DE2156425A1 - Heating or fuel oil mixture - Google Patents

Description

Esso Research and (Priority November 16, 1970 -

Engineering Company U.S. 90 115 - 8704)

Linden, NJ / Y.St.A. Hamburg, November 12, 1971

Heating or fuel oil mixture

The present invention relates to heating or fuel mixtures, in particular middle distillates with a content of pour point lowering polymers in combination »With oil-soluble additional compounds that improve the flow properties, which do not contain a nitrogen atom.

In the usual middle distillate fuels what is present works Kerosene as a solvent for the existing waxy η-paraffins. Because of the increased use of kerosene for jet fuels, the kerosene content in middle distillate fuels is increasing away. As a result, the addition of modifiers for wax crystals is increasingly necessary, i.e. it

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must add additives to the fuel to reduce the pour point can be added to make up for the lack of kerosene.

Effective pour point depressants for these middle distillates are copolymers of ethylene with numerous other monomers, such as copolymers of ethylene and vinyl esters of lower fatty acids, such as vinyl acetate, copolymers of ethylene and alkyl acrylates, terpolymers of ethylene with vinyl esters and alkyl furarates, polyethylene with other lower olefins or Homopolymers of ethylene and chlorinated polyethylene.

These pour point depressants with an ethylene chain are very good effective to lower the pour point of distillate oils but no or only a slight influence on the size of the wax crystals, so that wax crystals in these fuels with a particle size of 1 mm to 25 mm can be present. These larger crystals are made up of mostly Any sieves or piltering devices present in the tank trucks and fuel storage containers are removed, but the sieves will settle or filter closed, even if the temperature of the fuel or oil is significantly above the pour point or cloud point lies.

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The previously known additives for improving the flow properties These are naturally occurring waxes or nitrogen compounds, such as mixtures of copolymers made from polyethylene and polyvinyl acetate or polymers of acrylate or methacrylate esters together with microcrystalline waxes or normal Paraffins. For example, US Pat. No. 3,442,182 and British Pat. No. 1,1O 171 describe the use certain nitrogen-containing compounds.

It has now been found that additives other than nitrogen containing compounds or the naturally occurring mixtures are used to improve the flow properties can be.

According to the invention, therefore, a new heating or fuel oil mixture is proposed, which is characterized in that it contains:

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a) a major portion of a middle distillate fuel with a boiling range of 120 to 400 ° C and a smaller proportion of an additive to improve the pleating properties with a content of

b) as the first component, an oil-soluble, pour point lowering component Polymers with an average molecular weight M of 500 to 50,000 from the group of the following Links:

a polyethylene,

a hydrogenated polyolefin,

a C ₁₀ to CLg polyolefin,

a halogenated polyethylene and a polymer of 3 to ^ O moles of ethylene and 1 mole of a copolymerizable comonomer from the group of the following compoundsί

(i) a vinyl ester of a C ₁ to C ₁ - and

preferably C ₂ to C _q monocarboxylic acids

(ii) an ethylenically unsaturated ester of the formula

CH ₂ =

in which X is hydrogen, halogen or an alkyl radical and Y is halogen or a -COOR radical and R is a C ₁ to C ₁ ^ and preferably C ₂

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to Cg is an alkyl or aryl radical, (iii) an ethylenically unsaturated compound the formula

R ¹ - C - COOR "

Il

R ¹ - C - COOR ",

in which R ^{1 is} hydrogen or a lower alkyl radical and R "is hydrogen or a C ₁ -C ₁ ^ and preferably C 1 -C 6 alkyl radical; and

(iv) a C, to C ₁ Q, and preferably C, to Cg olefin hydrocarbon;

c) as the second component, an oil-soluble additive compound that does not contain nitrogen, which enhances the flow properties improved and the at least one straight-chain (CHp) polymethylene section with an η of 10 to 30 and a larger or more bulky substituent on the polymethylene segment has, namely

(i) a non-polar hydrocarbon group im

essentially without saturated cyclic hydrocarbons and / or

(ii) a polar group containing halogen, oxygen, sulfur or phosphorus.

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The preferred fuel or fuel oil mixtures contain middle distillates having a boiling point in the range of 120 to JlOO ⁰ C, usually with a boiling range of 10 to 90% of the middle distillate in this field, for example in a range of 150 drops to 37o ° C.

Polyethylenes with a molecular weight M of 800 to 2,500.

Hydrogenated polyolefins include hydrogenated copolymers of ethylene / butadiene, butadiene / styrene, Butadiene / isoprene, ethylene / styrene, butadiene / butene-1 and the like is used, with hydrogenated polybutadiene having a molecular weight of 3,000 being preferred.

When the first component of the flow properties improving If a halogenated polyethylene is added, this can be achieved by halogenation, for example chlorination or bromination of the polymer. In general, the halogenated polymers contain 2 to 30 and preferably 5 to 15 wt. Halogen. Chlorinated polyethylene with a content of 10 to 30 and, for example, 20 wt. Chlorine.

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In a preferred embodiment, a copolymer is used as the polymer used from ethylene with a second copolymerizable monomer containing 3 to 40 moles of ethylene per mole of copolymerizable Comonomer and optionally one or more moles of another copolymerizable monomer. The comonomer can be a vinyl ester of a monocarboxylic acid, such as vinyl acetate, vinyl propionate or vinyl caprylate. The comoonomer can also an ethylenically unsaturated ester of the formula

CH ₂ -

where X is hydrogen, halogen, alkyl and preferably a lower alkyl having 1 to 8 carbon atoms or an aryl, while Y is halogen or -COOR, where R is an alkyl radical, preferably a C ₁ to C ^ g alkyl and in particular a Cp to Cq is alkyl or an aryl radical. Examples of such esters are acrylates, such as methyl acrylate, isobutyl acrylate, methyl chloroacrylate, ethyl bromoacrylate, and also methacrylates, such as methyl methacrylate or isobutyl methacrylate; Vinyl chlorides or vinylidene chloride.

The preferred comonomer is isobutyl acrylate, which is preferred Polymers is the mixed polymer with 3 to IJO moles of ethylene each Moles of isobutyl acrylate with a molecular weight M of preferably 1,500 to 15,000.

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If the comonomer is an ethylenically unsaturated compound of the general formula

Rt-c- COOR "
π

R ¹ - C - COOR "

and R ^{1 is} hydrogen or a lower alkyl, for example a C ₁ to Cg alkyl and R "is hydrogen or an alkyl preferably having 1 to 16 carbon atoms, fumaric acid, maleic acid, monomethyl fumarate, diisopropyl maleate or dilauryl fumarate are preferred.

If the comonomer polymerized with ethylene is an olefinic C ₁ to C 1 Q hydrocarbon, propylene is preferred as the comonomer. Copolymers of ethylene and propylene with a content of 5 moles of ethylene per mole of propylene and a molecular weight M of 1,500 to 15,000, such as 5,000, are particularly preferred. Other typical comonomers include butene-1, pentene-1, 4-methylpentene-1, heptene-1, 4-methylhexene-1 or decene-1.

The second component of the additive which improves the flow properties can be a hydrocarbon, a halogenated carbon

hydrogen, an ester, an acid including acid anhydride, be an ether, a ketone, and the like. This second

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Component contains at least one (CHp) polymethylene segment, where η is a value of 10 to 30 and preferably 14 to 20. In general, such sections are hexadecyl, octadecyl or pentacosyl radicals.

The molecule can contain a larger substituent that is either is located at the end of the chain or between the chain, i.e. between two adjacent chains or a side chain on the chain. These larger substituents can be designed so that they are discontinuous or steric Have configuration and form a discontinuous envelope along the length of the molecule. Generally such larger or "bulky" substituents, aromatic rings such as phenyl, double bonds, halogens such as chlorine, bromine and the like or an oxygen atom as in an acid, an anhydride, an alcohol or ester radical or ether, as in polyoxyethylene groups.

Those compounds are preferred which contain a total of 12 to 200 and preferably 30 to 125 carbon atoms, which contain at least one of the mentioned C ₁₀ to C, _Q straight-chain radicals and which nevertheless have the following components:

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(1) alky! Aromatics including those containing 1 to 4 alkyl radicals have, each of which is a C ₁ to C, _Q is alkyl and one is a CQ to C, q alkyl one each aromatic ring containing 1 to 3 rings may have such as benzene, naphthalene, anthracene and the like. Examples are phenylpentadecane, dodecyltoluene and tetradecyltoluene.

(2) Halohydrocarbons with 1 to 4 halogen atoms per molecule, the hydrocarbons being straight-chain or branched, aliphatic or alkaryl and the like, including the alkylaromatics mentioned above under (1) or the acids mentioned below under (3), such as chloro wax , 21-chlorodotetracontane and C, _{Q +} alkyl bromides.

(3) Acids and their anhydrides with 1 to 3 carboxyl radicals, which contain aliphatic radicals, aryl or alkyl radicals or cycloaliphatic radicals, etc., such as octadecylsuccinic anhydrides, behenic acid and C ₂₂ to C ₂ g alkenysuccinic anhydride.

Esters, such as esters of the acids mentioned under (3) and preferably C ₂ to C ₂ ^ fatty acids, preferably of straight-chain and saturated esters with alcohols with 1 to 6 hydroxyl radicals, of which at least one radical is esterified, the alcohol 1 to 30 carbon atoms

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holds and a straight-chain or branched-chain aliphatic, can be an aryl or alkaryl alcohol. Sorbitols and manitols including the are particularly suitable for alcohols simply dehydrated compounds such as sorbitan and the like. Preferred esters are sorbitan monopalmitate, monostearate or tristearate and sorbitan laurate and stearate, also pentaarythrityl tetrastearate, sorbitan monooleate, Sucrose laurate, sorbitol oleate, tristearin and dibehenyl adipate.

Sorbitan esters are preferred, and especially compounds that contain the following structures:

CH ₂ OA / 0 V ^ CHOXCH ₂ OA yOZ YO- ^ ¹ M) Z

0
Y

Mixtures of these two formulas, in which A, X, Y and Z can have the following meanings, are generally available:

(a) a long chain fatty acid residue such as stearate, laurate, palmitate, etc. or

(b) hydrogen or

(c) a polyethoxy radical, such as - (CH ₂ CH ₂ O) ₂₀ H and where at least one of the radicals A, X, Y or Z is other than hydrogen or a polyoxyethylene radical (CH ₂ CH ₂ O) _n . Typical compounds or mixtures can contain sorbitan monostearate, sorbitan tristearate, polyoxyethylene (20) sorbitan tristearate.

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(5) Polyethers or alkoxylated compounds in which 1 to 30 alkoxy radicals with 2 to 26 carbon atoms, such as ethylene oxide, propylene oxide, docosanyl O ^ -olefin oxide are bonded to another group, for example to acids of the type mentioned under (3) or alcohols of the type mentioned under (4), such as, for example, C ₁ to C, Q alcohols with 1 to 6 hydrogen radicals. Examples are polyoxyethylene (8) stearate, polyoxyethylene (8) laurate, polyoxyethylene (20) stearyl ether, polyoxyethylene (20) sorbitan tristearate, polyoxyethylene (20) sorbitan trioleate, polyethylene glycol stearate and polyethylene glycol being named the numbers in brackets mean the average number of oxyethylene radicals per molecule. A preferred polyether has, for example, the general formula R- (OCH ₂ CH ₂ ) ₂ _ _2C) 0H, where R is a stearyl radical.

(6) Unsaturated aliphatic hydrocarbons with 1 to 4 Ethylenically unsaturated bonds, such as 19-octatriaconts.

(7) Derivatives of the compounds mentioned under (6) in which a further reaction is carried out on one or more of the unsaturated bonds has been performed, such as

(A) an acylation with acyl halides, the unsaturated aliphatic hydrocarbons of the compound mentioned under (6) having 1 to ¹ J moles of an acyl halide

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Il

RC-Cl are implemented, where R is a C ₁ to C ₂₀ hydrocarbon radical including straight-chain or branched aliphatics, aromatics or alkyl aromatics. Particularly suitable compounds derive from the Priedel-Crafts acylation, preferably in the presence of aluminum chloride, from long-chain symmetrical internal olefins having more than 30 carbon atoms with an acyl halide, such as, in particular, C ₂₀ H ^ ₁ CH = CH - ^C 2O ^H 4l with CgHj -COCl. Typical of the ketones are reaction products of 21-dotetracontene / benzoyl chloride, an inner Cj ₁₂ to C, _g olefin / benzoyl chloride and 11-docoses / benzoyl chloride.

(b) Halogenation or hydrohalogenation, especially chlorination and bromination, whereby derivatives of the above compounds are obtained, wherein the halogen or the hydrogen halide, such as, for example, HCl is attached to at least one of the ethylenically unsaturated double bonds.

(8) A saturated C ₁₀ to C ₂ g alkanol derivative, such as, for example, esters of acids of the compounds according to (3) and polyethers of alkoxy compounds according to (5).

The first and second components of the additives improving the peel properties are depending on the type and amount

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Properties of the fuel oil or fuel used. In general, the mixture contains from 1 to 99 and preferably from 1 to 97 % of the first component, while the remainder is formed by the second component.

The new fuel or propellant oil mixtures contain 0.001 to 0.5 and preferably 0.005 to 0.3 parts by weight of the first or second component per 100 parts by weight of oil.

The first and second components are preferably used as a concentrate in a diluting solvent which is soluble in the oil in question. Such concentrates can contain 5 to 70 and preferably 10 to 50 parts by weight, such as, for example, 10 parts by weight of the first and second components in 0 to 100 parts by weight of the diluting solvent. The latter can be an inert liquid in which the first and second components are soluble or dispersible.

Although both the first and the second component of the additive mixture Can be prepared separately in a diluting solvent, they are preferably as a concentrate in one only diluting solvent present, which is expediently the oil to which the mixture is also to be added. This

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Solvent can be, for example, a "Solvent 325 Neutral", a light base oil, a vacuum gas oil, a heavy one aromatic naphtha oil, kerosene or a fuel oil distillate.

To produce the additive according to the invention, the first and second components are added to the oil either separately or at the same time and mixed so that a petroleum mixture is formed. Mixing can be done continuously or intermittently. Usually these additives are prepared by adding a flow improving amount of this additive at temperatures above 150 ⁰ C and preferably above 37 ° C the base oil. If the first and second components are added as a concentrate in a diluting solvent, the preferred temperatures are, for example, 15 to 93 ° G, for example 5 ¹ J ⁰ C. If the first and second components are added without a diluting solvent, this takes place this preferably in a temperature range between 65 and 150 ° C, for example at 93 ° C.

It is surprising that numerous representatives of the first component, namely, the oil-soluble pour point depressants usually result in only a slight or hardly noticeable improvement in the flow properties, if they are added alone to propellants or propellants which are difficult to influence or which do not respond, for example,

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usual European fuel oils, such as distillate fuels with a 10 £ strength boiling point at 195 ° C and a 90 fcigen boiling point at 3IJO ⁰ C and an aniline point of 173 ° C, a pour point of -15 ° C and a cloud point of -3.3 ° C (Fuel oil C). Since the second component also normally produces no or only an extremely slight improvement in the pleat properties, it is surprising that it can be used to considerably increase the pleat properties of the first component.

The possibility of emerging with the combination according to the invention Achieving results depends on the fuel and combination involved. The best results is generally achieved, when a fuel which is generally considered to be difficult to be found, is based on the previously known Additives to improve the pleating properties did not respond or if one with conventional fuels or fuels The addition used fails for inexplicable reasons.

The middle distillate tribal oils treated according to the invention generally have a fluidity of 0 to 20 % prior to treatment, such as 0 to 10 and in particular 5 % according to the Enjay fluidity test. This test can be determined in a vessel corresponding to an hourglass, the upper chamber of which is separated from the lower chamber

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is separated by a capillary opening with a diameter of 2.5 ¹ l mm. In the experiment ¹ IO ml of the optionally to be examined oil in the lower chamber, after which the oil-containing unit from a temperature (P 10 ⁰⁾ is about 5 ° C above the ASTM cloud point, at a rate of about 2 ° C ( ¹ I ⁰ F) per hour to a temperature of about 5 ° C (10 ⁰ F). is cooled below the cloud point. The device is turned over so that the now cloudy oil flows under the influence of gravity into the empty lower chamber. The percentage by volume of the oil that runs through the opening within 3 minutes is measured. If the paraffin is present in large crystals, the opening will be clogged and the oil flow slowed, while on the other hand small crystals show good fluidity.

Another attempt that is used to determine the flow properties of a middle distillate is the so-called "Cold Filter Plugging Point Test" (CFPPT), which is described in detail in "Journal of the Institute of Petroleum" Volume 52, No. 510, June 1966 is described on pages 173 to 185. Here, a ^ 5 ml of the sample is cooled to be examined oil in a bath of -34, ¹ J ⁰ C. Every time the temperature drops about 0.5 ° C (2 ° F), starting from about 2 ° C ( ¹ I ⁰ P) above the cloud point, the oil will with a

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Investigated device consisting of a pipette, the lower end of which is attached to an inverted funnel.

At right angles to the funnel opening is a 35O mesh screen with a

ρ
Tensioned surface of about 2.9 cm. At the upper end of the pipette, a vacuum line of about 17.78 cm water column is applied with the funnel immersed in the oil. Due to the vacuum, the oil is drawn through the sieve into the pipette up to a mark corresponding to an amount of 20 ml of oil. The experiment is repeated after a temperature drop of 0.5 ° C (2 ° P) until the oil cannot fill the pipette up to the specified mark due to the clogged sieve with paraffin crystals. The results of this experiment are referred to as “working ^{limit 11} or cold point of the pilter clogging, which corresponds to the temperature in ⁰ P at which the oil can no longer fill the pipette within the prescribed time.

In the following examples, as before, all quantities are given given as parts by weight. In these examples the following middle distillate oils were tested based on either the hitherto known additives for improving the flow properties did not respond or only had a difficult or limited effect showed:

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.- 19 -

Fuel A - heating oil No. 2. A middle distillate with an IBP of 190 ⁰ C, a 10 % boiling point of 217 ° C, a 90 % boiling point of 299 ° C, a final boiling point of 324 ⁰ C, a cloud point of -18, 9 ° C, a pour point of -2O.6 ° C, an aniline point of 58 ⁰ C and a paraffin content of 3.1%.

Fuel B - A middle distillate fuel oil having a cloud point of -21.1 ° C, a pour point of -23.3 ° C, an aniline point of 58.5 C ^O, a 10% boiling point of 245 ° C, a 90% boiling point of 29o ° C.

Fuel C - A European middle distillate fuel oil with a 10% boiling point of 195 ⁰ C, a 90 % boiling point of 3MO ⁰ C, an aniline point of 73 ° C, a pour point of -15.0 ⁰ C, a cloud point of -3j3 ° C.

Fuel D - A middle distillate oil of European origin with a 10% boiling point of 195 ° C, a 90% boiling point of 321 ° C, an aniline point of 69 "5 ° C, a pour point of -17" 8 ⁰ C and a cloud point of -8 , 9 ° C.

Fuel E - A middle distillate fuel oil of European origin with a 10 % boiling point of 189 ⁰ C, a 90 % boiling point of

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313 C, an aniline point of 66 C, a pour point of -23.3 ° C and a cloud point of -14.4 ° C.

In each example of the following first series, the middle distillate was used examined in a control experiment for its flow properties after the Enjay test. In all cases Typical mixtures according to the invention with equal parts by weight of active components 1 and 2 were added. With more As a control, the total amount of either only the first or the second component was added to the fuel.

In these examples the following pour point depressants were used for Used middle distillates, namely concentrates that contained the following active ingredients as the first component:

I - A copolymer of ethylene / vinyl acetate with an average molecular weight M of about 2,000 with a content of about 38 % by weight vinyl acetate and a content of 5 moles of ethylene per 1 mole of vinyl acetate.

II - A chlorinated polyethylene with a molecular weight M of about 3,500 and a chlorine content of about 20 %.

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III - A polymer consisting essentially of ethylene and isobutyl acrylate, having a molecular weight M of about 3,000 and an isobutyl acrylate content of about 40 % .

In these examples, the following substances were used as the second component:

1. polyoxyethylene * (20) sorbitan tristearate,

2. polyoxyethylene (20) stearyl ether,

3. Polyoxyethylene (10) stearyl ether, H. Polyoxyethylene (20) stearyl ether,

5. sorbitan monopalmitate;

6. Sorbitan tristearate.

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Table I.

Example first second total concentration measured value No. Component Component tration

1* I. - 0.10 74 CVi I. 1 0.04 100 3 I. 2 0.04 100 4th I. 3 0.04 95 5 * II - 0.10 44 6th II 1 0.10 100 7th II 2 0.10 100 8th II 3 0.10 92 9 II 4th 0.10 92 10 * III - 0.10 45 11 III 2 0.10 78 12th III 3 0.10 100 13th III 4th 0.10 93

* These examples serve as a control test In the table above, fuel B was used as fuel oil,

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For example, were in the test according to Example 1 in the base oil B 0.10 parts by weight of the first component I per 100 parts by weight of base oil available and there was obtained an evaluation according to the Enjay test of 7 ^, ie 7 ¹ I% of the propellant oil ran during the Trial time through the opening. The source oil had a rating from 0 to 20.

Unexpectedly, it was found that when using 0.04 parts by weight of the total of the first component I and the second component 1, a rating of 100 is achieved, that is, with a total addition of Ί0 % compared to Example 1, the amount of oil flowing through the opening is 100 % , while in Example 1 only 7k% of the oil was allowed through. Comparatively is obtained a completely inadequate evaluation in an experiment in which 0.0 ¹ I parts by weight of the second component I without the addition of the first component I.

A comparison of control experiment 5 with the examples shows analogously 6 to 9 »that the pleating properties are more than doubled when the additives according to the invention are used will. A comparison of control test 10 with tests 11 to 13 shows similar surprisingly good effects.

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In the following examples, the blowing properties of fuels C, D and E were determined according to the above-mentioned CPPP test. In each example, 0.015 parts by weight of the first and second components were added per 100 parts by weight of fuel. The evaluation numbers correspond to the temperature in ⁰ P at which the oil no longer flows.

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first Tabel II Valuation numbers component second 20th example I. component fuel 6th 14 * I. C. 12th 15th I. 5 C. 14th 16 I. 6th C. 10 17th I. 1 C. 16 18th I. 3 C. 10 19th I. 4th C. 2 20 * I. - D. 4th 21st I. 5 D. 2 22nd I. 6th D. 4th 23 I. 1 D. 0 24 I. 2 D. 6th 25th I. 3 D. 2 26th I. 4th D. -8th 27 * I. - E. -4 28 I. 5 E. -4 29 I. 6th E. -6 30th I. 1 E. -12 31 I. 2 E. -8th 32 I. 3 E. 2 33 III 4th E. -2 34 * III - D. -4 35 III 4th D. -8th 36 * III - E. -8th 37 III 5 E. -8th 38 III 6th E. 39 1 E.

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Continuation from Table II

first second
Example component component fuel valuation payer i

40 III 2 E. -8th 41 III 3 E. -8th 42 III 4th E. -8th oil C 26th oil D 12th oil E 6th

The above table shows that unexpected results are obtained according to the invention. The base oil C has a rating number of 26 when neither the first nor the second component is present. In example 14, only the first component is present and a rating of 20 is obtained, while adding the equal total amount of a mixture consisting of equal parts by weight of the first component I and the second component (Example 15) the evaluation number is improved to 6.

Corresponding improvements are obtained by comparing the control experiments 20 and 27 with the subsequent examples up to 26 and 28 to 33

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Due to the highly fluctuating and completely unexpected behavior of the various oils which are difficult to influence, it is not always possible to determine the extent of the Predict improvement. For example, a combination of the first component results in I and the second component 4 only a slight improvement in the case of fuels C and D, as Examples 19 and 26 show, but leads to a considerable improvement Improvement in fuel E, as Example 33 shows. It is therefore unexpected that according to the invention one clearly improved evaluation of the flow properties of oils that do not respond to an added first component alone.

In the following second series of tests, a middle distillate fuel oil was examined in a control test with regard to the flow properties according to the Enjay test and then mixed with the mixture according to the invention, which contained the first and second components in equal amounts by weight. In the following experiment ¹ 13, the total amount added consisted only of the first component.

In these examples, a copolymer was used as the first component from ethylene / vinyl acetate with an average molecular weight of M about 2,000 with a content of 38 wt.? S vinyl acetate with a Content of 5 moles of ethylene per mole of vinyl acetate used.

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In the following Table III, the respective second components are given in each example, in a weight ratio of 50:50 together with the first component once in a total weight of 0.04 and on the other hand in a total weight of 0.02 parts by weight per 100 parts by weight of oil were used. The rating corresponds to that given above Enjay's test, where the numbers represent percentages.

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Table III 0.01 ^ 0.02 —-—- Examples 21-Dotetraconten 100 50 Dotetracontan - 98 second component valuation numbers for one 21-dotetracontyltoluene 10 10 13 * Total weight of additives from Cjjp to Cp., - internal olefin 90 11 19 octatriaconts 98 15 * 21-bromodotetracontane 100 16 21-chlorodotetracontane 100 100 17th ^C 42 ~ ^C ^ 6 ^sec * alkyl chloride - 100 18th Tristearin 98 19th Sorbitan monopalmitate 100 50 Sorbitan monostearate 98 98 51 Sorbitan tristearate 92 98 52 Sorbitol stearate 100 98 53 Sorbitan monostearate benzoate 100 100 51 Octadecyl succinic anhydride 98 73 55 Polyoxyethylene- (20) -steary1- 81 80 56 ether 85 77 57 Polyoxyethylene (10) stearyl 58 ether 95 98 59 60

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Continuation from Table III

Examples second component rating numbers Polyoxyethylene (20)
sorbitan tristearate 0.0 * 1 at a Total weight of Polyethylene glycol stearate 98 Additions of Polyethylene glycol stearate,
Methyl ether 80 0.02 61 21-Dotetraconten / Sebacoyl-
chloride 100 98 62 21-Dotetraconten / Sebacoyl-
chloride 100 63 C ^ p-Cf-g internal olefin /
Benzoyl chloride 100 64 92 85 65 66
67

* Control attempt

The above table clearly shows the surprising effects when using the mixtures according to the invention. For example, according to Example 43, with a base oil A and a content of 0.04 parts by weight of the first component alone per 100 parts by weight of base oil, a rating of 100 % _t is obtained, ie 100 % of the oil passes through the opening within the test time

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sucked in, while values of 0 to 20 % occur with the starting oil without additives. If the concentration of the first component is 0.02 parts by weight, the test conditions are not met, ie less than about 75 % is sucked through the opening. When examining fuel A with the second component alone, no passage measurement at all is achieved at high concentrations of up to 0.1%. For example, the second component according to Example 64, when used alone in a 0.1% concentration, gives a value number of 0 %.

It was surprisingly found that, according to Example 47, the use of 0.04 parts by weight of a mixture of the first and second components leads to a value number of 98, although the total value of the active first component is the same as the concentration at which one is in Example ^ 3 did not meet the test conditions. The amount of oil that got through in the test period is 98 % compared to less than 50 % in Example 43. Thus, although the second component alone is not effective, it unexpectedly improves the results.

A comparison of control experiment 43 with the experiments shows analogously 49, 50, 56, 61 and 63 etc. that the pleating properties

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can be significantly improved if mixtures according to the invention are added. It has also been found that mart can use, for example, smaller amounts of, for example, 0.01 parts by weight of a mixture of the first and second components according to Example 50 and, according to the Enjay test, receives a value of 100 % , which corresponds to at least a four-fold improvement.

For heating oil it has been found that the Enjay test is decisive, while for diesel fuel the CFPP test is decisive, i. that the test method for a certain oil depends on whether the oil is through small openings or nozzles, such as Heating oil must be forced through or, as with diesel oil, passed through a sieve.

In general, the polymeric additive to reduce the pour point is i.e. the first component is relatively expensive, while the second component is less expensive. As shown, the combination of the first and second components often leads to excellent behavior, especially with fuel oils, which normally do not respond to the polymeric additive to lower the pour point. In addition, there is the combination also an economic advantage, even with oils that

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otherwise respond to such additives to improve the flow properties by adding a more expensive polymer first component is replaced by a less difficult to manufacture and more readily available second component, wherein the desired effect is still achieved. In addition, according to the invention, by using the combination nation of the first and second components have lower pour points that are lower than when using the same amount of one single component.

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Claims (1)

Claims Heating or fuel oil mixture, characterized in that it contains: a) a major portion of a middle distillate fuel with a boiling range from 120 to 400 ° C and a smaller proportion of an additive to improve the flow properties with a content of b) as the first component, an oil-soluble, pour point-lowering polymer with an average Molecular weight M from 500 to 50,000 from the group of the following compounds: a polyethylene,
a hydrogenated polyolefin,
a C ₁₀ to C ₁ Q polyolefin,
W a halogenated polyethylene and a polymer of 3 to 40 moles of ethylene and 1 mole of a copolymerizable comonomer from the group of the following compounds: (i) a vinyl ester of a C ₁ to C ₁ - and preferably C "to C _g monocarboxylic acid, 209821/0944 (ii) an ethylenically unsaturated ester of the formula CH ₂ = in which X is hydrogen, halogen or an alkyl radical and Y is halogen or a -COOR radical and R is a C ₁ to C ₁ ^ and preferably C ₂ to Cg alkyl or aryl radical, (iii) an ethylenically unsaturated compound of the formula R ¹ - C - COOR " Il R ¹ - C - COOR ", in which R 'is hydrogen or a lower alkyl radical and R "is hydrogen or a C ₁ to C ₁ ^ and preferably C 1 to C 6 alkyl radical; and (iv) a C, to C.g and preferably C, to Cg Olefin hydrocarbon; c) as the second component, an oil-soluble additive compound which does not contain nitrogen and which improves the flow properties and which has at least one straight-chain (CH ₂ ) poly- 209821/0944 methylene section with an η of 10 to 30 and a larger or more space-filling substituent on the polymethylene section has, namely (i) a non-polar hydrocarbon group essentially without saturated cyclic hydrocarbons and / or (ii) a polar group comprising halogen, oxygen, Wk _; Contains sulfur or phosphorus. 2. Oil mixture according to claim 1, characterized in that the the first component is a copolymer of ethylene with either vinyl acetate or isobutyl acrylate. 3. Oil mixture according to claim 1, characterized in that the first component a copolymer of ethylene and a compound of the general formula R ¹ - C - COOR "
R ¹ - C - COOR "
is in which R 'and R "denote hydrogen or an alkyl radical. H. oil mixture according to claim 1, characterized in that the first component is a chlorinated polyethylene. 209821 / 094A 5. oil mixture according to claim 1 to 4, characterized in that the second component is a sorbitan ester. 6. Oil mixture according to claim 1 to M, characterized in that the second component is a polyoxyethylene sorbitan ester, preferably polyoxyethylene (20) sorbitan tristearate. 7. Oil mixture according to claim 1 to 6, characterized in that the first component and the second component in each case
Amounts from 0.001 to 0.5 parts by weight are present. 8. Additive for the production of fuel or heating oil mixtures according to claim 1, characterized in that the flow properties regenerative additives in an amount of 10 to 70 parts by weight with 0 to 100 parts by weight of an inert diluting solvent and the heating and fuel oils have been added. ue: wy 209821/0944