CS276968B6 - Additional concentrate into fuel oil - Google Patents

Abstract

Fuel oil compsn. comprises a middle distillate fuel oil (boiling range 120-500 deg.C) contg. 0.0001-0.5 wt.% of an ester, ether or ester/ether of formula R-O-(A)-O-R' (I) R and R' are each (i) n-alkyl, (ii) n-alkyl-CO-, (iii) n-alkyl-O-CO-(CH2)n- or (iv) n-alkyl-O-CO-(CH2)n-CO-, the alkyl gp. being linear and contg. 10-30 (pref. 18-22) C atoms; A is a polyoxyalkylene glycol of mol. wt. 100-5000 in which the alkylene group is 1-4C). Also claimed are (a) an additive concentrate contg. 3-75 wt.% (I), (b) a distillate fuel contg. (I) and an ethylene copolymer (II) or a 30-300C polar nitrogen cpd. (III) as wax crystal growth inhibitor, (c) an additive concentrate contg. (I) together with (II) or (III), and (d), more generally, the use of polyoxyalkylene ethers, esters or ester/ethers contg. at least two 10-30C linear alkyl gps. and a polyoxyalkylene glycol of mol. wt. 100-5000, the alkylene gps. being 1-4C, as flow improvers for distillate fuels. Cpds. (I) are esp. effective, and can be used as the sole additive, for narrow boiling distillate fuels which are often unresponsive to conventional flow improver additives. The combination of (I) with (II) or (III) is useful for broader boiling distillates.

Description

The invention relates to an additive concentrate for improving the flow characteristics of fuel oils derived from the distillation of crude oil (distillate fuel oils) through a cold weather conduit.

Additives for treating distillate fuel oils to improve flow characteristics of paraffin wax turbid fuels (hereinafter wax) through conduits and filters in cold weather are known, as is clear from the following patents. (The terms paraffin wax, paraffin wax and wax are considered synonymous for the purposes of this description).

For example, UK 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 UK Patent No. 1,374,051 relates to the use of an additive system which both increases the temperature at which wax crystallization begins. thus limits 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 fuel oils in U.S. Patent Nos. 3,374,073, 3,499,741, 3,507,636, 3,608,231 and 3,681,302.

It is also known that admixture mixtures may be used to further improve the flow properties and flow temperature of distillate fuels. For example, U.S. Pat. No. 3,661,541 uses a blend of an ethylene-unsaturated ester copolymer additive 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 such running properties of middle distillate fuel oils, including diesel.

U.S. Patent Nos. 3,444,082 and 3,946,093. the use of various amides and mine 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, ethers / esters and mixtures thereof is effective in itself to improve such characteristics of distillate oils and is particularly effective and can be used as the only additive for narrow boiling distillate fuels. (as will be further elaborated below), which are usually insensitive to conventional additives to improve flow properties. The use of such distillates 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 boiling point distillate fuel oils

120 to 500 ° C, in particular boiling point 160 to 400 ° C growth of the separating wax crystals, further improvement is needed. However, it has been found difficult to improve the flow properties and filterability of the distillate oils with a narrow boiling range. It has now been found that certain polyalkylene esters, ethers, ester / ethers or mixtures thereof are particularly suitable for improving such 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 an oil fuel distillate additive concentrate, characterized in that it comprises an oil solution containing 3 to 75% by weight of esters, and / or ether, and / or ester / ether of the formula I

R - O - (A) - R ¹ (I) where

R ¹ and R ¹ represent the same or different groups selected from the group consisting of n-alkyl

II n-alkyl-CO

II n-alkyl-OC (CH ₂ ) _n -a

CS 276968

O, O-n-alkyl-OC- (CH ₂ ) _n ^-c- , wherein the alkyl radicals are linear, saturated and contain from 10 to 30 carbon atoms, one of R a R ¹ also being hydrogen and

A is a polyoxyalkylene glycol moiety having a molecular weight of 100 to 5,000, wherein the alkylene groups contain 1 to 4 carbon atoms.

For example, polyoxyalkylene glycol moiety A is a polyoxymethylene, 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. If, however, the additives are to be used for distillates with a narrow boiling range, fatty acids having 18 to 24 carbon atoms are preferred, in particular behenic acid or mixtures of stearic and behenic acid. Esters may also be prepared by esterification of polyethoxylated fatty acids or polyethoxylated alcohols.

Suitable 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. Particularly preferred are stearic or behenic diesters with polyethylene glycol, polypropylene glycol or polyethylene / polypropylene glycol mixtures.

Polyoxylkylene 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 from 90 to 10, in particular from 50 to 10 and in particular from 20 to 40% by weight of the polyoxyalkylene ester or ether according to the invention, and from 10 to 90% by weight, preferably from 50 to 90 and in particular 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

Ro H

II r ₂ - c - c - r ₄ where denotes

R 8 is a hydrogen atom or a methyl group,

R _{2 is a} group of the formula -OOCR 8 wherein is

R @ ₅ is hydrogen or a straight or branched chain alkyl group having 1 to 17 carbon atoms and in particular 1 to 8 carbon atoms

R ( ₄₎ is hydrogen or -COOR8, wherein

R ₅ is as defined above.

Monomers of the above formula wherein R 8 and R ₄ are hydrogen and R ₂ is a group of the formula

-COOR 8 include 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 formula -COORg and Rg is hydrogen, suitable esters comprising methyl acrylate, isobutyl acrylate, methyl methacrylate, lauryl acrylate, esters of methacrylic acid with a C ₁₃ oxo alcohols, and similar compounds.

As examples of monomers, where R ₃ is hydrogen and R ₂ and R ₄ are groups of the general formula

Coor ₅ discloses monoesters and diesters of unsaturated dicarboxylic acids such as C ₁₃ oxofumarate, di-C ₁₃ oxofumarate, diisopropyl maleate, dilauryl fumarate and ethyl methyl fumarate.

The polyoxyalkylene esters, ethers or ester / ethers of the invention may be used in distillate fuels together with polar compounds, either ionic or nonionic, which are capable of acting in the fuels as crystal growth inhibitors. 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 of an organic acid having 1 to 4 carboxy groups or an anhydride 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 of 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 dioctadecylamine, methylbehenylamine and the like amines. Mixtures of amines are also suitable, and many naturally occurring amines are mixtures. A preferred amine is a secondary amine based on hydrogenated tallow fatty acids of formula

HNR-J is wherein R ^ and _R2 are alkyl groups derived from hydrogenated tallow fatty acids composed of approximately 4% _C14, ^{31% C16 '59% C18} 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-α-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 alkylaromatic compounds prepared, for example, by Friedel-Crafts condensation of a halogenated wax, preferably a straight chain wax, with an aromatic hydrocarbon such as naphthalate. 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 18%, halogen atoms, preferably chlorine.

Other additives for lowering the pour point of a lubricating oil include 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 Mechrolab Vapor Pressure Osmometer, or by 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.

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 oil boiling in the range of 120-500 ° C, including distillates with a narrow boiling range of 200 ° C ± 50 ° C to 340 ° C ± 20 ° C with improved low temperature flow properties containing 0% by weight. 0001 to 0.5%, for example 0.001 to 0.5% of additives to improve flow characteristics, 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 with 10 up to 30 carbon atoms and a polyoxyalkylene glycol moiety 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 to 90% for example vinyl acetate, 0 to 90% by weight, for example 50 to 90%, oil-soluble, polar nitrogenous compounds with 30 to 300, and % of a carbon which is an amine salt and / or an amide and / or ester / amide of a carboxylic acid having 1 to 4 carboxy groups or an anhydride thereof 0 to 50% by weight, for example of 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.

The tests described in the examples use fuels with the following characteristics (see Table I):

EN 276968 B6 no

Table

1 1 1 ιη 1 — i 1 σ CN σ * 9 Ο γ ~ Χ> 1—1 Γ- ΟΟ ΓΌ ιη σ , κ τ-4 i — 1 w 1 1 ο 00 ο 00 1 ΓΌ i — 1 ΓΌ χο κ » X) m O O «Τ’ ΓΌ Γ-4 ιη ιη 1 1 04 / ι ™ 4 ΓΌ ιη Ο Ο 00 m ιη ι — 1 γ—} 00 ιη fa 1 ι ι ΓΌ rH ΓΌ ιη σ * 04 / ιη fa ι — 1 η CM Ο ο 00 00 1 1 ΓΌ ι-Η ΓΌ ο 04 / ΓΌ Γ4 ιη ιη 00 «Τ ' ο «Τ’ O 1 ι ι 04 / 04 / ΓΌ 04 / with 1—1 00 «Τ’ ιη Γ- Ο 04 / 04 / «Τ’ at 1 1 1 «Τ’ 04 / ΓΌ ιη WITH Ο 04 / σι C4 ο γ-4 γΗ 00 ΓΌ « 1 ι — 1 1 «—1 1 ΓΌ ι — 1 ΓΌ 04 / ο 1-4 σ <Ν ο 00 04 / 04 / «Τ’ ι γΗ γ4 rH , ΓΝ ΓΌ

ι ι

AT AT 0 Μ 0 β <ο AT AND WITH κ μ 00 0 φ S »t β ιη Q β Ό β 44 0 Ρ WITH 3 φ ιη -WITH. β WITH φ β 4J > 0 Ή Ρ Η > Ρ AT ιη φ > Χ5 β 0 ω φ 0 β Ο -Ρ WITH β φ > Ή ch g Ή '> ι ιη XI 0 4-) WITH β □ φ β / 4 0 μ φ 0 φ Φ · ΓΌ Φ ο β ο ¥> 0 β ι — 1 ι — 1 -μ • ΓΌ γΗ > β Φ > • Η -Ρ ι — ι 44 Ό Ch 0 0) φ Ίύ rH Φ -Ρ 0 Ch ιη 0 φ ι ^- 1 ί-4 44 Ch β 0 ΓΌ Φ S β Φ 0 Ch 4-1 Ch 0 «Φ 0 μ X g Λ 44 4-1 > φ Ν β -Ρ g 0 0 ιη Φ Μ 4-1 'Sn Ι '> ι Ρ 0Ρ 0 Ό Ή 0 β > Φ • Η> Φ Φ '-s > 0 β Φ > Φ 'φ 0 4-> • μ Ή 0 -Ρ & Φ I — 1 Φ > > 0 0 > 0 Λ 44 χ > • μ 4-1 0 · Γ4 ι — 1 πΗ 0 · Η ι — 1 Φ Φ φ AT Φ 4-) «Φ υ I — 1 Λ ch X! Η Ch ιη -Ρ ιη 0 ΓΌ ιη > 0 β Φ Φ φ 'Φ Φ φ X «Φ XI XI Φ 0 0 fa Εη Ε-ι β Ch Εη Ι-1 Ο ιη 0 Q Ch 44

by fluorescence indicator analysis

Fuels are typical European fuel oils and diesel fuels. Fuels A, B, C and D are examples of fuel boilers with a narrow boiling range, while fuels E, F, G, H and I are examples of boiling boilers with a wide boiling range and fuel G is between boilers according to its boiling point fuels with a narrow boiling range and fuels with a wide boiling range. In this context, a narrow boiling range fuel refers to fuel oils having a boiling point of 200 ± 50 to 340 ± 20 ° C.

In one method, the fuel oil response to the additive is measured by determining the cold filter clogging temperature; the measurement is carried out as described in detail in Journal of the Institute of Petroleum Volume 52, No. 510, June 1966, pages 173-185. This test is intended for comparison with the cold flow of medium distillate fuel oil in automotive diesel engines.

A sample of 40 ml of the fuel oil to be tested is cooled in a bath which is maintained at a temperature of about -34 ° C with 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 turbidity temperature), cooled fuel oil shall be tested for its ability to flow through the fine sieve over a prescribed time using a test device, a pipette having an inverted funnel attached at its lower end. which is inserted below the surface of the oil to be tested. A sieve with an aperture diameter of approximately 45 microns and an intrinsic diameter of 12 mm is stretched across the funnel orifice. Periodic tests are started using a vacuum at the upper end of the pipette, pushing the oil through a pipette through the pipette up to the mark indicating 20 ml of oil. After each successful pass, the oil is immediately returned to the test sample. 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 is referred to as the cold filter clogging temperature. The difference between the clogging temperature of the additive-free fuel filter and the same fuel containing the additive is reported as the decrease in the clogging temperature of the cold filter caused by the test additive. A more efficient additive that improves creep characteristics has a greater cold filter clogging temperature value at the same additive concentration.

Another determination of the efficacy of the additive to improve creep characteristics is carried out by testing the applicability of distillate fuel oil; it is a slow cooling test designed to mimic the pumping of stored fuel oil. The creep characteristics of the described fuels containing additives are determined by testing the applicability of distillate fuel oil 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 stirring and a filter assembly is inserted to test the cold filter clogging temperature. The tap opens to apply vacuum

66.66 kPa and close when 200 ml of fuel passes through the filter into the tank. Compliance means that 200 ml of fuel oil passes through the screen in 10 seconds, failure to indicate that the filter passage rate is too slow, as the filter becomes clogged.

For the cold filter clogging test, a sieve with a mesh diameter of 833 microns, 495 microns, 420 microns, 246 microns, 175 microns, 147 microns, 124 microns, 104 microns, 74 microns, 61 microns and 43 microns is used to determine the finest sieve, through which the oil passes. The smaller the mesh meshes through which the oil passes, the smaller the waxy crystal particles in the fuel and the greater the efficiency of the additive to improve flow characteristics. The test results depend on the fuel oil used.

In the examples, additives A1 are used to improve the flow characteristics of distillate fuel oils 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 and as described in British Patent No. 1,374,051 and its corresponding U.S. Patent No. 3,961,916. The two polymers are in particular at a weight ratio of 75% wax crystal growth inhibitor to 25% nucleator. The crystal growth stopper is ethylene and approximately 38% vinyl acetate and the growth stopper has a number average molecular weight of about 1,800. It is referred to in the above-mentioned British Patent Specification No. 1,374,051 as copolymer B in Example 1 (column 8, lines 24-35). and in the corresponding U.S. Pat. No. 3,961,916, column 8, line 32. The nucleator consists of ethylene and approximately 16% by weight of vinyl acetate and has a number average molecular weight of approximately 3,000. In the aforementioned British patent, it is referred to as copolymer H. I, columns 7 to 8, and in the corresponding U.S. Pat. No. 8, line 45. An additive A2 to improve the flow properties of distillate fuel oil is the Al-wax crystal 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 diesters. Para-toluenesulfonic acid is added in an amount of 0.5% by weight, based on the reactants, as a 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 stream 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 given along with the 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 and 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 PEG 200, 400 and 600 weight mixture 200, 400 and 600 molecular weight polyethylene glycol. Mixtures of carboxylic acids may also be used; for example, PEG di (stearate) behenate 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 dihydrogenated tallow hydrogenated tallow to form the 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 monooctadecyl phthalate.

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.

Example 1

The properties of the low boiling distillate fuel oils normally difficult to work with containing the polyoxyalkylene esters of the present invention are compared to those of the same oils but containing an ethylene-vinyl acetate copolymer additive. The comparison is performed using a cold filter clogging test. The following results shall be achieved:

Cold Filter Clogging Down Temperature

Additive to improve creep characteristics Effective component ppm Fuel according to Table 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 / di / stearate / behanate 100 ALIGN! 4 4 5 2 Tween 65 500 1 1 - 0 / + / Negative value means 2Increase temperature clogging cold

filter

Tween 65 is polyethoxylated sorbitan stearate (non-linear)

The results show that in the fuel oils tested, a significant reduction in the cold filter clogging temperature can be achieved by simply adding 100 ppm of polyethylene glycol ester, while 500 ppm of ethylene vinyl acetate has no effect.

Example 2

The properties of the fuels used according to Example 1 containing certain polyglycol esters of the invention are compared using the test of the applicability of the distillate fuel oil described on page 17 at 5 and 7 ° C below the wax emergence temperature (as shown in Table 1) with certain commercially available additives to improve flow properties. The following results were obtained:

Fuel

A B C D ppm Additives to improve —--- creep characteristics 100 500 100 500 100 500 500 diameter of screen openings through which fuel is addedAddition passes in micrometers

none 495 u c p á v á 833 A2 495 246 833 420 420 420 Keroflux H 495 246 833 ⁺ 420 - - Al 833 246 420 833 - - 246 Keroflux M 833 ⁺ 495 833 ⁺ 420 - - Tween 65 · 246 124 420 495 - - Polyethylene glycol (600) dibehenate Mixed PEG / 200/400/600 / di / stearate / 175 124 420 175 124 147 behenate 104 74 246 74 147 104 147

⁺ means that the sieve with the corresponding hole size no longer passes through the fuel

Keroflux H is an ethylene vinyl acetate copolymer

Keroflux M is an ethylene-2-ethylhexyl acrylate copolymer

Tween 65 is polyethoxylated sorbitan tristearate (non-linear)

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

Example 3

The creep / usability / fuel oil tests are used to determine the applicability of fuel oils 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 (molecular weight) Pass through the finest sieve / micrometer

no ingredient 833 100 ALIGN! 420 144 420 200 104 400 147 600 175 1000 495 1500 420 4000 420

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

Example 4

The process of Example 3 is repeated using 100 ppm polyglycol ester and in the form of a polyethylene glycol diester of molecular weight 600, which is esterified with two moles of carboxylic acid of different lengths. The results are as follows:

Polyethylene glycol ester (number of carbon atoms) .Laurate / 12 carbon atoms / Myristate / 14 carbon atoms / Palmitate / 16 carbon atoms / Stearate / 18 carbon atoms / Behenate / 22 carbon atoms / Stearate / behenate

Mixed PEG / 200/400/600 / stearate / behenate

Pass through the finest mesh diameter in micrometers

833

495

420

420

175

147

104

The mixed stearate / behenate is obtained by reacting polyethylene glycol with 2 moles of an equimolar mixture of stearic and behenic acid.

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

Example 5

The creep tests are used to compare the creep characteristics of the polyethylene glycol esters, polypropylene glycol esters and blends of the polypropylene glycol esters and the polyethylene glycol esters of fuel oil A according to Table I at -15 ° C.

Esther (molecular weight) Esther ppm Pass through the finest mesh diameter in micrometers a / Mixed PEG / 200/400/600 / 100 ALIGN! 104 di / stearate / behenate / 500 74 b / PPG / 400 100 ALIGN! 833 di / stearate / behenate / 500 74 PPG / 1025 / 100 ALIGN! 495 di / stearate / behenate / 500 104 d / PPG / 2025 / 100 ALIGN! 833 di / stearate / behenate / 500 245 Ester mixture Mixture Pass through the finest sieve / weight ratio / ppm mesh diameter in micrometers / a / / / b / = 1/4 500 61 / a / / / c / = 1/4 500 104 / a / / / d / = 1/4 500 104

The results show 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. The activity of polypropylene glycol esters is also evidenced by the dependence on the molecular weight of the polypropylene glycol. Mixtures of polypropylene glycol esters and polyethylene glycol esters can also be used effectively.

Example 6

The clogging temperature of the cold fuel oil filter of Table I, denoted as fuel oils D containing polyethylene glycol esters at different molecular weight polyethylene glycol and using different carboxylic acids to the ester ifics, is measured.

Polyethylene glycol ester ppm of active substance in fuel oil Lowering the cold filter clogging temperature PEG 600 dilaurate 100 ALIGN! 0 PEG 600 dimyristate 100 ALIGN! 0 PEG 600 dipalmitate 100 ALIGN! 0 PEG 600 distearate 100 ALIGN! 0 PEG 600 dibehenate 100 ALIGN! 5 PEG 200 dibehenate 100 ALIGN! 0 PEG 400 dibehenate 100 ALIGN! 4 PEG 600 dibehenate 100 ALIGN! 5 Polyethylene glycol ester ppm of active ingredient Lowering the temperature / PEG ester / in fuel clogging of cold- PEG 1000 dibehenate oleji D 100 ALIGN! filter 0 PEG 1500 dibehenate 100 ALIGN! 0 Mixed PEG (200/400/600) dibehenate 100 ALIGN! 5 Mixed PEG (600/1000) dibehenate 100 ALIGN! 5

The results demonstrate that PEG 400 and PEG 600 dibehenates have an optimal molecular weight and an optimal carboxylic acid to reduce the cold filter clogging temperature of said fuel. By comparison, the clogging temperature of the cold filter for fuel D containing 100 ppm of additive a / - 1 is reduced.

Example 7

The potency of blended polyethylene glycol esters with other additives for narrow boiling distillate fuel oils is determined by the applicability test for fuel oil B according to Table I at -15 ° C. The weight ratio is 4/1.

Ingredient

Active substance ppm

Pass through the finest mesh diameter in micrometers

PEG 400 dibehenate BI

B1 / PEG 400 dibehenate at a ratio of 4/1 B1 / Tween 65 at a ratio of 4/1 A2

A / mixed PEG di / stearate / behenate in a 4/1 ratio

100 ALIGN! 420 500 246 500 74 500 420 500 420 500 245

The results demonstrate the advantages of a mixture of PEG ester with polar monomer B1 compared to using polar monomer BI alone as well as using blend B1 and Tween 65. The efficiency of ethylene vinyl acetate copolymer A2 is also improved by use together with polyethylene glycol ester.

Example 8

The effectiveness of polyethylene glycol esters in admixture with ethylene vinyl acetate copolymer as an inhibitor of wax crystal growth and its additive to lower the boiling point of fuel oil E according to Table I is as follows:

Polyethylene glycol ester

Ethylenvinyl- Type l Active ingredient Lowering the temperature acetate copo clogging of cold- lymer / A2 filter ppm ppm 100 ALIGN! - 0 0 200 - 0 2 80 PEG dibehenate 20 May 12 100 ALIGN! II 40 15 Dec 0 II 100 ALIGN! 0 0 II 200 2 80 mixed PEG (600/1000) dibehenate 20 May 13 160 II 40 18 0 II 200 2 150 C ₂₈ to C ₃ q mixed PEG ester ⁴ 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.

Example 9

The effectiveness of the polyethylene glycol esters in admixture with polar monomer compounds as an additive to reduce the clogging temperature of the cold fuel oil filter F of Table I is as follows:

Additive Polyethylene glycol ester Reduction of clogging temperature

Species ppm Species ppm cold filter 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 demonstrate that polyethylene glycol dibehenate (PEG dibehenate) is more preferred than 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 when used in admixture with the PEG 600 ester.

Example 10

The efficiency of a mixture of polyethylene glycol esters and A2 was tested by determining the applicability of fuel oils at -12 ° C.

Growth inhibitor Polyethylene glycol ester Passage of crystals wax finer sieve ppm Species ppm Mesh diameter micrometer Fuel E according to Table I A2 200 - 0 104 A2 170 PEG 600 dibehenate 30 61 A2 170 mixed PEG (400/600/1000) distearate / dibehenate 30 61 Fuel G according to Table I A2 500  - 0 420 A2 400 mixed PEG (200/400/600) distearate / dibehenate 100 ALIGN! 104 Bl 400 11 100 ALIGN! 74

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

Example 11

The results of the tests for fuel oil D according to Table I shall be reported from three 25 m tanks which are carried side by side. During three-week storage at natural low temperature conditions (including natural cyclic temperature variation), fuel oil at -13.5 ° C is pumped from the tank as in the sale of fuel oil, and the finest screen through which the fuel still passes is recorded.

Ingredient (at 0.1% active ingredient) Passage through the finest mesh diameter in micrometers a / Al 420 b / Mixed PEG / 200/400/600 / di / stearate / behenate / 246 c / A2 / mixed PEG ester as in b / ratio 3/1 175

The filter screens, typically used in fuel oil sales, have an orifice diameter of 246 microns and it is therefore clear that while fuel oil containing ethylene vinyl acetate copolymer A1 has insufficient performance for clogging a 246 micron mesh filter, fuel containing polyethylene glycol ester alone and fuel containing ethylene vinyl acetate blend % of the copolymer and ethylene glycol ester show sufficient flow characteristics when pumping.

Example 12

The three fuel oil drums A of 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 oil is tested for cold creep characteristics. The drums are then slowly heated above the wax emergence temperature in the fuel oil and then cooled again at a rate of 0.5 ° C / h to -13 ° C. The fuel oil is then pumped from the drums through a set of filter screens to determine the finest screen through which the cold, wax-containing fuel passes.

Ingredient Effective substance ppm AI 500 Mixed PEG (200) 400/600 / di / stea- 500 rát / behenát / 100 ALIGN!

Mixed PEG ester as characterized above (PPG / 10 25) dibehenate

Pass through the finest sieve after the first cooling after the second cooling

mesh diameter in micrometers 246 420 124 124 175 175

100/400

124

147

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

Example 13

The fuel oil usability test at -10 ° C is used to compare linear saturated esters with linear non-

saturated esters, for example with an acid ester oil. Fuel oil Ingredient ppm Passage the finest sieve according to Table I diameter mesh in micrometers D PEG (600) dibehenate 500 147 D PEG (600) dioleate 500 833 / not passing / D none 833 / not passing

Example 14

The test of the applicability of fuel oil in a series of three distillate fuel oils with a wide range of boiling points is repeated and the efficiency of the linear polyethylene glycol esters used alone in such fuel oils 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 oil according to Table I Ingredient ppm E A2 200 E PEG (600) dibehenate 200 E PEG (600) dioleate 200 E none - H A2 300 H PEG (600) dibehenate 300 H PEG (600) dioleate 300 H none - AND A2 250 AND PEG (600) dibehenate 250 AND PEG (600) dioleate 250 AND none -

Pass through the finest mesh diameter in micrometers

420

495

147

147

420

420

124

175

175

Example 15

Fuel oil with a relatively high boiling point has the following characteristics:

% by weight and 4 by weightTemperature, ° C +4

Wax discovery temperature, ° C - 0

Cold filter clogging temperature, ° C (untreated) - - 5

Distillation according to ASTM D86

Initial boiling point, ° C 185

Boiling point, ° C 386

Addition of an additive containing a mixture of 1 polyethylene glycol / 600 / dibehenate / PEG / 600 / dibehenate / components of the additive A2 gives the following results:

Additive amount, ppm

150

200

250

300

350

450

500

550

650

Cold filter clogging temperature, ° C

This example demonstrates that the cold filter clogging temperatures are the actual temperatures at which the fuel oil 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 14.5% by weight of chlorine, is added chlorinated wax and approximately 12 parts by weight of naphthalene (known as C) and the cold filter clogging temperature of the fuel oil containing the following 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 oil is achieved by incorporating additive C.

Example 16

Tests for determining the applicability of fuel oil to fuel A at -15 ° C are used to compare polyethylene glycol 600 distearate and polyethylene glycol 600 diisostearate using a 200 ppm additive. Results achieved:

Ingredient

Active substance ppm

Pass through the finest mesh diameter in micrometers

PEG 600 distearate 200

PEG 600 diisostearate 200

420

833 / clogged /

Thus, preference is given to a linear alkyl group.

Example 17

The polytetramethylene glycols of Teracols' of the general formula are prepared

HO - C / CH _2/4 - O] _"n - H with a molecular weight of 650, 1000 and 2000 and esterified with 2 moles of behenic acid. These substances are then tested in the fuel A test

Applicable fuel results: of oil at temperature -15 ° C with these Additive Active substance ppm Pass through the finest mesh diameter in micrometers Teracol (650) dibehenate 200 833 / clogged / Teracol (1000) dibehenate 200 495 Teracol (2000) dibehenate 200 420 Obviously, certain Terracol derivatives they are effective, however

compared to Example 3, they exhibit less efficacy 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 - o - / ch ₂ ch ₂ o / ₁₀ - C - c _{21 #} In the fuel oil usability and concentration test

200 ppm of active ingredient, this additive at -15 ° C allows fuel oil A to pass through a 175 micron screen. 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 mixed 22/24 carbon alcohol and a straight chain to give the product of the formula

0 0 0

II II II II ^{/ C} 22 / ^C 24 / ° ^{C CH} 2 ^CH 2 ^{C_O / PEG} 600 / -OC-CH ₂ CH ₂ -CO- / C ₂₂ / C ₂₄ /

This product is tested in fuel oil J having a turbidity temperature of + 4 ° C, a wax emergence 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. In the -6 ° C serviceability test, the additive-free fuel oil passes through a sieve with a mesh diameter of 420 m &lt; 7 &gt;

The introduction of 200 ppm of the fuel oil additive A shows a passage through the sieve with a mesh diameter of 147 microns in the -15 ° C serviceability test.

Example 20

The effect of polyethylene glycol (600) dibehenate is compared to that of polyethylene glycol (600) diethyl succinate in fuel oil K having a clouding 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. . Untreated fuel oil 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 the alkyl group saturation.

Example 21

A mixture of 4 parts additive to improve the flow properties of distillate fuel oil A2 and one part of various polyethylene glycol dibehenates is tested for the cold filter clogging temperature with fuel oil F with the following results:

Additive Decrease the cold filter clogging temperature

100 ppm additive 200 ppm additive

ethylene vinyl acetate and polyethylene- glycol 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 14 18 A2 itself 1 2 PEG (600) dibehenate alone 6 + P / EO / PQ / 8000dibehenate 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 tetracol derivatives instead of polyethylene glycol dibehenates with the following results:

Ingredient

Teracol 650 dibehenate 4: 1 + A2 Teracol / 650 / dibehenate + Teracol / 1000 / dibehenate + A2 Teracol / 1000 / dibehenate Teracol 2000 dibehenate + A2 Teracol / 2000 / dibehenate

Reduction of cold filter clogging temperature, 100 ppm of additive + ethylene vinyl acetate to teracoldibehenate ratio 4: 1

From these values, it is apparent that the Teracol derivatives are much less potent than the polyethylene glycol derivatives.

Example 23

Various additives are tested in the fuel oil usability test at -10 ° C in fuel oil L having a turbidity temperature of -4 ° C, a wax emergence temperature of -6 ° C, a 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 Exam usability passing through the finest sieve ppm diameter mesh in micrometers None - 833 clogging PEG (600) dibehenate 100 ALIGN! 104 PEG (600) monobehanate 100 ALIGN! 420 Teracol (650) dibehenate 100 ALIGN! 495 Teracol (1000) d ibehenate 100 ALIGN! 833 Terako1 / 2000 / dibehenate 100 ALIGN! 833 Poly / EO // PO 8000 / dibehenate 500 833 (molecular weight 8000) 100 ALIGN! 833

Example 24

The cold filter clogging temperature of fuel oil D containing various additives is as follows:

Ingredient Active substance Cold filter clogging temperature drop ppm Noc: 2 ° C PEG 200/400/600 / dibehenate 250 4 C21H43C- / OCH2CH2 / 8OH O 250 -1 500 -1 ^C 18 ^H 37 ° ° / ^CH 2 ^CH 2 ° / 10 ° ^H 250 -2 500 -5 ^C 18 ^H 27 ° ° ~ / ^CH 2 ^CH 2 ° / 10 ^ “ ^C 21 ^H 43 0 250 1 500 3

Claims (3)

PATENT CLAIMS 1. An additive concentrate for fuel oil derived from petroleum distillation, characterized in that it consists of an oil solution containing from 3 to 75% by weight of an ester and / or an ether and / or an ester / ether of the general formula I R - O - (A) - O - R ¹ (I) wherein R a R ¹ represent the same or different groups selected from the group consisting of n-alkyl .. «9 n-alkyl C n-alkyl-O-C (CH _{2) n} -, and n-alkyl-0 -? - _(CH2) _- C-, wherein the alkyl radicals are linear, saturated, and contain 10 to 30 carbon atoms, wherein one of R a R ¹ is also hydrogen and A is a polyoxyalkylene glycol moiety having a molecular weight of 100 to 5,000, wherein the alkylene groups contain 1 to 4 carbon atoms. 2. Additive concentrate according to claim 1, characterized in that it additionally contains 60 to 80% by weight, based on the total additive content of the concentrate, a paraffin crystal growth inhibitor based on an ethylene-vinyl acetate copolymer or an oil-soluble polar nitrogen compound containing 30 to 300 atoms. carbon which is an amine salt and / or an amide and / or esteramide derived from a carboxylic acid having from 1 to 4 carboxy groups or an anhydride thereof. 3rd The additive concentrate according to claim 1 or 2, characterized 'in that as a compound of formula I contains an ester or diester, i.e. a compound in which R and R ¹ represent the same or different n-alkylcarbonyl, linear and saturated alkyl radicals containing from 10 to 30 and A is as defined in point 1.