pyrene;
(Ii) condensed ring structures in which none of the rings or all of the rings are benzene, such as azulene, indene, hydroindene, fluorene and diphenylene oxide;
(III) rings joined at the end, such as diphenyl;
(IV) heterocyclic compounds such as quinoline, indole, 2: 3 dihydroindole, benzofuran, coumarin, isocoumarin, benzothiophene, carbazole and thiodiphenylamine;
(V) non-aromatic or partially saturated ring systems such as decalin (i.e., decahydronaphthalene), α-penene, cardinene, and boronylene; and
(VI) three-dimensional structures such as norbornene, bicycloheptane (i.e., norbornane), bicyclooctane and bicyclooctene.

Each hydrocarbyl group constituting R ¹ and R ² according to the invention (formula 1) may, for example, be an alkyl or alkylene group or a mono- or polyalkoxyalkyl group. Each hydrocarbyl group is preferably a straight chain alkyl group. The number of carbon atoms in each hydrocarbyl group is preferably 16-40, more preferably 16-24.

 It is also preferred that this cyclic system is replaced with only two substituents of the general formula (1) and that A is a methylene group.

 Examples of salts of chemical compounds are acetate and hydrochloride.

These compounds can be obtained by reducing the corresponding amide, which can be accomplished by reacting a secondary amine with the corresponding acid chloride; and
(c) Condensate of a long chain primary or secondary amine with an acid-containing polymer.

 Specific examples include the polymers described in UK patents A-2121807, France A-2592387 and Germany A-3941861; and esters of telemeric acid and alkanolamines described in US patent A-4639256; the reaction product is a long chain epoxide / amine that can further react with a polycarboxylic acid; and a reaction product of an amine containing a branched carboxylic ester, an epoxide and a polyester of a monobasic carboxylic acid, as described in US Pat. No. 4,631,071.

 (v) Hydrocarbon polymers.

в которой
T = H или R¹,
U = H, T или арил,
R¹ = гидрокарбил с C₁-C₃₀,
v и w обозначают молярные соотношения, при этом v находится в пределах 1,0-0,0, а w - 0,0-1,0.Examples are represented by the following general formula

wherein
T = H or R ¹ ,
U = H, T or aryl,
R ¹ = hydrocarbyl with C ₁ -C ₃₀ ,
v and w denote molar ratios, while v is in the range of 1.0-0.0, and w is 0.0-1.0.

 These polymers can be obtained directly from ethylenically unsaturated monomers or indirectly by hydrogenation of a polymer derived from monomers such as isoprene and butadiene.

 Preferred hydrocarbon polymers are copolymers of ethylene and at least one α-olefin having an average molecular weight of at least 30,000. Preferably, this α-olefin has no more than 20 carbon atoms. Examples of such olefins are propylene, 1-butene, isobutene, n-octene-1, isooctene-1, n-decene-1 and n-dodecene-1. This copolymer may also contain small amounts, for example, up to 10 wt.% Of other copolymerizable monomers, for example, olefins other than α-olefins, and non-conjugated dienes. A preferred copolymer is an ethylene propylene copolymer. Two or more different ethylene-α-olefin copolymers of this type are included within the scope of the invention.

 The average molecular weight of the ethylene-α-olefin copolymer, as described above, is not less than 30,000, which is measured by gel permeation chromatography (GPC) with respect to polystyrene standards, it is advisable not less than 60,000 and preferably not less than 80,000. Functionally there is no upper limit, but mixing difficulties result from increased viscosity at molecular weights above about 150,000, and a preferred molecular weight is in the range of 60,000 and 80,000 to 120,000.

 It is advisable that the copolymer has a molar ethylene content in the range of 50-85%. It is more advisable that the ethylene content is in the range of 57-80%, and preferably it is in the range of 58-73%; more preferably 62-71% and most preferably 65-70%.

 Preferred ethylene-α-olefin copolymers are ethylene-propylene copolymers with a molar ethylene content of 62-71% and with a number average molecular weight in the range of 60000-120000, the most preferred copolymers are ethylene-propylene copolymers with an ethylene content of 62-71% and mol .m. 80000-100000.

 These copolymers can be obtained by any of the methods known from the prior art, for example, using a Ziegler-type catalyst. It is advisable that the polymers are practically amorphous, since highly crystalline polymers are relatively insoluble in fuel oil at low temperatures.

 The additional composition may also contain another ethylene-α-olefin copolymer, suitably with a number average molecular weight of not more than 7500, suitably 1000-6000, and preferably 2000-5000, as measured by vapor phase osmometry. The corresponding α-olefins are those described above, or styrene, with propylene being preferred. It is advisable that the ethylene content is 60-77 mol.%, Although up to 86 mol.% By weight of ethylene is advisable for ethylene-propylene copolymers.

 Examples of hydrocarbon polymers are described in WO-A-9111488.

 (VI) Sulfur-containing carboxyl compounds.

в которой
-Y-R² обозначает SO $\genfrac{}{}{0ex}{}{\text{(-)(+)}}{\text{3}}$ NR $\genfrac{}{}{0ex}{}{\text{3}}{\text{3}}$ R² , SO $\genfrac{}{}{0ex}{}{\text{(-)(+)}}{\text{3}}$ NR $\genfrac{}{}{0ex}{}{\text{3}}{\text{2}}$ R², , -SO $\genfrac{}{}{0ex}{}{\text{(-)(+)}}{\text{3}}$ H₂NR³R² , -SO $\genfrac{}{}{0ex}{}{\text{(-)(+)}}{\text{3}}$ H₃NR², , -SO₂NR³R² или -SO₃R²;
-X-R¹ обозначает -Y-R² или -CONR³R¹, -CO $\genfrac{}{}{0ex}{}{\text{(-)(+)}}{\text{2}}$ NR $\genfrac{}{}{0ex}{}{\text{3}}{\text{3}}$ R¹, , -CO $\genfrac{}{}{0ex}{}{\text{(-)(+)}}{\text{2}}$ HNR $\genfrac{}{}{0ex}{}{\text{3}}{\text{2}}$ R¹, , -R⁴-COOR₁, -NR³COR¹, -R⁴OR¹, -R⁴OCOR¹, -R⁴, R¹, -N(COR³)R¹ или Z^(-)(+)NR $\genfrac{}{}{0ex}{}{\text{3}}{\text{3}}$ R¹; ;
-Z^(-) обозначает SO $\genfrac{}{}{0ex}{}{\text{(-)}}{\text{3}}$ или -CO $\genfrac{}{}{0ex}{}{\text{(-)}}{\text{2}}$ ;;
R¹ и R² обозначают алкил, алкоксиалкил или полиалкоксиалкил, содержащий по крайней мере 10 атомов углерода в главной цепи;
R³ обозначает гидрокарбил, и каждый R³ может быть одинаковым или различным, а R⁴ отсутствует или равно алкилену с C₁-C₅, и в

связь углерод-углерод (C-C) представляет собой либо а) этилен-ненасыщенную, когда A и B могут быть алкильными, алкенильными или замещенными гидрокарбильными группами, или б) часть циклической структуры, которая может быть ароматической, многоядерной ароматической или циклоалифатической, предпочтительно, чтобы X-R¹ и Y-R² между собой содержали по крайней мере три алкильных, алкоксиалкильных или полиалкоксиалкильных групп.Examples of sulfur-containing carboxyl compounds are given in European Patent A-0261957, which describes the use of compounds of the general formula

wherein
-YR ² is SO $\genfrac{}{}{0ex}{}{\text{(-) (+)}}{\text{3}}$ Nr $\genfrac{}{}{0ex}{}{\text{3}}{\text{3}}$ R ² SO $\genfrac{}{}{0ex}{}{\text{(-) (+)}}{\text{3}}$ Nr $\genfrac{}{}{0ex}{}{\text{3}}{\text{2}}$ R ² ,, -SO $\genfrac{}{}{0ex}{}{\text{(-) (+)}}{\text{3}}$ H ₂ NR ³ R ² , -SO $\genfrac{}{}{0ex}{}{\text{(-) (+)}}{\text{3}}$ H ₃ NR ² ,, -SO ₂ NR ³ R ² or -SO ₃ R ² ;
—XR ¹ is —YR ² or —CONR ³ R ¹ , —CO $\genfrac{}{}{0ex}{}{\text{(-) (+)}}{\text{2}}$ Nr $\genfrac{}{}{0ex}{}{\text{3}}{\text{3}}$ R ¹ ,, -CO $\genfrac{}{}{0ex}{}{\text{(-) (+)}}{\text{2}}$ Hnr $\genfrac{}{}{0ex}{}{\text{3}}{\text{2}}$ R ¹ ,, -R ⁴ -COOR ₁ , -NR ³ COR ¹ , -R ⁴ OR ¹ , -R ⁴ OCOR ¹ , -R ⁴ , R ¹ , -N (COR ³ ) R ¹ or Z ^{(-) ( +)} NR $\genfrac{}{}{0ex}{}{\text{3}}{\text{3}}$ R ¹ ; ;
-Z ^(-) is SO $\genfrac{}{}{0ex}{}{\text{(-)}}{\text{3}}$ or -CO $\genfrac{}{}{0ex}{}{\text{(-)}}{\text{2}}$ ;;
R ¹ and R ² are alkyl, alkoxyalkyl or polyalkoxyalkyl containing at least 10 carbon atoms in the main chain;
R ³ is hydrocarbyl, and each R ³ may be the same or different, and R ^{4 is} absent or equal to alkylene with C ₁ -C ₅ , and

the carbon-carbon bond (CC) is either a) ethylenically unsaturated when A and B can be alkyl, alkenyl or substituted hydrocarbyl groups, or b) part of a cyclic structure that can be aromatic, multinuclear aromatic or cycloaliphatic, preferably XR ¹ and YR ² each other contained at least three alkyl, alkoxyalkyl or polyalkoxyalkyl groups.

 (VII) Hydrocarbylated aromatic substances.

 These materials are condensates containing aromatic and hydrocarbyl parts. The aromatic part is suitably an aromatic hydrocarbon which may be unsubstituted or substituted, for example, with non-hydrocarbon substituents.

 Such an aromatic hydrocarbon preferably contains a maximum amount of these substituent groups and / or three fused rings and is preferably naphthalene. The hydrocarbyl part is hydrogen, and the carbon-containing part is connected to the rest of the molecule by a carbon atom. It may be saturated or unsaturated and straight or branched and may contain one or more heteroatoms, provided that they do not significantly affect the hydrocarbyl nature of this part. Preferably, the hydrocarbyl moiety is an alkyl moiety, suitably having more than 8 carbon atoms. The molecular weight of such condensates may, for example, be in the range of 2000-200000, about 2000-20000; preferably 2000-8000.

Examples are known in the art where hydrocarbylated aromatic substances can be obtained, for example, by condensation of halogenated paraffin with an aromatic hydrocarbon, primarily as lubricant hardening depressants and as paraffin control agents, as mentioned previously. More specifically, the condensation can be Friedel-Crafts condensation when a halogen-containing paraffin containing 15-60, for example 16-50 carbon atoms, has a melting point of about 200-400 ^° C. and is chlorinated to 5-25% by weight of chlorine, for example 10- 18 wt.%.

 Another way to obtain such condensates can be their production from olefins and from aromatic hydrocarbons.

 Multi-component additive systems may be used, and the proportions of additives to be used will depend on the fuel to be treated.

 Example 1

The following additives were used:
A: an ethylene / vinyl acetate copolymer having a vinyl acetate concentration of about 37 wt.% And an average molecular weight of about 2700.

 B: a 3: 1 mixture (wt.) Of the above additive A and an ethylene / vinyl acetate copolymer having a vinyl acetate concentration of about 13.5 wt.% And a number average molecular weight of about 5000.

 B: a mixture containing the same compounds as in B, but with a weight ratio of 13: 1.

 Number-average molecular weights, such as those measured using osmometry in the vapor phase (OPF).

 An experience. Each of additives A, B, and C was dissolved in samples of the same rapeseed oil methyl ester fuel, and the clogging temperature of the cold filter (CFPP) was measured using a procedure detailed in Journal of Institute of Petroleum, Volume 52 , Number 510, June 1966, pp. 173-285. CFPP is a measure of filterability. The results are shown in the table below.

In comparison, the CFPP of the untreated fuel was -9 ^o C. Thus, it can be seen that each of additives A, B, and C improved the filterability of the fuel, as measured by the CFPP experiment.

Claims (11)

 1. A composition comprising as a base animal or vegetable oil, characterized in that it further comprises an additive for improving cold flow selected from the group comprising one or more of the following substances: comb polymer, ester, polyoxyalkylene ester / ether or a mixture thereof, ethylene / unsaturated ester copolymer, polar organic nitrogen-containing paraffin crystal growth inhibitor, hydrocarbon polymer, sulfur-containing carboxyl compounds, alkyl aromatic depressant p, with the exception of complex mixtures of polymeric esters or copolymers of esters of acrylic and / or methacrylic acid and alcohols having 1 - 22 carbon atoms. 2. The composition according to p. 1, characterized in that the said ester, ester / ether polyoxyalkylene or a mixture thereof are defined by the formula
R - O - (A) - O - R ² ,
in which R and R ² are the same or different and may mean: a) n-alkyl,

where n is 1 to 30;
the alkyl group is linear and saturated and contains 10 to 30 carbon atoms;
A denotes a polyoxyalkylene segment with a mol.m. 100 - 5000,
where the alkylene group has 1 to 4 carbon atoms.  3. The composition according to claim 1, characterized in that the polar organic nitrogen-containing paraffin crystal growth inhibitor is an amine salt and / or amide obtained by reacting at least 1 mole of a hydrocarbon-substituted amine with at least 1 mole of hydrocarbon acid or an anhydride having 1 to 4 carboxyl groups, preferably benzenedicarboxylic acid or its anhydride.  4. The composition according to claims 1 to 3, characterized in that the base is a biofuel.  5. The composition according to any one of claims 1 to 4, characterized in that said biofuel is a vegetable oil or its derivative.  6. The composition according to claim 5, characterized in that said biofuel is selected from the group consisting of rapeseed oil, cottonseed oil, soybean oil, sunflower oil, olive oil, palm oil or their alkyl ester derivatives.  7. The composition according to claim 5, characterized in that the biofuel is a methyl ester of rapeseed oil.  8. The composition according to any one of claims 1 to 7, characterized in that said biofuel contains a mixture of vegetable oils and / or a mixture of their copolymers.  9. A composition according to any one of claims 1 to 8, characterized in that said additive contains an ethylene / vinyl ester copolymer or a mixture of their copolymers.  10. A method of modifying the growth of paraffin crystals in animal or vegetable oil, characterized in that the oil is mixed with an additive selected from the group comprising one or more of the substances described in claim 1.  11. The method according to claim 10, characterized in that the oil is a biofuel.

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