JP2001019982A - Phosphate-esterified thermostable additive for distillate fuel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fuel composition reduced in deposit production resulted from being subjected to thermal stress in an engine, in particular prevented from deposition in fuel injectors and thereby increased in fuel stability, therefore useful as a jet fuel or the like by adding a specific additive to a distillate fuel. SOLUTION: This fuel composition comprises (A) a distillate fuel and (B) the subject additive comprising a reaction product from (i) a dicarboxylic acid or derivative thereof substituted with at least one hydrocarbyl, (ii) a polyhydroxy compound and (iii) a phosphorus compound [pref. a reaction product from a compound of the formula (R is a 1-300C hydrocarbyl; R1 and R2 are each OH, Cl or the like), a polyhydroxy alcohol selected from those of the formula: R3-(OH)x (x is >=2; R3 is a 1-20C hydrocarbyl), the formula: HO-((CH2)y-O)z-H (y and z are each 1-10) and the like, and a phosphorus-contg. compound].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD This invention relates to additives for distillate fuels that reduce precipitate formation in thermally stressed fuels. More specifically, the present invention is directed to a fuel additive comprising a reaction product of a hydrocarbyl-substituted dicarboxylic acid or derivative thereof, a polyhydroxyl compound and a phosphorus-containing compound. The reaction products, when added to a fuel such as jet fuel, stabilize the fuel and reduce or prevent the formation of deposits in the fuel system. The present invention also includes in a distillate fuel an ester and a phosphorus-containing compound formed by reacting a) a hydrocarbyl-substituted dicarboxylic acid or derivative thereof with a polyhydroxyl compound to reduce thermal degradation of the fuel. Related to let.

[0002]

BACKGROUND OF THE INVENTION When a liquid hydrocarbon fuel is transported, stored and used, the fuel is subjected to thermal stress. When subjected to such high temperatures, that is, thermal stress, the fuel deteriorates. When subjected to thermal stress, sediment, sludge or gum usually forms,
And thermal stress also appears in a form that can be seen by the color change in the fuel.

When sediment, sludge or gum forms,
Blockage of the fuel system, at least degradation of the fuel system performance occurs.
For example, in modern civil or military jet aircraft, the fuel system is used to cool various components, such as engine parts, before it is burned in the engine (turbine). This exposure to heat has been shown to result in the formation of deposits on heat exchangers, fuel lines and engine injection nozzles. Clearly, reducing or eliminating such deposits would be an advance in the art. In particular, it is desirable to reduce deposit formation without the use of reactive nitrogen-containing components in the fuel that can interfere with other commonly used additives.

[0004] US Patent No. 4,292,186 to Chibnik et al. Discloses a fuel additive which is a metal salt complex containing a five or six membered ring. The metal complex is made by forming a non-acidic reaction product of a polyalkenyl succinic acid or anhydride with a polyhydric alcohol or amino alcohol. The reaction product is then combined with IB, IIB, IVB, VB, VI of the periodic table.
Reacting with a metal salt of a metal selected from groups B, VIIB and VIII. This patent covers polyalkenyl succinic acid /
No disclosure or suggestion is made of fuel additives derived from the reaction product of an alcohol reaction product and a phosphorus-containing compound.

A European patent (E) granted to Kendall
P) 288246 teaches a composition for stabilizing fuel oils comprising a phosphite compound and a carboxylic acid having 2 to 20 carbon atoms.
This document does not disclose the fuel stabilizing additive of the present invention.

US Pat. No. 5,160,507 to Horodysky discloses an ester-based ester system that additionally contains an integral sulfur-containing ester moiety that is effective to impart thermal stability to the fuel. An ashless dispersant is disclosed. The patent teaches that a sulfur-containing ester moiety is required to provide thermal and oxidative stability to the hydrocarbon fuel.

[0007] US Patent No. 5,38, issued to Lin et al.
No. 2,266 relates to an additive that suppresses deterioration of fuel oil. The additive is described as being a phosphine or phosphite such as triphenyl phosphite and triphenylphosphine. This document does not suggest the reaction products of the present invention as stabilizers for liquid hydrocarbon fuels.

[0008] US Patent No. 5,596,130 to Wright et al. Discloses jet fuel additives that are derivatives of (thio) phosphonic acid. This patent specifically discloses the use of pentaerythritol esters of polyisobutenylthiophosphonic acid in turbine combustion fuel oils to control soot and smoke production and emissions from engines. This document does not disclose or suggest the use of succinic anhydride or dicarboxylic acid to form an ester with a polyol followed by reaction with a phosphorus-containing compound.

WO9 given to Dillworth et al.
No. 6/23855 discloses a fuel oil lubricating additive comprising an ashless dispersant and a carboxylic acid. The carboxylic acid may be in the form of an ester with an alcohol having one or more carbon atoms. This document suggests a stabilizing additive for jet fuels comprising the reaction product of 1) a hydrocarbyl-substituted dicarboxylic acid or derivative thereof, 2) a polyhydroxyl compound and 3) a phosphorus-containing compound. is not.

[0010]

SUMMARY OF THE INVENTION As a first aspect of the present invention, a novel material composition is disclosed. The composition comprises: a) a structural formula

[0011]

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Wherein R is hydrocarbyl, preferably an alkyl or alkenyl group having 1 to 300 carbon atoms, preferably 6 to 150 carbon atoms, more preferably 10 to 100 carbon atoms; ¹ and R ₂ are each independently selected from —OH, —Cl, —O-lower alkyl, and when R ¹ and R ² together,
A compound having ¹ and R ² are —O—, and b) a structural formula R ³ — (OH) _x (II), wherein x is an integer of 2 or more, and R ³ is 1-2.
0 hydrocarbyl groups having carbon _{atoms), HO - ((CH 2} ) y -O) z -H (III) ( wherein, y is an integer of from 1 to 10 and z is from 1 to 10
0),

[0013]

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(Wherein each R ⁴ is independently H or -C
It can H is _3, x, reaction product of a polyhydroxyl alcohol selected from compounds and mixtures thereof having a y and n can range from 1 to 20 independently), and c ) Comprising a phosphorus-containing compound reactive with the reaction product of a) and b).

Hydrocarbyl, as used herein and in the claims, is alkyl, alkenyl, aryl,
Means aralkyl and alkaryl, and may be cyclic or polycyclic and may contain O, N, S or mixtures thereof.

In a preferred embodiment, R ¹ and R ²
Is -O-, and thus compound (I) has the structural formula

[0017]

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Succinic anhydride having

The molar ratio of a) to b) is from 1: 2
It can be in the range of 5: 1, more preferably 1: 2.
３3: 1, most preferably about 1: 2 to 2: 1.
The molar ratio of the reaction product (ester) of a) and b) to the phosphorus-containing compound can range from 10: 1 to 1:10, more preferably from 5: 1 to 1: 5, most preferably. It is about 3: 1.

The present invention also relates to the use of a physical mixture of the ester and the phosphorus-containing compound in a distillate fuel.
For example, the ester can be prepared as described below and added to a fuel already containing a phosphorus-containing compound. Alternatively, the ester and the phosphorus-containing compound can be combined in an additive package that can be added to the concentrate or distillate fuel. Accordingly, a fuel composition comprising a distillate fuel and an additive, the additive comprising: i) a reaction product of at least one hydrocarbyl-substituted dicarboxylic acid or a derivative thereof with a polyhydroxyl compound; and ii) Further disclosed are compositions comprising a phosphorus compound.

The mixture of the ester and the phosphorus-containing compound is
It is usefully used in a method to reduce deposit formation in an engine as a result of a distillate fuel being subjected to thermal stress. The method comprises a fuel composition comprising a distillate fuel and an additive, the additive comprising: i) at least one ester of a hydrocarbyl-substituted dicarboxylic acid or derivative thereof with a polyhydroxyl compound; and ii) supplying a composition comprising a phosphorus compound to the engine as fuel and operating the engine.

The two-component i) and ii) or ternary reaction products can be added to the distillate fuel in the usual way. For example, the two components can be added to the distillate fuel as a single mixture containing both components, or the individual components can be added separately or in any other desired combination. The additive according to the invention can be prepared as a concentrate, with a suitable dilution (c
arrier) It can be added to the distillate fuel even as a solution using a solvent.

Accordingly, the present invention also relates to a flowable concentrate additive containing at least the three-component reaction product and / or the two-component physical mixture described above for use in a distillate fuel. .

The invention furthermore relates to a jet comprising, as a main component, a jet fuel and, as a minor component, an additive comprising the above-mentioned three-component reaction product and / or the above-mentioned two-component physical mixture. It relates to a fuel composition.

The method and additives of the present invention stabilize distillate fuel during storage. As used herein, the term "stabilized" means that generation of fine particles in the distillate fuel and deterioration of the hue of the distillate fuel are suppressed. The term "particulate production" is taken to include the production of insoluble solids, deposits and gums.

Another embodiment of the present invention is a method for inhibiting the degradation of distillate fuel and for stabilizing the fuel, the method comprising an effective amount of a three component as described herein. Comprising adding the reaction product of the above or the mixture described herein to the distillate fuel. The present invention also relates to a method for reducing deposit formation in an engine, comprising a distillate fuel and the method described herein.
A fuel composition comprising an additive that is a reaction product of components or a mixture described herein is provided as a fuel to the engine and used therewith to operate the engine. Have been.

The present invention also provides a method for suppressing thermal degradation of a jet fuel, comprising reacting an effective amount of a dicarboxylic acid substituted with a hydrocarbyl or a derivative thereof with a polyhydroxyl compound to form a first reaction product. Forming a product (ester) and subsequently adding the reaction product from reacting the first reaction product with the phosphorus-containing compound to the jet fuel. This method is possible by using a three-component reaction product in which all three components are simultaneously reacted, or by using a mixture of the ester and a phosphorus-containing compound.

The present invention also discloses a stabilized distillate fuel composition comprising a distillate fuel and a stabilizing effective amount of the novel material composition described herein. Furthermore, the main component amount of liquid hydrocarbon fuel, and 0.000
Disclosed are compositions comprising 5% to 2% by weight of a product obtained by reacting a hydrocarbyl-substituted dicarboxylic acid or derivative thereof with a polyhydroxyl compound and a phosphorus-containing compound.

[0029]

DETAILED DESCRIPTION OF THE INVENTION Significant precipitate formation is likely to occur when a distillate fuel is subjected to thermal stress. The effect of the present invention is to reduce the formation of deposits both in the fuel and in the exhaust system. For example, in jet fuel compositions, this involves reducing the formation of deposits in fuel nozzles and spray rings and on surfaces such as heat exchangers, manifolds, actuators and turbine blades and vanes. . In other distillate fuel compositions, such as diesel fuel, the addition of the additives of the present invention prevents deposits in the fuel injector and increases fuel stability.

Phosphorus compounds suitable for preparing the additives of the present invention include phosphorus compounds capable of introducing a phosphorus atom into the reaction product of a polyhydroxyl compound and a dicarboxylic acid substituted with hydrocarbyl or a derivative thereof. Includes mixtures of phosphorus compounds. Any compound, whether organic or inorganic, can be used as long as it can perform such a reaction. Accordingly, inorganic phosphorus compounds such as inorganic phosphorous acids and inorganic phosphorus oxides and hydrates thereof can be used. An example of a typical organophosphorus compound is phosphoric acid (phosphorus acid).
ds) mono-, di- and triesters of thiophosphoric acid, dithiophosphoric acid, trithiophosphoric acid and tetrathiophosphoric acid;
Mono-, di- and triesters of phosphorous acid, thiophosphorous acid, thiophosphorous acid, dithiophosphorous acid and trithiophosphorous acid; trihydrocarbylphosphine oxide; trihydrocarbylphosphine sulfide; mono- and di-hydrocarbylphosphonic acid Esters (phosphonates) and their mono-, di-
Mono- and di-hydrocarbyl phosphonite and their mono- and di-thio homologs; and the full and partial esters of phosphoric acid. Thus, for example, phosphorous acid (sometimes referred to as H ₃ PO ₃ , H ₂ (HPO ₃ ) and sometimes referred to as ortho-phosphorus acid or phosphonic acid), phosphoric acid (H ₃ P
O ₄ , sometimes referred to as orthophosphoric acid), hypophosphoric acid (H ₄ P ₂ O ₆ ), metaphosphoric acid (HPO ₃ ), pyrophosphoric acid (H ₄ P ₂ O ₇ ), hypophosphorous acid (H ₃ PO ₂ ) ₂ , sometimes referred to as phosphinic acid), pyrophosphorous acid (H ₄ P ₂ O ₅ ,
Sometimes referred to as Pirohosuhon acid), the following hypophosphite _{(phosphinous acid, H 3 PO)} , tripolyphosphate _{(H 5 P 3 O 10)} , tetrapolyphosphate (H ₆
Compounds such as P ₄ O ₁₃ ), trimetaphosphoric acid (H ₃ P ₃ O ₉ ), phosphorus trioxide, phosphorus tetroxide, phosphorus pentoxide and the like can be used. Phosphorotetrathioic acid (H ₃ PS ₄ ),
Partial or all sulfur homologs such as phosphoromonothioic acid (H ₃ PO ₃ S) and phosphorodithioic acid (H ₃ PO ₂ S ₂ ) can also be used to prepare additives according to the invention.

Similarly, mono-, di- and triesters of phosphoric acid (eg, trihydrocarbyl phosphate, dihydrocarbyl phosphate, monohydrocarbyl phosphate and mixtures thereof), phosphorous acid (phosphorus acid)
d) mono-, di- and triesters (e.g. trihydrocarbyl phosphite, dihydrocarbyl hydrogen phosphite,
Monohydrocarbyl phosphites and mixtures thereof), esters of phosphonic acid (both "primary" and "secondary"), esters of phosphinic acid, phosphonyl halides, halogenated phosphites, phosphorus halides Acid esters, tertiary pyrophosphate esters and partial sulfur homologues of the above compounds, wherein each hydrocarbyl group has up to about 100 carbon atoms, preferably up to about 50 carbon atoms, more preferably about Organophosphorus compounds can be used, such as compounds containing up to 24 carbon atoms and most preferably up to about 12 carbon atoms.

Hydrocarbyl-substituted dicarboxylic acids and derivatives thereof suitable for use in the present invention (eg,
Acid halides, acid esters and acid anhydrides) have the structural formula

[0033]

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Wherein R is hydrocarbyl, preferably an alkyl or alkenyl group having 1 to 300 carbon atoms, preferably 6 to 150 carbon atoms, more preferably 10 to 100 carbon atoms. , R ¹ and R ²
Each independently, -OH, -Cl, selected from -O- lower alkyl and, if R ¹ and R ² taken together, R ¹ and R ² have the a is) -O- It can be a compound.

Examples of preferred hydrocarbyl-substituted dicarboxylic acids include hydrocarbyl-substituted succinic anhydrides. The hydrocarbyl substituent is usually a polyolefin, and preferably has a number average molecular weight of about 500-5,000, more preferably 600-3,
000 and most preferably from about 950 to about 2,000 polyisobutylene groups.

Polyhydroxyl alcohols suitable for use in the present invention contain two or more hydroxyl groups (-OH) and are capable of reacting with a dicarboxylic acid substituted with a selected hydrocarbyl. Includes all compounds that may be useful in making a fuel additive according to the invention.

Preferred polyhydroxyl alcohols are
Structural formula R ³ — (OH) _x (II) wherein x is an integer of 2 or more, and R ³ is 1-2
0 hydrocarbyl groups having carbon _{atoms), HO - ((CH 2} ) y -O) z -H (III) ( wherein, y is an integer of from 1 to 10 and z is from 1 to 10
0),

[0038]

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Wherein each R ⁴ is independently H or -C
It can H is _3, x, selected from compounds and mixtures thereof having a can is y and n ranges from 1 to 20 independently).

Examples of representative compounds having the above formula which are suitable for use in the present invention include: alkyl diols, alkyl triols, glycols, glycerin, pentaerythritol, tripentaerythritol, trimethylolethane, triethylol. propane,
1,2,6-hexanetriol, sorbitol, inositol and polyvinyl alcohol. Pentaerythritol propoxylate and pentaerythritol ethoxylate are also useful polyols for preparing the additives according to the invention. A preferred polyol for use in the present invention is pentaerythritol.

In carrying out the reaction of a dicarboxylic acid substituted with a hydrocarbyl with a polyhydroxyl compound,
The temperature at which the desired reaction occurs at a satisfactory rate can be employed. Typically, the reaction is carried out in a solvent such as mixed xylene, so a convenient reaction temperature is the reflux temperature of the mixture. The reaction with the phosphorus compound (whether performed simultaneously or separately) is usually performed at 80 to 200 ° C.
It is more preferably performed at a temperature in the range of 100 to 180 ° C.
However, one may depart from this range whenever deemed necessary or desirable. These reactions can be performed in the presence or absence of an auxiliary diluent or liquid reaction medium.

A number of catalysts can be used to prepare the compounds of the present invention, for example, materials that generate free protons can be used. Representative examples of such catalysts include sulfuric acid, acidic ion exchange resins, and hydrocarbon soluble sulfonic acids. Basic catalysts are also useful, for example, tertiary amines that are soluble in hydrocarbons.

The additives of the present invention are used in the fuel and in amounts sufficient to reduce the formation of deposits in engine exhaust systems such as internal combustion engines or jet engines. Preferably, the additive is present on an active ingredient basis, i.e., excluding diluents or solvents, from about 1 to about 1000 mg per liter of fuel, more preferably from about 5 to about 200 m / liter.
g and most preferably in an amount of about 10 to about 100 mg. Preferred distillate fuels for use in the present invention are diesel fuel and jet fuel, more preferably JP-8, Jet-A fuel and Jet-A1 fuel.

The additives according to the invention are usually added to the fuel at ambient temperature and pressure. It is preferred to add the additive of the present invention before the fuel undergoes any degradation, but the additive is effective even after some degradation.

Examples of other ingredients that can be used with the additives of the present invention include ashless dispersants, antioxidants,
Metal deactivator, corrosion inhibitor, conductivity improver (for example, static electricity dissipating agent), fuel deicing agent, distillate fuel stabilizer,
Cetane improvers and demulsifiers are included. Various additional components that can be included in the distillate fuel composition of the present invention are used in conventional amounts. Thus, the amount of such optional ingredients is not critical to the practice of the present invention. The amount used in each instance is sufficient to provide the desired functional properties to the fuel composition.

[0046]

EXAMPLES Example I Preparation of a Heat Stability Additive The following ingredients were added to a 1 liter reaction flask equipped with a (reflux) condenser.

1) 135.43 g of polyisobutenyl succinic anhydride (PBSA) (molecular weight = 1050 g / mol) (0.129 mol) 2) 13.77 g (0.101 mol) of pentaerythritol 3) Mixed xylene (solvent) 50 g 4) Amberlyst ™ 15 resin 1.30 g (catalyst) The mixture was heated to reflux (about 175 ° C.) and
Stirred for hours. The mixture was filtered to remove the catalyst and the filtrate was returned to the reaction vessel. Then, to the mixture was added diethyl phosphite (4.75 g) (0.034 mol). The molar ratio of PBSA: pentaerythritol: phosphite was therefore 1.0: 0.78: 0.26. The mixture was heated at reflux for about 1 hour with stirring. About 2.0 ml of water was removed by azeotropic distillation. The xylene was then removed by vacuum distillation. The final product is
It contained 0.656% by weight of phosphorus. The resulting product was treated with the following Hot Liquid Process S
The test was performed in an imulator (HLPS). HLPS Test To evaluate the additive according to the invention and its effect on thermally stressed fuel compositions, Hot Liquid
The sample of this example and the other samples described below were tested using the Process Simulator (HLPS) test. In this test, all additives were evaluated in conventional JetA fuel pumped at 2.0 ml per minute over a tube heated to 320 ° C. for 250 minutes. Record the weight of deposit that deposits on the tube. A low number of deposit weights indicates that the additive is effective in this test. Table I shows the results for the control sample (untreated fuel) and the fuel treated with the additive prepared in this example. All treat rates are based on the active ingredient, excluding diluent or carrier fluid.

[0048]

[Table 1]

PTS Test Another test used in the petroleum industry to evaluate the thermal stability properties of fuel additives is Pad Therma.
l Stability (PTS) test. No.
Treated and untreated samples of 2 diesel fuels at 150 ° C for 4 hours
, Cooled to room temperature, and then converted to WhatmanNo.
1 Filter through filter paper. Next, the reflectance of white light from the filter paper is measured. High reflectivity indicates that the additive is effective in this test. The results for the additive prepared in Example 1 and a control sample are shown in Table II.

[0050]

[Table 2]

These two tests clearly show that the additives according to the invention are very effective in reducing the thermal degradation of the fuel. In addition, the reaction products according to the invention do not require nitrogen (unlike succinimide and amine dispersants), which can adversely affect other commonly used additives, such as water separating agents and coagulants. Is small.

Experimental Example II The procedure of Example I was used, except that diethyl phosphite was not added. Therefore, this example was a control experiment and was simply an ester between succinic anhydride and pentaerythritol. The phosphorus content was zero (0).
The molar ratio of PBSA: pentaerythritol is 1.0
0: 0.78.

Experimental Example III The following materials were added to a 1-liter reaction flask equipped with a (reflux) condenser.

1) Polyisobutenyl succinic anhydride (PBSA) 238.74 g (molecular weight = 1400 g / mol) (0.171 mol) 2) Pentaerythritol 17.86 g (0.130 mol) 3) Xylenes 123.28 g 4) Amberlyst® 15 106 g mixture is heated to reflux (about 180 ° C.) and 4
Stirred for hours. About 2.6 ml of water formed by the reaction was removed by azeotropic distillation. The product was then filtered and the solvent was removed by vacuum distillation. This sample is also a control sample since no phosphorus was added.

Experimental Example IV The following ingredients were added to a 2 liter reaction flask equipped with a (reflux) condenser.

1) PBSA (molecular weight = 2200 g / mol) 312.21 g (0.142 mol) 2) pentaerythritol 14.97 g (0.110 mol) 3) sulfuric acid (catalyst) 4.0 drops 4) xylenes 136 The molar ratio of 0.0g PBSA to pentaerythritol is:
1: 0.77.

The mixture was heated to reflux and stirred for 4 hours. About 3.0 ml of water was removed by azeotropic distillation.
The product was then filtered and the solvent was removed by vacuum distillation.
This sample is also a control sample.

Example V Using Basic Catalyst The following ingredients were added to a 2 liter reaction flask.

1) polyisobutenyl succinic anhydride (PBSA) 576.84 g (molecular weight = 1050 g / mol) (0.549 mol) 2) pentaerythritol 86.34 g (0.635 mol) 3) diethyl phosphite 33.46 g (0.242 mol) 4) N, N'-dimethyl-cyclohexylamine (catalyst) 4.0 drops 5) Xylenes 188.8 g The molar ratio of PBSA: pentaerythritol: phosphite is 1: 1.16. : 0.44. The mixture was heated to reflux (about 173 ° C.) and stirred for 4 hours. About 10.5 ml of water was removed azeotropically from the reaction product, and the product was then filtered. The phosphorus content of the final product (without solvent) was 0.663% by weight.

Table III shows that the HL added to the fuel and HL
Various additives that have been tested using the PS test and / or the PTS test are listed.

In some tests, an ester product that has not reacted with phosphorus, such as the reaction product of Example II, is combined with one that has no (unreacted) phosphorus source (eg, Examples 8 and 9). Was.

[0062]

[Table 3]

From the data in Table III, it is clear that the reaction products according to the invention are effective fuel stabilizers.
The product obtained using a basic catalyst (Example V) is particularly preferred. PBS with lower molecular weight, eg, 1050 molecular weight
A (Example V) is also preferred for the preparation of a fuel stabilizer according to the invention.

From the above data, it can be seen that the reaction product of an ester (with succinic anhydride and / or dicarboxylic acid alcohol) and a phosphorus-containing compound is more effective than a physical mixture of the ester and a phosphorus-containing compound. Has also been found to be large. Sample No. 2 and sample no. 8
Or see contrast to 9.

The results of the HLPS show that, as shown in Table I, the additives of the present invention have significantly reduced precipitate formation when subjected to thermal stress compared to untreated fuel compositions. Is specifically shown. Similar to the PTS test, the phosphorus-containing reaction product is more effective than the physical mixture of the ester and the phosphorus compound. Sample No. 13 and sample no. See comparison with 14.

When the distillate fuel is exposed to heat, deposits are formed from the fuel in the fuel system, both during transportation and when used as a heat sink. This is highly undesirable and the petroleum industry is continually researching for additives that can reduce or prevent the formation of such precipitates. The additives according to the invention fulfill the need in an effective and economical way.

The present invention can be variously modified in the implementation. Accordingly, the present invention is not limited to the specific examples described herein. Rather, the invention is to be within the spirit and scope of the appended claims and their legal equivalents.

The main features and aspects of the present invention are as follows.

1. A fuel composition comprising a distillate fuel and an additive, wherein the additive comprises: i) at least one hydrocarbyl-substituted dicarboxylic acid or derivative thereof; ii) a polyhydroxyl compound; and iii) a phosphorus compound. A composition comprising a reaction product.

2. The composition of claim 1, wherein component i) is a hydrocarbyl-substituted succinic anhydride.

3. 2. The composition according to the above 1, wherein the phosphorus compound is an organic phosphorus compound.

4. The composition according to claim 1, wherein the phosphorus compound is an acid or anhydride containing inorganic phosphorus, and also includes a partial sulfur homolog thereof.

5. The composition according to claim 2, wherein the hydrocarbyl group is a polyisobutenyl group having a number average molecular weight of about 500 to 5,000.

6. The fuel composition according to claim 1, wherein the additive is present in an amount sufficient to reduce deposit formation in the fuel and exhaust systems of an engine operating with the fuel composition.

7. The fuel composition according to claim 1, wherein the additive is present in an amount from about 1 to about 1000 mg per liter of fuel.

8. The fuel composition according to claim 1, wherein said additive is present in an amount of about 30 to about 200 mg per liter of fuel.

9. 2. The fuel composition according to the above 1, wherein the distillate fuel is selected from diesel fuel or jet fuel.

10. 10. The fuel composition according to the above item 9, wherein the jet fuel is selected from JP-8 jet fuel, Jet-A fuel, and Jet-A1 fuel.

11. Selected from the group consisting of ashless dispersants, antioxidants, metal deactivators, corrosion inhibitors, conductivity improvers, fuel deicing agents, distillate fuel stabilizers, cetane improvers, and demulsifiers The above 1 further comprising an additive to be added
A fuel composition according to claim 1.

12. A method for reducing the formation of precipitates in an engine as a result of subjecting a distillate fuel to thermal stress, comprising supplying the fuel composition according to the above 1 as fuel to the engine, and using the fuel composition to fuel the engine. A method comprising operating.

13. a) Structural formula

[0082]

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Wherein R is a hydrocarbyl group having ¹ to 300 carbon atoms, and R ¹ and R ² are each independently selected from —OH, —Cl, and —O-lower alkyl; Then, when R ¹ and R ² come together, R
¹ and R ² is at least one compound having a a) -O-, b) i) R 3 - (OH) x ( wherein, x is an integer of 2 or more, and R ³ is 1-2
Is a hydrocarbyl group having 0 carbon atoms), ii) HO - (( CH 2) y -O) z -H ( wherein, y is an integer of from 1 to 10 and z is from 1 to 10
An integer of 0), and iii)

[0084]

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Wherein each R ⁴ is independently H or -C
It can H is _3, x, y and n can range from 1 to 20 independently), and iv) at least one polyhydroxyl alcohol selected from the mixtures thereof, and c) A material composition comprising a reaction product of at least one phosphorus-containing compound.

14. R ¹ and R ² are —O—, R is polyalkenyl, and polyhydroxyl alcohol is
The alkyl diol, alkyl triol, pentaerythritol, dipentaerythritol, tripentaerythritol, pentaerythritol propoxylate, pentaerythritol ethoxylate, sorbitol, glycol and mixtures thereof selected from the group consisting of: The above 1 selected from the group consisting of dialkyl, trialkyl phosphite, phosphorus pentoxide, phosphoric acid, phosphorous acid, hypophosphorous acid and mixtures thereof
3. The composition according to 3.

15. R has a number average molecular weight of about 500 to
The composition of claim 13, wherein the polyolefin is 5,000, the polyhydroxyl alcohol is pentaerythritol, and the phosphorus-containing compound is selected from diethyl phosphite, dibutyl phosphite, and mixtures thereof.

16. 14. The composition according to the above 13, wherein the molar ratio of the component (a) to the component (b) is in the range of 1: 2 to 5: 1.

17. A method of reducing deposit formation in an engine as a result of subjecting a distillate fuel to thermal stress, comprising: a fuel comprising a major amount of fuel and a minor amount of the material composition of claim 13. Supplying fuel to the engine as fuel and using the same to operate the engine.

18. 13 above for fuel to be stabilized
A method for stabilizing a fuel, comprising adding a composition according to claim 1.

19. A fuel composition comprising a distillate fuel and an additive, the additive comprising: a) a reaction product of a dicarboxylic acid or a derivative thereof substituted with at least one hydrocarbyl with a polyhydroxyl compound; A composition comprising a mixture of compounds.

20. 20. The fuel composition according to the above item 19, wherein the hydrocarbyl-substituted dicarboxylic acid or a derivative thereof is hydrocarbyl-substituted succinic anhydride.

21. 20. The fuel composition according to the above item 19, wherein the phosphorus compound is an organic phosphorus compound.

22. 20. The fuel composition according to the above item 19, wherein the phosphorus compound is an acid or anhydride containing inorganic phosphorus, and also includes a partial sulfur homolog thereof.

23. 20. The fuel composition according to the above item 19, wherein the hydrocarbyl group is a polyisobutenyl group having a number average molecular weight of about 500 to 5,000.

24. 20. The fuel composition according to claim 19, wherein said additive is present in an amount of about 1 to about 1000 mg / liter of fuel.

25. 20. The fuel composition according to 19 above, wherein the distillate fuel is selected from diesel fuel or jet fuel.

26. 19. A method for reducing precipitate formation in an engine as a result of subjecting a distillate fuel to thermal stress, comprising providing the fuel composition of claim 19 as fuel to the engine and using the fuel composition to fuel the engine. A method comprising operating.

27. A fluid concentrate for use in a distillate fuel, comprising: a) the reaction product of at least one hydrocarbyl-substituted dicarboxylic acid or derivative thereof with a polyhydroxyl compound; and b) a mixture of phosphorus compounds. Additive.

28. 27 above for the fuel to be stabilized
A method for stabilizing a fuel, comprising adding a flowable thickening additive according to claim 1.

29. a) Structural formula

[0102]

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Wherein R is a hydrocarbyl group having ¹ to 300 carbon atoms, and R ¹ and R ² are each independently selected from —OH, —Cl, and —O-lower alkyl; Then, when R ¹ and R ² come together, R
¹ and R ² is at least one compound having a a) -O-, b) i) R 3 - (OH) x ( wherein, x is an integer of 2 or more, and R ³ is from 1 to 20 Ii) HO — ((CH ₂ ) _y —O) _z —H, wherein y is an integer from 1 to 10 and z is from 1 to 10
An integer of 0), and iii)

[0104]

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(Wherein each R ⁴ is independently H or -C
It can H is _3, x, y and n can range from 1 to 20 independently), and iv) at least one polyhydroxyl alcohol selected from the mixtures thereof, and c) A fluid concentrate additive for use in a distillate fuel, comprising a reaction product of at least one phosphorus-containing compound.

30. 29 above for the fuel to be stabilized
A method for stabilizing a fuel, comprising adding a flowable thickening additive according to claim 1.

Claims (11)

[Claims] 1. A fuel composition comprising a distillate fuel and an additive, wherein the additive is: i) at least one hydrocarbyl-substituted dicarboxylic acid or derivative thereof; ii) a polyhydroxyl compound; iii) A composition comprising the reaction product of a phosphorus compound. 2. A method for reducing precipitate formation in an engine as a result of subjecting a distillate fuel to thermal stress, the method comprising:
A method comprising supplying the fuel composition of claim 1 to the engine as fuel and using the same to operate the engine. 3. a) Structural formula embedded image Wherein R is a hydrocarbyl group having ¹ to 300 carbon atoms, and R ¹ and R ² are each independently —O
H, —Cl, and —O-lower alkyl, and when R ¹ and R ² together, R ¹ and R ² are —
B) i) R ³ — (OH) _x , wherein x is an integer greater than or equal to 2 and R ³ is 1-2.
Is a hydrocarbyl group having 0 carbon atoms), ii) HO - (( CH 2) y -O) z -H ( wherein, y is an integer of from 1 to 10 and z is from 1 to 10
An integer of 0), and iii) Wherein each R ⁴ can be independently H or —CH ₃ , and x, y, and n can each independently range from 1 to 20), and iv) A material composition comprising at least one polyhydroxyl alcohol selected from mixtures, and c) a reaction product of at least one phosphorus-containing compound. 4. A method for reducing precipitate formation in an engine as a result of subjecting a distillate fuel to thermal stress, the method comprising:
A method comprising: supplying a fuel composition comprising a major amount of fuel and a minor amount of the material composition of claim 3 to the engine as fuel, and operating the engine with the fuel composition. 5. A method for stabilizing a fuel, comprising adding the composition according to claim 3 to the fuel to be stabilized. 6. A fuel composition comprising a distillate fuel and an additive, the additive comprising a) a reaction product of a dicarboxylic acid or a derivative thereof substituted with at least one hydrocarbyl with a polyhydroxyl compound. And b) a composition comprising a mixture of phosphorus compounds. 7. A method for reducing precipitate formation in an engine as a result of subjecting a distillate fuel to thermal stress, the method comprising:
A method comprising providing the fuel composition of claim 6 as fuel to the engine and using it to operate the engine. 8. Use in a distillate fuel comprising: a) the reaction product of at least one hydrocarbyl-substituted dicarboxylic acid or derivative thereof with a polyhydroxyl compound; and b) a phosphorus compound. Flowable concentrate additive for. 9. A method for stabilizing a fuel, comprising adding the flowable enrichment additive of claim 8 to the fuel to be stabilized. 10. a) Structural formula embedded image Wherein R is a hydrocarbyl group having ¹ to 300 carbon atoms, and R ¹ and R ² are each independently —O
H, —Cl, and —O-lower alkyl, and when R ¹ and R ² together, R ¹ and R ² are —
B) i) R ³ — (OH) _x , wherein x is an integer greater than or equal to 2 and R ³ is 1-2.
Is a hydrocarbyl group having 0 carbon atoms), ii) HO - (( CH 2) y -O) z -H ( wherein, y is an integer of from 1 to 10 and z is from 1 to 10
An integer of 0), and iii) Wherein each R ⁴ can independently be H or —CH ₃ , and x, y, and n can each independently range from 1 to 20), and iv) A flowable concentrate additive for use in a distillate fuel, comprising at least one polyhydroxyl alcohol selected from a mixture, and c) a reaction product of at least one phosphorus-containing compound. 11. A method for stabilizing a fuel, comprising adding the flowable enrichment additive of claim 10 to the fuel to be stabilized.