KR0163408B1 - Fuel oil compositions - Google Patents

Abstract

The addition to diesel or jet fuel of macrocyclic polyamines, especially those derived from PIBSA, or hydrocarbyl polyamines reduces particle emission, especially in association with organic nitrate cetan improvers.

Description

Fuel oil composition

The present invention relates to fuel oil compositions and additives for use in such fuel oil compositions. More specifically, the present invention relates to diesel, heating and jet fuel oil compositions, and to reducing particle emissions upon combustion.

Modern internal combustion engines are very efficient and burn almost completely the hydrocarbon fuel used, but with a slight decrease in total efficiency, soot is produced, mostly particulate carbon. In addition to the fact that soot is unpleasant and unpleasant to breathe, carbon particles are absorbed in the multinuclear hydrocarbons produced by incomplete combustion, some of which are known as carcinogens.

It has already been proposed to use certain additives to reduce soot. Additives based on metal salts emit soot in the form of oxides or sulfates that contribute to the mass of the particles in the exhaust gas, thereby reducing the soot instead of increasing the emissions of the particles.

There is still a need for emission-reducing additives for diesel and jet fuels that do not have metal by themselves and can be combusted without contributing to the weight of the emitted particles.

The present invention is based on the observation that, in some cases, when the dispersant is incorporated into diesel, heating or jet fuel together with a cetane improver, the emission of particles is reduced.

Thus, in its broadest aspect, the present invention provides the use of ashless oil soluble macrocyclic polyamine dispersants to reduce particle emissions upon combustion of fuel oils. More particularly, the dispersant is a dispersant containing group-N═CNC═O, wherein the —N═CN group forms part of the ring and the carbon and nitrogen atoms of CN═C═O form part of the different ring. .

The present invention therefore contemplates the use of the oil-soluble compounds of the general formula (I) or (II) or mixtures of two or more of these compounds as particle-reducing additives for fuel oil and for reducing particle emissions during combustion of the fuel oil. to provide.

In the above formula,

R ¹ , R ² and R ³ are the same or different and are independently hydrogen or a C ₂ to C ₆₀₀ hydrocarbyl substituent, or a keto, halo, hydroxy, nitro, cyano or alkoxy derivative thereof, provided that R ¹ , R ² And at least one of R ³ is a C ₂ to C ₆₀₀ hydrocarbyl substituent or a derivative thereof; or

R ¹ and R ² together form a C ₄ to C ₆₀₀ hydrocarbylene substituent or a keto, halo, hydroxy, nitro, cyano or alkoxy derivative thereof, provided that R ¹ and R ² form R ¹ and CR ¹ A 5 or more member ring is formed together with the carbon atom to be formed and the nitrogen atom to form NR ² ,

Z represents -R ¹⁰ [NR ¹¹ (R ¹⁰ )] _c -or-[R ¹⁰ R ¹¹ N] _d R ¹⁰ [NR ¹¹ R ¹⁰ ] _e , where R ¹⁰ is the same or different and in the chain is C ₁ to C _An alkylene group having ₅ ;

Each R ¹¹ is the same or different and represents a hydrogen atom or a hydrocarbyl group,

c is 0 to 6,

d is 1 to 4,

e is 1 to 4,

Provided that d + e is 5 or less,

Each R ⁴ is independently H or C ₅ or less alkyl group, and R ⁵ is an alkylene group having C ₆ or less in the chain, optionally substituted by one or more C ₁₀ or less hydrocarbyl groups; C ₂ to C ₁₀ acyl group; Or a keto, halo, hydroxy, nitro, cyano or alkoxy derivative of a C ₁ to C ₁₀ hydrocarbyl group or a C ₂ to C ₁₀ acyl group,

R ⁶ is a C ₂ to C ₆₀₀ hydrocarbyl substituent or derivative thereof,

a is 1 to 150,

b is 0 to 12. When c is zero, it is advantageous to have two or more carbon atoms in the R ¹⁰ alkylene chain.

The term hydrocarbyl, as used herein, refers to a group having carbon atoms directly bonded to the rest of the molecule and having a hydrocarbon or significant hydrocarbon character. Among them are aliphatic (such as alkyl or alkenyl), cycloaliphatic (such as cycloalkyl or cycloalkenyl), aromatic, aliphatic- and cycloaliphatic-substituted aromatics, and aromatic-substituted aliphatic and cycloaliphatic groups, including Hydrocarbon groups may also be mentioned. Aliphatic groups are advantageously saturated. As an example, methyl. Ethyl, propyl, butec, isobutyl, pentyl, hexyl, octyl, decyl, octadecyl, cyclohexyl and phenyl. These groups, as mentioned above, may contain non-hydrocarbon substituents, but do not alter the potent hydrocarbon characteristics of this group. Examples include keto, halo, hydroxy, nitro, cyano, alkoxy and acyl. If the hydrocarbyl group is substituted, a single (mono) substituent is preferred. Examples of substituted hydrocarbyl groups include 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-ketopropyl, ethoxyethyl and propoxypropyl. This group may also optionally contain atoms other than carbon in a chain or ring of carbon atoms. Suitable hetero atoms are, for example, nitrogen, oxygen and sulfur. The term hydrocarbylene is similarly used; This group binds to the other molecule at least at one end, preferably at both ends via carbon atoms.

It is advantageous to use compounds of the general formula

In the above formula,

R ⁷ is hydrogen or a C ₁ to C ₆₀₀ hydrocarbyl substituent,

R ⁸ is hydrogen or a C ₁ to C ₁₂ hydrocarbyl substituent,

When more than one R ⁸ is present in the compound, they are the same or different,

R ⁹ is a C ₂ to C ₆₀₀ hydrocarbyl substituent, in which two carbons are bonded to the α-carbon atom of the succinic anhydride basic ring,

X ₁ represents hydrogen or a C ₁ to C ₁₂ alkyl group,

X ₂ may represent hydrogen, a C ₁ to C ₁₂ alkyl group, a hydroxy group, or a C ₁ to C ₁₂ alkoxy group, or X ₁ and X ₂ together may represent an oxygen or sulfur atom, and Z is represented above Meaning, h is 1 to 20. It is advantageous that h represents one.

The alkylene chain in R ¹⁰ has up to 5 carbon atoms and may be branched, but the length of the branch or branches is not limited. When R ³ represents a hydrocarbyl substituent and Z contains a nitrogen atom, the hydrocarbyl substituent is advantageously bonded to the nitrogen atom or is a nitrogen atom. In this case, the nitrogen-hydrocarbyl bond may be an amide bond, for example.

It is preferable to use the macrocyclic polyamine compound of the following general formula or the mixture of 2 or more said compounds.

In the above formula,

R ¹² is a C ₂ to C ₄₀₀ hydrocarbyl substituent,

R ¹³ is hydrogen or a C ₁ to C ₁₂ hydrocarbyl substituent,

R ¹⁴ is a C ₄ to C ₄₀₀ hydrocarbylene substituent in which two carbon atoms are bonded to the α-carbon atom of the succinic anhydride basic ring,

Z is -CH ₂ CH ₂ CH ₂ -,-(CH ₂ CH ₂ CH ₂ NH) _n CH ₂ CH ₂ CH _2- (where n is 1 to 6) or-(CH ₂ CH ₂ CH ₂ NH ) _m (CH ₂ ) p (NHCH ₂ CH ₂ CH ₂ ) _q- (where m and q are each at least 1, the sum of m and q is 2 to 5 and p is 1 to 5) ,

a is 1 to 20

The invention also comprises mixing a compound of formula (I) or (II) as defined above, more particularly a compound of formula (III), (IV) or (V) with fuel oil prior to fuel oil combustion, It provides a method of reducing the emission of particles generated during fuel oil combustion. There is also a method for reducing the emissions of particles generated upon combustion of fuel oil, including the combustion of fuel oil containing the above-mentioned compounds.

The process for preparing the macrocyclic polyamines of the general formula is described, for example, in US Pat. No. 4,637,886, which is incorporated herein by reference. As mentioned in more detail in the United States patents in which macrocyclic and optional polymacrocyclic compounds are incorporated by reference above, the hydrocarbyl succinic anhydride, monocarboxylic acid or polycarboxylic acid is subjected to an aminoamino decomposition and the acid or anhydride is di- or polyamide It prepares by adding to a compound.

Hydrocarbyl and hydrocarbylene substituents R ¹² and R ¹⁴ are polymers based on large amounts of C ₂ to C ₅ olefins, for example ethylene, propylene, butylene (1- or 2-), pentylene and especially iso It is advantageous to derive from the homopolymer or copolymer of butylene. Polyisobutylene is particularly preferred. When the polymer is a copolymer, it may be a copolymer of two or more specific monomers or a copolymer of unsaturated monomers copolymerizable with one or more specific monomers; If the polymer is a copolymer, it may be a block or random copolymer.

It is advantageous for the polymer to have 5 to 300, preferably 10 to 200, most preferably 20 to 100 carbon atoms. The preparation of alkyl and alkenyl succinic anhydrides that form reactants that are convenient for cyclodehydration reactions to prepare macrocyclic polyamines is described, for example, in US Pat. Nos. 3,018,250 and 3,024,195, which are incorporated herein by reference. .

Suitable amine reactants are of the general formula NH ₂ -Z-NH ₂ , wherein Z has the meaning given above. Preferred amines include 1,3-propane diamine; 3,3'-iminobis-propylamine, N, N'-bis (3-aminopropyl) ethylene diamine; N, N'-bis (3-aminopropyl) -1,3-propane diamine; Other suitable amines are ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentamethylene hexamine, dipropylene triamine, tripropylene tetramine, tetrapropylene pentamine and pentapropylene hexaamine.

The molar ratio of alkenyl or alkyl succinic anhydride to the polyamine used in the preferred preparation of the macrocyclic polyamine can vary, for example, from 0.2: 1 to 5: 1, preferably from 0.5: 1 to 2: 1 most preferably 0.5: 1 to 1.5: 1.

As monocarboxylic acids, acids of the general formula can also be used:

R ¹⁵ -COOH

In the above formula,

R ¹⁵ is hydrogen or substituted or unsubstituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, or aryl group.

Examples of the acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, palmitic acid, stearic acid, cyclohexanecarboxylic acid, 2-methylcyclohexane carboxylic acid, 4-methylcyclohexane carboxylic acid, oleic acid, linoleic acid, linolenic acid, cyclohex 2-eneoic acid, benzoic acid, 2-methylbenzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid, salicylic acid, 2-hydroxy-4-methylbenzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid, salicylic acid, 2- Hydroxy-4-methylbenzoic acid, 2-hydroxy-4-ethylsalicylic acid, p-hydroxybenzoic acid, 3.5-di-tert-butyl-4-hydroxybenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, o Methoxybenzoic acid and p-methoxybenzoic acid.

As the dicarboxylic acid, for example, the general formula HOOC- (CH ₂ ) _t -COOH including oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid and suberic acid, wherein t is 0 or an integer Acid, or a general formula Acids may be used wherein x is 0 or an integer, y is 0 or an integer, x and y are the same or different, and R ¹⁵ is as defined above. Examples of the acid include alkyl or alkenyl succinic acid, 2-methylbutanedioic acid, 2-ethylpentanedioic acid, 2-n-dodecylbutanedioic acid, 2-n-dodecenylbutanedioic acid, 2-phenylbutanedio Acids and 2- (p-methylphenyl) butanedioic acid. Also included are polysubstituted alkyl dicarboxylic acids in which the other R ¹⁵ groups mentioned above may be substituted on the alkyl chain. Other groups may be substituted on the same carbon atom or on different atoms. Examples are 2,2-dimethylbutanedioic acid '2,3-dimethylbutanedioic acid; 2,3,4-trimethylpentanedioic acid; 2,2,3-trimethylpentanedioic acid; And 2-ethyl-3-methylbutanedioic acid.

Dicarboxylic acids also include acids of the general formula HOOC- (CrH ₂ r- ₂ ) COOH, where r is an integer of at least 2. Examples include maleic acid, fumaric acid, pent-2-enedioic acid, hex-2-enedioic acid; Hex-3-enedioic acid, 5-methylhex-2-enedioic acid; 2,3-di-methylpent-2-enedioic acid; 2-methylbut-2-enedioic acid; 2-dodecylbut-2-enedioic acid; And 2-polyisobutylbut-2-enedioic acid.

Dicarboxylic acids are also aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid and general formula

Wherein R ¹⁵ is as defined above and n is 1,2,3, or 4, and if n is greater than 1, the R groups may be the same or different. Examples of such acids include 3-methylbenzene-1,2-dicarboxylic acid; 4-phenylbenzene-1,3-dicarboxylic acid; 2- (1-propenyl) benzene-1,4-dicarboxylic acid and 3,4-dimethylbenzene-1,2-dicarboxylic acid.

Compounds of the general formula (II) are advantageously compounds of the following general formulas.

R ¹² R ¹³ N- (CR ¹⁶ R ¹⁷ ) _n- [NH (CR ¹⁸ R ¹⁹ ) _u ] _b -NR ¹³ R ¹³

In the above formula,

R ¹³ in each of these compounds may be the same or different,

R ¹² and R ¹³ have the meanings given above,

R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are independently hydrogen; C ₁ to C ₁₀ hydrocarbyl groups; C ₂ to C ₁₀ acyl group; Or monoketo, monohydroxy, mononitro, monocyano or alkoxy derivatives of C ₁ to C ₁₀ hydrocarbyl groups or C ₂ to C ₁₀ acyl groups,

n is 1 to 6,

u is 1 to 6,

b is 0 to 12.

Methods for preparing such compounds are described, for example, in US Pat. Nos. 3,438,757, 565,804, 3,574,576, 3,671,511, 3,989,056, 3,960,515, and British Patents 1,254,338 and No. 1,398,067. In this aspect, the preferred hydrocarbyl substituents represented by R are as set forth above in connection with the macrocyclic polyamines.

Polyamines used to derive hydrocarbyl polyamines are advantageously compounds having from 2 to 12 nitrogen atoms and from 2 to 40 carbon atoms. Preferred hydrocarbyl polyamines for use in the present invention are compounds derived from polyalkylene polyamines including alkylene diamines and substituted polyalkylene polyamines. The alkylene group preferably contains 2 to 6 carbon atoms, and preferably 2 to 3 carbon atoms are present between the nitrogen atoms. Examples of such polyamines include ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, di (trimethylene) triamine, propylene diamine, dipropylene triamine, tripropylene tetramine, N-methylethylene diamine, N, N-dimethyl ethylene diamine, N-methyl-1,3-diamino propane and N, N-dimethyl-1,3-diaminopropane.

The amines include cyclic structures and branched chain polyamines formed by the reaction of linear polyamines. Of the polyalkylene polyamines, particular preference is given to those containing 2 to 12 nitrogen atoms and 2 to 24 carbon atoms.

The molar ratio of alkyl or alkenyl halides to polyamines used in accordance with the preferred method of preparation of the compounds is as mentioned above for the succinic anhydride / polyamine reaction.

In another aspect of the invention, the additives used are derivatives of the aforementioned macrocyclic or hydrocarbyl polyamines, which derivatives are for example boron oxide, boron oxide hydrates, boron halides, boric acid, sulfur, sulfur chlorides, These are those which can be obtained by working up with phosphorus oxide or phosphorus sulfide, carboxylic acid or carboxylic anhydride, acyl halide, epoxide, episulfide or acrylonitrile, preferably those obtained by such workup. Methods for carrying out such treatments are known in the art; for example, in US Pat. No. 3,254.025, which is incorporated herein by reference, for boronation incorporating 0.1 to 1 boron atoms for each nitrogen atom. It may also be performed as described.

Preferred workup for the preparation of the additive is to treat with polyisobutylenesuccinic anhydride. Macrocyclic or hydrocarbyl polyamines are treated with, for example, 10 to 50 mole percent of anhydride formed by reacting, for example, polyisobutylene having a molecular weight of 900 to 1200 for 1 hour or at 120 ° C. until the reaction mixture contains no anhydride. It is advantageous to.

Accordingly, in a third aspect, the present invention relates to the use of the above-mentioned post-treated, in particular macrocyclic or hydrocarbyl polyamines treated with plyisobutylene succinic anhydride as particle-reducing additives for diesel or jet fuels and the diesel or It provides a use for reducing the emission of particles in the combustion of jet fuel.

The additives may be used alone or in combination with other additives according to the invention or in combination with other fuel additives. The concentration of the additive according to the invention in the fuel is advantageously 0.0005 to 2, preferably 0.001 to 0.5, more preferably 0.0005 to 0.3% by weight of the fuel.

The use of other additives does not adversely affect the performance of the macrocyclic compound. In some cases, using other additives or additives may reduce emissions more than expected. Other additives that may be used include, for example, diesel cleaners, antifoam additives, corrosion inhibitor additives and demulsifiers. Other additives may be present in the fuel at a total concentration of 0.001 to 1, preferably 0.005 to 0.2, most preferably 0.005 to 0.05%, based on the total weight of the fuel.

A specific example of this combination is the use of macrocyclic compounds in combination with detergents which are uncyclized reaction products formed from hydrocarbyl succinic anhydride and polyamines. The detergent is advantageously present at a concentration of 0.005 to 0.1, preferably 0.005 to 0.5, most preferably 0.005 to 0.2%, based on the total weight of the fuel.

It has also been unexpectedly found that the use of one or more additives according to the invention in combination with a cetane improver improves the reduction of particle emissions. Accordingly, the present invention also provides such a use.

Preferred cetane improvers are organic nitrates; For example, substituted triazoles and tetrazole can be used as described in EP 230783, which is incorporated herein by reference. Preferred organic nitrates are nitrate esters containing aliphatic or substituted aliphatic groups, preferably saturated groups, of C ₃₀ or below, preferably C ₁₂ or below. Examples of such nitrates are methyl ethyl, propyl, isopropyl, butyl, amyl, hexyl, heptyl, octyl, iso-octyl, 2-ethylhexyl, nonyl, denyl, allyl, cyclopentyl, cyclohexyl, methylcyclohexyl, cyclo Dodecyl, 2-ethoxyethyl and 2- (2-ethoxyethoxy) ethyl nitrate may be mentioned.

Cetane improvers are advantageously used in fuels in concentrations ranging from 0.0005 to 1, preferably from 0,005 to 0.5, most preferably from 0.01 to 0.2% by weight of the fuel.

The following examples illustrate all parts and percentages by weight unless otherwise noted.

Eight batches of polyisobutylene succinic anhydride (PIBSA) are synthesized by treating 450 MW polyisobutylene (PIB: 450 g: 1 mol) with maleic anhydride. The amount of maleic anhydride, reaction time and temperature, and catalyst concentration are shown in Table 1. Eight batches of hot PIBSA are mixed to obtain the final product. The analysis results of the product are as follows.

Saponification value = 128.7 mg KOH / g

Free Maleic Anhydride 0.1%

The saponification value indicates that the product has an effective molecular weight of 870. The IR spectra of the product in the carbonyl region (1900-1500 wavenumber or cm ⁻¹ ) show two major peaks at 1863 and 1786 wavenumber.

The catalyst is alkylaryl sulfonic acid and% is based on the PIB charge.

Example B

A solution of hot PIBSA from Example A (435 g: 0.5 mole) was dissolved in xylene (200 mL) and dissolved in a solution of 1,3-diaminopropane (37 g: 0.5 mole) in xylene (150 mL) at 100 ° C. Add slowly over 20 hours. The reaction temperature is increased at the end of the addition, and the refluxed xylene and water (16 mL: 0.89 moles) are collected using Dean and Stark traps. At the end of the removal of water, xylene is removed by distillation to 180 ° C. Vacuum is applied to remove remaining traces of solvent. The product is a thick viscous oil containing 2.8% nitrogen (theoretical value = 3.08%).

The product IR spectrum has four peaks at 1772 (w), 1738 (m), 1705 (s) and 1674 (vs) frequencies between 1900 and 1500 waves. The spectrum shows the presence of macrocyclic compounds. (In contrast, the IR spectrum of the uncyclized additive contains only three peaks in the same region.) Weak absorption is seen at 1771-1772 waves, strong absorption is observed at 1701-1704 waves, and medium intensity absorption is observed at 1667-1670 waves.

Example C

A solution of hot PIBSA (435 g: 0.5 mole) from Example A was dissolved in xylene (200 mL), which was 3,3'-imino-bis-propylamine (65.6 g: 0.5 water) in xylene (150 mL). To reflux solution slowly over 8.25 hours. As the reaction proceeds, the formed water (16.5 mL: 0.92 mol) is collected using a Dean and Stark trap. The addition is terminated and the solvent is removed by heating to 180 ° C. under vacuum when no more water is formed. The product is a thick viscous oil containing 4.0% nitrogen (theoretical value: 4.35%).

The IR spectrum of the product has four peaks at 177 (w), 1732 (w), 1702 (s) and 1668 (c) frequencies between 1900 and 1500 wavenumber.

Example D

The method of Example C is repeated using N, N'-bis- (3-aminopropyl) -ethylenediamine (87 g: 0.5 mole). A solution of hot PIBSA is added over 31.5 hours and water (17.5 mL: 0.97 moles) is removed using a Dean and Stark trap. After removal of the volatile solvent the product (475 g) is a thick viscous oil containing 5.4% nitrogen (theoretical value = 5.56%).

The IR spectrum of the product has four peaks at 1772 (w), 1737 (vs), 1701 (vs) and 1669 (vs) between 1900 and 1500 wavenumber.

Example E

The batch of PIBSA is synthesized by reacting 960 MW PIB with maleic anhydride at high temperature. The resulting material is diluted with solvent 150 base oil to produce a product having a saponification value of 70.7 mg KOH / g. The saponification value indicates that the product has an effective weight of 1584.

Example F

Hot PIBSA (500 g: 0.32 mol) from Example E is added to a solution of 1,3-diaminopropane (24 g: 0.32 mol) in toluene (200 mL) at 25 ° C. The reaction mixture is heated to reflux and then the solvent and water of the reaction are distilled off to a pot temperature of 170 ° C. The reaction mixture is maintained at 170 ° C. for 7 hours. During this time, the IR spectra of the product are recorded to monitor the formation of the macrocycle.

The product is a thick viscous oil containing 1.5% nitrogen (theoretical = 1.75%). The IR spectrum of the product contains four peaks at 1773 (w), 1739 (m), 1706 (s) and 1675 (vs) between 1900 and 1500 waves.

Example G

The method used in Example F is repeated using hot PIBSA (500 g: 0.32 moles) and 3,3'-imino-bis-propylamine (42 g: 0.32 moles) from Example E. The product is a thick viscous oil containing 2.3% nitrogen (theoretical value = 2.53%). The IR spectrum of the product contains four peaks at 1770 (w), 1730 (m), 1702 (s), and 1670 (s) between 1900 and 1500 wavenumber.

Example H

The method used in Example F is repeated using hot PIBSA (500 g: 0.32 moles) and 3,3'-bis- (3-aminopropyl) ethylene diamine (56 g: 0.32 moles) from Example E. The product is a thick viscous oil containing 3.2% nitrogen (theoretical value = 3.29%). The IR spectrum of the product contains four peaks at 1771 (w), 1731 (m), 1702 (vs) and 1668 (vs) between 1900 and 1500 wavenumber.

Example I

The method used in Example E using hot PIBSA (500 g: 0.32 moles) and N, N'-bis- (3-aminopropyl) -1,3-propylenediamine (61 g: 0.32 moles) from Example E Repeat. The product is a thick viscous oil containing 3.0% nitrogen (theoretical value = 3.26%). The IR spectrum of the product contains four peaks at 1770 (w), 1735 (m), 1699 (s) and 1668 (vs) between 1900 and 1500 wavenumber.

Example J

The method used in Example F is repeated using hot PIBSA (500 g: 0.32 moles) and pentapropylene hexamine (74 g: 0.32 moles) from Example E. The product is a thick viscous oil containing 3.8% nitrogen (theoretical value = 3.98%). The IR spectrum of the product contains five peaks at 1769 (w), 1732 (m), 1701 (s), 1668 (vs) and 1618 (w) between 1900 and 1500 wavenumber.

Example K

Samples of PIBSA are prepared by reacting 960 MW PIB with maleic anhydride. The resulting PIBSA has a saponification value of 96.3 mg KOH / g and the effective molecular weight of PIBSA is 1163.

PIBSA (300 g: 0.22 moles) is added to a reflux solution of N, N'-bis- (3-aminopropyl) ethylene diamine (44.8 g: 0.26 moles) in toluene (200 mL). After the addition of PIBS, the reaction mixture is distilled to a temperature of 170 ° C. to remove the solvent and water. The reaction mixture is kept at 170 ° C. for 7 hours under a spectrum of nitrogen. After this time the IR spectrum of the product indicates that no macrocycles were formed anymore. The product is a thick viscous oil containing 3.9% nitrogen (theoretical value = 4.28%). The IR spectrum of the product contains four peaks at 1771 (w), 1733 (m), 1701 (s) and 1667 (vs) between 1900 and 1500 wavenumber.

Example L

3500 g of N, N'-bis (3-aminopropyl) ethylenediamine is dissolved in 4750 g of xylene and heated to 80 ° C. Polyisobutylene succinic anhydride (26910 g) prepared from polyisobutylene of Mn1000 via an ene reaction is added to the amine solution over 2 hours. The reaction mixture is heated to reflux for 10 hours and the water is removed. After reflux, the solvent is removed by distillation to give the final product with 3.71% nitrogen and 97.7 mg KOH / g TBN.

Example 1

Additives from Examples F-K are tested in an engine to determine the effect on particle emissions. The engine used was a six-cylinder four-stroke natural intake DI engine having the following properties.

Displacement = 5958cc

Max output = 100KW at 2800rpm

Max torque = 402 NM at 1400 rpm

Compression Ratio = 17.25: 1

The fuel used for the test is a standard UK automotive diesel fuel. A typical analysis is as follows.

Specific gravity = 0.849 kg / ℓ

Cetane Index = 51

Distillation ℃

IBP 162

20% 252

50% 286

90% 338

FBP 369

Sulfur content = 0.23% Flash point = 69 ° C

The additives are compared at 500 ppm using tests conducted in the following manner:

1. Inspect the engine before testing each additive by running the engine on test fuel for 12 hours at 75% speed and 75% fill.

2. The emissions are then measured from the engine using the standard ECE R49 13 mode test.

The test results are shown in Table 2.

From the results in Table 2 it is clear that all additives tested reduce the mass of particles emitted by the engine during the R49 test. This reduction rate varies from 13.9% to 25.9%. It is clear that the size of the macrocyclic ring affects performance. Small ring macrocyclic compounds (Examples F and G) are more effective than large ring macrocyclic compounds (Examples H through K).

Example 2

The effect of additive concentration on the reduction of particles is measured using the engine and fuel of Example 1. The additive from Example L is tested at different concentrations. The test is carried out in the following manner:

1. Warm the engine to full speed and sufficient charge over 90 minutes.

2. Conduct stabilization tests using untreated fuel.

3. Test on untreated fuel and collect emissions data.

4. Conduct tests on fuel treated with additives and collect emissions data.

5. Repeat steps 3 and 4 with different concentrations of additives.

The measured emissions include a large amount of particles present in the exhaust gas. Table 3 shows the percent reduction of particles between steps 4 and 3 using different concentrations of additives.

The effect of the additive on particle reduction is evident.

Example 3

The additives from Example K are tested alone and in combination with cetane improvers. Cetane improvers are alkyl nitrates made from C alcohol. Experiment using standard ECE R 49 13 mode test. Tested using VOLVO TD121 / 122F engine. The fuel used is similar to that used in Example 1. The weight of the particles formed in each test step is measured by collecting the particles on the pre-weighed filter paper. The total amount of particles from 13 modes is measured using standard weight factors for each mode. The results are shown in Table 4.

It can be appreciated that only 500 ppm of macrocyclic polyamides reduce the weight of the particles by 7%. Reducing the amount of polyamines to 150 ppm and using a cetane improver (750 ppm) results in a 46% reduction in particles.

Example 4

Additives from Example L are tested using the standard ECE R49 13 mode test on a PERKINS PHASER 180 Ti engine, alone and in combination with the cetane improver used in Example 3. The fuel used is similar to that used in Example 1. The weight of particles formed in each test step is measured as in Example 3. The results are shown in Table 5.

It can be appreciated that only 500 ppm of the macrocyclic dispersant reduces the weight of the particles by 20%. The amount of dispersant is reduced to 150 ppm and the use of cetane improver (750 ppm) reduces particles by 24%.

Claims (9)

Oil-soluble compounds of the general formula (I) or (II) or mixtures of two or more such compounds for reducing particle emissions during combustion of fuel oil in addition to reducing particle emissions by reducing contamination of the injectors of diesel engines, Or use of such compounds as fuel oil additives in post-treatment derivatives: Wherein R ¹ , R ² and R ³ may be the same or different and are independently hydrogen or a C ₂ to C ₆₀₀ hydrocarbyl substituent, or a keto, halo, hydroxy, nitro, cyano or alkoxy derivative thereof, provided that At least one of R ¹ , R ² and R ³ is a C ₂ to C ₆₀₀ hydrocarbyl substituent or a derivative thereof, or R ¹ and R ² together are a C ₄ to C ₆₀₀ hydrocarbylene substituent, or a keto, halo, A 5- or more-membered ring with hydroxy, nitro, cyano or alkoxy derivatives, provided that R ¹ and R ² together with a carbon atom to form R ¹ and CR ¹ bonds and a nitrogen atom to form R ² and NR ² Z represents -R ¹⁰ [NR ¹¹ (R ¹⁰ )] _c -or-[R ¹⁰ R ¹¹ N] _d R ¹⁰ [NR ¹¹ R ¹⁰ ] _e , R ¹⁰ may be the same or different, represents an alkylene group having a C ₁ to C ₅ in the chain, each R ¹¹ may be the same or different, a hydrogen atom Represents a hydrocarbyl group, c is 0 to 6, d is 1 to 4, e is 1-4, with the proviso that d and a is 5 or less the sum of e, each R ⁴ is H or a C ₅ independently the following is an alkyl group, R ⁵ is an alkylene group having a C ₆ or less within, the chain optionally substituted with one or more hydrocarbyl groups of C ₁₀ or less; C ₂ to C ₁₀ acyl group; Or a keto, halo, hydroxy, nitro, cyano or alkoxy derivative of a C ₁ to C ₁₀ hydrocarbyl group or a C ₂ to C ₁₀ acyl group, R ⁶ is a C ₂ to C ₆₀₀ hydrocarbyl substituent or a derivative thereof , a is 1 to 150, and b is 0 to 12. Use according to claim 1, wherein the compound is a compound of formula (I) and of formula (III), (IV) or (V) or a post-treatment derivative of such a compound: Wherein R ⁷ is hydrogen or C ₁ to C ₆₀₀ hydrocarbyl substituent, R ⁸ is hydrogen or C ₁ to C ₁₂ hydrocarbyl substituent, and if two or more R ⁸ are present in the compound, they may be the same or different , R ⁹ is a C ₂ to C ₆₀₀ hydrocarbylene substituent, wherein _two carbon atoms are bonded to the α-carbon atom of the succinic anhydride basic ring, X ₁ represents hydrogen or a C ₁ to C ₁₂ alkyl group, X ₂ Represents hydrogen, a C ₁ to C ₁₂ alkyl group, a hydroxy group, or a C ₁ to C ₁₂ alkoxy group, or X ₁ and X ₂ together may represent an oxygen or sulfur atom, and Z is Given the meaning, h is 1 to 20. Use according to claim 2, wherein the compound is an oil soluble compound of the general formula or a mixture of two or more such compounds, or a post-treatment derivative of such compounds. Wherein R ¹² is a C ₂ to C ₄₀₀ hydrocarbyl substituent, R ¹³ is hydrogen or a C ₁ to C ₁₂ hydrocarbyl substituent, and if two or more R ¹³ are present in the compound, they are the same or different R ¹⁴ may be a C ₄ to C ₄₀₀ hydrocarbylene substituent in which two carbon atoms are bonded to the α-carbon atom of the succinic anhydride basic ring, and Z is —CH ₂ CH ₂ CH ₂ —, — (CH ₂ CH ₂ CH ₂ NH) _n CH ₂ CH ₂ CH _2- (where n is 1 to 6) or-(CH ₂ CH ₂ CH ₂ NH) m (CH ₂ ) p (NHCH ₂ CH ₂ CH ₂ ) _q -Wherein m and q are each at least 1, the sum of m and q is 2 to 5 and p is 1 to 5; and a is 1 to 20. The use according to any one of claims 1, 2 and 3, wherein at least one of R ¹² or R ¹⁴ is derived from polyisobutylene. The compound of any one of claims 1, 2, and 3, wherein -Z- is-(CH ₂ ) ₃ NH (CH ₂ ) ₃ -,-(CH ₂ ) ₃ NHCH ₂ CH ₂ NH (CH ₂ ) ₃ - or - (CH _{2) 3} - use indicating. 4. Use according to any one of claims 1, 2 and 3, wherein the oil soluble compound is prepared by reacting the hydrocarbyl polyamine reactant in a molar ratio of 0.2: 1 to 5: 1. Use of the oil-soluble compound as defined in any one of claims 1, 2 and 3 for reducing the emission of particles in fuel oil combustion. 4. Use according to any one of claims 1, 2 and 3, wherein the oil soluble compound is used in a mixture with a cetane improver or in combination with a cetane improver. The use according to claim 8, wherein the cetane improver is an aliphatic or cycloaliphatic nitrate.