KR101741851B1 - A method of treating a Bx fuel - Google Patents

Abstract

(i) R ¹ is 4 to 44, which represents a compound containing a carbon atom, including the -NR ¹ R ² portion of the R ² represent a hydrogen atom or R ¹ (for example, di-de-hydrogenation low amine) And (ii) an additive that is a reaction product of a carboxylic acid having 1 to 4 carboxylic acid groups, or an acid anhydride thereof or an acid chloride (e.g., phthalic acid or phthalic anhydride), to provide an improved biofuel do. The additives described prevent problems arising from settling at temperatures above the cloud point.

Description

[0001] The present invention relates to a method for treating Bx fuel,

The present invention relates to improvements in fuels derived entirely or partially from animal or vegetable oil sources. These fuels are referred to herein as Bx fuels. Bx fuel may be derived entirely from an animal or vegetable oil source (B100 fuel) or they may be mixed with fuel from other sources (e.g., a mineral source, or a synthesis source, e.g., a Fischer-Tropsch source) Or a portion of the fuel derived from an animal, vegetable, or vegetable source. For example, B20 herein is a fuel in which the animal or vegetable oil source is 20% by weight of the fuel and the other source is 80% by weight of the fuel. The ratio may be lower, for example in the case of B5 fuel.

One problem, such as a distribution system by sedimentation in such fuels and clogging of the filter in the vehicle, at temperatures above the turbidity point (CP) of the fuel typically becomes apparent in Bx fuel. The problem is found in a wide range of Bx fuel from B100 to B5.

WO 2007/076163 describes this problem and suggests that the problem of filter clogging is caused by the precipitation of crystals of styryl glycoside in the fuel derived from the biological source. Stearyl glycosides are found in plants and they are suggested to be delivered as Bx fuel.

WO 2007/076163 proposes a solution to the problem of filter clogging, i.e. the removal of styryl glycosides using an adsorbent as an additive, for example with a process of filtration or centrifugation, or both. In one embodiment, the soybean biodiesel was filtered through a layer of diatomaceous earth.

The proposal of WO 2007/076163 has the disadvantage that a separate step is required in addition to the treatment of Bx fuel using additives.

The present inventors are not limited to the description of the problem presented in WO 2007/076163. The present inventors believe that it will be more complicated, as well as to the overall glyceride content, including, for example, saturated or unsaturated, monoglycerides, diglycerides and triglycerides. The present inventors take a firm view that this problem currently found in Bx fuels is associated with Bx fuel components derived from vegetable or animal sources and is significantly different from the precipitation problems that have occurred in the past in mineral fuels. It is an object of the present invention to solve the above problems which may be accompanied by an agreed scientific explanation of its nature or cause, despite being a new problem.

The present inventors refer to the mineral fuel as purely a fuel derived from a mineral (e.g., petroleum) source. We refer to the mineral fuel components herein as mineral-derived components in the Bx fuel.

Filter clogging problems can occur at temperatures below the cloud point in minerals and other fuels. These problems have been scrutinized over the years. Have developed additives that enable the use of fuel at lower temperatures than otherwise possible.

The source of the problem of precipitation below the cloud point is the presence of constituents such as so-called "wax" (e.g., n-alkane and methyl n-alkanoate crystallized at low temperatures). This can cause the fuel to clog the filter and change it to non-flowable.

The temperature at which the fuel is clouded (cloud point-CP), the lowest temperature at which fuel can flow (pour point-PP) and the cold filter clog point (CFPP); And its changes caused by additives (ΔCP, ΔPP, ΔCFPP). Standardized tests for measuring PP and especially CP and CFPP are among the common working tools for those of skill in the art. CP and CFPP can be further described as follows:

The turbidity point (CP)

The turbidity point of the fuel is the temperature at which the turbidity of the wax crystals first appears in the liquid when the wax crystals are cooled under the conditions specified in the test method specified in ASTM D 2500.

Until recently, it was deemed that problems arising from the formation of precipitates would not occur at the turbidity point excess temperature.

Low temperature filter clogging point ( CFPP )

At temperatures below the cloud point, above the pour point, the wax crystals can reach sizes and shapes that can clog the fuel lines, screens, and filters even if the fuel is physically flowing. This problem is well recognized in the art and has a number of perceived test methods such as CFPP values (cold filter clogging points measured in accordance with DIN EN 116).

Since the haze point test was considered too pessimistic, the same test was introduced to show the sign of cold workability.

The designed low temperature flow improver (CFI) and wax deposition inhibitor additive (WASA) considerably improve the problem of settling below the turbidity point in the fuel and compare the results between the unadded fuel and the added fuel, You can study their effects by methods.

Some such additives may assist in maintaining a so-called "wax" in a solution in mineral fuel; Other additives can change their crystalline form or size to maintain filtrability and flowability despite settling.

Additives devised to solve the problem of causing precipitation below the turbidity point have been so successful that such fuels, such as CFI (with or without WASA) added properly, can be used even in cryogenic conditions. In many fuels, the CFPP value can be as low as 10-20 ° C when compared to the corresponding fuel without additive.

Additives that improve the Bx grade of CFPP, including the B100 grade, are also known, and thus the fuel treated in this way is expected to have no operational problems even at temperatures significantly below the turbidity point of the fuel.

However, as mentioned above, the problem that arises in Bx fuel is very different from the problem that can occur in mineral fuel. In particular, the precipitate causes filter clogging with Bx fuel at a temperature above the turbidity point, whereas precipitation problems in mineral fuels occur below the turbidity point, generally at much lower temperatures; The chemical properties of the precipitate are considered to be completely different. Although not completely understood as mentioned above, the source of the precipitation is considered to be an entirely different specific compound found in animal or vegetable sources but not found in mineral sources. Because the test rules described above do not predict the proper temperature at which the filter may clog in real life situations such as storage, distribution and use in vehicles and heating systems, this test rule is based on testing these settling issues in Bx fuel Inadequate.

One of the reasons for this failure is believed to be that the precipitation occurs during the period of "low temperature immersion" over several hours and is therefore not detected by tests such as turbidity or CFPP.

Critically, the sediment is not redissolved when the temperature rises again. This is very different from conventional wax depositions where the wax can easily be re-dissolved when the in-fuel dispersion is maintained, especially through the use of WASA, at turbidity point excess temperatures.

Without wishing to be bound by theory, the inventors believe that sediments that cause problems with filter clogging at turbidity point temperatures are present as minor components in B100 and are more soluble at B100 than mineral fuels and consequently Bx blends. In addition, when the polarity of the mineral fuel decreases, for example, the removal of sulfur, the solubility of this component will be much less and the problem will worsen.

Considering the difference, in the nature of these precipitation phenomena below and above the turbidity point, most of the additives developed to solve the problems arising from precipitation in the mineral fuel, below the turbidity point, arise from precipitation in Bx fuel, It does not guarantee a starting point to solve the problem arising from the fuel component derived from the vegetable oil channel. Indeed, it has been found that Bx fuel already contains additives of the type used to improve flow properties below the cloud point; It will also become clear that a new problem of higher temperature filter clogging still occurs.

However, the present inventors have recently unexpectedly discovered that there is a group of additives which are particularly effective in improving the flow characteristics of Bx fuel and hence the filterability at turbidity points exceeded. This group was already known to improve fuel flow characteristics below the turbidity point. Despite the different properties of the fuel and in particular the different properties and deposits of each problem,

(a) improve the flow characteristics of fuels having animal or vegetable origin in excess of the turbidity point,

(b) improving the flow characteristics of the fuel including the mineral fuel below the turbidity point;

The discovery of one group of additives was unexpectedly obtained.

According to one aspect of the present invention,

(i) R ¹ is a compound, and (ii) 1 to 4 carboxylic acid groups to show a group which contains from 4 to 44 carbon atoms includes a -NR ¹ R ² portion of the R ² represent a hydrogen atom or R ¹ There is provided a process for providing improved Bx fuel by the presence of an additive which is a reaction product of a carboxylic acid or an acid anhydride or an acid halide thereof.

Preferably R < ¹ > is a hydrocarbyl group or polyethoxylate or polypropoxylate group.

Preferably the R < ¹ > group is a hydrocarbyl group. Preferably the R < ^{1 >} group is predominantly a straight chain group.

The term " hydrocarbyl "as used herein refers to a group having a carbon atom attached directly to the remainder of the molecule and having predominantly aliphatic hydrocarbon character. Suitable hydrocarbyl-based groups may include non-hydrocarbon components. For example, if such non-hydrocarbyl groups do not significantly modify the overall hydrocarbon character of the group, they may contain at most one non-hydrocarbyl group for every ten carbon atoms. Those skilled in the art will know such groups including, for example, hydroxyl, halo (especially chloro and fluoro), alkoxyl, alkylmercapto, alkylsulfoxy and the like. Preferably, the R < ¹ > group is an organic group containing mainly carbon and hydrogen atoms.

The hydrocarbyl group R &^lt; ¹ > is preferably predominantly saturated, i.e. it contains no more than one carbon to carbon unsaturated bond per every number of carbon-to-carbon single bonds present (e.g., 6 to 10). In the case of the hydrocarbyl group R ¹ having 4 to 10 carbon atoms it may contain one unsaturated bond. In the case of the hydrocarbyl group R ¹ having from 11 to 20 carbon atoms, it may contain up to two unsaturated bonds. In the case of the hydrocarbyl group R ¹ having from 21 to 30 carbon atoms, up to three unsaturated bonds. And in the case of the hydrocarbyl group R ¹ having from 31 to 40 carbon atoms up to four unsaturated bonds. And in the case of the hydrocarbyl group R ¹ having from 41 to 44 carbon atoms up to five unsaturated bonds. Preferably, however, the hydrocarbyl group R &^lt; ¹ > is preferably a fully saturated alkyl group and is preferably a fully saturated n-alkyl group.

Preferably the R ¹ group contains from 6 to 36 carbon atoms, preferably from 8 to 32, preferably from 10 to 24, preferably from 12 to 22, most preferably from 14 to 20 carbon atoms.

It will be appreciated that the R < ^{1 >} group will typically comprise an element having a series of carbon atoms. Definitions C _{4 -44} ..... C _{14 -22} are not intended to indicate that all R ¹ groups must be in the above-mentioned range.

The R < ^{2 >} group, if present, is preferably as defined for R < ^{1 &} gt ;. R ¹ and R ² need not be the same. Preferably, however, R ¹ and R ² are the same.

Preferably, the species (ii) is a carboxylic acid or an acid anhydride thereof.

However, when 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 only form amine salts.

The secondary amine of the formula HNR ¹ R ² is a particularly preferred group of compounds (i). Examples of particularly preferred secondary amines include di-octadecylamine, di-cocoamine, di-hydrogenated tallow amine and methylbehenylamine. For example, amine mixtures derived from natural materials are also suitable. The preferred amine is a secondary hydrogenated tallow amine, the alkyl group thereof is derived from the about 3-5 _{wt% C 14, 30-32% C 16} , and 58-60 hydrogenated tallow fat composed of ₁₈ wt.% C wt. .

The quaternary amine of the formula [+ NR ¹ R ² R ³ R ⁴ -An] is a particularly preferred group of compounds (i). R ¹ and R ² are as defined below (but R ² is not hydrogen). R ³ and R ⁴ independently represent a C (1-4) alkyl group, preferably propyl, ethyl, or most preferably methyl. + NR ¹ R ² (CH ₃ ) ₂ represents a preferable cation. -An indicates negative ions. The anion may be any suitable species, but is preferably a halide, especially a chloride. When (i) comprises a quaternary amine, the reaction conditions can be adjusted to assist in the reaction between (i) and (ii). Preferably, the reaction conditions are adjusted by the introduction of an auxiliary base. The auxiliary base is preferably an inorganic base, such as sodium methoxide, sodium ethoxide, or sodium hydroxide. Preferably the inorganic base is a metal alkoxide or metal hydroxide. Alternatively, the quaternary amine salt may be carried out with the corresponding basic salt, for example a quaternary ammonium hydroxide or an alkoxide.

Mixtures of primary and secondary amines, such as species (i), are also preferred.

Mixtures of secondary and quaternary amines such as species (ii) are also preferred.

Preferred carboxylic acids include carboxylic acids containing 2, 3 or 4 carboxylic acid groups and acid anhydrides and acid halides thereof.

Examples of suitable carboxylic acids and their anhydrides include aminoalkylenecarboxylic acids such as nitrilotriacetic acid, propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid, and cyclic skeleton-based carboxylic acids such as pyromellitic acid, cyclo 1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid and naphthalene dicarboxylic acid, 1,4-dicarboxylic acid, And dialkyl spirobislactone. Generally, the 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 acid anhydrides or acid chlorides thereof, are preferred acids useful in the present invention. (1-4) alkoxy, halogen, C (1-4) haloalkyl, C (1-4) haloalkoxy, nitrile, -COOH, -CO-OC 1-4 substituents independently selected from alkyl, and -CONR ³ R ^{4 wherein} R ³ and R ⁴ are independently selected from hydrogen and C (1-4) alkyl. . Preferred halogen atoms are fluorine, chlorine, and bromine. However, unsubstituted benzene carboxylic acids are preferred. Phthalic acid and its acid anhydride are particularly preferred.

Preferably, the molar ratio of compound (i) to acid, acid anhydride or acid halide (ii) is at least 50% (preferably at least 75%, preferably at least 90%, and most preferably 100% for example, amide and / or amine salts, in the reaction between i) and (ii).

When compound (ii) comprises at least one free carboxylic acid group, the reaction conditions can be adjusted to enable a reaction between compounds (i) and (ii) to form, for example, an amide or amine salt, respectively . The reaction conditions can be adjusted by raising the reaction temperature. The reaction conditions can be adjusted by including a dehydrating agent in the reaction mixture. The one or more carboxylic acid groups may be activated in situ, for example, by the use of a carbodiimide (e. G. EDCI) to prepare to couple (i) and (ii). However, when the activated form of (ii) is used, the activated form of (ii) can be preferably carried out, for example, as an acid halide or an acid anhydride. Most preferred is an acid anhydride.

In the case of a preferred reaction, the reaction between compound (i) and dicarboxylic acid, or an acid anhydride or acid halide thereof, preferably compound (i) (or mixture of compound (i) Or the acid halide (ii) (or the mixed compound (ii) in other situations) is at least 0.7: 1, preferably at least 1: 1, more preferably at least 1.5: 1. Preferably it is up to 3: 1, preferably up to 2.5: 1. Most preferably it ranges from 1.8: 1 to 2.2: 1. The molar ratio of 2: 1, (i) to (ii) is particularly preferred. A molar ratio of 1: 1 is also preferred.

It will be understood by those skilled in the art that compound (ii) is defined as an initial starting material. However, preferred materials are obtained by a stepwise reaction involving the reaction of compound (i) with an adduct of compound (ii), especially when compound (ii) has already reacted with compound (i) Can be. Such intermediates may be completely isolated or partially isolated to enable a stepwise reaction. Such an intermediate can be, for example, a mono-amide / mono-carboxylic acid adduct (i) when the first equivalent of (i) in the first step is reacted with a dicarboxylic acid, an acid anhydride, . ≪ / RTI > The partial isolation may thus be an isolation of the reaction mixture resulting from the first step of the reaction to form mono-amide / mono-carboxylic acid only. In this environment, the sequential reaction of the mono-amide / mono-carboxylic acid adduct with the compound (i) (optionally the compound (i) other than that used in the first step) leads to the formation of additional derivatives, - amide / ammonium carboxylate salts. This stepwise process is particularly advantageous when the amide groups and the amines of the ammonium group are different, such as when (i) contains essentially more than one amine, a greater choice of one or both of the amide groups and / or ammonium salts .

In the case of the preferred reaction, the amine (i) to acid, acid anhydride or acid halide (ii), preferably between the secondary amine and the dicarboxylic acid, or the acid anhydride or acid halide thereof, Is at least 1: 1, preferably at least 1.5: 1. Most preferably it ranges from 1.8: 1 to 2.2: 1. The molar ratio of 2: 1, (i) to (ii) is particularly preferred.

In the case of another preferred reaction, the quaternary ammonium salt and dicarboxylic acid, or an acid anhydride or acid halide thereof, as the sole compound (i), preferably between the quaternary ammonium salt (i) and the acid, acid anhydride or acid The molar ratio of halide (ii) is at least 1: 1, preferably at least 1.5: 1. Most preferably it ranges from 1.8: 1 to 2.2: 1. The molar ratio of 2: 1, (i) to (ii) is particularly preferred.

The preferred reaction product for use in the present invention comprises at least a mono-amide adduct and a quaternary ammonium salt, which can be achieved by using a mixture of compounds, preferably a secondary amine and a quaternary ammonium compound as compound (i) have.

Another preferred reaction uses both a secondary amine and a quaternary ammonium salt as compound (i). Preferably the ratio of the secondary amine to the quaternary ammonium salt in the reaction mixture is 30-70% to 70-30% mol / mol, preferably 40-60% to 60-40%, most preferably they are in an equivalent molar amount exist. Thus, consistent with the foregoing, this reaction uses the equivalent molar amount of the secondary amine, quaternary ammonium salt and acid, acid anhydride or acid halide (ii) in the most preferred embodiment.

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

Thus, in one preferred embodiment, the dicarboxylic acid, acid anhydride, or acid halide reacts with the secondary amine in a molar ratio of 1: 2 such that one mole of the amine forms an amide and one mole forms ammonium.

A particularly preferred additive is an N, N-dialkylammonium salt of 2-N ', N'-dialkylamidobenzoic acid, which is suitably di (hydrogenated) tallow amine (i) and phthalic acid or an acid anhydride thereof ); Preferably a molar ratio of 2: 1.

Particularly preferred additives are reaction products of di (hydrogenated) tallow amine (i) and phthalic acid or an acid anhydride thereof (ii); And preferably has a molar ratio of 1: 1.

Another preferred additive is a reaction product of a (hydrogenated) tallow amine reaction with EDTA at a molar ratio of 4: 1, which forms a tetramide derivative or a diamide diammonium salt derivative, respectively, with removal of 4 moles of water or 2 moles of water to be.

Another preferred additive is the reaction product of 1 mole of mono-tallow amine and 1 mole of di-tallow amine with 1 mole of alkyl spiro bis lactone, such as dodecenyl-spirobislactone.

The fuel composition of the present invention may comprise at least 1% by weight of fuel derived from an animal or vegetable source, for example at least 2% by weight, at least 3% by weight, at least 4% by weight, at least 5% by weight, 6 wt% or more, 8 wt% or more, or 10 wt% or more. Some embodiments may comprise at least 15 wt%, or at least 20 wt%, of fuel derived from an animal or vegetable source. The fuel composition may contain up to 99% by weight of fuel derived from animal or vegetable sources, for example up to 95% by weight, up to 90% by weight, up to 85% by weight, up to 80% , Up to 70 wt%, up to 60 wt%, up to 50 wt%, up to 40 wt%, up to 30 wt%, up to 25 wt%, up to 20 wt%, up to 15 wt% or up to 12 wt% .

Fuel containing 100% of the fuel produced from an animal or vegetable source is designated as B100, fuel containing 90% mineral diesel and 10% biodiesel is known as B10; Fuel containing 50% mineral diesel and 50% biodiesel is known as B50; And so on.

Fuel of animal or vegetable origin may include ethyl or methyl esters of biological source fatty acids. Starting materials for the production of such fuels include, but are not limited to, materials comprising fatty acids. This material includes, without limitation, triacylglycerols, diacylglycerols, monoacylglycerols, phospholipids, esters, free fatty acids, or any combination thereof. The diesel is produced by incubating a material comprising a fatty acid with a short chain alcohol in the presence of heat, pressure, a catalyst, or any combination thereof to produce a fatty acid ester of a short chain alcohol.

The fatty acids used to produce the fuel may be selected from vegetable oils, canola oil, safflower oil, sunflower oil, nasturtium oil, mustard oil, olive oil, sesame oil, soybean oil, corn oil, peanut oil, , Palm kernel oil, lupine oil, jatropha oil, coconut oil, flaxseed oil, evening primrose oil, jojoba oil, camellia oil, talos, beef tallow Oil, grease, butter oil, butter fat, pork oil, dairy buttermilk, shea butter, used frying oil, miscellaneous oil, used cooking oil, yellow trap grease, ≪ / RTI > and any mixture thereof, including, but not limited to, < RTI ID = 0.0 >

Precipitates which are preferably formed at above the turbidity point and which the present invention intends to avoid are not revealed by the turbidity point test ASTM D 2500.

The precipitate, which is preferably formed above the cloud point and which the present invention is intended to prevent, is not immediately visible by simply cooling the fuel to a given temperature. Preferably they are formed after the incubation time, by maintaining the fuel at the turbidity point excess temperature during the incubation time. Preferably, the incubation time is 4 hours or more, preferably 12 hours or more, preferably 16 hours or more, preferably 48 hours or more, preferably 96 hours or more.

The precipitates which are preferably formed above the turbidity point and which the present invention is intended to prevent are not removed by simply raising the temperature of the fuel above the temperature at which they are formed.

Preferably, the Bx fuel is a middle distillate fuel and boils generally in the range of 110 to 500, e.g., 150 to 400 ° C. Bx fuel is preferably used in diesel engines or heated fuel oils.

In one embodiment, the fuel is B100. Preferably, however, the fuel is a blend of fuels and mineral sources and / or synthetic sources (e.g., FT fuels derived from a Fischer-Tropsch process) derived from animal or vegetable sources.

Preferably the fuel comprises a fuel and a non-vegetable source derived from a vegetable source; Preferably a blend of fuels derived from a mineral source.

The Bx fuel may include other flow enhancing additives to provide a general advantage in reducing CP and CFPP. Such compounds may include CFI and WASA.

Examples of their use in these additives and oil-based oils are described in US 3048479; GB 1263152; US 3961916; US 4211534; EP 153176 A; And EP 153177A.

US 3048479 describes an ethylene-vinyl ester flow inhibitor for a medium distillate. GB 1263152 describes a distillate oil oil composition comprising an ethylene ester copolymer. Preferred copolymers are ethylene and vinyl acetate. US 3961916 describes a middle distillate composition with improved filtration comprising a mixture of two different EVA copolymers. US 4211534 describes a combination of ethylene polymers, polymers with alkyl side chains, and nitrogen, including compounds that improve the low temperature flow characteristics of distillate fuel oil. EP 153176A and EP 153177A describe polymers or copolymers comprising n-alkyl esters of mono-ethylenically unsaturated C4 to C8 mono- or dicarboxylic acids.

The use of ethylene vinyl acetate copolymers as CFI with adducts of compounds (i) and (ii) as defined herein is particularly preferred.

Preferably the Bx fuel is a low sulfur containing fuel having a sulfur content of preferably less than 200 ppm, preferably less than 100 ppm, preferably less than 50 ppm, preferably less than 20 ppm, preferably less than 15 ppm, preferably less than 10 ppm.

Preferably, the additive is present from 5 mg / kg fuel in fuel, preferably from 10 mg / kg fuel, preferably from 20 mg / kg fuel, preferably from 30 mg / kg fuel (as active material).

Preferably the additive is present in the fuel up to 500 mg / kg, preferably up to 200 mg / kg fuel, preferably up to 100 mg / kg fuel, preferably up to 80 mg / kg fuel, preferably up to 60 mg / mg / kg of fuel (as active material).

The additive can be added to the Bx fuel known to exhibit filtration problems at turbidity points in excess to reduce the problem or to avoid precipitation, preferably at precipitation above the turbidity point.

Reducing or solving the above problems can be achieved by reducing the size or amount of precipitates that may appear in the Bx fuel at turbidity points, or by adjusting the shape of the precipitates in the Bx fuel at turbidity points exceeding.

Preferably, however, the additive is added to the Bx fuel to prevent the formation of precipitates at the turbidity point. Preventing the formation of precipitates at turbidity points above means that the detectable precipitates do not appear in Bx fuel under standard storage or use conditions.

According to a second aspect of the present invention, there is provided a method for maintaining the filterability of Bx fuel at an excess turbidity point of Bx fuel,

(i) R ¹ is 4 to 44 show a group which includes a carbon atom, and the compound R ² is -NR ¹ R ² include a portion indicating a hydrogen atom or R ^1, and (ii) 1 to 4 carboxylic acid groups ≪ / RTI > or an acid anhydride or an acid halide thereof.

According to a third aspect of the present invention, there is provided a method for preventing generation of a precipitate in Bx fuel at an excess turbidity point of Bx fuel,

(i) R ¹ is 4 to 44 show a group which includes a carbon atom, and the compound R ² is -NR ¹ R ² include a portion indicating a hydrogen atom or R ^1, and (ii) 1 to 4 carboxylic acid groups ≪ / RTI > or an acid anhydride or an acid halide thereof.

Preferred embodiments of the above-mentioned aspects and preferred features of the first aspect, namely preferred compounds (i) and (ii), (I) to (II) Preferred Bx fuel; And Bx The preferred concentration of the additive in the fuel can also be maintained by the method of filtration; The present invention is applied to the second and third aspects including a method in which precipitation can be controlled, suppressed or prevented.

According to a fourth aspect of the present invention,

(i) R ¹ is 4 to 44 show a group which includes a carbon atom, and the compound R ² is -NR ¹ R ² include a portion indicating a hydrogen atom or R ^1, and (ii) 1 to 4 carboxylic acid groups Wherein the Bx fuel has improved flow characteristics at a turbidity point in excess of the Bx fuel, wherein the additive is a reaction product of a carboxylic acid having an acid anhydride or an acid halide thereof.

According to a fifth aspect of the present invention,

(i) R ¹ is 4 to 44 show a group which includes a carbon atom, and the compound R ² is -NR ¹ R ² include a portion indicating a hydrogen atom or R ^1, and (ii) 1 to 4 carboxylic acid groups ≪ / RTI > or an acid anhydride thereof in a solvent.

According to a sixth aspect of the present invention there is provided a method for improving the filter clogging tendency of Bx fuel by the addition of additives as defined in any preceding paragraph.

The present invention will now be further described, by way of example, with reference to the following test descriptions.

Example  Set A

This test included the use of a modified version of the IP387 (measurement of the filter clogging tendency of gas oil and distillate diesel fuel) methods.

In the IP 387 method, a sample of the fuel to be tested is passed through the glass fiber filter medium at a constant flow rate. The pressure drop across the filter is monitored and the volume of fuel passing through the filter media is measured within a predetermined pressure drop.

The filter clogging tendency (FBT) can be described in one of the following ways:

Record the pressure drop (P) over the GF / A (glass fiber) filter media for 300 ml of fuel passing at a rate of 20 ml / min.

- When the pressure of 105 kPa is reached, the volume of fuel (v) passes. Use this reporting method when less than 300 ml passes through the pressure drop.

The FBT can be represented on a single scale by combining them using the following equation:

So when exactly 300 ml passes through the filter at a pressure of 105 kPa, the FBT is 1.41. A FBT value of greater than 1.41 means that less than 300 ml passes through the filter before reaching a pressure of 105 kPa. An FBT value of less than 1.41 means that 300 ml passes through the filter at pressures less than 105 kPa.

FBTs below 1.4 are considered good results.

Modification of the IP 387 method involves thermal conditioning and low temperature immersion of the sample to be tested.

1. The sample is heated for 3 hours at a temperature of 60 ° C and then cooled to 20 ° C.

2. Samples are then cooled to 5 ° C for 16 hours and then allowed to warm to room temperature.

Following this conditioning, the filter plugging tendency (FBT) is measured using IP 387.

The base fuel used in this test was a B5 fuel which contained a commercially available low temperature flow additive believed to contain the EVA copolymer in an amount effective to meet the requirements of DIN EN 590 and achieve CFPP of less than -15 ° C . The fuel had the following characteristics:

a) the base fuel,

b) the base fuel to which 37.5 mg / kg of Compound A has been added, and

c) the substrate fuel to which the successfully used long-lived commercial WASA (considered nitrogen-containing polymer WASA) has been added to improve the flow characteristics of the mineral diesel fuel below the turbidity point;

Were used to conduct the test.

To prepare Compound A, phthalic anhydride (7.4 g) was dissolved in 50.02 g of di (hydrogenated tallow) amine (commercially available as Armeen 2HT) and Shellsol AB solvent (57.5 g) 1: 2. The reaction mixture was heated at 65 [deg.] C for about 6 hours.

The results are as follows:

Using Compound A, all 300 ml of fuel passed through the filter without reaching a pressure of 105 kPa. The improvement in the performance of the base fuel was very clear. In contrast, commercial WASA observed that at higher processing rates, it did not show any noticeable improvement in the flow characteristics of the base fuel.

Example  Set B

In Example Set B, the test was the same as in Example Set A, except that the base fuel ("Base Fuel 2") had an EVA copolymer in an amount effective to meet the requirements of DIN EN90 and to achieve CFPP of less than -15 ° C And a B10 fuel made from standard diesel that meets the specifications of the CEC Fuel Specification RF-06-03, in which rapeseed methyl ester (RME) is blended.

The FBT of the base fuel 2 was 2.52.

The FBT of the base fuel 2 to which 37.5 mg / kg of the compound A was added was 1.03.

The FBT of the base fuel 2 to which 150 mg / kg of WASA (considered to be a nitrogen-containing polymer WASA) was added was 2.03.

Claims (16)

(i) R ¹ is a compound that includes a -NR ¹ R ² represents a section to display, and, R ² is a hydrogen atom or ^one R containing from 4 to 44 carbon atoms, and
(ii) a carboxylic acid having 1 to 4 carboxylic acid groups or an acid anhydride or acid halide thereof
Of Bx fuel to improve the filterability of Bx fuel by exceeding the turbidity point of Bx fuel by addition of the reaction product of Bx fuel,
Wherein the Bx fuel comprises a fuel derived from an animal or vegetable oil source mixed with a mineral or a fuel derived from a synthetic source, having a sulfur content of less than 200 ppm and comprising at least 4% by weight of fuel derived from an animal or vegetable oil source Including,
Wherein the additive is present in the Bx fuel in an amount of 10 mg / kg to 200 mg / kg or less (as the active material)
A method for treating Bx fuel to improve the filtration properties of Bx fuel at the turbidity point of Bx fuel. 2. The method of claim 1, wherein the R < ¹ > group is a linear saturated group comprising from 10 to 24 carbon atoms. 4. The method according to any ^{one of} claims ¹ to ³ , wherein the group R < ² > is as defined in claim 1 or 2 with respect to R &^lt; 1 >. 4. The compound of claim 3, wherein the compound (i) is a secondary amine of the formula HNR ¹ R ² wherein R ¹ and R ² are as defined in claim 3; Wherein R ¹ and R ² are as defined in claim ³ and R ³ and R ⁴ are independently an ammonium salt having a cation + NR ¹ R ² R ³ R ⁴ representing a C (1-4) alkyl group. 3. The composition of claim 1 or 2, wherein the carboxylic acid is selected from the group consisting of aminoalkylene polycarboxylic acids, dialkyl spirobislactones, and cyclic skeleton-based carboxylic acids having from 5 to 13 carbon atoms in the cyclic moiety (and its acid anhydrides and Acid halides) and the cyclic skeletal-based carboxylic acid is selected from the group consisting of pyromellitic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane- Naphthalene dicarboxylic acid, 1,4-dicarboxylic acid, and benzene dicarboxylic acid. 6. The process of claim 5, wherein the benzene dicarboxylic acid is selected from isophthalic acid, terephthalic acid, and phthalic acid (and acid anhydrides or acid halides thereof). 3. A process according to claim 1 or 2, wherein the molar ratio of compound (i) to acid anhydride or acid halide (ii) is such that at least 50% of the acid groups are allowed to react in the reaction between compounds (i) and (ii) Way. 3. The process according to claim 1 or 2, wherein the compound (i) is a secondary amine and / or a quaternary ammonium salt and the compound (ii) is a dicarboxylic acid, or an acid anhydride or an acid halide thereof, (i) the molar ratio of the diacid, acid anhydride or acid halide (ii) is at least 1: 1. 3. The method of claim 1 or 2, wherein the additive is present in the Bx fuel in an amount of from 20 mg / kg fuel to less than 80 mg / kg fuel. 3. The method of claim 1 or 2, wherein the Bx fuel is a blended fuel comprising a fuel component derived from an animal or vegetable oil source and a fuel component derived from a mineral source. 11. The method of claim 10 wherein the Bx fuel comprises at least one compound that improves fuel flow characteristics derived from a mineral source at a temperature below the turbidity point of the Bx fuel. (i) R ¹ is a compound that includes a -NR ¹ R ² represents a section to display, and, R ² is a hydrogen atom or ^one R containing from 4 to 44 carbon atoms, and
(ii) an optionally substituted benzene dicarboxylic acid or acid anhydride or acid halide thereof
Lt; RTI ID = 0.0 > Fx < / RTI > additive,
Wherein the Bx fuel has a sulfur content of less than 200 ppm and comprises at least 4% by weight of fuel derived from an animal or vegetable oil source,
Wherein the additive is present in the Bx fuel in an amount of from 10 mg / kg to 200 mg / kg or less (as the active material) to provide improved filtration of Bx fuel in excess of the turbidity point of Bx fuel.
Bx fuel. 6. The process according to claim 5, wherein the aminoalkylene polycarboxylic acid is nitrilotriacetic acid, propylene diamine tetraacetic acid or ethylenediaminetetraacetic acid. delete delete delete