HU202267B - Doped fuel oil fraction of improved flow character - Google Patents

Abstract

The present invention relates to an improved dewatering oil distillate having a boiling point of 120 to 500 ° C, in particular 160 to 400 ° C, with an additive content of 0.01 to 0.05%, characterized in that I) is the total weight of the additive. 15 to 100% of a polyoxyalkylene glycol derivative of formula (I) wherein R1 and R2 are a) are identical and can be from 10 to 30 carbon atoms in straight chain alkanoyl; or 15 -CO- (CH2) k-COO-R3 wherein k is 1,2,3 or 4 and Ra is a straight chain alkyl having from 18 to 26 carbon atoms or b is different and may be i) R 1, R 2 are both straight-chained; C10-30 alkanoyl, or ii) R1 is a straight chain C10 to C30 alkanoyl and R2 is a straight chain alkyl having from 20 to 20 carbon atoms, A is a polyoxyalkylene glycol of from 100 to 4000, preferably from 200 to 2000; - (RO) n- rt - wherein R is C2-C4 alkylene and n is from 25 to 85% by weight of the total additive, and optionally II) by weight of the total additive ethylene vinyl acetate copolymer having an average weight of 1800-3000 or III) 25-75% by weight of dicarboxylic acid or anhydride or 14-24 straight chain alkyl esters of alkyl and about 14 to 24 carbon atoms in the chain of straight chain alkyl alkyl groups, half-amide / semi-amine salt or semi-ester / semi-amine contains salt. EN 202267 B 4 description: 17 pages, without figure -1-

Description

The present invention relates to a fuel oil composition comprising a fluidizing agent.

Additive systems for treating fuel oil distillates are known to improve the flow properties of waxy, cloudy fuels through pipes and filters in cold weather. Some of the literature references describing such additives are listed below.

Nos. 900,202 and 1,263,152. British patents relate to the use of low molecular weight ethylene copolymers and unsaturated esters, in particular vinyl acetate, while U.S. Pat. U. S. Patent No. 4,122,125 to Dawson describes the addition of an additive system that both raises the initial temperature of paraffin crystallization and limits the size of the paraffin crystals. Nos. 848,777, 993,744 and 1,068,000. British Patent Specifications; and U.S. Patent No. 3,679,380; U.S. Pat. Nos. 3,374,073, 3,499,741, 3,557,636, 3,524,732, 3,608,231, and 3,681,302. U.S. Pat.

It has also been proposed to use additive combinations to improve the flow properties of the fuel oil distillates and to change their pour point. For example, U.S. Patent No. 3,661,541. United States Patent No. 5,193,744 discloses an additive combination consisting of an ethylenically unsaturated ester copolymer and a compound of U.S. Pat. is a low molecular weight copolymer of ethylene-propylene as described in the British patent.

No. 3,658,493. U.S. Pat. No. 4,123,198 to Deer et al. proposes a composition comprising a mixture of various nitrogen-containing salts and acid amides, such as mono- or dicarboxylic acids, phenols or sulfonic acids, in combination with homo- or copolymers of ethylene.

No. 3,982,909. U.S. Pat. and improve the cold-flow properties of fuel oil middle distillates, including diesel oil.

Nos. 3,444,082 and 3,946,093. U.S. Patent Nos. 5,119,125 to 5,198 and 6,198, teaches the use of amine salts of various amides and alkenyl succinic anhydrides, together with ethylene copolymer pour point depressants, as additives in fuel oil distillates.

No. 3,762,888. U.S. Pat. contains a similar straight-chain polymethylene moiety. The most important part of this patent specification for the present invention is that the second component without the first polymer component has little or no improvement in fluidity.

The composition of the present invention is based on the discovery that certain polyoxyalkylene esters, ethers, ether esters and mixtures thereof alone are effective in improving the fluidity of distilled fuels and can be used as a single additive for boiling point distillates of a particular boiling range. in the case of conventional flux enhancers are often ineffective. The use of said narrow source boiling oil distillates is increasing as refineries are required to produce more distillates from the boiling point range of kerosene, which results in an increase in the initial boiling point of middle distillates, so that the final boiling point is required to comply with the turbidity point. These narrow source distillates therefore have relatively high initial boiling points and relatively low final boiling points.

While additives known in the literature are generally suitable for fuel oil distillates boiling at 120-500 ° C, especially 160-400 ° C, further improvement is required to control the growth of excellent paraffin crystals. However, there are problems in improving the fluidity and filterability of oil distillates, when these oils have a relatively narrow source range. It has now been found that certain polyalkylene esters, ethers, esters or mixtures thereof are particularly suitable for the addition of narrow boiling oil distillates to improve their fluidity properties. The term "narrow-source distillate *" refers to fuel distillates boiling in the range of 200 ± 50 ° C to 340 ± 20 ° C; fuels whose source range is outside this zone are referred to hereafter as wide-range distillates.

Thus, in accordance with the invention, fuel oil distillates, particularly those boiling at a narrow boiling range of 120-500 ° C, preferably

HU 202267 Β is a fuel oil distillate containing from 0.01 to 0.05 tX of liquid enhancer which

I) from 15 to 100 tX, based on the total weight of the additive, of a polyoxyoxyalkylene glycol derivative of the formula I-O-A-R2

- where R1 and R2 are represented

a) the same and may be a straight-chain alkanoyl group having from 10 to 30 carbon atoms, or -CO- (CH2, k-COO-R3) group wherein k is 1,2,3 or 4 and R3 is a straight-chain alkyl group having 18 to 26 carbon atoms;

b) different and optionally i, R 1, R 2 are simultaneously linear C 10 -C 30 alkanoyl groups, or ii) R 1 is a straight-chain C 10 -C 30 alkanoyl group and R 2 is C 16 -C 20 straight chain alkyl group,

A is selected from the group consisting of polyoxyalkylene glycols having a molecular weight of 100-4000, preferably 200-2000 molar, where R is a C 2 -C 4 alkylene group and n is the molar weight and optionally

(Ii) one or more ethylene-vinyl acetate copolymers having an average molecular weight of 1800 to 3000, based on the additive at 25 to 85 tX; or

III) diamide, half-amide / half-amine salt or halide formed by reaction of 25 to 75% by weight of the dicarboxylic acid or its anhydride or C 14 -C 24 straight chain alkyl ester with a C 14 -C 24 linear alkyl group containing alkyl groups as alkyl moiety. contains salt.

The compounds of formula (I) may be used alone or in combination with components II or III as described above.

The compounds of formula (I), as preferred examples the following ^compounds may be mentioned:

1. Esters of polyethylene glycol having a molecular weight of 100 to 4000 moles and two moles of saturated carboxylic acid having from 12 to 22 carbon atoms,

2. Esters of poly (ethylene oxide / propylene oxide) and saturated carboxylic acids having 12 to 22 carbon atoms per mol,

3. The so-called. esters of teracols with {HO - [(CH2) 4-O] n-H} and two moles of saturated carboxylic acid having 12-22 carbon atoms,

4. A compound of formula RO- (CH 2 CH 2 O) R * wherein R is a straight-chain alkyl group, R 'is an acyl group derived from a C 12 -C 22 saturated carboxylic acid,

5. Product obtained by reaction of polyethylene glycol and 2 moles of succinic ester with 2 moles of straight-chain saturated, mixed C22-C24 alcohol.

Preferred compounds of formula (I) which are preferred among the compounds of formula (I) include, for example, polyethylene glycol of 100-400 molar mass and esters or lauric, myristic, palmitic, stearic, and benzoic acids. mixed ester. (Embodiments 1-16).

Examples of preferred compounds 2 include poly (ethylene oxide) (propylene oxide) and behenic acid diester (Examples 21 and 23).

Examples of preferred compounds 3 include esters of teracols of 650, 1000 and 2000 moles and two moles of behenic acid (Examples 17 and 22).

Examples of preferred compounds 4 include the esters of Cl8H37-O- (CH2CH2O) l-C (O) -C2H2O, C21H43C (O) - (OCH2CH2) 6OH, CisH37-0- (CH2CH2O) 10-H ( 18 and

Embodiment 24).

Examples of preferred compounds 5 include (C22H45-C24H49) -OC (O) -CH2-CH2-C (O) -O- [PEG, (600)] C (O) -CH2CH2C (O) O (C22H45-C24H49). The compounds of Formula I (Example 19) may be mentioned.

Suitable glycols for the preparation of the compounds of formula I used in the fuel oil distillate of the present invention are generally substantially straight-chain polyethylene glycols (PEG) and polypropylene glycols (PPG) having a molecular weight of 100-4000, preferably 200-2000. to improve the flow properties of distillates.

Preferred representatives of the compounds of formula (I) of the present invention are ester-type compounds prepared from C 10 -C 30 fatty acids by reaction with glycols; for narrow-source distillates, they are preferably used in the form of esters formed with a mixture of C 18 -C 24 fatty acids, most preferably behenic acid, and stearic acid. The above esters can be prepared by esterifying polyethoxylated fatty acids or polyethoxylated alcohols.

For narrow-range distillates, polyoxyalkylene diesters, ether esters or a mixture thereof may be used in addition to the diesters, and smaller amounts of monoethers and monoesters may be present, which are often formed during the production process; however, it is important for the additive that the dialkyl compound is present in the highest amount. Particularly preferred are diesters of stearic acid or behenic acid with polyethylene glycol, polypropylene glycol or a mixture of polyethylene and polypropylene glycol.

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Compounds of formula (I) are effective in themselves as a fluid-improving agent (contrary to the teachings of U.S. Patent No. 3,762,888), but may also be used effectively in combination with additives II or III.

Polyoxyalkylene esters or ether esters may be used as a single additive or in combination with other additives. In the case of narrow boiling distillates which are generally not amenable to conventional additives, the polyoxyalkylene esters or esters of the invention are often effective as a single additive. However, in wide-range fuel oil distillates, the ester or ester ether derivatives of the present invention are preferably used in combination with other fluid-improving additives.

Preferred component II in the composition is a copolymer of ethylene and vinyl acetate.

In addition to the compounds of formula I, the composition of the invention may also contain nitrogen compounds. These are described, for example, in U.S. Patent No. 4,211,534.

In general, they are oil-soluble,

Derivatives of C12-C40 secondary amines.

A preferred amine is the secondary hydrogenated tallow amine having the general formula HNR'iR'z, wherein R'1 and R'2 are an alkyl group derived from hydrogenated tallow fat, and the alkyl groups are about. 4X-a 14, approx. 31% is 16, approx. 59% of them have 18 carbon atoms.

It is preferred that the nitrogen-containing compound contains at least one straight carbon chain having from 14 to 24 carbon atoms.

A particularly preferred amine compound is the amine salt which can be prepared by reacting one mole of phthalic anhydride with 2 moles of dihydrogenated tallow amine. Another particularly preferred amine compound may be prepared by dehydration of this amine.

The efficacy of the formulations of the present invention is illustrated by the following examples, without limiting the invention to the examples. In the examples, the abbreviations refer to the following fluid-improving additives:

Al: Two types of ethylene / vinyl acetate copolymer (1 and 2) of 50% by weight in aromatic solvent,

Copolymer 1: It consists of ethylene and 38% by weight of vinyl acetate having an average molecular weight by vapor pressure osmometry of 1,800 (see copolymer B of British Patent No. 1,374,051).

Copolymer 2: It consists of ethylene and 16% by weight of vinyl acetate having an average molecular weight of 3000 (determined by copolymer H according to British Patent No. 1,374,051).

The weight ratio of the two types of copolymer is copolymer 1: copolymer 2 = 3: 1.

A2: 1 used in the additive Al.

copolymer alone.

Keroflux H: ethylene / vinyl acetate copolymer; (BASF)

The following components, designated B1, B2, B3 and B4, were used as polar, monomeric nitrogen-containing growth inhibitors:

B1: Product obtained by reaction of one mole of phthalic anhydride with one mole of dihydrogenated tallow, which is a semi-amide / semi-amine salt (European Patent Application 0061/894)

B2: Phthalic diamide produced by removing one mole of water from product B1.

B3: The dihydrogenated tallow salt of monooctadecyl phthalate.

B4: Semi-amine / semi-amide salt obtained by reacting two moles of dihydrogenated anthrax with one mole of maleic anhydride (U.S. Pat. No. 3,982,909).

Although many of the additives are available in the form of an oily solution, what is hereinafter referred to as the active ingredient is the amount actually present.

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Table 1

Fuel THE B C D E F G H I cloud point (° C) -9 -9 -4 -2 1 -4 0 wax appearance point (WAP) (° C) -10 -10 -7 -5 -2.5 -5.5 -4 -0.5 1.5 CFPP (° C) (Untreated) aromatic substance (massX) (fluorescent -12 -12 -6 -5 -3 -5 -4 indicator analysis) wax content (massX) 18 31 40 28 30 31 23 38 29 5 "C below WAP ASTM D86 Distillation 2.2 1.5 2.2 4.0 0.9 1.0 1.6 0.9 0.9 initial boiling point ° C 220 180 221 202 182 180 156 161 167 final boiling point ° C 341 332 348 343 385 368 355 381 387

The fuels are typical European heating and diesel fuels, the letters A, B, C and D are narrow-source distillates, while the letters E, F, H and I are the wide-source distillates; fuel G is the boundary between narrow and wide source fuels.

One method of measuring the effect of additives on oil is the so-called. Cold Filter Plugging Point Test (CFPPT), published in the Journal of the Institute of Petroleum. 526, June 1966, pages 173-185. This test shows the cold-liquid properties of middle distillates in automatic diesel engines.

In this procedure, a 40 ml sample of the oil to be tested is cooled in a bath maintained at -34 ° C so that it is cooled to ca. Non-linear cooling at a rate of 1 ° C / minute should occur. Occasionally, at a temperature of at least 2 ° C above the turbidity point, each drop of temperature is examined to determine whether the cooled oil can pass through a fine sieve over a prescribed time interval. As a test device, use a pipette attached to an inverted funnel located below the surface of the oil to be tested.

At the mouth of the funnel, place a 12 mm diameter sieve with a 0.04 mm mesh. Each periodic test begins by placing the upper end of the pipette under vacuum so that 20 ml of oil is drawn through the sieve into the pipette. Immediately after each successful suction, the oil is returned to the CFPP tube. Lowering the temperature by 1-1 ° C, the test is repeated until more than 60 seconds are needed to draw the oil into the pipette. This temperature is considered CFPP temperature. The difference between non-additive and additive oil CFPP values is that the additive causes a decrease in CFPP value. The more effective fluidity enhancer causes greater CFPP reduction at the same concentration.

Another method for determining the effectiveness of a fluid-improving additive is the so-called. A flow iinprover distillate operubility test (DOT), in which the stored fuel oil is slowly cooled while measuring its pumpability. The cold flow properties of the oils containing the additives described were determined by the DOT test as follows. 300 ml of fuel were cooled linearly

At a rate of 1 ° C / hour to the test temperature, the temperature was then maintained at this value. After holding the test substance at the test temperature for two hours, the surface of the test substance was exposed for approx. 20 ml were aspirated to avoid the formation of abnormally large paraffin crystals at the oil-air interface which would interfere with the assay. The paraffin settled in the vessel was dispersed with gentle agitation and a CFPP filter was placed in the vessel. The tap was opened to create a vacuum of 0.665 bar and was closed when 200 ml of fuel passed the filter into the collecting vessel. The experiment was judged positive if 200 mL of fuel passed a sieve of specified mesh size within 10 seconds and was unsuccessful when the flow rate was too low, indicating that the filter was clogged.

0.84, 0.55, 0.42, 0.25, 0.18, 0.149, 0.134,

The 0.111, 0.074, 0.047, and 0.04 mm mesh filter screens were used in the CFPP filter equipment to determine which of the smallest mesh screens the fuel would pass through. The smaller the mesh through which the distillate passes, the smaller the paraffin crystals, and thus the greater the efficiency of the fluid improving additive. It should be noted that two oils do not give exactly the same test results-59

EN 202267 Β under the same operating conditions for the same fluid-improving additive and therefore the effectiveness of the additive depends on the quality of the fuel.

The (PEG) esters of formula (I) and the polypropylene glycol (PPG) esters were prepared by mixing one mole of glycol with two moles of carboxylic acid and adding 0.5 wt% p-toluenesulfonic acid as a catalyst. The mixture was heated to 150 ° C with stirring and slowly purged with nitrogen gas to distill the water formed during the reaction, and upon completion of the reaction, determined by infrared spectra, the product was poured and allowed to solidify to give a waxy solid. The product is characterized by data obtained by elemental analysis, gel permeation chromatography, saponification and spectroscopy.

PEG and PPG derivatives are generally referred to together with molecular weights, for example, PEG (600), means polyethylene glycol of average molecular weight 600. This nomenclature is also incorporated here, with respect to esters, such as

PEG (600, -dibehenate) refers to the product obtained by reacting two moles of behenic acid and one mole of PEG (600). It is also possible to use mixtures of PEGs of different molecular weights, such that the , Having molecular weights of 400 and 600

It refers to the distearate ester of a 1: 1: 1 by weight mixture of PEGs. Carboxylic acid mixtures may also be used, such as PEG-di (stearate / beheate), the product obtained by reacting 1 mole of PEG with 1 mole of stearic acid and 1 mole of behenic acid. In each type of mixture, 2, 3 or more different types may be used

PEG or PE / PP-G copolymers and carboxylic acids.

Example 1

The CFPP test was performed on the range distillates having the characteristics listed in Table 1 which are generally difficult to add. In the course of the experiment, the compounds of formula (1) were administered as an additive. for comparison, ethylene / vinyl acetate (EVA) Ai and A copolymer additive were added. The results are shown in the following table.

Fluid enhancer Active ingredient con- Decrease in CFPP * • concentration (ppm, First spreadsheet of fuel THE B C D the, al 100 -1 0 - 0 b) al 500 -1 -1 - 0 c) THE 2 100 -1 0 c -1 d) THE 2 500 -1 2 1 0 e, PEG (600, -dibehenate 100 3 3 4 4 f) PEG (200/400/600, - 100 4 4 5 2 - di- (stearate / bezate), g) Tween 65 500 1 1 0

* a negative value indicates an increase in CFPP

Tween 65 is a polyethoxylated sorbitan tristearate (non-linear, manufactured by ICI. 50

The results showed that a significant decrease in CFPP could be achieved with 100 ppm of the compound of formula (1), while 500 ppm of Ai or A additive was expected to be ineffective.

Example 2

The behavior of the fuels used in Example 1 was investigated in the DOT test by the addition of additives. As an additive, the compounds of formula (I) of the present invention and available fluid enhancers were used. The DOT test

5-7 ° C below the wax appearance point of the fuel (taking into account the values given in Table 1). The quantities indicated in the table for fuels refer to the sieve with the smallest aperture (mm) through which the fuel still passes.

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Fluidity enhancement in fuel Fuel THE B 100 pPM 500 pPM C 100 pPM 500 pPM D 500 pPM 100 ppm 500 ppm Folyékonyságjavitó no 0:59 0.84 0.84 0.84 THE 2 0:59 0:25 0.84 0:42 - 0:42 0:42 Keroflux H 0:59 0:25 0.84 0:42 - - - al 0.84 0:25 0:42 0.84 - - 0:25 Tween 65 (ICI) 0:25 0134 0:42 0:59 0149 - - Polyethylene Glycol (600) -dibehenát PEG (200/400/600) - 0:18 0134 0:42 0:18 - 0134 0149 -di (stearate / behenate) 0111 0074 0:25 0074 0149 0111 0149

The results show the fluid-improving effect of PEG ester compared to the conventional copolymer fluid-improving additives. The table also shows the improved effect of PEG esters over the non-linear ethoxylated ester Tween 65.

Example 3

The DOT test was performed on fuel A of Table 1 at -15 ° C using 100 ppm of different polyoxyethylene dibenzene < tb > additive in each case. The table shows the molecular weight of PEG in the PEG dibehenate copolymer.

polyethylene glycol molecular weight the smallest mesh sieve through which the fuel still passes (Mm) - 0.84 100 0:42 144 0:42 200 0111 400 0149 600 0:18 1000 0:59 1500 0:42 4000 0:42

The table shows that PEG esters having a PEG molecular weight of 200-600 are preferred.

Example 4

The experiment of Example 3 was repeated, but using 100 ppm of a compound of formula (I) which is a diol ester of 600 moles of polyethylene glycol with 2 moles of different chain length carboxylic acids.

The results are shown in the following table:

35 polyethyleneglycol ester (Number of carbon atoms) the smallest mesh sieve through which the fuel still passes (mm) PEG (600) -dilaurate (Cr2) 0.84 PEG (600, -dimyristate (C14) 0:59 40 PEG (600) Dipalmitate (Cu) 0:42 PEG (600) -Distearate (Cis) 0:42 PEG (600) -dibehenate (C22) 0:18 PEG (600) - (distearate / be- henate] (C18 / C22) 0149 45 PEG (200/400/600) - (di- stearate / behenate) 0111

The mixed stearate / behenate ester was obtained by reacting the polyethylene glycol with a mixture of 2 molar equivalents of stearic acid and behensic acid.

The example shows that PEG esters of higher molecular weight carboxylic acids are more preferred and also that carboxylic acid esters of PEG or mixtures of different molecular weight PEGs may be preferred.

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Example 5

The DOT test was performed on fuel A of Table 1 at -15 ° C to compare the fluid improving properties of polyethylene glycol esters (PEG) with polypropylene glycol esters (PPG) and a mixture of PPG and PEG esters. The results are shown in the table below:

Example 6

The decrease in CFPP of fuel D as shown in Table 1 was measured for PEG of various molecular weights. containing PEG esters prepared by esterification with various carboxylic acids.

The results are shown in the table below:

ester (molecular weight) the ester The amount (Ppm) the smallest mesh sieve through which the fuel passes (mm) (a) PEG (200 / 100 0111 / 400/600) - di (stearate / 500 0074 / Behenate) (h) PPG (400) -di- 100 0.84 - (stearate / / Behenate) 500 0074 (c) PPG (1.025) - 100 0:59 di (stearic 500 0111 rat / behenate] (d) PPG (2.025) - 100 0.84 —Di (stearate / 500 0:25

/ Behenate)

este relay (mass ratio) agent The amount (Ppm) the smallest mesh sieve through which the fuel still passes (mm) (A) / (b) = l / 4 500 0047 (A) / (c) = 1/4 500 0111 (A) / (d) = l / 4 500 0111

PEG ester amount of active substance In fuel D (ppm) CFPP kiss- lubrication PEG (600) di laureate (Cl2) 100 0 PEG (600) di myristate (Cm) 100 0 PEG (600) -dipal- Mita (Cm) 100 0 PEG (600) di stearate Cis 100 0 PEG (600) di behenate (C22) 100 5 PEG (200) di behenate (C22) 100 0 PEG (400) di behenate (C22) 100 4 PEG (600) -dibe- behenate (C22) 100 5 PEG (1000) di behenate (C22) 100 0 PEG (1500) di behenate (C22) 100 0 PEG (200/400 / / 600) -dibe- behenate (C22) 100 5 PEG (600/1000) - -dibehenát (C22) 100 5 al 100 -1

The results show that PPG-di (stearate / behenate) is also a very effective liquidity enhancer at higher concentrations but not as effective as PEG esters at lower concentrations. The potency of PPG esters also appears to depend on the molecular weight of PPG. A mixture of PPG and PEG esters also appears to be effective.

The results show that PEG (400) and PEG (600) dibehenates are compounds that are optimal for the molecular weight of PEG and the composition of carboxylic acids in reducing CFPP in this fuel. For comparison, the CFPP reduction for D fuel containing 100 ppm Al was taken as -1 (based on the experiment of Example 1).

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Example 7

The effect of mixtures of PEG esters and other additives on the properties of the narrow-range distillates was investigated by DOT-test on fuel B of Table 1 at -15 ° C. , (4: 1) 'represents the appropriate weight ratio.

The results are shown in the table below:

additive active ingredient is the smallest concentration (ppm) mesh diameter through which the material still passes (mm) PEG (400) -dibehenate 100 0:42 B 500 0:25 Bl / PEG (400) -dibe- heno (4: 1) 500 0074 B1 / Tween 65 (4: 1) 500 0:42 A2 500 0:42

A2 blended PEG (4001-

di (stearate / inputs henate) (4: 1) 500 0:25

The results show that the combination of PEG ester with B1 polar monomer is better than either the ester alone or B1 with Tween 65. The effect of the EVA copolymer (A2) is also enhanced by the PEG ester.

Example 8

The CFPP reducing effect of PEG esters was investigated in combination with ethylene / vinyl (-acetate A2) copolymer on the wide-range fuel E of Table 1. The results are shown in the following table:

EVA (A2) polymer (Ppm) PEG ester CFPP decrease (° C) type authorities material pPM 100 - 0 0 200 - 0 2 80 PEG-dibe- behenate 20 12 100 PEG-dibe- behenate 40 15 0 PEG-dibe- behenate 100 0 0 80 PEG-dibe- behenate mixed PEG (600/1000) - 200 2 160 -dibehenate mixed PEG (600/1000) - 20 13 0 -dibehenate mixed PEG (600/1000) - 40 18 150 -dibehenate C28-C30 200 2 yeast PEG ester 50 16

Preparation: 1 mol of mixed PEG (200/400/600) is esterified with 2 mol of saturated carboxylic acid prepared by reaction of 26 to 28 carbon olefins with acetic anhydride in the presence of di-t-butyl peroxide catalyst. These results show the efficacy of the combinations over the individual effects of the components.

Example 9

The CFPP reducing effect of PEG esters in combination with a polar monomer on fuel F of Table 1 was investigated. The results are shown in the table below:

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Additive bulk chemicals concentration (Ppm) PEG-és2ter bulk chemicals concentration rationality (Ppm) CFPP decrease nand A2 (total similar) 75 - 0 0 THE 2 75 PEG (600) - -dibehenát 25 10 THE 2 75 PEG (600) - 25 0 bl 75 - 0 0 bl 75 PEG (600) - -dibehenát 25 6 B2 75 - 0 4 B2 75 PEG (600) - -dibehenát 25 7 B3 75 - 0 2 B3 75 PEG (600) - -dibehenát 25 12

The results thus indicate that PEG dibehenate in combination with A2 is more preferred than distearate and that PEG (600) dibehenate is preferred in the present invention. Thus, polar monomeric compounds may also be potent CFPP lowerers in combination with PEG 600 ester.

Fuel A and B give the following results.

Operating Additive ppm substance PEG 200/400 / CFPP / 600 dipstick lubrication ppm THE THE 2 75 PEG 0 -0.5 (comparative) THE THE 2 75 PEG 25 -1 THE B5 75 PEG 0 0 THE B5 75 PEG 25 2 B THE 2 75 PEG 0 -1

(comparative)

B THE 2 75 PEG 25 -2 B B4 75 PEG 0 0 B B4 75 PEG 25 1

Fuel distillation (° C) B fuel D 86 IBP 200 188 20% 276 256 50% 294 284 90% 334 322 FBP 352 343 CP (° C) -4 -7 CFPP (° C) -5.5 -8

Example 10

In this assay, the efficacy of combining PEG ester with A2 was tested by a DOT test at -12 ° C.

PEG ester the active ingredient the active ingredient the most growth concentration sicker hi- inhibitory concentric established by them tanyilás- ration (ppm) (Ppm) -diameter

on which his plant. still passing (mm)

1. spreadsheet E fuel using THE 2 200 - 0 0111 THE 2 170 PEG (600) - -dibehenát 30 0047 THE 2 170 PEG (400/600 / / 1000, -di [stearate behenate] 30 0.71 1. spreadsheet G fuel using THE 2 500 - 0 0:42 THE 2 400 PEG (200/400 / 600) di (Stearate / / Behenate) 100 0111 bl 400 PEG (200 / / 400/600, - di [stearic rat / behe- sulfonate] 100 0074

The results show that the compound of formula (I) in combination with A2 or B1 is more effective than A2 at the same concentration.

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Example 11

This experiment was conducted with three 25 m ³ tanks containing fuel D as shown in Table 1. After three weeks of storage under natural temperature conditions (including natural temperature cycles), the fuel was pumped out of the tanks at -13.5 ° C and the level of fuel still flowing through was recorded.

Additive (at 0, lt% active ingredient) Minimum sieve diameter through which fuel passes (mm) (a) Al 0:42 (b) PEG (200/400/600) - 0:25 di (stearate / behenate) (c) Al PEG (200/400/600) - 0:18 -difsztearát / behenate) (3/1 ratio)

The fuel dispensers such as those used in the experiment generally have a 0.25mm filter insert, so it can be seen that while the Al-containing fuel blocked the 0.25mm filter, the PEG-ester-only fuel , and fuel containing a combination of Al and PEG ester could be properly pumped through this filter.

Additive agent concentration (Ppm) The smallest szitanyílás- -diameter, on which it is fuel still going through (Mm) first cooling second cooling al 500 0:25 0:42 PEG (200/400 / / 600) di (stearic 100 0:18 0:18 rat / behenate) 500 0134 0134 PEG (200/400 / / 600) di (stearic 100/400 0134 0149

(behenate) and

Mixture of PPG (1025) dibibenate

Again, the PEG ester or the advantage of the PEG ester and PPG ester mixture over the known ethylene / vinyl acetate Al copolymer.

Example 13

A DOT assay was performed at -10 ° C to compare straight-chain saturated esters with straight-chain unsaturated esters, e.g. with oleic acid ester.

Example 12

The three barrels of Table 1 Fuel A were cooled to -13 ° C at 0.5 ° C / h and then allowed to stand cold and the 300 mL sample was tested for cold fluidity similar to the DOT test. The barrels were then slowly heated above the fuel WAP value and then cooled again at 0.5 ° C / h to -13 ° C. The fuel was then pumped out of the barrel through filters with different size liners to determine the smallest screen opening diameter that the waxy fuel could still pass through.

Table 1 additive ppm is the smallest sisal material diameter at which the fuel is operated. still passing (mm)

D PEG (600) -dibehenát 500 0149 D PEG (600) - -dioleát 500 0.84 D no 0 0.84

Example 11

The DOT test was repeated with 3 broad-source distilled fuels and the efficacy of linear PEG esters on the properties of such fuels was investigated. Comparative studies were conducted with ethylene vinyl acelate copolymer A2 and dioleate ester to demonstrate the benefits of linear saturated alkyl ester.

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Table 1 additive ppm is the smallest screen opening fuel through which the fuel still passes (mm)

E THE 2 200 0074 E PEG (600) dibehenate 200 0074 E PEG (600) -dioleate 200 0:42 E no - 0:59 H THE 2 300 0149 H PEG (600) dibehenate 300 0149 H PEG (600) -dioleate 300 0:42 H no - 0:42 I THE 2 250 0134 I PEG (600) dibehenate 250 0074 I PEG (600, - 250 0:18 -dioleát 250 0:18 I no - 0:18

Example 15

Relatively high boiling point fuel with the following characteristics:

cloud point +4 ° C wax appearance point -0.7 ° C CFPP (untreated) -5 ° C; ASTM D86 Distillation Data: starting boiling point 185 ° C final boiling point 386 ° C

with different amounts of additives

containing 1 part by weight of PEG (600) dibehenate and 4 parts by weight of additive A2. The following results were obtained: Additive Ratio (ppm) CFPP ° C 150 -14 200 -14 250 -14 300 -14 350 -16 450 -16 500 -16 550 -7 650 -7

In this example, CFPP values represent the temperature at which the fuel no longer meets the requirements of the CFPP test.

10% by weight, based on the total weight of the additive, of a paraffin-naphthalene (C) prepared by Friedel-Crafts condensation is prepared as follows: 100 parts by weight of n-paraffin wax melting at 52-54 ° C are chlorinated so that The wax contained 14.5% by weight of chlorine based on its total weight, then condensed with 12 parts by weight of naphthalene. The CFPP value of the fuel containing the above blend is given below.

additives

Treatment rate CFPP ° C

550 ppm PEG (600) -dibehenate +

A 1: 4 by weight mixture of A2 is -19 + 55 ppm C

650 ppm PEG (600) -dibehenate +

A 1: 4 by weight mixture of A2 is -20 +65 ppm C

For example, these data also show the additional improvement in fuel properties that can be achieved by adding C.

Example 16

A DOT test was performed with fuel A of Table 1 at -15 ° C to compare the effect of PEG (600) -distearate and PEG (600) -disostearate added at 200 ppm to the additive. The results are as follows:

Additive ppm (active - smallest material, mesh diameter at which the plant. Still passes (mm)

PEG (600) Dystearate 200 0.42

PEG (600, diisostearate 200 0.84

The results show the advantageous effect of the straight-chain alkyl group.

J Example 7

Poly (tetramethylene glycols), so-called .Teracols, (DuPont) having the general formula HO - [(CH2) 4-O] n-H, have a molecular weight of 650, 1000 and 2000 and are esterified with 2 mol of behenic acid.

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The effect of these materials on the properties of the fuel A of Table 1 is then examined in a DOT test at -15 ° C.

The results are as follows:

additives material ppm (active ingredient) Minimum sieve diameter through which fuel passes (mm) Teracol (650) —di— behenate 200 blocks 0.84 Teracol (1000) —di— behenate 200 blocks 0.59 Teracol (2000) di behenate 200 blocks 0.42

The data show that Teracol derivatives are potent, but compared to the results of Example 3, they are less active than PEG and PPG esters.

Example 18

C18 straight chain alcohol is ethoxylated and the resulting product is esterified with 1 mol of behenic acid to give an ester ether derivative having the following structure:

II

ClsH37-O- (CH2CH2O) l0-C C2lH43

Using this additive, fuel A passes through a 0.18 mm strainer at -15 ° C in the DOT test at 200 ppm additive concentration.

Example 19

Reaction of PEG (600) with 2 molar succinic acid followed by reaction with 2 molar mixed straight chain saturated C 22-24 alcohols gives the product of the following formula:

0

II II (C, H, _Z2 '-C24H49) -OC-CH2-CH2-CO (PEG 600), 0 o

II II

- C-CH2-CH2-C-O2C22H45-C24H49)

This material was tested by adding it to the substance I of Table 1, which has a cloud point of + 4 ° C. The waxing point is 0 ° C, the CFPP value is -1 ° C, the initial boiling point is 195 ° C and the final source 14 is 375 ° C. The product was tested in a DOT test at -6 ° C and found that the fuel without additive passed through a 0.42 mm sieve and a 0.18 mm filter with 200 ppm additive.

Adding 200 ppm of additive to fuel A in the DOT test at -15 ° C also penetrates through a 0.149 mm screen.

Example 20

The effect of PEG (600) -dibehenate is compared to that of PEG (600) -distributate on fuel K having a cloud point of -2 ° C, a waxing point of -6 ° C, an initial boiling point of 200 C and a final boiling point of 354 ° C. The crude fuel has a CFPP of -7 ° C and remains unchanged after the addition of the PEG (600) di-derucate, but decreases by 4 ° C for the addition of PEG (G00) dibehenate, indicating the importance of the presence of a saturated alkyl group.

Example 21

Four parts

A2 and 1 part of various PEG dibehenates are tested in the CFPP test on fuel E. The following results were obtained:

Additive CFFP 100 ppm additive Decrease 200 ppm additive A2 alone A2 PEG ester 4: 1 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 PEG (600) -dibehenate alone 14 6 18 * P (EO / PO, (8000) -dibehenate) 0 0

* Condensed with 8 M molecular weight poly [(ethylene oxide) (propylene oxide)] in 2 mol of behenic acid.

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Example 22

Example 21 is repeated using Teraeol derivatives instead of PEG dibehenates. The following results are obtained:

Example 24

The reduction in CFPP for fuel B containing various additives was found to be as follows:

Additive CFPP decrease

100 ppm additive

Teracol (650, -dibehenate 3

4: 1 * A2 Teracol (650, -dibehenate 0

Teracol (1000, -dibehenate 0 * A2 Teracol (1000, -dibehenate 3

Teracol (2000, Dibehenate 3 * A2 Teracol (2000, Dibehenate 0 *) The ratio of EVA to Teracol dibehenate is 4: 1.

Teraeol derivatives have been shown to be less potent than PEG derivatives.

Example 23

The effect of various additives was investigated in the DOT test at -10 ° C on fuel L with a cloud point of -4 ° C, a waxing point of -6 ° C, and in the untreated state a CFPP of -6 ° C and an initial boiling point of 216 ° C. and its final boiling point is 353 ° C.

The results are as follows:

Additive ppm DOT test is the (smallest material) sieve size that the fuel still passes through (mm,

without additives - 0.84 PEG (600) -dibehenát 100 0111 PEG (600) -monobehe- sodium 100 0:42 Teracol (650, -d behenate 100 0:59 TeracoK 1000) dibehenate 100 0.84 TeracoK 2000) -dibehenate 100 0.84 Poly [(ethylene oxide, - 500 0.84

- {propylene oxide,] (molecular weight 8000, dibehenate

Additive ppm (active ingredient) CFFP decrease (° C, PEG [200/400/600] dibehenate 250 4 C2ilh3C- (Oll2CCH2, bOH H 250 -1 II 0 500 -1 Ciill37-0- (CH2CH20) io-H 250 -2 ClsH37-O- (CH2CH2O, 10- 500 -δ -C-C21H43 li 250 1 II 0 500 3

'HNMR ANALYSIS OF PEG ESTERS Ή NMR Speetrum:

- PEG (200/400/600, -dibehenate 0.9 ppm Lt, 6H, COOCH2CH2 (CH2, nCtf3) dibehenate methyl group

1.2 ppm [m, 72H, methylene groups of dibehenate of COOCH2CH2CH2CH2JnCHs]

1.6 ppm lt, 4H, β-methylene of COOCH2C / fc (CH2, nCH3)

2.3 ppm [t, 4H, oC-methylene of COOC / ftCH2 (CH2, ₀ CH3)

3.6 ppm (ni, 32H, O-CH 2 CH 2 -O) PEG methylene

4.2 ppm (t, 4H, O-CH 2 CR 2 -O-CO) PEG methylene group adjacent to the carboxyl group

The chemical shift is determined in a known manner relative to TMS. T and m refer to the NMR signal which splits into triplets (t) and multiplets (ni). A multiplet can consist of many layers stacked together. The number of H 's corresponds to the number of protons to which the signal corresponds.

2. PEG (400, -dibehenate

0.9 ppm lt, 6H, Me group of COOCH2CH2 (CH2) nCto] dibehenate

1.2 ppm [m, 72H] methylene groups of dibehenate of COOCH2CH2 (Cfl2, nCH3)

1.6 ppm β-methylene of [t, 4H, COOCH2Ctt: (CH2)> CH3]

2.3 ppm [t, 4H, oC-methylene of COOCtf2CH2 (CH2, nCH3]

3.6 ppm (m, 3211, O-CH 2 CH 2 -O) PEG methylene

4.2 ppm (t, 4H, O-CH 2 C / Fe-O-CO) PEG with methylene at the carboxyl group, i.e. the spectrum is as above.

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3. PEG (100) -dibehenate 2.3 ppm ft, 4H, CO 2 tf 2 CH 2 (CH 2) n CH 3] lene .alpha.-meti- 0.9 ppm [t, 6H, COOCH2 CH2 (CH2) 1 Ctti] dibehe- 3.6 ppm (m, 78H, O-CH 2 CH 2 -O) PEG methylenes sodium 4.2 ppm (t, 411, O-CH 2 CH 2 -O-CO) PEG CH 1.2 ppm (m, 72H, COOCH2 CH2 (CH2) nCH3) dibe next to the carboxyl group methylene groups of henate 1.6 ppm [t, 4H, COOCH 2 C / 2 (CH 2) n CH 3] β-methyl 8. PEG (1500) dibehenate polyoxyethylene-group 2.3 ppm [t, 4H, COOC / 2CH2 (CH2) nCH3] o -C-0.9 ppm [t, 6H, COOCH ₂ CH 2 (CH 2) nCtf3] < iibehe- polyoxyethylene-group 10 sodium 3.6 ppm (m, 4H, O-CH 2 CH 2 -O) PEG methylene 1.2 ppm [m, 72H, COOClUClUlCtfilnCl2] dibe- 4.2 ppin (t, 4H, O-CH 2 CH 2 -O-CO) PEG methylene, methylene groups of henate carboxyl group 1.6 ppm [t, 4H, COOCH ₂ CH 2 (CH 2) _n CH 3] dibehe β-methylene of sodium 4. PEG (200) dibehenate 15 2.3 ppm [t, 4H, COOC // 2CH2 (CH2) _n CH3] p (-meti- polyoxyethylene-group 0.9 ppm [t, 6H COOCfoClhfCHzlnCttj] dibehe- 3.6 ppm (ni, 132H, O-CH 2 CH 2 -O) PEG methylenes nate Me group 4.2 ppm (t, 4H, O-CH 2 CN 2 -O-CO) PEG CH 1.2 ppm [in, 72H, COOCH2 CH2 (CH2) nCH3] dibe- next to the carboxyl group methylene groups of henate 20 1.6 ppm [t, 4H, COOCH2C / 12 (CH2) nCH3] β-methyl 9. PEG (600) -dilaurate polyoxyethylene-group 2.3 ppin [t, 4H, COOCH2CH2 (CH2) nCH3j cf-meth- 0.9 ppm [t, 6H, COOCH2CH2 (CH2) nCtf3] dilau- polyoxyethylene-group methyl 3.6 ppm (m, 14Η, O-CH 2 CH 2 -O) PEG methylene 1.2 ppm [ni, 32H, COOCH2CH2Cl2CH2] dilau- 4.2 ppm (t, 4H, O-CH 2 CH 2 -O-CO) PEG CH of methylene groups next to the carboxyl group 1.6 ppm ft, 4H, COOCH2C / fc (CH2) nCH3] dilau- β-methylene group 5. PEG (144) dibehenate 2.3 ppm [t, 4H, COOCtt »CH 2 (CH ₂₎ n CH 3] ° meti- 30 polyoxyethylene-group 0.9 ppm lt, 6H, COOCHzCHzlCHzlnCte] dibehe- 3.6 ppm (m> 48H, O-CH 1 CH 2 -Q) PEG methylene nate ME group 4.2 ppm (t, 4H, O-CH 2 CH 2 -O-CO) PEG CH 1.2 ppm [m, 72H, COOCH2CH2 (C // ₂₎ n CH 3] dibe- next to the carboxyl group methylene groups of henate 6.1 ppm [t, 4H, COOClUCttU _{CH2) n} CH3] β-methi- 35 9.: PEG (600) -dimirisztát polyoxyethylene-group 2.3 ppm [t, 4H, COOCtf2CH2 (CH2) nCH3] title-meti- 0.9 ppm [t, 6H, COOCH2CH2 (CH2) nCH3] dimi- polyoxyethylene-group a methyl group of crystal 3.6 ppm (m, 8H, O-CH 2 Cl 2 -O) PEG methylene 1.2 ppm [m, 40H, ₂ COOCH2CH (Ctf2) n CH 3] dimi- 4.2 ppm (t, 4H, O-CH 2 CH 2 -O-CO) PEG methylene 40 the methylene groups of the crystal next to the carboxyl group 1.6 ppm [t, 411, COOCH2 (CH2) nCH3] dimi- myristate 6. PEG (600) dibehenate 2.3 ppm lt, 4H, COOCH2CH2 (CH2) nCH3] β-meti- lene group, title-methylene-c swept 0.9 ppm [t, 6H, COOCH2CH ₂ (CH ₂₎ n CH 3] dibe- 45 3.6 ppm (m, 48H, O-CH 2 CH 2 -O) PEG methylenes henna group Me 4.2 ppm (1,411, O-CH 2 CH 2 -O-CO) carboxyl 1.2 ppm [m, 72H, ₂ COOCH2CH (Ctf2) n CH 3] dibe- a PEG methylene group adjacent to the powder methylene groups of henate 1.6 ppm lt, 4H, COOCH2Ctf2 (CH2) nCH3] dibehe-10, PEG (600) -dipalmitát β-methylene of sodium 50 2.3 ppm [t, 4H, COOC / -CH2 CH2 CH2] CH3] o -C-0.9 ppm [t, 6H, COOCH ₂ CH 2 (CH 2) n C // 3] dipal- lene group is PEG methylene the methyl group of mitate 3.6 ppm (m, 48H, O-C / c / cZZft-O) PEG methylene as shown in 1.2 ppm 1m, 48H, COOCH 2 CH 2 (C / fc) nCH 3] dipal- 4.2 ppm (t, 4H, O-CH 2 CH 2 -O-CO) carboxyl methylene groups of mitate port 55 1.6 ppm [t, 4H, COOCl2C2 (CH2) nCH3] dipal- the β-methylene group of mitate 7. PEG (10000) dibehenate 2.3 ppm [t, 411, COOCH2CH2 (CH2) nCH3] ° meti- polyoxyethylene-group 0.9 ppm en, 611, COOCfoClkfCtoJnC / fc] dibehe- 3.6 ppm (m, 4811, O-C // 2CC //-O) PEG methylenes sodium 60 4.2 ppm (t, 4H, O-CH 2 CH 2 -O-CO) PEG CH 1.2 ppm [in, 72H, COOCH2 CH2 (C / ft) nCH3l dibe- next to the carboxyl group methylene groups of henate 11th PEG (600) distearate 1.6 ppm lt, 4H, COOClUC / ftiCHlnCHs) dibehe- β-methylene of sodium 0.9 ppm [t, 6H, COOCH2 CH2 (CH2)., CH3] diszte- 16 65 arate methyl group

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1.2 ppm methylene groups of distearate [m, 56H, COOCH2CHFlC / ftnCHa]

1.6 ppm lt, 4H, β-methylene group of distearate of COOCH2CWz (CH2) nCH3]

2.3 ppm lt, 4H, COOC / fcCH2 (CH2) nCH3] o -C-methylene

3.6 ppm (ni, 48H, O-CW2CH2-O) PEG methylenes

4.2 ppm (L, 4H, O-CH2C / Fe-O-CO) PEG methylene group in addition to carboxyl group

12. PEG (600) -di (stearate / behenate)

0.9 ppm [t, 6H, COOCH2 CH2 (CH2) nC / ft] Methyl group of the esters

Methylene groups of 1.2 ppm [m, 64H, COOCH2CH2ClFlClCl] esters

1.6 ppm lt, 4H, γ-methylene group of COOCH2C / fc (CH2) nCH3] esters

2.3 ppm [t, 4H, oC-methylene of COOCtoCH2CH2CH2CH2CH]

3.6 ppm (m, 48H, O-CH 2 CH 2 -O) PEG methylene

4.2 ppm (t, 4H, O-CH 2 CH 2 -O-CO) PEG with methylene carboxyl group

13. PEG (200/400/600) - di (stearate / behenate)

0.9 ppm [t, 6H, COOGHzCHztCHzlnC / ft] methyl group

Methylene groups of 1.2 ppni [ni, 64H, COOCH2CH2 (C / fe) nCH3] esters

1.6 ppm [t, 4H, γ-methylene group of the esters of COOCH2C / ftfCHzlnCHsJ

2.3 ppm cZ-methylene of [t, 4H, COOC / fcCH2 (CH2) nCH3]

3.6 ppm (m, 32H, O-CleC / ft-O) PEG methylenes

4.2 ppm (t, 4H, O-CH 2 CH 2 -O-CO) PEG with methylene carboxyl group

14. PEG (600/1000) dibenzene

0.9 ppm methyl ester of [t, 6H, COOCH2CH2 (CH2) nCtf3] esters

1.2 ppm [m, 72H, methylene group of esters of COOCH2CH2 (C12) nCH3]

1.6 ppm [methylene group of [t, 4H, COOCH2Ctf2 (CH2) nCH3] esters

2.3 ppm [t, 4H, oC-methylene of COOC12CH2 (CH2) nCH3]

3.6 ppm (m, 68H, O-CW 2 C 2 -O) PEG methylenes

4.2 ppm (t, 4H, O-CH 2 CH 2 -O-CO) PEG with methylene carboxyl group

Claims (10)

PATENT CLAIMS An additive fuel oil distillate having a boiling point in the range of from 120 to 500 ° C, in particular from 160 to 400 ° C, wherein the additive is 0.01 to 0.05 tX, characterized in that: I) from 15 to 100% by weight, based on the total weight of the additive, of a polyoxyalkylene glycol derivative of the formula R 1 -O-A-R 2 in which R 1 and R 2 are (a) is identical and may be a straight chain alkanoyl having from 10 to 30 carbon atoms, or -CO- (CH 2) k -COO-R 3 - wherein k is 1, 2, 3 or 4 and R 3 is C 18 -C 26 straight alkyl or (b) different and may be i) R 1, R 2 are simultaneously C 10 -C 30 alkanoyl, or ii) R 1 is C 10 -C 30 alkanoyl and R 2 is C 16 -C 20 alkyl, A is a group of the formula - (RO) n - derived from polyoxyalkylene glycol having a molecular weight of 100-4000, preferably 200-2000 molar, where R is a C 2 -C 4 alkylene group and n is the value given by II) one or more ethylene-vinyl acetate copolymers in an amount of 25 to 85 tX, based on the additive, or having an average molecular weight of 1800 to 3000; or III) diamide, half amide salt or half ester formed by reaction of 25 to 75% by weight of the dicarboxylic acid or its anhydride or C 14 -C 24 straight chain alkyl ester with a C 14 -C 24 alkyl chain-linked alkyl dialkyl moiety contains salt. (Priority: March 31, 1982) 2. Additive petroleum distillate with improved flow properties, boiling in the range of 120 ° C to 500 ° C, especially 160 ° C to 400 ° C, wherein the additive is 0.01 to 0.05 tX, characterized in that: I) from 15 to 100% by weight, based on the total weight of the additive, of a polyoxyalkylene glycol derivative of the formula (I) wherein R 1 and R 2 are the same and may be straight chain of 10 to 30 carbon atoms. alkanoyl; or -1 631 HU 202267 Β -CO- (CH2) ii-COO-R3 wherein k is 1,2,3 or 4 and Ra is a straight-chain alkyl group of 18 to 26 carbon atoms or (b) different and may be i) R 1, R 2 are simultaneously straight-chain C 10 -C 30 alkanoyl, A is a compound of the formula - (RO) n - derived from polyoxyalkylene glycol having a molecular weight of 100-4000, preferably 200-2000 molar, wherein R is a C 2 -C 4 alkylene group and n is the molar weight and optionally (Ii) one or more ethylene-vinyl acetate copolymers having an average molecular weight of 1800 to 3000, in the range of 25 to 85 tX, based on the additive, or III) diamide, half amide salt or half ester formed by reaction of 25 to 75% by weight of the dicarboxylic acid or its anhydride or C 14 -C 24 straight chain alkyl ester with a C 14 -C 24 alkyl chain-linked alkyl dialkyl moiety contains salt. (Priority: March 31, 1981) Composition according to claim 2, characterized in that the fuel oil distillate has a boiling point of 180-350 ° C and the difference between the initial boiling point and the final boiling point is not more than 150 ° C. (Priority: March 31, 1981) Composition according to Claim 2, characterized in that R1, R2, R3 have from 18 to 24 carbon atoms. (Priority: March 31, 1981) 5. A composition according to claim 2, wherein the molecular weight of the moiety A is 200-800 when R is ethylene. ₅ (Priority: March 31, 1981) 6. The composition of claim 2, wherein the molecular weight of the A moiety is 200-600. (Priority: March 31, 1981) jq 7. A composition according to claim 2, characterized in that it comprises polyoxyethylene glycol dibehenate. (Priority: March 31, 1981) 8. A composition according to claim 2, characterized in that it comprises polyoxyethylene glycol distearate. (Priority: March 31, 1981) Composition according to claim 2, characterized in that it contains polyoxyethylene bee 2 N sodium stearate. (Priority: March 31, 1981) Composition according to claim 2, characterized in that the additive besides the additive I) as additive II) has an average molecular weight of 1800, Or a copolymer of ethylene vinyl acetate consisting of 38% by weight of vinylacetal and ethylene -1800 average molecular weight, 38 weight% vinyl acetate and ethylene and 3000 average molecular weight, 30 3: 1 by weight mixture of ethylene-vinyl acetate copolymers consisting of 16% vinyl acetate and ethylene. included. (Priority: March 31, 1981) 11. The composition according to claim 2, wherein the additive is, in addition to I), as the additive III) by the reaction of one mole of phthalic anhydride with two moles of dihydrogenated tallow amine salt. Contains 40.