KR20210027403A - Compositions, uses and methods for improving the low temperature properties of medium distillate fuels - Google Patents

Abstract

여기서 R은 알킬 기이고, 각각의 R¹ 및 R²는 알킬 기이다.The present invention
(a) nitrogen-containing dispersants; And
(b) (x) wax anti-settling additives; (y) at least one low-temperature property enhancer selected from intermediate distillate flow improvers and mixtures thereof, and which are not fumarate vinyl ester copolymers.
It relates to a method for improving the low-temperature characteristics of the intermediate distillate fuel composition comprising a, the method comprises adding an additive (c), which is a copolymer comprising a unit of formula (A) and a unit of formula (B), to the fuel. Includes:

Where R is an alkyl group and each of R ¹ and R ² is an alkyl group.

Description

Compositions, uses and methods for improving the low temperature properties of medium distillate fuels

The present invention relates to additives that affect the low temperature properties of intermediate distillate fuel compositions. In particular the invention relates to additives that counteract the negative interactions between different additive compounds in the fuel at low temperatures.

The low-temperature properties of fuels have been extensively studied, and it is common and required in many countries to incorporate additives into fuels to avoid problems when storing fuels at low temperatures.

Standardized tests are devised to measure the temperature at which the fuel is clouded (cloud point-CP), the lowest temperature the fuel can flow through (pour point-PP), and low-temperature filter clogging point-a variety of low-temperature properties of medium distillate fuels, including CFPP. Became.

The cloud point of the fuel is the temperature at which the fogging of wax crystals in the liquid first appears when cooled under specified conditions as measured by, for example, a test method as specified in ASTM D 2500.

At temperatures above the pour point but below the cloud point, the wax crystals can reach a size and shape that can clog fuel lines, screens and filters, even if the fuel is physically flowing. This problem is well recognized in the art and there are a number of accepted test methods, such as the CFPP value (low temperature filter plugging point determined according to DIN EN 116).

Since the cloud point test was considered too pessimistic, tests like these were introduced to indicate low temperature workability.

Fuel additives in the form of cold flow improvers (CFI, also known as intermediate distillate flow improvers or MDFI) and wax anti-settling additives (WASA) are designed to improve the problem of precipitation of fuels at low temperatures, which are used as intermediate distillate fuels. It is commercially added to.

Some of these additives can help keep the so-called "wax" in solution in mineral fuel; Other additives can alter their crystal morphology or size to maintain filterability and injectability despite precipitation. Other additives can be used to prevent the settling wax from settling during storage.

These additives have generally been found to be so successful that suitably added fuels can be used even in extremely low temperature conditions. For many fuels, the CFPP value can be as low as 10 to 20° C. compared to the corresponding fuel without additives.

Therefore, it is common practice to include additives that improve low temperature properties such as WASA and/or MDFI in intermediate distillate fuels. Additive packages comprising a combination of WASA and MDFI are also commonly used and known as WAFI.

The Short Sediment Test (SST) can be used to measure the tendency of the wax content of fuel oils to settle, and to determine the effectiveness of a wax anti-settling additive or combination of additives. In the test, the cloud point (CP) of the base fuel is measured. The additive(s) under study is added to the base fuel and the sample is stored for 16 hours at a specified temperature, typically 7° C. below the measured CP. The amount of wax that is judged to have settled can be seen by eye. Then, depending on the specific test conditions, the bottom 20% of the fuel is taken, the CP of this sample is measured and compared to the CP of the base fuel or the CP of the top 80%. The difference between the CP of the base fuel or the top 80% and the bottom 20% of the added fuel (ΔCP) is a measure of the degree of wax sedimentation. Preferably a low value of ΔCP of approximately zero indicates good wax dispersion. Low levels of sediment can be used as an additional measure of good wax dispersion.

It is also common practice to include nitrogen-containing detergent/dispersant compounds in medium distillate fuels. These are necessary to ensure engine cleanliness and improve engine performance. Typical classes of nitrogen-containing detergents will be known to those skilled in the art and include, for example, succinimide, Mannich reaction products and quaternary ammonium salts.

However, in certain intermediate distillate fuels, antagonistic interactions may occur between nitrogen-containing detergents and wax anti-settling additives and/or intermediate distillate flow improvers that affect the low temperature properties of the fuel.

The antagonism makes the wax dispersion worse during storage, resulting in unexpected poor performance when the fuel is stored at low temperatures. This effect can be seen in the short-term sediment test (SST).

Antagonism between detergents and WASA/MDFI is a well-known phenomenon in the art. However, this does not occur in all fuels, and it is difficult to predict whether or not it will occur in a particular fuel.

A number of solutions have been proposed to this problem, and various additives have been described that can be used to improve negative interactions (see, for example, EP1932899, US8021444, US8153567, US8628590, US8628591, US8734542, US20100154294, US20100180492 and US20100236139). .

However, due to the considerable variability of fuels, the proposed solution does not always solve the problem, and therefore an alternative solution to this problem is constantly needed.

According to the first aspect of the invention,

(a) nitrogen-containing dispersants; And

(b) (x) wax anti-settling additives; (y) medium distillate flow improver; And at least one low-temperature property enhancer selected from a mixture thereof and not a fumarate vinyl ester copolymer.

As a method of improving the low-temperature characteristics of the intermediate distillate fuel composition comprising a, a method comprising adding an additive (c), which is a copolymer comprising a unit of formula (A) and a unit of formula (B), to a fuel is provided. do:

Where R is an alkyl group and each of R ¹ and R ² is an alkyl group.

According to the second aspect of the present invention,

(a) nitrogen-containing dispersants; And

(b) (x) wax anti-settling additives; (y) medium distillate flow improver; And at least one low-temperature property enhancer selected from a mixture thereof and not a fumarate vinyl ester copolymer.

There is provided the use of a copolymer (c) comprising a unit of formula (A) and a unit of formula (B) for improving the low temperature properties of an intermediate distillate fuel composition comprising:

Where R is an alkyl group and each of R ¹ and R ² is an alkyl group.

According to the third aspect of the present invention,

(b) (x) wax anti-settling additives; (y) medium distillate flow improver; And at least one low-temperature property enhancer selected from a mixture thereof and not a fumarate vinyl ester copolymer; And

(c) a copolymer comprising a unit of formula (A) and a unit of formula (B)

There is provided an additive composition for improving the low temperature properties of the intermediate distillate fuel composition comprising:

Where R is an alkyl group and each of R ¹ and R ² is an alkyl group.

According to the fourth aspect of the present invention,

(a) nitrogen-containing dispersants;

(b) (x) wax anti-settling additives; (y) medium distillate flow improver; And at least one low-temperature property enhancer selected from a mixture thereof and not a fumarate vinyl ester copolymer; And

(c) a copolymer comprising a unit of formula (A) and a unit of formula (B)

There is provided an intermediate distillate fuel composition comprising:

Where R is an alkyl group and each of R ¹ and R ² is an alkyl group.

Preferred features of the first, second, third and fourth aspects of the invention will now be described.

The present invention relates to improving the low temperature properties of intermediate distillate fuel compositions by the addition of additive (c), which is a copolymer comprising units of formula (A) and units of formula (B):

Wherein each of R ¹ and R ² is an alkyl group.

Additive (c) can be prepared by copolymerizing a vinyl ester monomer and a fumaric acid monomer, and then esterifying an acid moiety.

Preferably the additive (c) is prepared by copolymerizing a vinyl ester monomer and a dialkyl fumarate monomer.

The additive (c) is preferably a copolymer prepared by reacting a monomer of a vinyl ester of formula (C) and a dialkyl fumarate monomer of formula (D):

.

.

Each of the monomers of formula (C) used to prepare the copolymer additive (c) may be the same, or the copolymer may be prepared from a mixture of two or more different monomers of formula (C).

R is an alkyl group, preferably an unsubstituted alkyl group.

Preferably R is an alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.

Preferably R is an unsubstituted alkyl group having 1 to 4 carbon atoms.

Most preferably R is methyl and the monomer of formula (C) is vinyl acetate.

Each of the monomers of formula (D) used to prepare the copolymer additive (c) may be the same, or the copolymer may be prepared from a mixture of two or more different monomers of formula (D).

Preferably all monomers of formula (D) used to prepare additive (c) are the same.

Each of R ¹ and R ² may be the same or different. Preferably R ¹ is the same as ^{R 2.}

Each of R ¹ and R ² is an alkyl group. Preferably each is an unsubstituted alkyl group. R ¹ and R ² may be straight-chain or branched. Preferably each of R ¹ and R ² is a straight chain alkyl group.

Preferably each of R ¹ and R ² is an alkyl group having less than 18 carbon atoms.

Preferably each of R ¹ and R ² is 6 to 17 carbon atoms, preferably 6 to 16 carbon atoms, more preferably 8 to 16 carbon atoms, preferably 10 to 16 carbon atoms, more It is preferably an alkyl group having 12 to 16 carbon atoms, suitably 12 to 14 carbon atoms, most preferably 14 carbon atoms. Most preferably R ¹ is C ₁₄ H ₂₉ and R ² is C ₁₄ H ₂₉ .

The additive (c) is a copolymer comprising units of formula (A) and units of formula (B). In some embodiments additive (c) may comprise additional units other than formula (A) or formula (B). In this embodiment the copolymer is suitably prepared from a vinyl ester monomer, a fumaric acid derived monomer (preferably a dialkyl fumarate) and one or more additional monomer units. In a preferred embodiment the at least one additional monomer unit is less than 20 mol%, preferably less than 10 mol%, more preferably less than 5 mol%, more preferably of all monomer units used to prepare the additive (c). Occupies less than 1 mol%.

In a preferred embodiment additive (c) consists essentially of units of formula (A) and units of formula (B). It is at least 80 mol%, preferably at least 90 mol%, more preferably at least 95 mol%, more preferably at least 80 mol%, preferably at least 90 mol%, more preferably at least 95 mol%, of all monomer-derived units present in the copolymer together with the unit of formula (A) and the unit of formula (B). It is meant to provide at least 99 mol%, for example at least 99.5 mol% or at least 99.9 mol%.

Suitably the additive (c) comprises 10 to 90 mol% of units of formula (A) and 90 to 10 mol% of units of formula (B); Preferably 25 to 75 mol% of units of formula (A) and 25 to 75 mol% of units of formula (B); More preferably, it contains 40 to 60 mol% of the unit of formula (A) and 60 to 40 mol% of the unit of formula (B).

Preferably the additive (c) is a random copolymer.

Suitably the copolymer additive (c) has a number average molecular weight of 1000 to 100000, preferably 2000 to 50000, more preferably 5000 to 30000, for example 8000 to 25000.

In some preferred embodiments the copolymer additive (c) has a number average molecular weight of 20,000 to 25000.

In some particularly preferred embodiments the copolymer additive (c) has a number average molecular weight of 8000 to 12000.

In a particularly preferred embodiment the additive (c) is a copolymer comprising units of formula (A) and units of formula (B):

Where R is an alkyl group, each of R ¹ and R ² is an alkyl group having less than 18 carbon atoms, preferably 12 to 16 carbon atoms, and the copolymer has a number average molecular weight of 8000 to 25000 . Most preferably the copolymer comprises 40 to 60 mol% of units of formula (A) and 60 to 40 mol% of units of formula (B).

Additive (c),

(a) nitrogen-containing dispersants; And

(b) (x) wax anti-settling additives; (y) at least one low-temperature property enhancer selected from intermediate distillate flow improvers and mixtures thereof, and which are not fumarate vinyl ester copolymers.

It is used to improve the low temperature characteristics of the intermediate distillate fuel composition comprising a.

Any suitable nitrogen-containing detergent can be used as component (a).

Nitrogen-containing detergents suitable for use herein are

(i) quaternary ammonium salt additives;

(ii) the Mannich reaction product between an aldehyde, an amine and an optionally substituted phenol;

(iii) the reaction product of a carboxylic acid-derived acylating agent and an amine;

(iv) the reaction product of a carboxylic acid-derived acylating agent and hydrazine;

(v) a salt formed by reaction of a carboxylic acid and di-n-butylamine or tri-n-butylamine;

(vi) the reaction product of a hydrocarbyl-substituted dicarboxylic acid or anhydride and an amine compound or salt comprising at least one amino triazole group; And

(vii) polyalkylene substituted amines

Includes.

Preferably component (a) is

(i) quaternary ammonium salt additives;

(ii) the Mannich reaction product between an aldehyde, an amine and an optionally substituted phenol; And

(iii) Reaction product of carboxylic acid-derived acylating agent and amine

Includes one or more of.

In some embodiments component (a) comprises (i) a quaternary ammonium salt additive.

The quaternary ammonium salt additive is suitably the reaction product of a nitrogen-containing species having at least one tertiary amine group and a quaternizing agent.

Nitrogenous species

(p) a reaction product of a hydrocarbyl-substituted acylating agent and a compound comprising at least one tertiary amine group and a primary amine, secondary amine or alcohol group;

(q) a Mannich reaction product comprising a tertiary amine group; And

(r) polyalkylene substituted amines having at least one tertiary amine group

Can be selected from

Examples of quaternary ammonium salts and methods for their preparation are described in the following patents, US2008/0307698, US2008/0052985, US2008/0113890 and US2013/031827, which are incorporated herein by reference.

The preparation of some suitable quaternary ammonium salt additives comprising nitrogen-containing paper component (p) is described in WO 2006/135881 and WO2011/095819.

Component (q) is a Mannich reaction product with a tertiary amine. The preparation of quaternary ammonium salts formed from nitrogen-containing species comprising component (y) is described in US 2008/0052985.

The preparation of quaternary ammonium salt additives comprising a nitrogen-containing paper component (r) is described for example in US 2008/0113890.

In a preferred embodiment the nitrogen-containing species used to prepare the quaternary ammonium salt additive (i) are of type (p), i.e. a hydrocarbyl-substituted acylating agent, and an oxygen or nitrogen atom capable of condensing with the acylating agent. It is a reaction product of a compound having and further having a tertiary amino group.

The hydrocarbyl substituted acylating agent is preferably a monocarboxylic acid or polycarboxylic acid (or a reactive equivalent thereof), for example substituted succinic acid, phthalic acid or propionic acid.

Most preferably the acylating agent is a hydrocarbyl substituted succinic acid or anhydride.

Hydrocarbyl substituents in such acylating agents preferably contain at least 8, more preferably at least 12, for example 30 or 50 carbon atoms. It may contain up to about 200 carbon atoms. Preferably, the hydrocarbyl substituent of the acylating agent has a number average molecular weight (Mn) between 170 and 2800, for example between 250 and 1500, preferably between 500 and 1500, more preferably between 500 and 1100. Mn of 700 to 1300, for example 700 to 1000, is particularly preferred.

In some preferred embodiments, the hydrocarbyl-based substituent is poly-(isobutene) known in the art. Thus, in a particularly preferred embodiment, the hydrocarbyl substituted acylating agent is polyisobutenyl substituted succinic anhydride.

The preparation of polyisobutenyl substituted succinic anhydride (PIBSA) has been documented in the art.

Examples of nitrogen or oxygen-containing compounds capable of condensation with an acylating agent and further having a tertiary amino group include N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, N,N-dimethylamino ethylamine, 1-(3-aminopropyl)imidazole, 4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-diamino-N-methyldipropylamine, and 3 '3-iminobis (N,N-dimethylpropylamine), triethanolamine, trimethanolamine, N,N-dimethylaminopropanol, N,N-dimethylaminoethanol, N,N-diethylaminopropanol, N,N -Diethylaminoethanol, N,N-diethylaminobutanol, N,N,N-tris(hydroxyethyl)amine, N,N,N-tris(hydroxymethyl)amine, N,N,N-tris (Aminoethyl)amine, N,N-dibutylaminopropylamine and N,N,N'-trimethyl-N'-hydroxyethyl-bisaminoethyl ether; N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine; N-(3-dimethylaminopropyl)-N,N-diisopropanolamine; N'-(3-(dimethylamino)propyl)-N,N-dimethyl 1,3-propanediamine; 2-(2-dimethylaminoethoxy)ethanol, and N,N,N'-trimethylaminoethylethanolamine.

Most preferably the alcohol or amine compound which reacts with the acylating agent and has a tertiary amino group is dimethylaminopropylamine or dimethylaminopropanol.

The quaternary ammonium salt additive (i) is formed by reacting a nitrogen-containing species having a tertiary amine group with a quaternizing agent.

The quaternizing agent may suitably be selected from esters and non-esters.

The quaternizing agent is suitably a dialkyl sulfate; Esters of carboxylic acids; Alkyl halides; Benzyl halide; Hydrocarbyl substituted carbonate; And a hydrocarbyl epoxide combined with an acid or a mixture thereof.

Examples of hydrocarbyl epoxides may include styrene oxide, ethylene oxide, propylene oxide, butylene oxide, stilbene oxide and C2-50 epoxide.

Suitable ester quaternizing agents include esters of carboxylic acids selected from one or more of oxalic acid, phthalic acid, salicylic acid, maleic acid, malonic acid, citric acid, nitrobenzoic acid, aminobenzoic acid and 2,4,6-trihydroxybenzoic acid.

Preferred quaternizing agents for use herein include dimethyl oxalate, methyl 2-nitrobenzoate, methyl salicylate and styrene oxide or propylene oxide (optionally in combination with additional acids).

Particularly preferred quaternary ammonium salts for use herein are methyl salicylate or dimethyl oxalate with the reaction product of polyisobutylene-substituted succinic anhydride and dimethylaminopropylamine having a PIB number average molecular weight of 700 to 1300. It is formed by reacting.

Other suitable quaternary ammonium salts include, for example, quaternized terpolymers as described in US2011/0258917; Quaternized copolymers, for example as described in US2011/0315107; And acid-free quaternized nitrogen compounds disclosed in US2012/0010112.

Further suitable quaternary ammonium compounds for use in the present invention are the quaternary ammonium compounds described in the applicant's co-pending applications WO2011095819, WO2013/017889, WO2015/011506, WO2015/011507, WO2016/016641 and PCT/GB2016/052312. Includes.

In some embodiments component (a) comprises (ii) a Mannich reaction product between an aldehyde, an amine and an optionally substituted phenol. This Mannich reaction product is suitably not a quaternary ammonium salt.

Preferably the aldehyde component used to prepare the Mannich additive is an aliphatic aldehyde. Preferably the aldehyde has 1 to 10 carbon atoms. Most preferably, the aldehyde is formaldehyde.

Amines suitable for use in preparing the Mannich additive include monoamines and polyamines. One suitable monoamine is butylamine.

The amine used to prepare the Mannich additive is preferably a polyamine. It can be selected from any compound containing two or more amine groups. Preferably the polyamine is a polyalkylene polyamine, preferably a polyethylene polyamine, in particular a polyethylene polyamine having 1 to 10 ethylene groups and 2 to 11 amine groups.

Commercially available sources of polyamines typically contain mixtures of isomers and/or oligomers, and products made from such commercially available mixtures that fall within the scope of the present invention.

Suitably the polyamine is ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, propane-1,2-diamine, 2(2- Amino-ethylamino)ethanol, and N',N'-bis (2-aminoethyl) ethylenediamine (N(CH ₂ CH ₂ NH ₂ ) ₃ ).

Most preferably the polyamine comprises tetraethylenepentamine or ethylenediamine.

The optionally substituted phenolic component used to prepare the Mannich additive may be substituted with 0 to 4 groups (other than phenol OH) on the aromatic ring. For example it can be a hydrocarbyl-substituted cresol. Most preferably the phenolic component is a mono-substituted phenol. Preferably it is a hydrocarbyl substituted phenol. Preferred hydrocarbyl substituents are alkyl substituents having 4 to 28 carbon atoms, in particular 10 to 14, for example 12 carbon atoms. Another preferred hydrocarbyl substituent is a polyalkenyl substituent. These polyisobutenyl substituents have a number average molecular weight of 400 to 2500, for example 500 to 1500.

Suitable Mannich reaction products useful as additives herein include hydrocarbyl-substituted acylating agents and compounds comprising at least one tertiary amine group and a primary amine, secondary amine or alcohol group in the applicant's patents and applications. It is described as a reaction product; WO2009/040582, WO2009/040583, WO2009/040584, WO2009/040585, WO2010/097624, WO2013/017884, WO2013/017886 and WO2013/017887.

Preferred Mannich reaction product additives for use herein are the reaction products of hydrocarbyl substituted phenols, formaldehyde and polyamines, preferably polyethylene polyamines.

Preferably, the Mannich reaction product additive is by reaction of a phenol substituted with an alkyl group having 6 to 30 carbon atoms or a polyisobutenyl group having a number average molecular weight of 500 to 2000 with formaldehyde and a polyamine, preferably polyethylene polyamine. Is formed.

A particularly preferred Mannich reaction product for use herein as a nitrogen-containing detergent (a) is the reaction product of dodecylphenol, formaldehyde, and ethylene diamine or tetraethylpentamine.

In some embodiments component (a) comprises the reaction product of (iii) a carboxylic acid-derived acylating agent and an amine.

They may also be referred to herein generally as acylated nitrogen-containing compounds.

Suitable acylated nitrogen-containing compounds can be prepared by reacting a carboxylic acid acylating agent with an amine and are known to those skilled in the art.

A preferred hydrocarbyl substituted acylating agent is polyisobutenyl succinic anhydride. These compounds are commonly referred to as “PIBSA” and are known to those skilled in the art.

Conventional polyisobutenes and so-called "highly-reactive" polyisobutenes are suitable for use in the present invention. Highly reactive polyisobutenes are preferred.

Particularly preferred PIBSAs are those having a PIB molecular weight (Mn) of 300 to 2800, preferably 450 to 2300, more preferably 500 to 1300.

In a preferred embodiment the reaction product of a carboxylic acid derived acylating agent and an amine comprises at least one primary or secondary amine group.

Preferred acylated nitrogen-containing compounds for use herein are poly(isobutene)-substituted succinic acid-derived acylating agents having a number average molecular weight (Mn) of 170 to 2800 of the poly(isobutene) substituent (e.g., Anhydrides, acids, esters, etc.) with a mixture of ethylene polyamines having 2 to about 9 amino nitrogen atoms, preferably about 2 to about 8 nitrogen atoms, and about 1 to about 8 ethylene groups per ethylene polyamine. do. These acylated nitrogen compounds are suitably 10:1 to 1:10, preferably 5:1 to 1:5, more preferably 2:1 to 1:2, most preferably 2:1 to 1: It is formed by the reaction of an acylating agent:amino compound in a molar ratio of 1. In a particularly preferred embodiment, the acylation nitrogen compound is from 1.8:1 to 1:1.2, preferably from 1.6:1 to 1:1.2, more preferably from 1.4:1 to 1:1.1, most preferably from 1.2:1 to It is formed by the reaction of an acylating agent to an amino compound in a molar ratio of 1:1. Acylated amino compounds of this type and their preparation are well known to those skilled in the art and are described, for example, in EP0565285 and US5925151.

In some preferred embodiments the composition comprises a detergent of the type formed by the reaction of a polyisobutene-substituted succinic acid-derived acylating agent and a polyethylene polyamine. Suitable compounds are described, for example, in WO2009/040583.

A particularly preferred additive of this type is the reaction product of a polyisobutenyl substituted succinic acid/anhydride having a PIB molecular weight (Mn) of 500 to 1300 and a polyethylene polyamine having 1 to 9 amino groups and 1 to 8 ethylene groups.

In some embodiments component (a) comprises the reaction product of (iv) a carboxylic acid-derived acylating agent and hydrazine.

Suitably the additive comprises a hydrocarbyl-substituted succinic acid or reaction product between anhydride and hydrazine.

Preferably, the hydrocarbyl group of the hydrocarbyl-substituted succinic acid or anhydride comprises C ₈ -C ₃₆ groups, preferably C ₈ -C ₁₈ groups. Alternatively, the hydrocarbyl group may be a polyisobutylene group having a number average molecular weight of 200 to 2500, preferably 800 to 1200.

Hydrazine has the formula NH ₂ -NH ₂ . Hydrazine can be hydrated or dehydrated. Hydrazine monohydrate is preferred.

The reaction between hydrocarbyl-substituted succinic acid or anhydride and hydrazine yields various products as disclosed in US 2008/0060259.

In some embodiments component (a) comprises a salt formed by the reaction of (v) a carboxylic acid with di-n-butylamine or tri-n-butylamine. Exemplary compounds of this type are described in US 2008/0060608.

Such additives are suitably di- of fatty acids of the formula [R'(COOH) _X ] _y' (wherein each R'is independently a hydrocarbon group of 2 to 45 carbon atoms, and x is an integer from 1 to 4). It may be -n-butylamine or tri-n-butylamine salt.

In a preferred embodiment, the carboxylic acid comprises tall oil fatty acids (TOFA).

Further preferred features of this type of additive are described in EP1900795.

In some embodiments component (a) comprises the reaction product of (vi) a hydrocarbyl-substituted dicarboxylic acid or anhydride and an amine compound or salt comprising at least one amino triazole group.

Further preferred features of this type of additive compound are as defined in US2009/0282731.

In some embodiments component (a) comprises (vii) a polyalkylene substituted amine.

Polyalkene-substituted amines can be derived from olefin polymers and amines such as ammonia, monoamines, polyamines or mixtures thereof. They can be prepared by various methods such as those described and mentioned in US 2008/0113890.

Suitably the polyalkene substituent of the polyalkene-substituted amine is derived from polyisobutylene.

The number average molecular weight of the polyalkene-substituted amine may range from 500 to 5000, or from 500 to 3000, for example from 1000 to 1500.

Preferably component (a) is

-A quaternary ammonium salt additive formed by reaction of a reaction product of a hydrocarbyl-substituted acylating agent and a compound comprising at least one tertiary amine group and a primary amine, secondary amine or alcohol group with a quaternizing agent;

-Mannich reaction product between hydrocarbyl substituted phenol, formaldehyde and polyamine; And

-Reaction product of hydrocarbyl substituted succinic acid-derived acylating agent and amine

Includes one or more of.

More preferably component (a) is

-A quaternary ammonium salt additive formed by reaction of a reaction product of a polyisobutenyl substituted succinic anhydride and an amine or alcohol (which additionally contains a tertiary amino group) with a quaternizing agent, preferably wherein the quaternizing agent is Dialkyl sulfates; Esters of carboxylic acids; Alkyl halides; Benzyl halide; Hydrocarbyl substituted carbonate; And a hydrocarbyl epoxide combined with an acid or a quaternary ammonium salt additive selected from the group consisting of a mixture thereof;

-A phenol substituted with an alkyl group having 6 to 30 carbon atoms or a polyisobutenyl group having a number average molecular weight of 500 to 2000; Formaldehyde; And ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, propane-1,2-diamine, 2(2-amino-ethylamino ) A Mannich reaction product between ethanol, and a polyamine selected from N',N'-bis (2-aminoethyl) ethylenediamine (N(CH ₂ CH ₂ NH ₂ ) _{3 );} And

-Reaction product of polyisobutenyl substituted succinic acid-derived acylating agent and polyamine

It is selected from one or more of.

Most preferably component (a) is

-A quaternary ammonium salt additive formed by reacting methyl salicylate or dimethyl oxalate with the reaction product of polyisobutylene-substituted succinic anhydride and dimethylaminopropylamine having a PIB number average molecular weight of 700 to 1300;

-Mannich reaction product of dodecylphenol, formaldehyde, and ethylene diamine or tetraethylpentamine; And

-Reaction product of polyisobutenyl substituted succinic acid/anhydride with PIB molecular weight (Mn) of 500 to 1300 and polyethylene polyamine having 1 to 9 amino groups and 1 to 8 ethylene groups

It is selected from one or more of.

Component (b) comprises: (x) a wax anti-settling additive; (y) at least one low temperature property enhancer selected from intermediate distillate flow improvers and mixtures thereof, which are not fumarate vinyl ester copolymers.

Preferably component (b) comprises at least one wax anti-settling additive (x).

Preferably component (b) comprises at least one intermediate distillate flow improver (y).

More preferably component (b) comprises at least one anti-settling additive (x) and at least one intermediate distillate flow improver (y).

Preferred wax anti-settling additives (x) contain (I) segment -NR ³ R ⁴ (where R ³ represents a group containing 4 to 44 carbon atoms, R ⁴ represents a hydrogen atom or a group R ³ ) And (II) a reaction product of a carboxylic acid having 1 to 4 carboxylic acid groups or a reactive equivalent thereof.

Preferably R ³ is a hydrocarbyl group or a polyethoxylate or polypropoxylate group.

Preferably the group R ³ is a hydrocarbyl group. Preferably R ³ is a hydrocarbon group, preferably a straight chain hydrocarbon group.

Preferably the group R ³ contains 6 to 36, preferably 8 to 32, preferably 10 to 24, preferably 12 to 22, most preferably 14 to 20 carbon atoms.

One of skill in the art will recognize that commercial sources of alkylamines and dialkylamines may contain mixtures of homologues. Additives derived from these compounds are within the scope of the present invention.

R ⁴ may be a group according to the definition of R ^{3 or hydrogen.}

R ⁴ preferably follows the same definition as given for ^{R 3.} R ³ and R ⁴ need not be the same. However, preferably, R ³ and R ⁴ are the same.

Species (II) is a carboxylic acid or a reactive equivalent thereof.

Reactive equivalents of carboxylic acids include acid anhydrides, spirobislactones and acid halides.

Acid halide is not preferred. However, if an acid halide is used it is preferably an acid chloride.

Suitable compounds (I) include primary, secondary, tertiary, and quaternary amines. Only tertiary and quaternary amines form amine salts.

Secondary amines of the formula HNR ³ R ⁴ are a particularly preferred class of compounds (I). Examples of particularly preferred secondary amines include di-octadecylamine, di-cocoamine, di-hydrogenated tallow amine and methylbehenyl amine. Mixtures of amines such as those derived from natural substances are also suitable. A preferred amine is a secondary hydrogenated tallow amine, the alkyl group of which is derived from hydrogenated tallow fat consisting of _{approximately 3-5 wt% C 14} , 30-32 wt% C ₁₆ , and 58-60 wt% C _18.

It is a further preferred class of compounds (I) of quaternary amines of the formula [+NR ³ R ⁴ R ⁵ R ^{6 -An].} R ³ and R ⁴ are as defined above (but R ⁴ is not hydrogen). R ⁵ and R ⁶ independently represent a C(1-4) alkyl group, preferably propyl, ethyl, or most preferably methyl. +NR ³ R ⁴ (CH ₃ ) ₂ represents a preferred cation. -An represents an anion. The anion can be any suitable species, but is preferably a halide, especially chloride. When (I) contains a quaternary amine, the reaction conditions can be adjusted to assist the reaction between (I) and (II). Preferably, the reaction conditions are adjusted by the introduction of an auxiliary base. The auxiliary base is preferably a metal alkoxide or a metal hydroxide. Alternatively, the quaternary amine salt can be carried out as a corresponding basic salt, for example a quaternary ammonium hydroxide or alkoxide.

A mixture of a primary amine and a secondary amine or a mixture of a secondary amine and a quaternary amine may be provided as species (I).

Preferred carboxylic acids (II) include carboxylic acids containing 2, 3 or 4 carboxylic acid groups, and reactive equivalents thereof.

Examples of suitable carboxylic acids and their anhydrides are aminoalkylenepolycarboxylic acids such as nitrilotriacetic acid, propylene diamine tetraacetic acid, ethylenediamine tetraacetic acid, and carboxylic acids based on cyclic backbones, such as pyro Melitic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid and naphthalene dicarboxylic acid, 1,4-dicarboxylic acid Carboxylic acids, and dialkyl spirobislactones. Typically, these acids have about 5 to 13 carbon atoms in the cyclic moiety. Optionally substituted benzene dicarboxylic acids, such as phthalic acid, isophthalic acid, and terephthalic acid, and their acid anhydrides or acid chlorides are preferred acids useful in the present invention. Optional substituents are C(1-4)alkyl, C(1-4)alkoxy, halogen, C(1-4)haloalkyl, C(1-4)haloalkoxy, nitrile, -COOH, -CO-OC( 1-4) alkyl, and ^{1 to 5 substituents independently selected from -CONR 3} R ⁴ (R ³ and R ⁴ are independently selected from hydrogen and C(1-4)alkyl), preferably 1 to 3 Includes a substituent. Preferred halogen atoms are fluorine, chlorine, and bromine. However, unsubstituted benzene carboxylic acids are preferred. Phthalic acid and its acid anhydrides are particularly preferred.

Another suitable compound of formula (II) is an alkyl spirobislactone.

Preferably the molar ratio of compound (I) to acid or reactive equivalent (II) thereof is at least 50% (preferably at least 75%, preferably at least 90%, most preferably 100%) of the acid groups, the compound It is to react in the reaction between (I) and (II) to form, for example, amide and/or amine salts.

When compound (II) contains one or more free carboxylic acid groups, the reaction conditions can be adjusted to allow the reaction between compounds (I) and (II), for example to form the respective amide or amine salt. The reaction conditions can be appropriately adjusted using methods known to those skilled in the art.

In the case of a preferred reaction, between compound (I) and a dicarboxylic acid or a reactive equivalent thereof (for example an acid anhydride), or preferably compound (I) (or in this situation, a mixture of compounds (I)) The molar ratio of the acid or its reactive equivalent (or in this situation, the mixed compound (II)) is at least 0.7:1, preferably at least 1:1, preferably at least 1.5:1. It is preferably at most 3:1, preferably at most 2.5:1. Most preferably, it is in the range of 1.8:1 to 2.2:1. It is particularly preferred that the molar ratio of (I) to (II) is 2:1. In another preferred embodiment a molar ratio of 1:1 is used.

In the case of a preferred reaction, between the secondary amine as compound (I) and the dicarboxylic acid or acid anhydride, preferably the molar ratio of amine (I) to acid or acid anhydride (II) is at least 1:1, preferably Is at least 1.5:1. Most preferably, it is in the range of 1.8:1 to 2.2:1. It is particularly preferred that the molar ratio of (I) to (II) is 2:1.

Preferably the reaction between compound (I) and carboxylic acid, acid anhydride or acid halide (II) forms one or more amide, imide or ammonium salts, combinations thereof in the same compound, and mixtures of these compounds.

Thus, in one preferred embodiment the dicarboxylic acid, acid anhydride or acid halide (II) is reacted with a secondary amine (I), preferably in a molar ratio of 1:2, so that 1 mole of amine forms an amide and 1 mole of amine is Forms ammonium salts.

Particularly preferred additives are the dialkylammonium salts of the monoamides of dialkylamines and phthalic acids, which suitably di(hydrogenated) tallow amines (I) and phthalic acids or their acid anhydrides (II) (preferably 2:1 Molar ratio).

Particularly preferred anti-settling additives are the reaction products of di(hydrogenated) tallow amine (I) and phthalic acid or its acid anhydride (II), preferably in a 1:1 molar ratio.

Another preferred anti-settling additive is the reaction product of (hydrogenated) tallow amine (I) and EDTA (II), preferably in a 4:1 molar ratio, wherein the removal of 4 moles of water or 2 moles of water, respectively, is a tetraamide. Derivatives or diamide diammonium salt derivatives.

Another preferred additive is an alkylspirobislactone (II), for example the reaction product of dodecenyl-spirobislactone with mono-tallow amine and/or di-tallow amine (I); It is preferably the reaction product of 1 mole of alkylspirobislactone, for example dodecenyl-spirobislactone, with 1 mole of mono-tallow amine and 1 mole of di-tallow amine.

Another preferred additive is the reaction product of benzene-1,2,4,5-tetracarboxylic acid or its dianhydride (II) and di(hydrogenated tallow) amine (I), preferably in a 1:4 molar ratio. This reaction product may be termed pyromellitic tetraamide, but in practice may typically be a mixture of tetraamide, triamide/mono salt and diamide/disalt.

Another suitable anti-settling additive is the half amide half of the maleic anhydride α olefin copolymer, wherein the α olefin has 10 to 36 carbon atoms, preferably 12 to 24 carbon atoms, for example 16 to 20 carbon atoms. It is an ammonium salt. The amine which reacts with the maleic anhydride α olefin copolymer is suitably a dialkylamine having 6 to 30, preferably 12 to 24, for example 18 carbon atoms in the alkyl group. These additives can be formed, for example, according to the following scheme:

One additional class of wax anti-settling additives that may be useful herein are alkylphenol aldehyde resins modified by Mannich reaction with alkylamines. These compounds are suitably formed by forming an alkylphenol condensate having an aldehyde, and then reacting the condensate with an alkylamine and an aldehyde or ketone (preferably and an aldehyde) by a Mannich reaction. The alkyl phenol is suitably mono-substituted with 1 alkyl group having 1 to 30 carbon atoms; The aldehyde used to prepare the resin preferably has 1 to 4 carbon atoms. Preferably the alkylamine contains 1 primary amine group and has 12 to 24 carbon atoms. Aldehydes having 1 to 4 carbon atoms, preferably formaldehyde, are used in the Mannich reaction. Such compounds are described in more detail in US9169452.

A preferred intermediate distillate flow improver (y) is a copolymer of ethylene and olefinically unsaturated compounds.

Preferred copolymers of ethylene and olefinically unsaturated compounds for use in the present invention, in addition to ethylene, are 1 to 23 mol%, preferably 6 to 21 mol%, more preferably 7 to 18 mol%, preferably 9 To 16 mol%, in particular 10 to 15 mol% of olefinically unsaturated compounds as comonomers.

The olefinically unsaturated compounds are preferably vinyl esters, acrylic acid esters, methacrylic acid esters, alkyl vinyl ethers and/or alkenes, and the compounds mentioned may be substituted by hydroxyl groups. One or more comonomers may be present in the polymer.

The vinyl ester is preferably the vinyl ester of formula (1).

CH ₂ -CH-OCOR ⁷ (1)

Wherein R ⁷ is a C1 to C30 alkyl group. In some embodiments R ⁷ can be a C4 to C16 alkyl group, such as a C6 to C12 alkyl group. In some embodiments, alkyl groups may be substituted by one or more hydroxyl groups. In a preferred embodiment R ⁷ is a C1 to C10 alkyl group, more preferably a C1 to C4 alkyl group, most preferably a C1 to C2 alkyl group.

Suitable vinyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl hexanoate, vinyl heptanoate, vinyl octanoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl laurate, Vinyl stearate and Versatic esters such as vinyl neononanoate, vinyl neodecanoate, and vinyl neoundecanoate. A particularly preferred vinyl ester is vinyl acetate.

In some embodiments these ethylene copolymers are vinyl acetate and ^{at least one further vinyl ester of formula (1), wherein R 7} is C4 to C30 alkyl, preferably C4 to C16 alkyl, especially C6 to C12 alkyl. It may contain.

In a preferred embodiment, the compound of formula (1) is vinyl acetate and the middle distillate flow improver (y) comprises a copolymer of ethylene and vinyl acetate. Preferably the copolymer comprises 76 to 63 wt% of ethylene and 24 to 37 wt% of vinyl acetate, more preferably 74 to 65 wt% of ethylene and 26 to 35 wt% of vinyl acetate.

The acrylic acid ester is preferably an acrylic acid ester of formula (2).

CH ₂ -CR ⁸ -COOR ⁹ (2)

Wherein R ⁸ is hydrogen or methyl, and R ⁹ is C1- to C30-alkyl, preferably C4- to C16-alkyl, in particular C6- to C12-alkyl. Suitable acrylic acid esters are, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n- and isobutyl (meth) acrylate, hexyl, octyl, 2-ethylhexyl, Decyl, dodecyl, tetradecyl, hexadecyl, octadecyl (meth) acrylate and mixtures of these comonomers. In a further embodiment, the mentioned alkyl groups may be substituted by one or more hydroxyl groups. An example of such an acrylic acid ester is hydroxyethyl methacrylate.

The alkyl vinyl ether is preferably a compound of formula (3).

CH ₂ -CH-OR ¹⁰ (3)

Wherein R ¹⁰ is C1- to C30-alkyl, preferably C4- to C16-alkyl, in particular C6- to C12-alkyl. Examples include methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether. In a further embodiment, the mentioned alkyl groups may be substituted by one or more hydroxyl groups.

Alkenes are preferably monounsaturated hydrocarbons having 3 to 30 carbon atoms, in particular 4 to 16 carbon atoms, in particular 5 to 12 carbon atoms. Suitable alkenes include propene, butene, isobutylene, pentene, hexene, 4-methylpentene, octene, diisobutylene and norbornene and derivatives thereof such as methylnorbornene and vinylnorbornene. In a further embodiment, the mentioned alkyl groups may be substituted by one or more hydroxyl groups.

In some embodiments, the middle distillate flow improver (y) may comprise a terpolymer comprising ethylene, vinyl acetate and additional monomers such as long chain vinyl esters or long chain alkenes.

Some particularly preferred terpolymers, in addition to ethylene, are 1 to 23 mol%, preferably 3 to 20 mol%, in particular 8 to 15 mol% of vinyl acetate, and 0.1 to 12 mol%, in particular 0.2 to 5 mol% of vinyl acetate. Contains at least one relatively long chain and preferably branched vinyl ester, for example vinyl 2-ethylhexanoate, vinyl neononanoate or vinyl neodecanoate, the total comonomer content of the terpolymer It is preferably 8 to 21 mol%, in particular 12 to 18 mol%. Other preferred copolymers are, in addition to vinyl esters of ethylene and 8 to 18 mol% C2- to C12-carboxylic acids, also 0.5 to 30 mol%, preferably 0.5 to 10 mol% olefins such as propene, Butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene and/or norbornene.

In some embodiments, it is preferred to use a mixture of two or more of the aforementioned ethylene copolymers. More preferably, the polymers on which the mixture is based differ in at least one characteristic. For example, they may contain different comonomers or may have different comonomer content, molecular weight and/or degree of branching.

Most preferably the middle distillate flow improver (y) is a copolymer of ethylene and vinyl acetate.

Preferably the weight ratio of the wax anti-settling additive (x) to the intermediate distillate flow improver (y) present in component (b) is 10:1 to 1:10, preferably 5:1 to 1:10, more preferably Preferably it is 2:1 to 1:10, most preferably 1:1 to 1:10.

The ratio is calculated based on the active amount of all anti-settling additives (x) and all intermediate distillate flow improvers (y) present in component (b).

The additive composition of the third aspect comprises component (b) and additive (c).

The weight ratio of additive (c) to component (b) is preferably 1:100 to 1:1, more preferably 1:40 to 1:2, suitably 1:20 to 1:3.

Preferably the additive composition of the third aspect comprises a wax anti-settling additive (x), an intermediate distillate flow improver (y), and a copolymer additive (c).

Preferably the additive composition of the third aspect, based on the total active weight of (x), (y) and (c), comprises 10 to 40 parts of the wax anti-settling additive (x); 50 to 88 parts of a middle distillate flow improver (y) and 2 to 20 parts of a copolymer additive (c) (by weight).

The additive composition of the third aspect suitably further comprises a diluent or a carrier. Suitable diluents and carriers will be known to the person skilled in the art and include, for example, solvents, especially aromatic and aliphatic organic solvents and mixtures thereof.

The additive composition of the third aspect may further contain additional additives such as esters, carboxylic acids and alcohols to improve handling.

The intermediate distillate fuel composition of the fourth aspect of the present invention comprises component (a), component (b) and additive (c).

Suitably component (a) is present in the intermediate distillate fuel composition in an amount of at least 0.1 ppm, preferably at least 1 ppm, more preferably at least 10 ppm, suitably at least 30 ppm, for example at least 50 ppm do.

Suitably component (a) is present in the intermediate distillate fuel composition in an amount of at most 10000 ppm, preferably at most 1000 ppm, more preferably at most 500 ppm, for example at most 250 ppm or at most 200 ppm.

Suitably component (b) is present in the intermediate distillate fuel composition in an amount of at least 1 ppm, preferably at least 10 ppm, more preferably at least 50 ppm, suitably at least 80 ppm.

Suitably component (b) is added to the intermediate distillate fuel composition in an amount of at most 10000 ppm, preferably at most 5000 ppm, more preferably at most 1000 ppm, for example at most 500 ppm, at most 400 ppm or at most 350 ppm. exist.

Suitably the wax anti-settling additive (x) is present in the intermediate distillate fuel composition in an amount of at least 0.1 ppm, preferably at least 1 ppm, more preferably at least 5 ppm, suitably at least 10 ppm.

Suitably the wax anti-settling additive (x) is present in the intermediate distillate fuel composition in an amount of at most 10000 ppm, preferably at most 1000 ppm, more preferably at most 500 ppm, for example at most 200 ppm or at most 100 ppm. do.

Suitably the middle distillate flow improver (y) is the middle distillate in an amount of at least 0.1 ppm, preferably at least 1 ppm, more preferably at least 10 ppm, suitably at least 50 ppm, for example at least 60 ppm Present in the fuel composition.

Suitably the middle distillate flow improver (y) is added to the middle distillate fuel composition in an amount of at most 10000 ppm, preferably at most 1000 ppm, more preferably at most 500 ppm, for example at most 350 ppm or at most 300 ppm. exist.

Suitably the additive (c) is present in the intermediate distillate fuel composition in an amount of at least 0.1 ppm, preferably at least 1 ppm, more preferably at least 5 ppm.

Suitably the additive (c) is a medium distillate in an amount of at most 10000 ppm, preferably at most 1000 ppm, more preferably at most 500 ppm, suitably at most 200 ppm, for example at most 100 ppm or at most 60 ppm. Present in the fuel composition.

Components (a), (b), (x), (y) and (c) may each contain a mixture of compounds. For the avoidance of doubt, the amount refers to the total amount of additives (a), (b) (x), (y) and (c) respectively present in the composition.

Unless otherwise specified, all amounts of additives mentioned herein relate to the amount of active substance present in the composition, and all parts per million (ppm) are by weight.

In a preferred embodiment the fuel composition of the invention comprises 10 to 250 ppm, preferably 30 to 200 ppm of component (a); 40 to 400 ppm, preferably 50 to 350 ppm of component (b); And 1 to 100 ppm, preferably 5 to 60 ppm of additive (c).

The base fuel used in the present invention may include or consist of a petroleum-based intermediate distillate fuel oil. These intermediate distillate fuel oils generally boil in the range of 110°C to 500°C, for example 150°C to 400°C. The intermediate distillate fuel oil is a blend of direct and refinery streams in any ratio from the conversion unit, such as atmospheric distillate or vacuum distillate, cracked gas oil, or thermal and/or catalytic cracking and hydrocracked distillate. It may include.

The fuel composition of the present invention may comprise or consist of non-renewable Fischer-Tropsch fuels such as those described as GTL (gas liquefied) fuel, CTL (coal liquefied) fuel and OTL (oil sand liquefied). have.

The fuel composition may comprise a first generation biofuel. First generation biofuels contain, for example, esters of vegetable oils, animal fats and used cooking fats. Biofuels of this type are oils in the presence of catalysts, such as rapeseed oil, soybean oil, safflower oil, palm oil, corn oil, peanut oil, cottonseed oil, tallow, coconut oil, physic nut oil (jatropha), It can be obtained by transesterification of sunflower seed oil, used cooking oil, hydrogenated vegetable oil or any mixture thereof with an alcohol, usually a monoalcohol.

This first generation biofuel can be termed fatty acid alkyl esters (FAAE), preferably fatty acid methyl esters (FAME).

The fuel composition may comprise a second generation biofuel. Second generation biofuels are derived from renewable sources such as vegetable oils and animal fats and are often processed in refineries, often using hydrotreatments such as the H-Bio process developed by Petrobras. Second generation biofuels can be similar to petroleum fuel oil streams in terms of properties and quality, and are produced from, for example, vegetable oils, animal fats, etc., and Renewable Diesel by ConocoPhillips. As, and by Neste is a renewable fuel sold as NExBTL.

The fuel composition of the present invention may include a third generation biofuel. Third generation biofuels use gasification and Fischer-Tropsch technology and include those described as BTL (biomass liquefied) fuels. Third generation biofuels are not very different from some second generation biofuels, but aim to expand the feedstock base by utilizing whole plants (biomass).

The fuel composition may contain any or all blends of the above fuel compositions.

In some embodiments the fuel composition of the present invention may be a blended fuel comprising a biofuel and a second fuel. In such blends the biofuel may be present in an amount of 0.1% to 99% (vol/vol), preferably 0.1 to 25%. The biofuel component in such a blend may comprise a mixture of first generation biofuels and second generation biofuels. The first generation biofuels, preferably FAAE, in particular FAME, suitably contain 0.1 to 25% (vol/vol) of the fuel composition, preferably 0.1 to 20%, more preferably 0.1 to 12%, for example It provides 0.1 to 10%. The second fuel may be a petroleum based fuel oil, in particular an intermediate distillate fuel oil including non-renewable Fischer-Tropsch fuel.

All of these fuels can be used in embodiments of the present invention.

In some embodiments the fuel composition of the present invention may comprise a petroleum-based intermediate distillate fuel oil and optionally 0.1% to 25% (vol/vol) of biofuel, wherein the fuel composition is optionally 0.1% to 12% (volume) /Volume) of FAAE.

The fuel composition of the present invention may have a relatively high sulfur content, for example greater than 0.05 wt%, such as 0.1 wt%, or 0.2 wt%, 0.5 wt% or higher.

However, in a preferred embodiment the fuel has a sulfur content of at most 0.05 wt %, more preferably at most 0.035 wt% and in particular at most 0.015 wt %. Fuels with lower levels of sulfur are also suitable, such as fuels with less than 50 ppm by weight sulfur, preferably less than 20 ppm by weight sulfur, for example less than 10 ppm by weight sulfur.

The fuel composition of the present invention can be used as a fuel for transportation in automobiles, ships and boats, as a burner fuel in home heating and power generation, and as a fuel for a multipurpose stationary engine.

The fuel composition may contain one or more additional additives such as those commonly found in fuels used in the present invention. These are, for example, antioxidants, additional dispersants and/or detergents, cetane number improvers, defoamers, stabilizers, demulsifiers, defoamers, corrosion inhibitors, lubricity improvers, dyes, markers, combustion improvers and odor masking agents, and low-temperature performance agents. It contains additional additives useful to achieve the improvement.

In a preferred embodiment of the invention component (a) is

-A quaternary ammonium salt additive formed by reaction of a reaction product of a hydrocarbyl-substituted acylating agent and a compound comprising at least one tertiary amine group and a primary amine, secondary amine or alcohol group with a quaternizing agent;

-Mannich reaction product between hydrocarbyl substituted phenol, formaldehyde and polyamine; And

-Reaction product of hydrocarbyl substituted succinic acid-derived acylating agent and amine

Is selected from one or more of;

Component (b) is

-Copolymers of ethylene and vinyl acetate; And

-(I) ^{a compound containing the segment -NR 3} R ⁴ (where R ³ represents a group containing 4 to 44 carbon atoms, R ⁴ represents a hydrogen atom or a group R ³ ) and (II) 1 to 4 Reaction products of carboxylic acids having four carboxylic acid groups or acid anhydrides or acid halides thereof

Includes;

Additive (c) comprises a copolymer of vinyl acetate and a monomer of formula (D):

Wherein each of R ¹ and R ² is an alkyl group having less than 18 carbons.

In the present invention, the copolymer additive (c) improves the low temperature characteristics of the intermediate distillate fuel composition.

Preferably the additive reduces the value of ΔCP as measured by short-term sediment testing.

A number of short-term sediment tests are known. However, all of these attempts to minimize the difference (ΔCP) between the cloud point (CP) of the fuel in the bottom portion and the added fuel or base fuel in another portion.

Suitably the copolymer additive (c) provides a ΔCP of less than 5° C., preferably less than 3° C. and more preferably less than 2° C. in a short-term sediment test. A ΔCP of suitably less than 3° C., preferably less than 2° C. is provided according to the short-term sediment test protocol described in Example 2, Procedure A.

Preferably the copolymer additive (c) improves the low temperature properties of the intermediate distillate fuel composition by affecting the antagonistic interaction between components (a) and (b).

According to a fifth aspect of the invention, in an intermediate distillate fuel composition, (a) a nitrogen-containing dispersant and (b) (x) a wax anti-settling additive; (y) units of formula (A) and of formula (B) for improving the antagonistic interaction between at least one low temperature property enhancer selected from intermediate distillate flow improvers and mixtures thereof, which are not vinyl ester copolymers. The use of additive (c), which is a copolymer comprising units, is provided:

Where R is an alkyl group, and each of R ¹ and R ² is an alkyl group.

Improving the antagonistic interaction in the medium distillate fuel composition is meant to indicate that it provides an additional effect of preventing and/or inhibiting the antagonistic effect and/or countering the antagonism. Thus, the addition of the copolymer additive (c) can prevent or reduce the occurrence of negative interactions between components (a) and (b), or antagonistic interactions between components (a) and (b) It can provide an additional effect, meaning that it has no negative effect on the low temperature properties of the fuel.

Suitably the addition of the copolymer additive (c) improves the low temperature properties of the intermediate distillate fuel composition as measured by the short sediment test (SST). This test is suitably as described in Example 2, Procedure A. Suitably the improvement in performance is measured by decreasing the ΔCP value. A ΔCP of suitably less than 3° C., preferably less than 2° C. is provided according to the short-term sediment test protocol described in Example 2, Procedure A.

Therefore, the present invention further,

(a) nitrogen-containing dispersants; And

(b) (x) wax anti-settling additives; (y) at least one low temperature property enhancer selected from intermediate distillate flow improvers and mixtures thereof

The use of a copolymer additive (c) as defined herein for improving the performance in short-term sediment testing of an intermediate distillate fuel composition comprising: can be provided.

Advantageously, the copolymer additive (c) is very effective in improving the antagonistic interactions between components (a) and (b) even at low throughputs. Accordingly, the present invention can provide for the use of less than 120 ppm of copolymer additive (c) to improve the antagonistic interaction between components (a) and (b) in an intermediate distillate fuel composition.

Suitably the invention can provide for the use of less than 100 ppm of additive (c) to improve the antagonistic interaction between components (a) and (b) in intermediate distillate fuel compositions.

In some embodiments the invention may provide for the use of less than 75 ppm or less than 50 ppm of additive (c) to improve the antagonistic interaction between components (a) and (b) in an intermediate distillate fuel composition. .

The invention will now be further illustrated with reference to the following non-limiting examples.

Example

In the examples, the following additives are added to the intermediate distillate fuel:

A—Ethylene vinyl acetate copolymer comprising 30 to 32 wt% of vinyl acetate units and having a number average MW of approximately 4 to 5000, supplied in an aromatic solvent.

B-Half amide half ammonium salt reaction product formed by reaction of 2 moles of di(hydrogenated) tallow amine and 1 mole of phthalic anhydride, supplied in an aromatic solvent.

C-copolymer of vinyl acetate in a 1:1 molar ratio, and a diester of fumaric acid and tetradecanol, having a number average MW of approximately 10,000, supplied in an aromatic solvent.

D-A polyisobutylene succinimide reaction product formed by reacting a mixture of polyisobutenyl succinic anhydride having a PIB number average molecular weight of 750 and polyethylene polyamine corresponding to tetraethylenepentamine, supplied to an aromatic solvent.

E-Mannich reaction product of dodecyl phenol, formaldehyde and ethylene diamine, supplied in an aromatic solvent.

F-The imide formed by the reaction of polyisobutene-substituted succinic anhydride and dimethylamino propylamine having a PIB number average molecular weight of 1000 is then quaternized by reaction with methyl salicylate, supplied to the aromatic solvent .

G—Ethylene vinyl acetate copolymer comprising 28 wt% of vinyl acetate units and having a number average MW of approximately 3 to 4000, supplied in an aromatic solvent.

H-copolymer of vinyl acetate in a 1:1 molar ratio, and a diester of fumaric acid and tetradecanol, having a number average MW of approximately 21,000, supplied in an aromatic solvent.

I (Comparative Example)-Copolymer of α olefin and behenyl maleate, supplied in an aromatic solvent.

J (Comparative Example)-C16/18 diester of C24/26 alpha olefin maleic anhydride copolymer, supplied in an aromatic solvent.

K (Comparative Example)-C16/C18 alkyl imide of C14/C16 α olefin maleic anhydride copolymer, supplied in an aromatic solvent.

L-copolymer of vinyl acetate in a 1:1 molar ratio and a diester of fumaric acid and dodecanol, having a number average MW of approximately 30,000, supplied in an aromatic solvent.

M-copolymer of vinyl acetate in a 1:1 molar ratio and a diester of fumaric acid and dodecanol, having a number average MW of approximately 33,000, supplied in an aromatic solvent.

Example 1

The fuel composition was prepared by adding the amounts specified in Tables 4 and 5 to the fuel composition as described below.

Compositions 1 to 10 were prepared from Fuel 1, which is an intermediate distillate fuel composition having specifications corresponding to EN 590 and having the properties shown in Table 1.

Compositions 11 and 12 were prepared from fuel 2, an intermediate distillate fuel composition having the specifications corresponding to EN 590 and having the properties shown in Table 2.

Compositions 13 to 16 were blended with 7 vol% fatty acid methyl ester in Fuel 3, which is an intermediate distillate fuel composition having the specifications corresponding to EN 590 and having the properties shown in Table 3, It was prepared by providing fuel with CFPP.

Table 1-Characteristics of Fuel 1

Table 2-Characteristics of fuel 2

Table 3-Characteristics of fuel 3

Table 4

Table 5

Example 2

Fuel compositions 1 to 17 were tested according to procedure A and/or procedure B in the short-term sediment test. The results are presented in Table 6.

Procedure A

450 g of base fuel was mixed with an appropriate amount of additive and the cloud point of the treated fuel was determined. 500 ml of the treated fuel was transferred to a 500 ml graduated cylinder, cooled to the test temperature in a climate chamber or cooling bath, and then held at that temperature for 16 hours. After a period of 16 hours, the upper 80% and the lower 20% of the fuel were separated and heated to redissolve the precipitated wax. The blur points of the two parts were determined. ΔCP is reported as the difference between the cloud point of the upper 80% and the lower 20% of the fuel.

Procedure B

150 g of base fuel was mixed with an appropriate amount of additives and stored at 40° C. for 1 hour. 100 ml was transferred to a 100 ml graduated cylinder. The cloud point of the treated fuel was determined. The sample was cooled to the test temperature in a cooling bath/climate chamber and then held at that temperature for 16 hours. After a period of 16 hours, the appearance of the fuel and the amount of sediment were recorded. The upper 50% and the lower 50% of the fuel were separated, and the lower 50% was stored at 40° C. for 1 hour, and the cloud point was determined. ΔCP is recorded as the difference between the cloud point of the lower 50% portion of the fuel and the original cloud point of the treated fuel before cooling.

Table 6

Claims (16)

(a) nitrogen-containing dispersants; And
(b) (x) wax anti-settling additives; (y) at least one low-temperature property enhancer selected from intermediate distillate flow improvers and mixtures thereof, and which are not fumarate vinyl ester copolymers.
It is a method of improving the low temperature characteristics of the intermediate distillate fuel composition comprising a,
A method comprising adding to the fuel an additive (c), which is a copolymer comprising units of formula (A) and units of formula (B):

Where R is an alkyl group and each of R ¹ and R ² is an alkyl group. (a) nitrogen-containing dispersants; And
(b) (x) wax anti-settling additives; (y) at least one low-temperature property enhancer selected from intermediate distillate flow improvers and mixtures thereof, and which are not fumarate vinyl ester copolymers.
In order to improve the low temperature characteristics of the intermediate distillate fuel composition comprising a,
(c) Use of a copolymer comprising units of formula (A) and units of formula (B):

Where R is an alkyl group and each of R ¹ and R ² is an alkyl group. (b) (x) wax anti-settling additives; (y) at least one low temperature property enhancer selected from intermediate distillate flow improvers and mixtures thereof, which are not fumarate vinyl ester copolymers; And
(c) a copolymer comprising a unit of formula (A) and a unit of formula (B)
An additive composition for improving the low temperature properties of the intermediate distillate fuel composition comprising:

Where R is an alkyl group and each of R ¹ and R ² is an alkyl group. (a) nitrogen-containing dispersants;
(b) (x) wax anti-settling additives; (y) at least one low temperature property enhancer selected from intermediate distillate flow improvers and mixtures thereof, which are not fumarate vinyl ester copolymers; And
(c) a copolymer comprising a unit of formula (A) and a unit of formula (B)
Middle distillate fuel composition comprising:

Where R is an alkyl group and each of R ¹ and R ² is an alkyl group. The method, use or composition according to any one of claims 1 to 4, wherein the additive (c) is prepared by copolymerizing a vinyl ester monomer and a dialkyl fumarate monomer. The method, use or composition according to any one of claims 1 to 5, wherein R is methyl. 7. The method, use or composition of any of the preceding claims, wherein each R ¹ and R ² is an alkyl group having less than 18 carbon atoms. The method according to any one of claims 1 to 7, wherein component (a) is
(i) quaternary ammonium salt additives;
(ii) the Mannich reaction product between an aldehyde, an amine and an optionally substituted phenol;
(iii) the reaction product of a carboxylic acid-derived acylating agent and an amine;
(iv) the reaction product of a carboxylic acid-derived acylating agent and hydrazine;
(v) a salt formed by reaction of a carboxylic acid and di-n-butylamine or tri-n-butylamine;
(vi) the reaction product of a hydrocarbyl-substituted dicarboxylic acid or anhydride and an amine compound or salt comprising at least one amino triazole group; And
(vii) polyalkylene substituted amines
A method, use or composition selected from. The method according to any one of claims 1 to 8, wherein component (a) is
(i) quaternary ammonium salt additives;
(ii) the Mannich reaction product between an aldehyde, an amine and an optionally substituted phenol; And
(iii) Reaction product of carboxylic acid-derived acylating agent and amine
A method, use or composition selected from. The method according to any one of claims 1 to 9, wherein component (a) is
-A quaternary ammonium salt additive formed by reacting methyl salicylate or dimethyl oxalate with the reaction product of polyisobutylene-substituted succinic anhydride and dimethylaminopropylamine having a PIB number average molecular weight of 700 to 1300;
-Mannich reaction product of dodecylphenol, formaldehyde, and ethylene diamine or tetraethylpentamine; And
-Reaction product of polyisobutenyl substituted succinic acid/anhydride with PIB molecular weight (Mn) of 500 to 1300 and polyethylene polyamine having 1 to 9 amino groups and 1 to 8 ethylene groups
A method, use or composition selected from one or more of. The method according to any one of claims 1 to 10, wherein component (b) comprises at least one wax anti-settling additive (x) and at least one intermediate distillate flow improver (y), Use or composition. The method according to any one of claims 1 to 11, wherein component (b) is the (I) segment -NR ³ R ⁴ , wherein R ³ represents a group containing 4 to 44 carbon atoms, and R ⁴ is A method comprising a wax anti-settling additive (x) which is a reaction product of a compound containing a hydrogen atom or a group R ³ ) and (II) a carboxylic acid having 1 to 4 carboxylic acid groups or a reactive equivalent thereof. , Uses or compositions. The wax anti-settling additive (x) according to any one of claims 1 to 12, wherein component (b) is a reaction product of di(hydrogenated) tallow amine (I) and phthalic acid or acid anhydride (II) thereof. A method, use or composition comprising a. 14. The method, use or composition according to any one of claims 1 to 13, wherein component (b) comprises an intermediate distillate flow improver (y) which is a copolymer of ethylene and olefinically unsaturated compounds. The intermediate distillate flow improver (y) according to any one of claims 1 to 14, wherein component (b) contains 1 to 23 mol% of an olefinically unsaturated compound as a comonomer in addition to ethylene. Method, use or composition. (A) a nitrogen-containing dispersant and (b) (x) a wax anti-settling additive in the intermediate distillate fuel composition; (y) units of formula (A) and formula (B) for improving the antagonistic interaction between at least one low temperature property enhancer selected from intermediate distillate flow improvers and mixtures thereof, which are not fumarate vinyl ester copolymers. Use of additive (c), which is a copolymer comprising units of ):

Where R is an alkyl group, and each of R ¹ and R ² is an alkyl group.