CS276707B6 - Fuel oil - Google Patents

Description

(57)

Fuel oil comprising a medium distillate fuel oil having a boiling point of 120 to 500 ° C and a weight of 0.0001 to 0.5% of ester and / or ether and / or ester (s) of the formula RO- (A) -OR, wherein R and R ¹ represent the same or different groups selected from the group consisting of n-alkyl, n-alkyl-C (O) -, n-alkyl-OC (O) - (CH ₂ ) _n - and n-alkyl-O-C ( O) - (CH ₂ ) _n -CO- in which the alkyl radicals are linear, saturated and contain 10 to 30 carbon atoms, one of R and R ¹ also being hydrogen and A being a polyoxyalkylene glycol moiety having a molecular weight of 100 to 5 000 wherein the alkylene group contains 1 to 4 carbon atoms.

276,727 B6

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EN 276 707 B6 ø ¹

The present invention relates to a medium fuel oil having a boiling point of 120-500 ° C with improved cold flow properties.

Additives for treating distillate fuel to improve flow properties of paraffin wax turbid fuels and cold weather filters are known, as is clear from the following patents. The terms paraffin, paraffin wax and wax are considered synonymous for the purposes of this description.

United Kingdom Patent Nos. 900,202 and 1,263,152 relate to the use of low molecular weight copolymers of ethylene and unsaturated esters, especially vinyl acetate, while United Kingdom Patent No. 1,374,051 relates to the use of an additive system which both increases the temperature at which crystallization begins thus limiting the size of the wax crystals formed. The use of low molecular weight copolymers of ethylene and other olefins to lower the flow point of distillate fuels is described in United Kingdom Patent Nos. 848 777, 993 744 and 1,068,000 and in U.S. Patent 3,679,380. Various other special types of polymers are recommended as additives to distillate fuels in U.S. Patent Nos. 3,374,073, 3,499,741, 3,550,636, 3,524,732, 3,660,231 and 3,681,302.

It is also known that admixture mixtures may be used to further improve the flow characteristics and flow temperature of distillate fuels. For example, U.S. Pat. No. 3,661,541 uses mixtures of an additive based on an ethylene-unsaturated ester copolymer and a low molecular weight ethylene-propylene copolymer according to British Patent No. 993,744.

U.S. Pat. No. 3,658,493 discloses various nitrogen salts and acid amides such as monocarboxylic and dicarboxylic acids, phenols and sulfonic acids in admixture with ethylene homopolymers or copolymers to lower the flow point of medium distillate oils. U.S. Pat. No. 3,982,909 discloses that nitrogenous compounds such as amides, diamides, and ammonium salts of monoamides or monoesters of dicarboxylic acids alone or in admixture with microcrystalline petroleum waxes and / or flow point depressants, especially polyethylene backbone, are modifiers and improve the flow properties of middle distillate fuel oils, including diesel, in the cold.

U.S. Patent Nos. 3,444,082 and 3,946,093 disclose the use of various amides and amine salts of alkenylsuccinic anhydride in admixture with ethylene copolymer-based additives to lower the flow point of distillate fuels.

U.S. Pat. No. 3,762,888 discloses an additive to improve the flow of medium distillate fuels containing, as a first component, a polymer, such as an ethylene copolymer and, as a second component, various organic compounds characterized by comprising a straight chain polymethylene segment selected from polyol fatty esters. , alkoxylated polyethers, alcohol esters and the like.

With respect to the present invention, the most important fact is that the aforementioned U.S. Pat. No. 3,762,888 discloses that the second component, when used in the absence of the first polymer component, generally does not improve or only slightly improves the flow properties of oils.

The invention is based on the discovery that a certain group of polyoxyalkylene esters, ethers, ether / esters and mixtures thereof is effective in itself to improve the flow characteristics of distillate oils and is particularly effective and can be used as the only additive for narrow distillate fuels. a range of boiling points (as will be elaborated hereinafter) which are usually insensitive to conventional additives to improve flow properties. Use of such spirits

CS 276 707 B6 with a narrow boiling range is increasing as the requirements for refineries to produce more petroleum-type distillates are increasing. A corresponding increase in the initial boiling point of the middle distillate necessitates a reduction in the final boiling point of the distillate to achieve the prescribed oil haze temperature. These narrow boiling distillates have a relatively high initial boiling point and a relatively low final boiling point.

Although prior art additives usually effectively limit the growth of separating wax crystals in distillate fuel oils boiling in the range of 120-500 ° C, in particular boiling in the range of 160-400 ° C, further improvement is needed. However, it has been found difficult to improve the flow characteristics and filterability of distillate oils with a narrow boiling range. It has now been found that certain polyalkylenostomers, ethers, ester / ethers or mixtures thereof are particularly suitable for improving the flow properties of distillate fuels with a narrow boiling range. By narrow boiling range is meant the boiling range of distillate fuels 200 ° C - 50 ° C to 340 ° C - 20 ° C. Fuels having boiling points outside this range are referred to herein as distillates with a wide boiling range.

The present invention relates to a fuel oil comprising a medium distillate fuel oil having a boiling point of 120 to 500 ° C and a weight of 0.0001 to 0.5% of ester and / or ether and / or ester / ether of the formula I

R - O - (A) - O - R ^1/1 , wherein R and R ¹ have the same or different meanings and are a group of formula n-alkyl with

n-alkyl-C0

In n-alkyl-OC - / CH ₂ / _n O 0 P n -alkyl-O-C - / CH ₂ / _n - C wherein the alkyl group is linear and saturated and contains from 10 to 30 carbon atoms, one of the R a symbols ¹ also represents hydrogen, and A represents a polyoxyalkylene glycol moiety having a molecular weight of 100 to 5,000, wherein the alkylene group contains 1 to 4 carbon atoms.

An example of polyoxyalkylene glycol moiety A is a polyexymethylene, polyoxyethylene or polyoxytrimethylene moiety that is substantially linear. While some degree of branching through the lower alkyl side chain (as in polyoxypropylene glycol) is permissible, the glycol should be substantially linear to achieve the result of the invention.

Suitable polyoxyalkylene glycols are generally substantially linear polyethylene glycols (PEG) and polypropylene glycols (PPG) having a molecular weight of 100 to 5,000, preferably about 200 to 2,000, with a range of 200 to 2,000 particularly suitable for improving the flow characteristics of distillates with a narrow temperature range. boiling.

Esters are preferred additives of the invention and C 10 -C 30 fatty acids are suitable for reaction with glycols to prepare the ester additives of the invention. However, if additives are to be used for distillates with a narrow boiling range, fatty acids with 18 to 24 carbon atoms are preferred, especially behenic acid or mixtures of ste4.

CS 276 7.07 B6 r

aric and behenic acids. Esters may also be prepared by esterification of polyethoxylated fatty acids or polyethoxylated alcohols.

suitable as additives are polyoxyalkylene diesters, diethers, ether / esters and mixtures thereof, the diesters being preferred for use in distillates with a narrow boiling range. Although minor amounts of monoethers or monoesters may also be present and are often formed during manufacture, it is important for the utility properties of the additive that a predominant amount of the dialkyl compound be present. Particular preference is given to diesters of stearic or behenic acid with polyethylene glycol, polypropylene glycol or polyethylene / polypropylene glycol mixtures.

Thus, according to a preferred embodiment of the invention, narrow boiling distillate fuels with improved flow and filterability characteristics comprise an ester, and / or an ether and / or ester / ether of polyethylene glycol or polypropylene glycol having a molecular weight of 100 to 5,000 and fatty acids as an additive to improve the flow properties. C18-C24 in an amount of about 0.0001 to 0.5% by weight, preferably about 0.005 to 0.05 by weight based on the weight of the fuel to be treated. When using a polyethylene glycol derivative, a polyethylene glycol having a molecular weight of 200 to 1500 is preferred, and a polypropylene glycol having a molecular weight of 200 to 2000 is preferred. Polyalkylene glycol having a molecular weight of 200 to 800 is most preferred.

Polyoxyalkylene esters and / or ethers and / or ether / esters may be used as a single additive or together with other additives. In the case of distillates with a narrow boiling range, which usually have no response to conventional additives, the polyoxyalkylene esters, ethers or ester / ethers of the invention are often effective as a single ingredient. In the case of distillate fuels with a wide boiling range, the esters, ethers or esters / ethers according to the invention are used as additives preferably in admixture with other additives to improve the flow properties.

For distillate fuels with a wide range of boiling points, further additives are preferably halogenated polymers of ethylene, in particular chlorinated polyethylene and, in particular, copolymers of ethylene with other unsaturated monomers. Generally, these other conventional additives are ethylene copolymers typically referred to as crystal modifiers, having a number average molecular weight of 500 to 10,000, as determined by vapor pressure osmometry containing 3 to 40, preferably 4 to 20 moles of ethylene per mole of second ethylenically unsaturated monomer. . A particularly preferred additive to improve flow properties is an ethylene / vinyl acetate copolymer. Preference is given to mixtures of 90 to 10, in particular 50 to 10 and in particular 20 to 40% by weight of the polyoxyalkylene ester or ether according to the invention, and 10 to 90, preferably 50 to 90 and especially 80 to 60%, ethylene-unsaturated ester copolymer. Copolymers of ethylene and vinyl acetate, especially containing 10 to 40% by weight and in particular containing 25 to 35% by weight vinyl acetate and having a number average molecular weight determined by an osmometric determination of approximately 1,000 to 6,000, preferably 1,500 to 4,500, are particularly preferred additives. . A preferred glycol ester for use in such mixtures is polyethylene glycol dibehenate having a molecular weight of 200 to 1,500, in particular 800 to 1,500.

Unsaturated monomers that can be copolymerized with ethylene include unsaturated monoesters and diesters of the general formula

R, H

II r ₂ - c = c - r ₄

CS 276 707 B6 where is

R 1 is a hydrogen atom or a methyl group,

R _{2 is a} group of the formula -00CR ₅ , wherein is

R ₃ is hydrogen or a straight- or branched chain having 1-28 carbons, particularly 1-17 carbons and especially 1 to 8 carbon atoms

R ^ is hydrogen or -COOR ^, wherein Rj is as defined above.

Monomers of the above formula wherein R ^ and R ^ is hydrogen and R ₂ represents a group of formula

Coor ₅ includes esters of vinyl alcohol with a monocarboxylic acid of 1 to 29 carbon atoms, in particular of 1 to 18 carbon atoms, and especially a monocarboxylic acid of 2 to 5 carbon atoms. Examples of such esters are vinyl acetate, vinyl isobutyrate, vinyl laurate, vinyl myristate and vinyl palmitate; a preferred vinyl ester is vinyl acetate.

In the case where R ₂ represents a group of the general formula

-coor ₅ and R ₃ are hydrogen, esters including methyl acrylate, isobutyl acrylate, methyl methacrylate, lauryl acrylate, methacrylic acid esters of oxoalcohols and the like are suitable.

Examples of monomers wherein R₁ is hydrogen and R ₂ and R represent groups of formula

Coor ₅ discloses monoesters and diesters of unsaturated dicarboxylic acids such as C 1-6 oxofumarate, di-C 1-4 oxofumarate, diisopropyl maleate, dilauryl fumarate and ethyl methyl fumarate.

The polyoxyalkylene esters, ethers or ester / ethers of the invention can be used in distillate fuels together with polar compounds, either ionic or non-ionic, which are capable of acting as crystal growth inhibitors in fuels. The compounds containing a polar nitrogen atom are particularly effective when used in admixture with the glycol esters, ethers or ester / ethers of the invention and are generally amine salts of 30 to 300 carbon atoms, preferably 50 to 150 carbon atoms and / or amides, prepared by reacting at least one molar part of amines with a molar equivalent fraction of an organic acid having 1 to 4 carboxy groups or anhydrides thereof; ester amides may also be used. These nitrogen compounds are described in U.S. Pat. No. 4,211,534. Suitable amines are generally primary, secondary, tertiary, or quaternary amine of 12 to 40 carbon atoms or mixtures thereof, but shorter-chain amines may also be used provided The composition according to claim 1, wherein the nitrogen compound formed is oil-soluble and therefore generally contains about 30 to 300 carbon atoms in total. The nitrogen compound should also have at least one straight-chain C 8 to C 40 alkyl segment.

Suitable amines include primary, secondary, tertiary or quaternary amines, but especially secondary amines. Only tertiary and quaternary amines can form salts. Examples of amines are tetradecylamine, cocoamine, tallow hydrogenated fatty acid amine and similar amines. Examples of secondary amines are given

Dioctadecylamine, methylbehenylamine and similar amines. Mixtures of amines are also suitable, and many naturally occurring amines are mixtures. The preferred amine is a secondary amine is based on hydrogenated tallow fatty acids of the general formula HNR ₁ R ₂ where R '^ and _R2 are alkyl groups derived from fatty acids hydrogenated tallow composed approximately 4% C-31% C-59% Ο ^ θ fatty acids.

Examples of suitable carboxylic acids for the preparation of such nitrogen compounds and their anhydrides include cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, cyclopentanedicarboxylic acid, di-alpha-naphthylacetic acid, naphthalenedicarboxylic acid, and the like. Generally, these acids should have 5 to 13 carbon atoms in the cyclic moiety. Preferred acids of the invention are benzenedicarboxylic acids such as phthalic acid, terephthalic acid and orthophthalic acid. Particularly preferred are ortho-phthalic acid or anhydride thereof.

It is preferred that at least one straight-chain alkyl segment of from 8 to 40, and preferably from 14 to 24, carbon atoms is provided from the nitrogen-containing compound. Also, at least one ammonium salt, amine salt or amine bond group should be included in the molecule. A particularly preferred amine compound is an amidamine salt formed by reacting a 1 molar portion of phthalic anhydride with two molar portions of a diamine derived from hydrogenated tallow. Another preferred compound is a diamide formed by dehydration of the amidamine salt.

In distillate fuels with a wide boiling range, mixtures containing from 10 to 90% by weight, preferably from 50 to 80% by weight and in particular from 60 to 80% by weight of the abovementioned nitrogen compound and approximately from 90 to 10%, preferably from 50 to 80% by weight are particularly effective. 20% and in particular 20 to 40% by weight of a polyoxyalkylene ester, an ether, an ether / ester or mixtures thereof.

The invention also relates to a fuel oil comprising an additive for reducing the pour point of the lubricating oil. This is particularly useful in improving the flow characteristics of distillate fuels having higher boiling points, especially distillate oils having a boiling point above 385 ° C. Preferred additives for lowering the pour point of lubricating oils include alkylaroroatic compounds, prepared, for example, by Friedel-Crafts condensation of a halogenated wax, preferably a straight chain wax, with an aromatic hydrocarbon such as naphthalene. Typical suitable halogenated waxes are those containing 15 to 60, for example 16 to 50, carbon atoms and 5 to 25% by weight, preferably 10 to 11% by weight, of halogen atoms, preferably chlorine.

Other additives for lowering the pour point of a lubricating oil include the well-known oil-soluble esters and / or. higher olefin polymers having a number average molecular weight of about 1,000 to 200,000, for example 1,000 to 100,000, and preferably 1,000 to 50,000, as determined, for example, by osmometry based on vapor pressure, for example with a Mechrólab Vapor Pressure Osmometer, or gel permeation chromatography. These polymers include copolymers with other unsaturated monomers, for example with olefins other than ethylene. Typical polymers are described in British Patent Application Publication No. 2,023,645 A.

CS 276 707 B6

The relative proportions of polyoxyalkylene esters, and / or ethers, and / or ester (s), the flow point reducing agents of lubricating oils and other additives used also depend on the nature of the fuel. However, it is preferred to use from 0% to 50%, preferably from 5% to 30%, by weight of the additive to reduce the pour point of the lubricating oil based on the total amount of additives in the distillate fuel, and the fuel may also contain 0% to 90% .

Thus, the invention includes distillate fuel oils boiling in the range of 120 to 500 ° C, including distillates with a narrow boiling range of 200 ° C - 50 ° C to 340 ° C and 20 ° C with improved low temperature flow properties containing 0.0001 to 0.5% by weight, for example 0.001 to 0.5% creep enhancing additives, comprising 10 to 100% by weight of a polyoxyalkylene substance which is an ester, an ether / ester or a mixture thereof containing at least two linear saturated alkyl groups having 10 up to 30 carbon atoms and the remainder of a polyoxyalkylene glycol having a molecular weight of 100 to 5,000, for example 200 to 5,000, wherein the alkylene moiety in the polyoxyalkylene contains 1 to 4 carbon atoms by weight of 0 to 90% for example 50-90% ethylene with another unsaturated monomer vinyl acetate, 0 to 90% by weight, for example 50 to 90%, oil-soluble, polar nitrogen compounds with up to 300 atoms % of a carbon which is an amine salt and / or an amide and / or an ester / amide of a carboxylic acid having 1 to 4 carboxy groups or an anhydride thereof 0 to 50% by weight, for example 5 to 30%

The additive to improve flow properties may be the polyoxyalkylene compound itself or any combination of the polyoxyalkylene compound with one or more of the above-described components. Other ingredients may also be included.

The invention is further illustrated by the following practical examples, which are not to be construed as limiting.

In the tests described in the examples, the fuels used have the properties given in Table I.

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CS 276 707-6

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Fuels are typical European fuel oils and diesel fuels. Fuels A, B, C and D are examples of distillates with a narrow boiling range (NBD), while fuels E, F, H and I are examples of desillates with a wide boiling range (BBD) and fuel G is according to its boiling point between a group of fuels with a narrow boiling range and fuels with a wide boiling range.

In one method, the oil response to the additive is measured by determining the cold filter clogging temperature (CFPPT); the measurement is carried out as described in detail in the Journal of the Institution of Petroleum, Volume 52, No. 510, June 1966, pages 173-185. This test is intended for comparison with the cold flow of middle distillate in automatic diesels.

CS 276 707 85

A sample of 40 ml of the test oil is cooled in a bath which is maintained at a temperature of about -34 ° C under non-linear cooling at a rate of about 1 ° C / min. Periodically (at any one-stage temperature drop from at least 2 ° C above the oil base temperature), refrigerated oil shall be tested for its ability to flow through the fine sieve over a prescribed time using a test device which is a pipette at the bottom end of which is inverted. it is inserted below the surface of the oil to be tested. A 350 mesh screen (approximately 43 microns) is stretched across the funnel orifice with an area defined by 12 mm diameter. Periodic tests are started using a vacuum at the upper end of the pipette, pushing the oil through the pipette up to the mark indicating 20 ml of oil. After each successful pass, the oil is immediately returned to the CFPP tube. The test is repeated each time the temperature drops by one ° C until the oil can no longer fill the pipette within 60 seconds. This temperature is referred to as the cold filter clogging temperature. The difference between the clogging temperature of the additive-free cold filter and the same fuel containing the additive is reported as a reduction in the CFPP - cold filter clogging temperature caused by the test additive. A more efficient additive improving creep characteristics has a greater CFPP reduction value at the same additive concentration.

Another determination of the efficacy of the additive to improve flow properties is performed by the distillate usability test (DOT test), which is a slow cooling test designed to mimic the pumping of stored fuel oil. The cold flow characteristics of the described fuel containing additives are determined by the distillate applicability test (DOT test) as follows: 300 ml of fuel oil is cooled linearly at 1 ° C per hour to the test temperature and the temperature is then kept constant. After two hours at the test temperature, approximately 20 ml of the coating is aspirated to prevent the test from being affected by abnormally large wax crystals that tend to form during cooling at the oil / air interface. The wax deposited in the flask is dispersed by gentle agitation and a filter assembly to test the cold filter clogging temperature (CFPP) is inserted. Open the cock to apply a vacuum of 66.66 kPa and close when the filter passes 200 ml of fuel into the graduated container. Compliance is noted if 200 ml of fuel oil passes through the sieve within 10 seconds, or fails if the filter penetration rate is too slow as the filter becomes clogged.

A mesh screen of 20/833 microns is used to test the clogging temperature of the cold filter - mesh sizes are always given in brackets, 30 / approximately 495 microns /, / 420 microns /, 60/246 microns /, 80/175 microns / , 100 (147 micrometers), 120 (about 124 micrometers), 150 (104 micrometers), 200 (74 micrometers), 250/61 micrometers (350) and about 43 micrometers (to determine the finest mesh (largest mesh number) through which the oil going through. The larger the mesh screen number through which the wax-containing fuel passes, the smaller the waxy crystal particles and the greater the efficiency of the additive to improve flow properties. It is recalled that no two fuels give exactly the same test results with the same amount of the same additive to improve creep characteristics, and therefore the actual additive concentration varies somewhat with the fuel oil used.

In the examples, additives Al are used to improve the flow properties of the distillate as a concentrate in an aromatic diluent containing 50% by weight of a mixture of two ethylene-vinyl acetate copolymers with different solubility in oil so that one functions primarily as a wax crystal growth caliper. described in British Patent No. 1,374,051 and its corresponding U.S. Pat. No. 3,961,916. The two polymers are in particular at a weight ratio of 75% wax crystal growth inhibitor to 25% nucleator. The growth retardant is ethylene and approximately 38% vinyl9.

And the growth caliper has a number average molecular weight of about 1,800 (VPO). It is referred to in the aforementioned British Patent Specification No. 1,374,051 as Copolymer B in Example 1 (column 8, lines 25 to 35) and in the corresponding U.S. Patent No. 3,961,916, column 8, line 32. The nucleator consists of ethylene and approximately % by weight of vinyl acetate and has a number average molecular weight of about 3,000 (VPO). In the aforementioned British Patent Specification No. 1,374,051, it is referred to as copolymer H (see Table I, columns 7 to 8) and in the corresponding U.S. Patent No. 3,961,916, column 8, line 45. Additive A2 to improve the flow characteristics of distillate is the Al wax growth inhibiting component used as such.

Polyethylene glycol (PEG) esters and polypropylene glycol (PPG) esters are prepared by mixing one molar portion of glycol with one or two molar portions of carboxylic acids for monoesters and diestres. Para-toluenesulfonic acid is added in an amount of 0.5% by weight based on the reactants as catalyst. The mixture was heated to 150 ° C with stirring and a slow stream of nitrogen distilled off the reaction water. When the reaction is complete according to the infrared spectrum, the product is poured in the melt state and allowed to cool to give a waxy solid. The products were identified by elemental analysis, gel permeation chromatography, saponification and spectroscopic techniques. Polyethylene glycols and polypropylene glycols are generally referred to together with molecular weight, for example polyethylene glycol PEG 600 is a polyethylene glycol with an average molecular weight of 600. This nomenclature is also maintained for esters, such that PEG 600 dibehenate is the reaction product of two molar proportions of behenic acid with one mole. It is also possible to use mixtures of polyethylene glycols of different molecular weights, for example the mixed PEG / 200/400/600 / distearate is a distearate ester of a 1: 1: 1 weight ratio of PEG 200, 400 and 600, i.e. 200, 400, and 600 molecular weight polyethylene glycol. Mixtures of carboxylic acids may also be used; for example, PEG di (stearate) is the product of the reaction of one mole of PEG (polyethylene glycol) with one mole of both stearic and behenic acid. Two, three or more different polyethylene glycols, polypropylene glycols or copolymers of ethylene glycol and propylene glycol and carboxylic acids can be used in both types of mixtures.

As examples of polar, monomeric, nitrogen-containing growth inhibitors, the following compounds, referred to as B1, B2, B3 and B4, are used:

B1 is the reaction product of one mole of phthalic anhydride with two moles of a hydrogenated tallow fatty acid amine to form a semi-amine salt / semi-amide.

B2 is a phthalic acid diamide prepared by removing one mole of water from mole B1.

B3 is a fatty acid secondary amine salt of hydrogenated tallow and monooctadecyclophthalate.

B4 is a diamide formed by reacting two moles of a secondary amine based on hydrogenated tallow with one mole of maleic anhydride and dehydrating the product obtained.

While many additives are available in the form of oily solutions of the active ingredient, in the following examples, the figures refer to the actual amount of the additive.

CS 276 707 B6

Example 1

The properties of narrow boiling distillate fuels normally difficult to behave in the cold filter clogging test (CFPP test) containing polyoxyalkylene esters of the invention are compared to the same distillate fuels but containing ethylene vinyl acetate (EVA) as a copolymer additive with the following results:

Lowering the cold filter clogging temperature / lowering CFPP /

Additive to improve ppm effective

Fuel according to Table

creep characteristics folders AND (B) C D Al 100 ALIGN! -1 0 - 0 Al 500 -1 -1 - 0 A2 100 ALIGN! -1 0 0 -1 A2 500 -1 2 1 0 PEG 600 dibehenate 100 ALIGN! 3 3 4 4 Mixed PEG / 200/400/600 / 100 ALIGN! 4 4 5 2 di / stearate / behenate Tween 65 500 1 1 0

+ A negative value indicates an increase in CFPP

Tween 65 is a polyethoxylated sorbitan tristearate (non-linear).

The above results show that in the fuels tested, a significant reduction in CFPP can be achieved by simply adding 100 ppm of polyethylene glycol ester, while 500 ppm of ethylene vinyl acetate is ineffective.

Example 2

The properties of the fuels used in Example 1 containing certain polyglycol esters of the invention are compared to the DOT test (see page 21, distillate flow characteristics test) at 5 ° C and 7 ° C below WAP (wax discovery) (as shown in Table 1) with certain commercially available ingredients to improve flow properties to obtain these results

Fuel

AND (B) C D ppm additives to improvement 100 ALIGN! 500 .100 500 100 500 500 characteristics creep Ingredient None 30 blocks 20 blocks 20 blocks 20 A2 30 60 20 May 40 40 40 Keroflux H 30 60 B20 40 - - Al 20 May 60 40 20 May - 60 Keroflux M B20 30 B20 40 - Tween 65 60 120 40 30 100 ALIGN! -

CS 276 707 B6

Fuel D AND (B) C ppm additives to improve creep characteristics 100 ALIGN! 500 100 500 100 ALIGN! 500 500 Polyethylene glycol (600) dibehenate 80 120 40 80 - - 120 100 ALIGN! Mixed PEG / 200/400/600 150 200 60 200 100 ALIGN! 150 100 ALIGN!

Di / stearate / behenate

Keroflux H is an ethylene vinyl acetate copolymer.

Keroflux M is an ethylene-2-ethylhexyl acrylate copolymer.

Tween 65 is a polyethoxylated sorbitan tristearate (non-linear).

The above results demonstrate the advantage of polyethylene glycol esters as additives to improve flow properties over various conventional flow additives based on various conventional copolymers for the fuels used. The advantages of polyethylene glycol esters over the non-linear ethoxylated Tween 65 ester are also illustrated.

Example 3

The DOT test (distillate flow characteristics test) is used to determine the applicability of fuel A according to Table I at -15 ° C containing 100 ppm additives based on various polyoxyethylene dibehenates in which the polyoxyethylene segments have different number average molecular weights. The results are as follows

Polyethylene glycol Passage the finest sieve Molecular weight mesh no. / micrometers / no ingredient 20 May 833 100 ALIGN! 40 420 144 40 420 200 150 104 400 100 ALIGN! 147 600 80 175 1 000 30 approximately 495 1 500 40 420 4 000 40 420

The results demonstrate the advantages of polyethylene glycols having a molecular weight of 200 to 600.

CS 276 707 85

Example 4

The process of Example 3 was repeated using the polyglycol ester in an amount of 100 ppm and v

in the form of a polyethylene glycol diester of molecular weight 600 which is esterified by two moles of carboxylic acid of varying length. The results are as follows: Polyethylene glycol ester Passage the finest sieve / number of carbon atoms / mesh no. / micrometers / Laurate (12 carbon atoms) 20 May 833 Myristate (14 carbon atoms) 30 approximately 495 Palmitate (16 carbon atoms) 40 420 Stearate (18 carbon atoms) 40 420 Behebat (22 carbon atoms) 80 175 Stearate / behenate 100 ALIGN! 147 Mixed PEG / 200/400/600 stearate / behenate 150 104

The mixed stearate / behenate is obtained by reacting polyethylene glycol with two moles of an equimolar mixture of stearic and behenic acid.

This example illustrates the advantage of higher molecular weight polyethylene glycol esters of carboxylic acids and the fact that esters of one or mixed ethylene glycols with mixtures of carboxylic acids may be advantageous.

Example 5

DOT assays are used to compare the creep characteristics of polyethylene glycol esters, polypropylene glycol esters as well as improved performance by using polypropylene-

lenglycol esters and polyethylene glycol esters in fuel A according to tables ] [/ at -15 Esther ppm of ester Passage the finest sieve (molecular weight) / active ingredients / mesh no. / micrometers / a / Mixed PEG / 200/400/600 / 100 ALIGN! 150 104 di- / stearate / behenate / 500 200 74 b / PPG / 400 100 ALIGN! 20 May 833 di- / stearate / behenate / 500 200 74 c / PPG / 1,025 / 100 ALIGN! 30 approximately 495 di- / stearate / behenate / 500 150 104 d / PPG / 2,025 / 100 ALIGN! 20 May 833 di- / stearate / behenate / 500 60 245 Ester mixture ppm of the mixture Passage the finest sieve / weight ratio / / a / / / b / = 1/4 500 250 61 / a / / / c / = 1/4 500 150 104 / a / / / d / = 1/4 500 150 104

CS 276 707 B6

The results above demonstrate that polypropylene glycol distearate / behenates are also very effective additives to improve creep characteristics at higher concentrations but are not as effective as polyethylene glycol esters at lower concentrations. Mixtures of polypropylene glycol esters and polyethylene glycol esters can also be used effectively.

Example 6

The reduction in CFPP / cold filter / fuel blocking temperature D of Table I containing polyethylene glycol esters at different molecular weight polyethylene glycol and using different carboxylic acids for esterification is measured.

Polyethylene glycol ester (PEG ester)

PEG 600 dilaurate PEG 600 dimyristate PEG 600 dipalmitate PEG 600 distearate PEG 600 dibehenate PEG 200 dibehenate

Polyethylene glycol ester (PEG ester)

PEG 400 dibehenate PEG 600 dibehenate PEG 1,000 dibehenate PEG 1,500 dibehenate Mixed PEG / 200/400/600 / dibehenate

Mixed PEG (600 / 1,000) dibehenate ppm active ingredient Reduction in fuel 0 CFPP

100 0

100 0

100 0

100 0

100 5

100 0 ppm active substance Reduction in fuel D CFPP

100 4

100 5

100 0

100 0

100 5

100 5

The above results demonstrate that PEG 400 and PEG 600 dibehenates have optimal molecular weight and optimal carboxylic acid to reduce CFPP in said fuel. For comparison, the CFPP reduction for fuel D containing 100 ppm Al - 1 additive.

Example 7

The potency of mixed polyethylene glycol esters with other additives for distillates with a narrow boiling range is determined by the DOT test for fuel B of Table I at -15 ° C. The weight ratio is 4/1.

CS 276 707 B6

Ingredient ppm of active ingredient Passage Mesh the finest net micrometers PEG 400 dibehenate 100 ALIGN! 40 420 Bl 500 60 245 B1 / PEG 400 dibehenate in a ratio of 4/1 500 200 74 Bl / Tween 65 in a ratio of 4/1 500 40 420 A2 500 40 420 A2 / mixed PEG di / stearate / behenate in a ratio of 4/1 500 60 245

The results demonstrate the advantages of a mixture of PEG ester with polar monomer B1 compared to using polar monomer B1 alone and in comparison with mixture B1 and Tweeiu 65. The efficiency of ethylene vinyl acetate copolymer A2 is also improved by use in the presence of polyethylene glycol ester.

Example B

The effectiveness of polyethylene glycol ester in admixture with ethylene vinyl acetate copolymer as a growth inhibitor and as a CFPP reducing additive for fuels with a broad boiling range E according to Table I is as follows:

Polyethylene glycol ester

Ethylenvinylacetátový Type Active ingredient Reduction copolymer (A2) CFPP ppm ppm 100 ALIGN! - 0 0 200 - 0 2 80 PEG dibehenate . '20 12 100 ALIGN! II 40 15 Dec 0 II 100 ALIGN! 0 O' II 200 2 B0 Mixed PEG (600/1000) dibehenate 20 May 13 160 II 40 18 0 II 200 2 150 ^C 28 ^ 30 ^mixed PEG ester * 50 16

+ Prepared by esterifying one mole of mixed polyethylene glycol (200/400/600) with 2 moles of saturated carboxylic acid derived from the reaction product of C 26 to C 28 alpha-olefins with acetic anhydride in the presence of di-tert-butyl peroxide as a catalyst.

The results show considerable efficacy of such mixtures compared to the individual components,

CS 276 707 B6

Example 9

The activity of polyethylene glycol esters in admixture with polar monomer compounds as

additives to reduction Cold Filter Clogging Temperature (CFPP) for fuel F according to the table is following: Ingredient Polyethylene glycol ester ppm ppm CFPP reduction A2 / pro comparison/ 75 - 0 0 A2 75 PEG 600 dibehenate 25 10 A2 75 PEG 600 distearate 25 0 Bl 75 - 0 0 Bl 75 PEG 600 dibehenate 25 6 B2 75 - 0 4 B2 75 PEG 600 dibehenate 25 7 B3 75 0 2 B3 75 PEG 600 dibehenate 25 12

The results above demonstrate the advantages of polyethylene glycol dibehenate (PEG dibehenate) over distearate when used in admixture with A2 and the benefits of using a component such as PEG 600 dibehenate for the above purpose. Thus, polar monomer compounds may also be effective in lowering the cold filter clogging temperature (CFPP) when used in admixture with a PEG 600 ester.

Example 10

In this example, the efficacy of mixtures of polyethylene glycol esters and A2 was tested by 00T at -12 ° C.

Ihnibitor wax crystal growth ppm

Fuel E according to Table I A2 200

A2 170

A2 170

Polyethylene glycol ester Passage the finest sieve ppm Mesh / micrometers / - 0 150 104 PEG 600 dibehenate 30 250 61 mixed PEG / 400/600/1000 / distearate / dibe- henate 30 250 61

Fuel G according to Table I A2 500

A2 400

Bl 400

- 0 40 420 mixed PEG / 200/400/600 / stearate / behenate 100 ALIGN! 150  104 _ II _ 100 ALIGN! 200 74

The above results demonstrate greater efficacy of mixtures of polyethylene glycol esters with ethylene vinyl acetate copolymer or wax crystal growth inhibitors based on a polar monomer compound compared to an equivalent concentration of wax crystal growth inhibitor alone.

CS 276 707 B6

Example 11

In this example, the results of fuel test 0 according to Table 1 are reported from three tanks of 25 m · ⁵ being carried side-by-side. During three weeks of storage at natural low temperature conditions (including natural cyclic temperature variation), fuel is pumped from the tank at -13.5 ° C as in the fuel distribution and the finest filter screen through which the fuel passes is recorded.

Additive (at 0.1% active substance) Passage mest finest sieve (micrometers) a / Al 40 420 b / Mixed PEG / 200/400/600 / di / stearate / / behenate 60 246 c (A2) mixed PEG ester as in b) / ratio 3/1 / 80 175

The filter screens typically used in such fuel distribution have a mesh number of 60 (246 microns) and it is therefore clear that while fuel containing ethylene vinyl acetate cpolymer A1 has insufficient performance properties for mesh filter number 60 (with 246 microns), fuel containing polyethylene glycol ester alone and a fuel comprising a mixture of ethylene vinyl acetate copolymer and ethylene glycol ester provides sufficient flow upon pumping.

Example 12

Three drums of fuel A according to Table I are cooled at a rate of 0.5 ° C / h to a temperature of -13 ° C and after temperature equalization, a sample of 300 ml of fuel is tested for cold creep characteristics of the DOT test. The drums are then slowly heated above the wax emergence temperature (WAP) in the fuel and then cooled again at a rate of 0.5 ° C / h to -13 ° C. The fuel is then pumped from the drums through a set of filter screens to determine the finest screen through which the cold wax fuel passes.

Ingredient Active substance PPm AI 500 Mixed PEG (200/400) / 600 / di / stearate / 100 ALIGN! / behenát / 500 Mixed PEG ester as from above characterized (PPG / 1025) dibehenate 100/400

Pass through the finest sieve

after the first cooling after the second cooling Mesh micrometers mes h micrometers 60 246 40 420 80 175 80 175 120 124 120 124 120 124 100 ALIGN! 147

The above results confirm the advantages of polyethylene glycol esters and a mixture of polyethylene glycol ester with polypropylene glycol ester over ethylene vinyl acetate copolymer A1.

CS 276 707 Be

Example 13

The DOT test is used in the -10 ° C test to compare linear

linear esters unsaturated esters for example p an ester of an oil Fuel according to Table Ingredient ppm Passage the finest sieve mes h ¹ / micrometers / D PEG 600 / dibehenate 500 100 ALIGN! 147 D PEG / 600 / dioleate 500 clogging 20 833 0 none clogging 20 833

Example 14

The DOT test is repeated in a series of three distillate fuels with a wide range of boiling points and the efficiency of the linear polyethylene glycol esters used alone in such fuels is clarified.

The values obtained are compared with those obtained with the ethylene vinyl acetate copolymer A2 and the dioleate ester to demonstrate the importance of the linear saturated alkyl ester.

Fuel according to Table I Additive ppm Pass through the finest mesh (micrometer)

E A2 200 200 74 E PEG / 600 / dibehenate 200 200 . 74 E PEG / 600 / dioleate 200 40 420 E none - 30 about 495 H A2 300 100 ALIGN! 147 H PEG / 600 / dibehenate 300 100 ALIGN! 147 H PEG / 600 / dioleate 300 40 420 H none - 40 420 AND A2 250 120 about 124 AND PEG / 600 / dibehenate 250 200 74 AND PEG / 600 / dioleate 250 80 175 AND none - 80 175

Example 15 Fuel with a relatively high boiling point has these characteristics Oil turbidity temperature / ° C / +4 Wax appearance temperature / ° C / -0.7 Cold filter clogging temperature / ° C / untreated / CFPP temperature / -5

CS 276 707 B6

Distillation according to ASTM D86

Initial boiling point / ° C / 185

Boiling point / ° C / 386

It is treated with varying amounts of blend additive comprising a mixture of one part by weight of polyethylene glycol (600) dibehenate / PEG (600) dibehenate) and 4 parts by weight of additive A2. The following results are achieved:

Additive amount, ppm

150

200

250

300

350

450

500

550

650

Cold filter clogging temperature, ° C -14 -14 -14 -14 -16 -16 -16

Thus, this example demonstrates that the cold filter clogging temperature values are the actual temperatures at which the fuel fails the cold filter clogging test.

10% by weight, based on the total weight of the additive, of waxed naphthalene prepared by Friedel Crafts condensation of about 100 parts by weight of n-paraffin wax having a melting point of about 50-55 ° C, chlorinated to about 1% by weight, is added.

14.5% of chlorine, based on the weight of chlorinated wax and about 12 parts by weight of naphthalene (known as C), and the clogging temperature of the cold fuel filter containing the above mixture is tested:

Additive Cold filter clogging temperature, ° C

550 ppm mixture + 55 ppm C-19

650 ppm mixture + 65 ppm C -20

These values, for example, show that further improvement of said fuel is achieved by incorporating additive C.

Example 16

The DOT test for fuel A at -15 ° C is used to compare polyethylene glycol 600 distearate and polyethylene glycol 600 diisostearate using a 200 ppm additive. Results achieved:

Ingredient Active substance PPm Passage Mesh finest sieve (micrometers) PEG 600 distearate 200 40 420 PEG 600 diisostearate 200 clogging 20 833

Thus, preference is given to a linear alkyl group.

CS 276 707 B6

Example 17

Prepare polytetramethylene Terakoly of the formula HO - CH // _2/4 -0_7 - H with a molecular weight of 650, 1000 and 2000 and esterified with two moles of behenic acid. These substances are then tested in fuel A by the DOT test at - 15 ° C with the following results:

Ingredient Active substance ppm Pass through the finest sieve Mesh / micrometers / Teracol (650) dibehenate 200 clogs 20 833 Teracol (1000) dibehenate 200 30 495 approximately Teracol / 2000 / debehenate 200 40 420

It will be appreciated that certain terracotta derivatives are effective, but exhibit less potency compared to Example 3 than comparable polyethylene glycol esters and polypropylene glycol esters.

Example 18

The C18 linear alcohol is ethoxylated and the product is esterified with one mole of behenic acid to give the ester ether of formula

C ₁₈ - 0 - / CH ₂ CH _{2 0/10} - c ^J 21

In the DOT test and at a concentration of 200 ppm of the active ingredient, the additive at -15 ° C allows fuel A to pass through an 80 mesh sieve, orifices of 175 microns.

Example 19

The polyethylene glycol 600 is reacted with two moles of succinic acid and the product obtained is reacted with two moles of a straight chain 22/24 carbon alcohol to give the product of the formula

0 0 0

II Η II II ^{/ C} 22 ^{/ C} 24 ^{/ -0} ' ^C-CH 2' ^CH 2 ^{-C 0 / PEG 600} / "° - ^c * ^CH 2" ^CH 2 " ^{G 0 /, C} 22 ^/ ' ^C 2y

This product is tested in fuel 0 having a turbidity temperature of +4 ° C, a wax discovery temperature of 0 ° C, a cold filter clogging temperature of -1 ° C, an initial boiling point of 195 ° C and a final boiling point of 375 ° C. The product is tested in the DOT test at -6 ° C and the additive-free fuel passes through a 40 mesh sieve, a 420 micron sieve, while a fuel containing 200 ppm of the additive passes through an 80 mesh filter, 175 microns.

The introduction of 200 ppm of this additive into fuel A in the DOT test at -15 [deg.] C. shows a 100 mesh screen of 147 microns.

Example 20

The effect of polyethylene glycol (600) dibehenate is compared to that of polyethylene glycol (600) dierucate in fuel K, which has a haze temperature of -2 ° C, a wax discovery temperature of -6 ° C, an initial boiling point of 200 ° C and a final boiling point of 354 ° C. The untreated fuel has a cold filter clogging temperature of -7 ° C, which is not altered by the addition of polyethylene glycol (600) dierucate, but is reduced by 4 ° C by the addition of PEG (600) dibehenate, illustrating the importance of saturated alkyl groups.

CS 276 707 B6

Example 21

A mixture of 4 parts of the flow distillate additive A2 and one part of various polyethylene glycol dibehenates was tested for the cold filter clogging temperature of fuel F with these results;

Ingredient Decrease in clogging temperature 100 ppm additives cold filter 200 ppm additives A2 itself 1 2 ethylene vinyl acetate and Polyethylene glycol ester 4: 1 ratio 1 2 A2 PEG (200) dibehenate 1 2 A2 PEG (400) dibehenate 1 2 A2 PEG (600) dibehenate 13 16 A2 PEG (1000) dibehenate .14 17 A2 PEG (1500) dibehenate 14 17 A2 PEG (4000) dibehenate 3 3 A2 PEG / 600/1000/1500 / - dibehenate 14 18 PEG (600) dibehenate itself 6 + P / EO / PO / 8000 dibehenate 0 0

+ P / EO / PO / 8000 is a poly (ethylene oxide / propylene oxide) of 8000 molecular weight and is condensed with 2 moles of behenic acid.

Example 22

The method of Example 21 was repeated using teracol derivatives instead of polyethylene glycol dibehenates with the following results:

Additive Decrease the cold filter clogging temperature

100 ppm additives

Teracol 650 dibehenate

4: 1 .3

Claims (1)

⁺ A2 Terracol / 650 / dibehenate 0 Terracol / 1000 / dibehenate 0 ⁺ A2 Terracol / 1000 / dibehenate 3 Terracol 2000 dibehenate 3 ⁺ A2 Terracol / 2000 / dibehenate 0 ⁺ The ethylene vinyl acetate to teracoldibehenate ratio is 4: 1, From the above, it is apparent that the Teracol derivatives are much less potent than the polyethylene glycol derivatives. CS 276 707 B6 Example 23 Various additives are tested in the DOT test at -10 ° C in fuel L having a turbidity temperature of -4 ° C, a wax discovery temperature of -6 ° C, an uncorrected cold filter clogging temperature of -6 ° C, an initial boiling point of 216 ° C and a final boiling point of 353 ° C. The results are as follows: Additive Active substance DOT ppm test Pass through the finest mesh (micrometers) None - clogs 20 833 PEG (600) dibehenate 100 ALIGN! 150 104 PEG (600) monobehenate 100 ALIGN! 40 420 Teracol (650) dibehenate 100 ALIGN! 30 495 approximately Teracol (1000) dibehenate 100 ALIGN! 20 May 833 Teracol (2000) dibehenate 100 ALIGN! 20 May 833 Poly / E.0 / P.0.-8000 / di- 100 ALIGN! 20 May 833 behenate / molecular mass- 8000 / 500 20 May 833 Example 24 Clogging temperature drop a cold fuel filter D comprising Various ingredients are following: Ingredient Active substance Decrease clogging temperatures Ppm ° C cold filter PEG 200/400/600 dibehenate 250 4 ^C 21 ^H 43 ^{C (OCH} 2 ^CH 2 ^{), 80H} II 250 -1 0 500 -1 ^C 18 ^H 37 O- / CH ₂ CH ₂ O / ₁₀ -H 250 -2 500 -5 ^C 18 ^H 37 ° ^{C / CH} 2 ^CH 2 ^{O /} 10 ~ ^CC 21 ^H 43 ²⁵⁰ II 1 0 500 3 PATENTOVÉ Claims What is claimed is: 1. A fuel oil comprising: medium distillate fuel oil temp boiling point 120 to 500 ° C; and weight 0.0001 up to 0.5% of an ester, and / or an ether, and / or ester / ether of formula I R - 0 - / A / - 0 - R ¹ / 1 / where R and r! have the same or different meanings and represents a group of the general formula n-alkyl It n-alkyl - CS 276 707 86 II n-alkyl-O-C- (CH ₂ ) _n -O 2 (I n-alkyl-O-C - / CH ₂ / _n - C 2). 3. 4. 5. 6. 7. 8. 9. wherein the alkyl group is linear and saturated and contains from 10 to 30 carbon atoms, wherein one of R a R ¹ also represents hydrogen and A is a polyoxyalkylene glycol moiety having a molecular weight of 100 to 5,000, wherein the alkylene group contains 1 to 4 carbon atoms. Fuel oil according to claim 1, characterized in that it comprises medium distillate fuel oil having a boiling point of 200-50 ° C to 340-20 ° C. 1. The fuel oil of claim 1, wherein, in the additive of formula (I), R &lt; ¹ &gt; is alkyl of 18 to 22 carbon atoms. The fuel oil of any one of claims 1 to 3, wherein the polyoxyalkylene glycol is polyethylene glycol. 6. The fuel oil of claim 4, wherein the polyethylene glycol has a molecular weight of about 200 to about 2000. The fuel oil of any one of Claims 1 to 3, wherein the polyoxyalkylene glycol is a mixture of polyethylene glycol and polypropylene glycol. The fuel oil of any one of claims 1 to 6, wherein R a R ¹ is an acyl residue of behenic acid and the polyoxyalkylene glycol has a molecular weight of 200 to 800. Fuel oil according to any one of Claims 1 to 7, characterized in that it also contains an additive for lowering the pour point of the lubricating oil selected from a) condensates of a halogenated paraffin wax with an aromatic hydrocarbon and b) an oil-soluble ester and / or olefinic polymer weighing between 1,000 and 200,000. Fuel oil according to any one of Claims 1 to 8, characterized in that it additionally comprises a paraffin wax crystal growth inhibitor based on an ethylene / vinyl acetate copolymer or on the basis of an oil-soluble polar nitrogen compound having 30 to 300 carbon atoms which is an amine salt and / or amide; and / or a carboxylic acid ester / amide having 1 to 4 carboxy groups or an anhydride thereof. 9. The fuel oil of claim 9 comprising from about 20% to about 40% by weight of the additive of the formula (I) from about 80% to about 60% of ethylene vinyl acetate copolymer based on the total weight of the additive to the fuel distillate oil.