JP2723972B2 - Fluidity improver for fuel oil - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to fuel oil compositions containing flow improvers.

BACKGROUND OF THE INVENTION Wax separation in crude oils, middle distillate fuels, heavy residual fuels, and lubricating oils limits their flow at low temperatures. Conventional methods of solving these problems are wax crystal modifying compounds (nucleating agents) that make the wax crystals smaller and / or wax crystal modifying compounds (growth) that make the wax crystals smaller and more compact. Inhibitor).

Another difficulty is that small braze crystals can stick together to form larger agglomerates, and these agglomerates as well as individual crystals can block the filter screen through which the individual crystals pass, and they can Is to settle faster than small crystals.

Means for Solving the Problems The present inventors have found that the addition of certain amino salts or quaternary ammonium salts allows wax crystals to be modified to improve filterability and reduce pour point, Have been found to be able to reduce the tendency to aggregate.

In accordance with the present invention, the fuel composition comprises a high proportion by weight of liquid hydrocarbon fuel and a low proportion by weight of a polymer containing more than one amino group, wherein the amino group is a primary, secondary or tertiary amine or quaternary. It is an ammonium salt. Also in accordance with the present invention, a polymer comprising one or more amino groups, wherein the amino group is a salt of a primary, secondary or tertiary amine or a quaternary ammonium salt, flows in a liquid hydrocarbon fuel. Used as a modifier. The liquid hydrocarbon fuel oil can be a distillate fuel oil, such as a middle distillate fuel oil, for example, diesel fuel, aviation fuel, kerosene, fuel oil, jet fuel, heating oil, and the like. In general, suitable distillate fuels are distillate fuels having a boiling point in the range of from 120C to 500C (ASTM DT86), preferably from 150C to 400C. Typical heating oil specification is 10%
Require a distillation point of about 226 ° C or less, 50% of about 272 ° C or less and 90% of at least 282 ° C at a temperature of about 338 ° C to 343 ° C or less. About 90
Set the% distillation point. The heating oil is preferably made from a blend of a virgin distillate, such as light oil, naphtha, etc., and a cracked distillate, such as a contact circulating oil.

Polymers containing one or more amino groups are classified into polymers having a plurality of carboxylic acid groups or acid anhydride groups as primary,
It can be prepared by reacting with a secondary or tertiary amine.

The polymer may be reacted with a tetrahydrocarbyl ammonium halide to prepare a quaternary ammonium salt. Also, they may be prepared by the reaction of a tertiary amine with a hydrocarbyl halide, so that the polymer from which the desired polymer is derived should have halide groups and be reacted with the tertiary amine, respectively.

There are many different types of polymers that can be further reacted to produce the desired polymer containing two or more amine bases.

(I) Examples thereof are polymers of one or more unsaturated monomers containing ester groups and free acid groups and copolymers of unsaturated ester monomers in which at least one monomer also has free acid groups. Specific examples include dialkyl fumarate, maleate, citraconate or itaconate copolymers, vinyl acetate and monoalkyl fumarate, maleate, citraconate or itaconate copolymers, alkyl acrylate or alkyl methacrylate and monoalkyl fumarate, maleate, citraconate or itaconate. And dialkyl fumarate, maleate, citraconic or itaconate copolymers with monoalkyl fumarate and vinyl acetate.

A particularly preferred example of a polymer of type I is a copolymer of vinyl acetate, a monoalkyl fumarate and a dialkyl fumarate, wherein the alkyl group is a copolymer of dodecyl and tetradecyl.
A 1: 1 mixture) and vinyl acetate and monododecyl,
It is a copolymer with monotetradodecyl or monohexadecyl fumarate.

(II) Other examples are copolymers of unsaturated esters and / or olefins with unsaturated carboxylic anhydrides.
These copolymers can give half amide / half amine salts by reaction with anhydride groups upon reaction with primary or secondary amines. Specific examples are (a) copolymers of dialkyl fumarate, maleate, citraconate or itaconate with maleic anhydride, or (b) vinyl esters, such as copolymers of vinyl acetate or vinyl stearate with maleic anhydride, or (c) ) Copolymers of dialkyl fumarate, maleate, citraconate or itaconate, maleic anhydride and vinyl acetate. Other examples are maleic acid with styrene or aliphatic olefins anhydrides, for example decene, dodecene, tetradecene, hexadecene, copolymers of eicosene, docosene, tetracosene, octacosenoic, and such C ₁₀ -C ₃₀ olefins propylene tetramer or propylene hexamer .

Particularly preferred examples of Type II polymers include copolymers of didodecyl fumarate with vinyl acetate and maleic anhydride, copolymers of di-tetradecyl fumarate with vinyl acetate and maleic anhydride, dihexadecyl fumarate with acetic acid A copolymer of vinyl and maleic anhydride, or a similar copolymer in which itaconate is used instead of fumarate.

(III) The desired polymer can be prepared by partially hydrolyzing a polymer containing an ester group to obtain a carboxylic acid group or an acid anhydride group. Thereafter, the partially hydrolyzed polymer is reacted with an amine to produce the desired polymer containing two or more amine bases. Thus, polymers of acrylate, methacrylate, alkyl fumarate, alkyl maleate, or copolymers thereof or copolymers thereof with olefins can be hydrolyzed.

Particularly preferred examples of Type III polymers are partially hydrolyzed polymers of alkyl acrylates or methacrylates, such as dodecyl acrylate, tetradecyl acrylate, or hexadecyl acrylate.

(IV) Also suitable polymers are polymers of unsaturated carboxylic acids, such as polyacrylic or polymethacrylic acid, copolymers of acrylic acid and olefins, such as ethylene or alkyl fumarate, and methacrylic acids and olefins, such as ethylene or alkyl. It is a copolymer with fumarate.

In preferred polymers of all the above types (I, II, III and IV), the desired amine salt is obtained by combining a polymer containing carboxylic acid or anhydride groups with a primary, secondary or tertiary amine. And react with the corresponding amine salt (if necessary,
In the case of reacting with an alcohol, an ester-amine salt is produced). Very often, for example, when reacting polymers containing acid anhydride groups, the resulting amino groups are amine salts and amides. Such polymers may be used, provided that they contain at least two amine bases.

To prepare a quaternary ammonium salt, one of the above polymers (I, II, III or IV) is reacted with tetrahydrocarbyl ammonium halide,
Alternatively, the polymers are converted so that they contain halide groups instead of carboxylic acid groups, or are formed by polymerizing them with unsaturated halides, such as vinyl chloride. They are then reacted with a tertiary amine to form a quaternary ammonium salt.

(V) Other suitable polymers are partially hydrolyzed polymers of unsaturated esters, followed by reaction with carboxylic anhydrides, which are then reacted with primary, secondary or tertiary amines to give the desired amine Obtained by forming a salt. Suitable polymers of unsaturated esters are homopolymers of acrylates, methacrylates, alkyl fumarate or olefins with these, for example copolymers with ethylene or copolymers of vinyl acetate with olefins. A particular example is a copolymer of ethylene and vinyl acetate. After partial hydrolysis, the polymer is reacted with an acid anhydride, such as succinic or maleic anhydride,
The resulting product may be reacted with a primary, secondary or tertiary amine to give the corresponding amine salt, or it may be reacted with tetrahydrocarbyl ammonium halide to give the corresponding quaternary ammonium salt. .

The polymer containing at least two amine bases or quaternary ammonium bases has at least one group containing hydrogen and carbon (the total number of carbon atoms in the one or more groups is at least 10 carbon atoms). Is not essential, but highly desirable. More preferably, there are 12 to 18 carbon atoms in at least one of the above groups. Such groups, which are preferably straight or branched chain alkyl groups, may be present directly in the polymer backbone or linked through a carboxylate group, or may be an amine or quaternary ammonium base. It may be present bonded to a nitrogen atom. It may also include such groups bonded to both the polymer nitrogen atom and the backbone or carboxylate groups. Thus, in polymers of types I, II, III and IV, the alkyl groups of the mono- and di-alkyl fumarate, alkyl acrylate, or alkyl methacrylate from which the polymer is derived can contain at least 10 carbon atoms. Therefore, particularly preferred monomers are didodecyl fumarate, ditetradecyl fumarate, dioctadecyl fumarate and the corresponding monoalkyl fumarate and mixtures thereof. Also,
Dodecyl, tetradecyl, hexadecyl and octadecyl acrylates and methacrylates are particularly preferred.
In type III polymers, for example, didecyl maleate, didodecyl maleate, ditetradecyl maleate can be used.

Alternatively or in addition, a long chain primary in the formation of a salt,
Long chain groups can be introduced into the polymer by using secondary or tertiary amines or tetrahydrocarbyl ammonium halides or mixtures thereof.

Amines can be represented by the formulas R ¹ NH ₂ , R ¹ R ² NH and R ¹ R ² R ³ N, and tetrahydrocarbyl ammonium halides can be represented by the formula R ¹ R ² R ³ R ⁴ NX (formula During,
R ¹ , R ² , R ³ and R ⁴ are hydrocarbyl groups, preferably alkyl groups, wherein at least one of R ¹ , R ² , R ³ and R ⁴ has at least 10 carbon atoms, for example 12-18 Carbon atom,
It preferably comprises, for example, dodecyl, tetradecyl, hexadecyl and octadecyl, X being a halogen, preferably chlorine).

Suitable polyamines of the formula H ₂ N [RHN] xH and R ¹ NH [RNR ^1]
xH wherein R ¹ is a hydrocarbyl group, R is a divalent hydrocarbyl group, preferably an alkylene or hydrocarbyl-substituted alkylene, and x is an integer.

Examples of suitable primary amines are hexylamine, octylamine, and primary amines containing at least 10 carbon atoms, such as decylamine, tetradecylamine, octadecylamine, eicosylamine, mixed amine RNH ₂ (Armeen C) Wherein R is 0.5% by weight C ₆ alkyl, 8% by weight C ₈ alkyl, 7% by weight C ₁₀ alkyl, 50% by weight C ₁₂ alkyl, 18% by weight C ₁₄ alkyl,
8% by weight C ₁₆ alkyl, 1.5% by weight C ₁₈ alkyl and
7.0% by weight of C ₁₈ / C ₁₉ unsaturated groups).

Examples of suitable secondary amines, secondary amines containing alkyl groups having dioctyl amine and at least 10 carbon atoms, for example didecylamine, Jidoshiruamin, dicocoamine (i.e., di - mixed C ₁₂ -C ₁₂ alkyl amines),
Dioctadecylamine, hexadecyl, octadecylamine, di-hydrogenated tallowamine (Armeen 2H
T) (approximately 4% by weight of nC ₁₄ alkyl, 30% by weight of nC ₁₆
Alkyl, 60 wt% of C ₁₈ alkyl, the remainder of the unsaturated group), n-coco - propyl diamine (C ₁₂ / C ₁₄ alkyl - propyl diamine - Juomin (Duomeen) C),
n-tallow-propyldiamine (C ₁₆ / C ₁₈ alkylpropyldiamine-Duomien T).

Examples of suitable tertiary amines are trihexylamine, trioctylamine and tertiary amines containing an alkyl group having at least 10 carbon atoms, such as hexyldidecylamine, tridecylamine and trihexadecylamine .

Examples of suitable quaternary ammonium halides are trioctyl-methylammonium chloride and quaternary ammonium halides containing alkyl groups having at least 10 carbon atoms, such as tridodecyl-methylammonium chloride, tritetradecyl, dodecylammonium chloride, and Hexadecyl, dimethyl, phenylamine.

Examples of suitable polyamines are N-octadecylpropanediamine, N ', N'-dioctadecylpropanediamine, N-tetradecylbutanediamine and N, N'-dihexadecylhexanediamine.

The polymer salt of the present invention is usually 1,000 to 500,000, for example,
It has a number average molecular weight of 10,000-100,000.

Particularly preferred examples of amino group-containing polymers for use in the present invention are as follows.

(1) Di C ₁₆ / C ₁₈ n-alkylamine (C ₁₆ alkyl / C
_18- alkyl is about 1: 2) to form half-amide, half-amine salts of carboxylic acid groups derived primarily from maleic anhydride units of the copolymer.
Copolymer of ditetradecyl fumarate, vinyl acetate and maleic anhydride (the molar ratio of vinyl acetate: fumarate: maleic anhydride is approximately 50: 45: 5).

(2) reacting with 5 mol% of trioctylamine to form a half amide, half amine salt of carboxylic acid groups derived from maleic anhydride units of the copolymer;
Mol% of vinyl acetate, 45 mol% of the di-C ₁₂ / C ₁₄ alkyl fumarate (1: 1 mixture) and 5 mole percent of the copolymer of maleic anhydride.

(3) Copolymer similar to (2) above, except that it is produced by the reaction of 10 mol% of dicoco (C ₁₂ -C ₁₄ alkyl) amine in place of trioctylamine.

(4) Copolymer similar to (2) above, except that it is formed by the reaction of 5 mol% of trioctyl-methyl ammonium chloride and 5 mol% of sodium hydroxide in a minimum amount of water in place of trioctylamine. This results in a quaternary ammonium salt of the polymer.

(5) A copolymer similar to (1) above, except that it is produced by reacting a mixture of dodecylamine and tetradecylamine in place of dialkylamine.

(6) A copolymer similar to (1) above, except that it is produced by the reaction of n-coco (C ₁₂ -C ₁₄ alkyl) propylamine in place of dialkylamine.

(7) The above (1) to (1), wherein the copolymer is based on an equimolar ratio of alkyl fumarate and vinyl acetate and the amount of maleic anhydride is 10 mol% based on the total weight of fumarate and vinyl acetate. Copolymer similar to (6).

Improved results are often obtained when the fuel composition of the present invention incorporates other additives known to generally improve the cooling flow of distilled fuels. Examples of these other additives are polyoxyalkylene esters, ethers, esters / ethers, amides / esters and mixtures thereof, especially with a molecular weight of from 100 to 5,000, preferably from 200 to 5,000.
At least one of 5,000 polyoxyalkylene glycols (the alkyl group in the polyoxyalkylene glycol containing from 1 to 4 carbon atoms), preferably at least two linear saturated alkyl C ₁₀ -C ₃₀ Group. European Patent Publication No. 0,061,895 A2 describes some of these additives.

Preferred esters, ethers or ester / ethers are structurally represented by the formula:

R ⁵ —O— (A) —O—R ⁶ , wherein R ⁵ and R ⁶ are the same or different, The alkyl group may be linear and saturated,
Polyol of glycol containing 30 carbon atoms and A is substantially linear, such as a polyoxymethylene, polyoxyethylene or polyoxytrimethylene group, wherein the alkylene group has 1 to 4 carbon atoms. Some branching representing an oxyalkylene segment and having a lower alkyl side chain (such as in polyoxypropylene glycol) is acceptable, but it is preferred that the glycol be substantially linear).

Suitable glycols are substantially linear polyethylene glycols (referred to as PEG) and polypropylene glycols (referred to as PPG), generally having a molecular weight of about 100 to 5,000, preferably about 200 to 2,000. Esters are preferred, are useful in the fatty acid containing 10 to 30 carbon atoms to produce a reacted with glycol ester additive, C ₁₈ -C ₂₄ fatty acids, it is particularly preferred to use behenic acid. Esters can also be prepared by esterifying polyethoxylated fatty acids or polyethoxylated alcohols. A particularly preferred additive of this type is polyethylene glycol dibehenate in which the glycol moiety has a molecular weight of about 600, often abbreviated as PEG600 dibehenate. Similar polyethylene glycol dibehenates in which the glycol moiety contains a molecular weight of about 200 and 400 are often abbreviated as PEG200 and PEG400, respectively.

Other additives suitable for the fuel composition of the present invention are ethylenically unsaturated ester copolymer flow improvers. Unsaturated monomers that can be copolymerized with ethylene include unsaturated monoesters and diesters of the formula:

Wherein R ₈ is hydrogen or methyl and R ₇ is a —OOCR ₁₀ group (wherein R ₁₀ is hydrogen or C ₁ -C ₂₈ , more usually C ₁ -C ₁₇ ,
Or preferably is a linear or branched alkyl group of C ₁ -C _8), or R ₇ is -COOR ₁₀ radical (wherein, R ₁₀ is as hereinbefore defined not hydrogen) And R ₉
Is hydrogen or —COOR ₁₀ as defined above). A monomer wherein R ₇ and R ₈ are hydrogen and R ₈ is —OOCR ₁₀ is a C ₁ -C ₂₉ , more usually a C ₁ -C ₁₈ monocarboxylic acid. acid, preferably monocarboxylic acids of C ₂ -C _29, more usually C ₁ -C _18, preferably includes a vinyl alcohol ester of a monocarboxylic acid C ₂ -C _5. Examples of vinyl esters that can be copolymerized with ethylene include vinyl acetate, vinyl propionate and vinyl butyrate or vinyl isobutyrate, with vinyl butyrate being preferred. Preferably, the copolymer contains 20 to 40% by weight of vinyl ester, more preferably 25 to 35% by weight of vinyl ester. They may also be mixtures of two copolymers, such as those described in U.S. Pat. No. 3,961,916. These copolymers preferably have a number average molecular weight of from 1,000 to 6,000, preferably from 1,000 to 3,000, as measured by gas phase osmometry.

Other additives suitable for the fuel composition of the present invention have the ability to act as braze growth inhibitors in the fuel,
It is an ionic or nonionic polar compound. Polar nitrogen-containing compounds have been found to be particularly effective when used in combination with glycol esters, ethers or esters / ethers. These polar compounds are generally the amine salts formed by the reaction of at least one molar ratio of a hydrocarbyl-substituted amine with one molar ratio of 1 to 4 carboxylic acids or hydrocarbyl acids having their anhydrides. And / or amides. Also, 30-30
Esters / amides containing 0, preferably 50 to 150 total carbon atoms may be used. These nitrogen compounds are described in U.S. Pat. No. 4,211,534. Suitable amines are usually long chain C ₁₂ -C ₄₀ primary, secondary, tertiary or quaternary amines or mixtures thereof but nitrogen resulting compound is oil soluble about 30 to 300 amino therefore Shorter chain amines may be used provided they usually contain total carbon atoms. Nitrogen compound of at least one linear C ₈ -C _40, preferably preferably contains alkyl grayed segment of C ₁₄ -C _24.

Suitable amines include primary, secondary, tertiary and quaternary amines, with secondary amines being preferred. Tertiary and quaternary amines can form only amine salts. Examples of asines include tetradecylamine, cocoamine, hydrogenated tallowamine, and the like. Examples of secondary amines include dioctadecylamine, methyl-behenylamine, and the like. Amine mixtures are also preferred, and many amines derived from natural substances are mixtures. Preferred amines have the formula HNR ₁ R _{2 where} R ₁ and R ₂ are approximately 4%
C _14, 31% of the C _16, alkyl radical derived from hydrogenated Kaushi fats containing 59% C ₁₈₎ are of secondary hydrogenated tallow amine.

Examples of carboxylic acids (and their acid anhydrides) suitable for preparing these nitrogen compounds include cyclohexane-1,
Includes 2-dicarboxylic acid, cyclohexanedicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalenedicarboxylic acid and the like. Generally, these acids contain about 5 to 13
Contains carbon atoms. Preferred acids are benzenedicarboxylic acids such as phthalic, terephthalic, and isophthalic acids. Phthalic acid or its anhydrides are particularly preferred. A particularly preferred compound is an amide-amine formed by reacting 1 mole fraction of phthalic anhydride with 2 mole fraction of di-hydrogenated tallowamine. Another preferred compound is a diamide formed by dehydrating the amide-amine salt.

The relative proportion of the additives used in the above mixture is preferably 0.05 to 20 parts by weight, more preferably 1 part by weight, based on 1 part of other additives such as polyoxyalkylene ester, ether, ester / ether or amide ether. 0.
A polymer containing 1 to 5 parts by weight of an amine salt or a quaternary ammonium salt. The amount of the amine salt or quaternary ammonium salt-containing polymer added to the liquid hydrocarbon fuel is preferably about 0.1% based on the weight of the hydrocarbon fuel.
0001-5.0% by weight, for example 0.001-0.5% by weight, especially 0.01
0.050.05% by weight (active substance).

The polymer may be conveniently dissolved in a suitable solvent to form a 20-90%, for example 30-80%, by weight polymer concentrate in the solvent. Suitable solvents include kerosene, aromatic naphtha, lubricating mineral oil and the like.

Example 1 In this example, a vinyl acetate, dialkyl fumarate copolymer AA was prepared by combining a copolymer BB and CC containing two amine salts and a copolymer DD containing a quaternary ammonium salt with two copolymers having the following properties: Distilled fuel oil F1 and
A comparison was made for the case where it was added to F2.

The details of the polymer are as follows.

AA: vinyl acetate and C ₁₂ alkyl / C ₁₄ alkyl equimolar ratio (1: 1) copolymer BB of dialkyl fumarate: was reacted with 5 mole% of trioctylamine, 50
Mol% of vinyl acetate, 45.0 mole% of C ₁₂ alkyl / C ₁₄ alkyl (1: 1) dialkyl fumarate and 5 mole% of maleic anhydride motor - Polymer CC: 10 mol% of the di - coco (C ₁₂ -C ₁₄₎ was reacted with an amine, of 50 mole% vinyl acetate, 45.0 mole% of C ₁₂ alkyl / C ₁₄ alkyl (1: 1) dialkyl fumarate and 5 mole% of maleic anhydride motor - polymer DD: 5 mol% of trioctylmethylammonium chloride and 5 mol% in the minimum amount of water (when NaCl separates)
47.5 mol% of vinyl acetate, 4
Copolymer of 7.5 mol% of C ₁₂ alkyl / C ₁₄ alkyl (1: 1) dialkyl fumarate and 5 mol% of maleic anhydride Each of the polymers AA, BB, CC and DD was weighed in half the weight of PEG 200 behenate. PEG 400 behenate and a mixture of PEG behenate in a molar ratio of 1: 1: 1 and in each case 0.1% (1000 pp.)
m) to the fuel F1 and fuel F2 at the active substance concentration of CFPPT
The results obtained when tested in were as follows. Polymer fuel F1 Fuel F2 AA -11 -10 BB -13 -12 CC -14 -12 DD -14 -13 Polymer BB, CC and DD have no amino group
It is clear that the results are better than those shown by AA.

 Details of CFPPT are as follows.

Cooling Filter Plugging Point Test (CFPPT) The cooling filterability of the blend was measured by the Cooling Filter Plugging Point Test (CFPPT). This test is “J
ournal of the Institute of Petroleum "Volume 52, Issue 510,
(June 1966) by the operation described in detail on pages 173-185. Briefly, a 40 ml sample of the oil to be tested is cooled by a bath maintained at about -34 ° C. Periodically (starting at 2 ° C above the cloud point, every 1 ° C drop)
The cooling oil is tested for its ability to pass through a fine screen during a given period. This cooling property is tested using a device consisting of a pipette fitted with a reverse funnel located below the surface of the oil to be tested at the lower end. About 0.
A 350-mish screen having an area of 45 square inches (0.20 cm ² ) is stretched across the mouth of the funnel. Each periodic test is started by applying a vacuum to the top of the pipette, thereby pulling the oil through the screen to the mark indicating 20 ml of oil. The test is repeated at every 1 ° C temperature drop until the oil no longer fills the pipette within 60 seconds. The results of the test are shown as ΔCFPPT (° C.), which is the difference between the reject temperature of the untreated fuel (CFPP ₀ ) and the reject temperature of the fuel treated with the flow modifier (CFPP ₁ ). ΔCFPP = CFPP ₀ −CFPP ₁ Example 2 In this example, polyethylene glycol dibehenate (PEG6) in which the glycol moiety has a molecular weight of about 600
A polymer containing various amine salts based on alkyl fumarate vinyl acetate-maleic anhydride mixed with a distillate fuel oil blend known as F3 having the properties shown in Table 1 Was added.

The various polymers blended with PEG 600 dibehenate in each case in a weight ratio of 4 parts polymer per part of PEG 600 dibehenate were as follows:

CFPPT was measured on the fuel oil blend containing Polymer A and the blend was subjected to PCT (Programmed Cooling Test). Details of the PCT are as follows.

Programmed Cooling Test (PCT) This is a slow cooling test designed to correlate with pumping of stored heated oil. The cooling fluidity of the above fuel containing additives is measured by PCT as described below. 300 ml of fuel are cooled linearly to the test temperature at 1 ° C./hour, then the temperature is kept constant. After 2 hours at the test temperature, approximately 20 ml of the surface layer is removed by suction to prevent the test from being affected by unusually large wax crystals that tend to form at the oil / air interface during cooling. The wax settled in the bottle is dispersed by gentle stirring, and then the CFPPT filter assembly is inserted. Open the tap and apply a 500 mm mercury vacuum and close the tap when 200 ml of fuel has passed through the filter and into the graduated receiver. A pass is recorded if 200 ml is collected within 10 seconds through the given mesh size, and a reject is recorded if the flow rate is too slow to indicate that the filter has become blocked.

 The mesh number that passed at the test temperature is recorded.

 The results obtained were as follows.

Another measurement by CFPPT was performed on F3 blends containing polymers BI blended with PEG 600 dibehenate in a 4: 1 weight ratio each. Copolymer X included for comparison purposes is a copolymer of vinyl acetate and ditetradecyl fumarate. The results are as follows.

PCT (+ 2 ° C.) was also performed on F3 blends containing each of Polymers D, E, F, G, H and I each blended with PEG 600 dibehenate in a 4: 1 weight ratio. The results obtained were as follows.

The benefits of the blends containing the polymer over the fuel base oil alone are clearly seen.

Example 3 In this example, the polymer salts D, E, F, G, H and I used in Example 2 were added to F4, a high boiling distillation fuel, and CFPP (F4 alone) and ΔCFPP were added. It was measured in each case. Details of the ASTM D86 distillation of F4 are as follows.

IBP 172 ℃ D20 228 ℃ D50 276 ℃ D90 362 ℃ FBP 389 ℃ 300ppm and 500ppm (active ingredient) in fuel base oil, ie 0.03
The results are shown below when compared to the untreated fuel oil for each of the polymer salts added at weight percent and 0.05 weight percent.

Also, polymer salts D, E, F, G, H and I were each blended with copolymer Y in a molar ratio of 1: 4, and then 300 ppm
(0.03% by weight) and 500 ppm (0.05% by weight) were added to F4. Copolymer Y is an ethylene / vinyl acetate copolymer having a molecular weight of about 2000 containing 36% by weight of vinyl acetate and an ethylene / vinyl acetate copolymer having a molecular weight of about 3000 containing 13% by weight of vinyl acetate.
3: 1 weight ratio mixture with vinyl acetate copolymer.

As described above, CFPP (processed fuel oil) and ΔCFPP were measured in each case.

The results are as follows.

In all cases, it can be seen that there is a significant decrease in pour point when the polymer salt is added to the fuel base oil.

Example 4 Various polymer salts, alone or mixed with polymer Y (see second table below), form the following ASTM D
It was added to distilled fuel oil F5 with 86 distillation properties.

IBP 188 ° C D20 236 ° C D50 278 ° C D90 348 ° C FBP 376 ° C The results of CFPPT and PCT were as follows.

Example 5 In this example, polymer salt C (as used in Example 2) and another polymer salt J were added to a distillate fuel F6 having the following D86 distillation characteristics.

IBP 173 ° C D20 222 ° C D50 297 ° C D90 356 ° C FBP 371 ° C Polymer salt J is a half-amide, half-amine salt of a copolymer of di-tetradecyl fumarate-vinyl acetate-10% by mole of maleic anhydride (amine is R ₂ NH (where R is C
₁₆ / _C18 alkyl)).

Also, these polymer salts C and J were combined with an ethylene-vinyl acetate copolymer mixture (see Example 3).
Blend at a 1: 1 molar ratio.

The polymer salts and their 1: 1 molar ratio mixture with Y are combined with 300 ppm and 600 ppm (active ingredient) (0.03% by weight and 0.3% by weight).
(06% by weight) to the fuel oil and the resulting blend was subjected to PCT and CFPPT. The results are as follows.

Example 6 In this example, polymer salts A and B (Example 2)
And J (used in Example 5)
Was added to the distilled fuel oil F6 of Example 5. Furthermore, the following polymer salts were added to this fuel oil. Each polymer salt was blended with the copolymer mixture Y used in Example 3 in a 1: 1 molar ratio.

Each polymer salt blended with copolymer mixture Y was prepared at two different concentrations: 300 ppm (0.03% by weight) and
600ppm (0.06% by weight) (active ingredient) added to fuel oil
PCT and CFPPT. The results obtained were as follows.

In general, it has been found that the addition of a polymer salt improves the flowability of the fuel base oil.

Example 7 In PCT and CFPPT, a copolymer of styrene and maleic anhydride partially esterified with tetradecanol (referred to as copolymer XX), an unesterified group of XX is hydrolyzed, and then a carboxylic acid group is formed. A comparison was made with the polymer salt (N) obtained by reacting the contained polymer with trioctadecylamine.

N is by CFPP at 2 ℃ and PC at -14 ℃
The 6-mesh process of T is more effective than XX, ie, when N and XX were added to the fuel oil F5 used in Example 4 at a concentration of 500 ppm, N passed at 60 μm, whereas XX was 250 μm Was found to pass.

Example 8 In this example, the diamine R ₂ NH (where R is nC ₁₆
A mixture of n-octadecene and maleic anhydride, which has been reacted with / nC ₁₈ alkyl mixture to form a polymer salt (P), comprising a distillate fuel alone and a copolymer Y (see Example 3) To the PCT (−1
A test (at 0 ° C.), a CFPPT test and a DSC test were performed to compare with prior art copolymers also added to the same fuel.

Distilled fuel oil F7 to which the copolymer was added at concentrations of 175 ppm and 300 ppm had the following ASTM D86 properties:

IBP 184 ° C D20 226 ° C D50 272 ° C D90 368 ° C FBP 398 ° C Comparison was also made with other prior art copolymers BB and CC. Details of these copolymers (including copolymer AA) are as follows.

Copolymer AA: Copolymer of octadecene and maleic anhydride Copolymer BB: Copolymer AA reacted with hexadecanol to form an ester Copolymer CC: Copolymer AA reacted with octadecanol to form an ester Differential scanning calorimeter ( DSC) In a DSC (differential scanning calorimeter), ΔWAT (wax precipitation temperature, ° C) is measured. This is the difference between the temperature (WAT ₁ brazing is precipitated relates distillate fuel oil wax was processed temperature (WAT ₀₎ to precipitate respect distillate fuel base oil alone when calorimeter is cooled at 2 ° C. / min In the DSC test, the results were obtained for 300 ppm using only one concentration, ie 25 μl of the fuel sample: ΔWAT = WAT ₀ −WAT _{1 The} results obtained were as follows: Is
Values from 175 ppm, the second number (excluding DSC) is 300
This is a value related to ppm.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Kennis Rutus Oxfordshire, UK OX129 EX Wantage Black Croft 21 (56) Reference US Pat. No. 3,157,595 (US, A) US Pat. US, A) British publication 895086 (GB, A) British publication 802589 (GB, A) British patent 2129012 (GB, B) European publication 61895 (EP, A1) West German patent 1595333 (DE, A)

Claims (13)

(57) [Claims] A fluidity improver for fuel oils comprising a polymer or copolymer containing more than one amino group in the form of a salt of a primary, secondary or tertiary amine or a quaternary ammonium salt, The polymer or copolymer contains acid groups or anhydride groups, and I. a polymer of one or more unsaturated ester monomers further containing free acid groups or at least one monomer of unsaturated ester monomers having free acid groups. Copolymers, II. Copolymers of unsaturated carboxylic esters and unsaturated carboxylic anhydrides, III. Polymers obtained by partially hydrolyzing polymers or copolymers containing ester groups to obtain carboxylic acid groups or acid anhydride groups, or Copolymers, IV. Selected from one or more polymers or copolymers obtained by the reaction of the polymer of III above with carboxylic anhydride. Derived from a reaction with an intermediate polymer or copolymer and an amino compound selected from primary, secondary or tertiary alkylamines and tetraalkylammonium halides, the polymer or copolymer containing one or more hydrogen and carbon containing The fluidity improver for a fuel oil, comprising a group having a total number of carbon atoms of 10 or more. 2. A flow improver according to claim 1, wherein the intermediate polymer or copolymer comprises a copolymer of dialkyl fumarate, maleate, citraconate or itaconate and maleic anhydride. 3. A flow improver according to claim 1, wherein the intermediate polymer or copolymer comprises a copolymer of a vinyl ester and maleic anhydride. 4. A flow improver according to claim 1, wherein the intermediate polymer or copolymer comprises a copolymer of dialkyl fumarate, maleate, citraconate or itaconate with maleic anhydride and vinyl acetate. 5. The intermediate polymer or copolymer is a partially hydrolyzed polymer of alkyl fumarate, maleate, citraconate or itaconate, or C ₁₀
Including copolymers of -C ₃₀ olefins, fluidity improving agent according to claim 1. 6. A fluidity improver according to claim 1, wherein one or more of the hydrogen and carbon containing groups contains from 12 to 18 carbon atoms. 7. An intermediate polymer or copolymer comprising:
7. The hydrogen and carbon containing group is attached to the polymer backbone directly or via a carboxylate group.
The flow improver according to any one of the above. 8. In an intermediate polymer or copolymer,
The flow improver according to any one of claims 1 to 7, wherein hydrogen and a carbon-containing group are bonded to a nitrogen atom of an amine salt or a quaternary ammonium salt. 9. The amino compound according to claim 1, wherein the amino compound is a primary, secondary or tertiary alkylamine containing at least one alkyl group having 10 or more carbon atoms.
The fluidity improver according to any one of claims 1 to 8. 10. The amino compound is a secondary or tertiary amine, such as trioctylamine, di (hydrogenated) tallowamine, mixed C ₁₂ -C ₁₄ alkyl-propyldiamine, and n-tallow-propyldiamine. The fluidity improver according to any one of claims 1 to 8, which comprises one selected from the group consisting of: 11. A fuel oil composition comprising a flow improver according to claim 1, wherein the amount of the amine salt-containing polymer or copolymer is based on the weight of the fuel. The fuel oil composition of 0.0001 to 5.0% by weight (active substance). 12. A fuel oil composition comprising the flow improver according to any one of claims 1 to 10, comprising a polyoxyalkylene ester, an ether, an ester / ether, or an ethylenically unsaturated ester copolymer. The above fuel oil composition, comprising another flow improver selected from an improver, a polar nitrogen-containing compound, and a mixture thereof. 13. The fuel oil composition according to claim 12, wherein the other flow improver is an ethylene-vinyl acetate copolymer.