Compositions, methods and uses

Abstract

A fuel composition comprising a middle distillate fuel oil obtained from distillation of pyrolysis oil and, as an additive, one or more of: (a) an antioxidant; and (b) a stabilizing additive selected from the group consisting of (x) alkoxylated amine compounds; (y) an aldehyde-alkylphenol copolymer; (z) an acylated nitrogen compound; and mixtures thereof. Also disclosed are methods and uses for improving the stability of a fuel composition comprising a middle distillate fuel oil obtained from the distillation of pyrolytic oil comprising the addition to the composition of one or more additives selected from (a) and (b).

Description

[0001] The present invention relates to fuel compositions derived from plastic pyrolysis oils and methods and uses thereof. In particular, the present invention relates to additives for improving the stability of fuel compositions derived from plastic pyrolysis oils.

[0002] Pyrolysis oil is a fluid produced directly from the pyrolysis of waste, such as plastic waste, biomass such as agricultural waste, forestry waste, waste cooking oil, algae waste, scrap tires, or scrap rubber. Examples of waste plastics that can be pyrolyzed to produce plastic pyrolysis oil include low-density polyethylene, high-density polyethylene, ultra-high-density polyethylene, polypropylene, polystyrene, polyethylene terephthalate (PET), rubber (e.g., from tires), polyacrylates, and polynitriles.

[0003] Processing waste plastics to provide pyrolysis oil typically involves first grinding the plastic and then optionally melting it, for example at about 200°C. The molten plastic can optionally be further processed, for example by passing it through a heated screw heater before heating it at a temperature of 400 to 600°C in the absence of oxygen, which causes thermal decomposition of the plastic. The resulting mixture can then be contacted with a suitable catalyst. The mixture is then condensed to produce crude plastic pyrolysis oil, which may also be referred to as synthetic crude oil. The crude plastic pyrolysis oil can be sold as crude oil or processed in a refinery to provide finished fuel. At the refinery, the pyrolysis oil can optionally be washed to remove char and reduce its metal content. The various processing steps and temperatures used depend on the nature of the plastic feedstock.

[0004] Refining the optionally washed crude plastic pyrolysis oil involves heating the oil in a distillation column and collecting the desired fractions. This can be done on-site at the production site of the crude plastic pyrolysis oil, or in a separate refinery. The diesel fuel fraction typically constitutes about a quarter of the distillate obtained from this refining of the crude plastic pyrolysis oil.

[0005] Although the fuel obtained from the distillation of crude pyrolysis oil has the same boiling point range as the middle distillate fuel obtained from mineral sources, the chemical composition of the distillate fuel oil obtained is completely different.

[0006] Fuels obtained from the fractionation of crude oil typically contain high levels of sulfur and aromatic compounds. These fuels usually require hydrotreating before use.

[0007] The fuels obtained from the fractionation of plastic pyrolysis oils generally have a much lower proportion of sulfur compounds than those obtained from the fractionation of crude oil. This means that hydrotreatment is not always necessary and the straight run distillate fractions can be used directly in internal combustion engines, such as diesel engines, especially diesel engines with high pressure fuel systems. Suitably, such diesel engines have a pressure of more than 1350 bar (1.35 x 10 8Pa). Diesel engines can have fuel pressures up to 2000 bar (2x10 8 However, because the chemical composition of the fuels obtained from plastic pyrolysis oil is very different from that of fossil-derived fuels, the stability of these fuels is different.

[0008] Additive is usually added in the fuel to reduce or prevent sedimentation and / or oxidation during storage.Different fuels degrade in different ways, for example, by heat, oxidation, polymerization or condensation pathways.The sediment or sediment that can form in the fuel derived from pyrolysis oil when storing or at low temperatures is different from the sediment or sediment that forms in mineral oil derived fuels.In addition, the amount and type of the straight chain alkane compound (paraffin) contained in the fuel obtained from pyrolysis oil can be significantly different from the fuel obtained from mineral oil.This means that the additive that is used for example to provide stability in mineral distillate fuel is not necessarily effective in the fuel obtained from the distillation of pyrolysis oil.In order to be able to make full use of this fuel, it is necessary to provide stabilizing additive to guarantee that this fuel meets required standard, especially ASTM D975.

[0009] The present inventors have discovered that certain compounds are effective in reducing sedimentation and / or improving the stability of fuel compositions obtained from distillation of pyrolysis oil.

[0010] According to a first aspect of the present invention, there is provided a fuel composition comprising a middle distillate fuel oil obtained from the distillation of a pyrolysis oil and one or more of the following as additives: (a) antioxidants; and (b) a stabilizing additive selected from the group consisting of (x) alkoxylated amine compounds; (y) aldehyde-alkylphenol copolymers; (z) acylated nitrogen compounds; and mixtures thereof.

[0011] A first aspect of the present invention relates to a fuel composition comprising a middle distillate fraction obtained from the distillation of pyrolysis oil.

[0012] Pyrolysis oil can be obtained from the pyrolysis of any type of waste. The composition of the pyrolysis oil and its properties, as well as the fraction of distillates obtained therefrom, will depend on the type of waste being pyrolyzed and the pyrolysis conditions. For example, pyrolysis oil can be obtained from the pyrolysis of plastic waste, agricultural waste, forestry waste, waste cooking oil, algae waste, waste tires, and rubber waste.

[0013] Preferably, the pyrolysis oil comprises plastic pyrolysis oil.Plastic pyrolysis oil can be obtained from the pyrolysis of any type of plastic.

[0014] Preferred plastic pyrolysis oils are obtained from the pyrolysis of one or more polymers selected from the group consisting of low density polyethylene, high density polyethylene, ultra high density polyethylene, polypropylene, PET, polyacrylates, polynitrile and mixtures thereof.

[0015] The fuel composition of the present invention comprises a middle distillate fuel oil obtained from the distillation of pyrolysis oil, preferably plastic pyrolysis oil. Suitably, the middle distillate oil boils in the range of 110°C to 500°C, preferably 150°C to 400°C.

[0016] Fuel composition of the present invention is suitable for use as diesel fuel oil.Preferably, fuel composition conforms to ASTM D975.The fuel component of fuel composition can be made up of the middle distillate fuel oil obtained from pyrolysis oil basically, or it can comprise co-blended fuel, this co-blended fuel comprises from pyrolysis oil, the distillate oil that preferably plastics pyrolysis oil obtains and one or more other middle distillate components, for example one or more other middle distillate components that obtain from mineral and / or renewable source.Also can comprise the fuel component that obtains from other synthetic source.

[0017] The middle distillate fuel oil obtained from the pyrolysis oil may optionally be hydrotreated and / or treated using a cracking process.However, due to the generally low aromatics and sulphur content of the middle distillate fuel oil obtained from the pyrolysis oil, straight run distillates may be used.

[0018] In some embodiments, the fuel composition of the first aspect comprises a straight run middle distillate obtained directly from the distillation of pyrolysis oil without further treatment.

[0019] In some embodiments, the fuel composition of the first aspect may comprise a blended fuel oil comprising a middle distillate fuel oil obtained from the fractionation of plastic pyrolysis oil and one or more fuel oils obtained from hydrocarbon and / or renewable sources.

[0020] The fuel composition may comprise a petroleum-based fuel oil, particularly a middle distillate fuel oil. Such distillate fuel oils typically boil in the range of 110-500° C., for example 150-400° C. The middle distillate fuel oil may comprise atmospheric or vacuum distillates, cracked gas oils, or a blend of straight run and refinery streams (e.g., thermally and / or catalytically cracked and hydrocracked distillates) in any proportion.

[0021] The fuel composition may comprise non-renewable Fischer-Tropsch fuels, such as those described as GTL (gas-to-liquids) fuels, CTL (coal-to-liquids) fuels, and OTL (oil sands-to-liquids).

[0022] The fuel composition may comprise a renewable fuel, such as a biofuel composition or a biodiesel composition.

[0023] Fuel composition can comprise first generation biodiesel.First generation biodiesel contains esters of for example vegetable oils, animal fats and waste cooking fats.This form of biodiesel can be obtained by transesterification of oil (for example rapeseed oil, soybean oil, safflower oil, palm oil, palm kernel oil, corn oil, peanut oil, cottonseed oil, tallow, coconut oil, jatropha oil (Jatropha), sunflower oil, waste cooking oil, hydrogenated vegetable oil or its any mixture) with alcohol (normally monohydric alcohol) in the presence of a catalyst.

[0024] The fuel composition can comprise second generation biodiesel. Second generation biodiesel is derived from renewable sources, such as vegetable oils and animal fats, and is typically processed in refineries using hydrotreating, such as the H-Bio process developed by Petrobras. Second generation biodiesel can be similar to petroleum-based fuel oil streams in nature and quality, such as the renewable diesel produced by vegetable oils, animal fats, etc. and sold by ConocoPhillips as Renewable Diesel and by Neste as NExBTL.

[0025] The fuel composition of the present invention may comprise third generation biodiesel. Third generation biodiesel utilizes gasification and Fischer-Tropsch technology, including those described as BTL (biomass to liquid) fuels. Third generation biodiesel is not very different from some second generation biodiesels, but aims to utilize the whole plant (biomass), thereby broadening the raw material base.

[0026] The fuel composition may contain a blend of any or all of the above diesel fuel oils.

[0027] In some embodiments, the fuel composition comprises a blended fuel comprising 5 to 10% by volume of a middle distillate fuel oil obtained from distillation of a pyrolysis oil and 90 to 95% by volume of one or more fuel oils obtained from hydrocarbon and / or renewable sources.

[0028] Fuel composition of the present invention comprises the middle distillate fuel oil obtained from the distillation of pyrolysis oil.This component of fuel composition comprises paraffin.Preferably, at least 50 weight % of the paraffinic compounds present in this component of fuel composition (that is, the middle distillate fuel oil obtained from the distillation of pyrolysis oil), preferably at least 60 weight %, suitably at least 70 weight %, for example at least 80 weight % have at least 18 carbons.

[0029] In a preferred embodiment, the fuel composition has a sulphur content of at most 0.05 wt %, more preferably at most 0.035 wt %, especially at most 0.015 wt %. Fuels with even lower levels of sulphur are also suitable, for example having a fuel content by weight of less than 50 ppm, preferably less than 20 ppm, for example 10 ppm or less sulphur.

[0030] The fuel composition of the first aspect comprises one or more of (a) an antioxidant and (b) a stabilizing additive.

[0031] In some embodiments, the composition of the first aspect comprises (a) an antioxidant. A mixture of two or more antioxidants may be present.

[0032] In some embodiments, the composition of the first aspect comprises (b) a stabilizing additive.

[0033] In some embodiments, the composition of the first aspect comprises (a) an antioxidant and (b) a stabilizing additive.

[0034] The stabilizing additive may comprise (x) an alkoxylated amine compound, (y) an aldehyde-alkylphenol copolymer, (z) an acylated nitrogen compound, or a mixture thereof.

[0035] In some embodiments, the composition of the first aspect comprises (b) a stabilizing additive comprising (x) an alkoxylated amine compound.

[0036] In some embodiments, the composition of the first aspect comprises (b) a stabilizing additive comprising (y) an aldehyde-alkylphenol copolymer.

[0037] In some embodiments, the composition of the first aspect comprises (b) a stabilizing additive comprising (z) an acylated nitrogen compound.

[0038] In some preferred embodiments, the composition of the first aspect comprises (b) a stabilizing additive comprising (x) an alkoxylated amine compound and (y) an aldehyde-alkylphenol copolymer.

[0039] In some embodiments, the composition of the first aspect comprises (b) a stabilizing additive comprising (x) an alkoxylated amine compound and (z) an acylated nitrogen compound.

[0040] In some embodiments, the composition of the first aspect comprises (b) a stabilizing additive comprising (y) an aldehyde-alkylphenol copolymer and (z) an acylated nitrogen compound.

[0041] In some embodiments, the composition of the first aspect comprises (b) a stabilizing additive comprising (x) an alkoxylated amine compound, (y) an aldehyde-alkylphenol copolymer, and (z) an acylated nitrogen compound.

[0042] In some embodiments, the composition of the first aspect comprises (a) an antioxidant and (b) a stabilizing additive comprising (x) an alkoxylated amine compound.

[0043] In some embodiments, the composition of the first aspect comprises (a) an antioxidant and (b) a stabilizing additive comprising (y) an aldehyde-alkylphenol copolymer.

[0044] In some embodiments, the composition of the first aspect comprises (a) an antioxidant and (b) a stabilizing additive comprising (z) an acylated nitrogen compound.

[0045] In some preferred embodiments, the composition of the first aspect comprises (a) an antioxidant and (b) a stabilizing additive comprising (x) an alkoxylated amine compound and (y) an aldehyde-alkylphenol copolymer.

[0046] In some preferred embodiments, the composition of the first aspect comprises (a) an antioxidant and (b) a stabilizing additive comprising (x) an alkoxylated amine compound and (z) an acylated nitrogen compound.

[0047] In some embodiments, the composition of the first aspect comprises (a) an antioxidant and (b) a stabilizing additive comprising (y) an aldehyde-alkylphenol copolymer and (z) an acylated nitrogen compound.

[0048] In some preferred embodiments, the composition of the first aspect comprises (a) an antioxidant and (b) a stabilizing additive comprising (x) an alkoxylated amine compound, (y) an aldehyde-alkylphenol copolymer, and (z) an acylated nitrogen compound.

[0049] Suitable antioxidants for use herein include phenolic antioxidants and nitrogen-containing antioxidants.

[0050] In some preferred embodiments, the fuel composition of the first aspect comprises a phenolic antioxidant.

[0051] In some embodiments, the fuel composition of the first aspect comprises a nitrogen-containing antioxidant and a phenolic antioxidant.

[0052] Any suitable phenolic antioxidant may be used. Suitable antioxidants will be known to those skilled in the art.

[0053] A phenolic antioxidant compound is any compound that includes a phenolic moiety, i.e., a benzene ring substituted with a hydroxyl group. This can be a very simple compound, such as benzenediol, an alkyl-substituted phenol, or benzenetriol. Alternatively, a phenolic antioxidant can be part of a more complex molecule. It can include two phenolic moieties, for example, as disclosed in US 2006 / 0219979.

[0054] Phenolic antioxidant compounds suitable for use in the present invention include those of formula (I): where R 1is selected from optionally substituted alkyl or alkenyl, aryl, aralkyl; ester, carboxylic acid, aldehyde, ketone, ether, alcohol, amine or amide; R 2 and R 3 are independently selected from hydrogen, optionally substituted alkyl or alkenyl groups, aryl groups, ester groups, ketones, aldehydes, carboxylic acids, ethers, alcohols, amines, or amides; and n is an integer from 1 to 5.

[0055] Preferred R 1 is an alkyl group, preferably having 1 to 9 carbon atoms, and may be straight chain or branched. 1 is selected from methyl, ethyl, isopropyl and tert-butyl. 1 and R 2 They may be taken together to form a cyclic substituent, an alkyl group or an aryl group. 2 and R 3 Preferably, it is hydrogen or an alkyl group having 1 to 9 carbon atoms. 2 and R 3 n is independently selected from hydrogen, methyl, ethyl, tert-butyl and isopropyl. Preferably n is 1, 2 or 3.

[0056] Preferred phenolic antioxidant compounds for use in the present invention are substituted benzene compounds having one or more hydroxyl substituents. Examples include tert-butylhydroquinone (TBHQ or MTBHQ), 2,5-di-tert-butylhydroquinone (DTBHQ), pyrogallol, pyrocatechol, 2,6-di-tert-butyl-4-methylphenol (BHT), 2,6-di-tert-butylphenol, propyl gallate, and tert-butylcatechol.

[0057] One particularly preferred phenolic antioxidant for use herein is 2,6-di-tert-butylphenol. However, as will be appreciated by those skilled in the art, commercial sources of this compound typically include mixtures comprising tert-butylphenol and tri-tert-butylphenol.

[0058] Suitable nitrogen-containing antioxidants include aromatic amines, hindered amines, N-oxides, polyalkylene polyamines, phenylenediamines, substituted hydroxylamines, and mixtures thereof.

[0059] Suitable aromatic amines include diaminobenzenes and alkylated diaminobenzenes, especially dialkylated and trialkylated diaminobenzenes, such as p-phenylenediamine, 3,5-diethyltoluene-2,4-diamine; 3,5-diethyltoluene-2,2-diamine; 2,4,6-triethylbenzene-2,6-diamine, alkylated diphenylamines; diphenylamines and alkylated diphenylamines, such as N,N-diphenyl-1,4-phenylenediamine; and naphthylamines, such as N-phenyl-1-naphthylamine and N-phenyl-2-naphthylamine.

[0060] Suitable hindered amines include aliphatic secondary and tertiary amines, such as dimethylcyclohexylamine and diethylhydroxylamine.

[0061] Suitable N-oxides include (2,2,6,6-tetramethylpiperidin-1-yl)oxy (TEMPO) and its derivatives.

[0062] Preferably, the one or more nitrogen-containing antioxidants (a) are selected from: (i) phenylenediamine; (ii) substituted hydroxylamines; and (iii) mixtures thereof.

[0063] Some preferred phenylenediamine antioxidants (i) suitable for use in the present invention include those of the formula: where R 1 、R 2 、R 3 、R 4 、R 5 、R 6 and R 7 R is independently selected from hydrogen, optionally substituted alkyl, alkenyl, aryl, alkaryl or aralkyl, ester, carboxylic acid, aldehyde, ketone, ether, alcohol, amine or amide. 1 is hydrogen. 3 is hydrogen. 2 is an alkyl group, preferably having 1 to 10 carbon atoms. More preferably, R 2 is an alkyl group having 1 to 5 carbon atoms. 2 is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl. 2 is isopropyl or sec-butyl. 4 is an alkyl group, preferably having 1 to 10 carbon atoms. More preferably, R 4 is an alkyl group having 1 to 5 carbon atoms. 4 It is preferably selected from methyl, ethyl, propyl, isopropyl, sec-butyl, butyl, tert-butyl and isobutyl. 4 is isopropyl or sec-butyl.

[0064] R 5 、R 6 and R 7 Preferably, R is selected from hydrogen or an alkyl group, more preferably selected from hydrogen and an alkyl group having 1 to 10 carbon atoms, more preferably selected from hydrogen and an alkyl group having 1 to 5 carbon atoms. 5 、R 6 and R 7 are independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl and isobutyl. 5 is hydrogen. Most preferably R 6 is hydrogen. Most preferably R 7 It's hydrogen.

[0065] In a particularly preferred embodiment, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 and R 7 Each is hydrogen, and component (i) comprises p-phenylenediamine.

[0066] Component (i) may comprise a mixture of compounds and / or a mixture of isomers.

[0067] Preferred substituted hydroxylamine compounds (ii) for use herein are compounds of the formula R2NOH, wherein at least one R group is an optionally substituted hydrocarbyl group. Another R group may be hydrogen. Preferably, each R is an optionally substituted hydrocarbyl group. Each R may be the same or different. Preferably, each R is the same.

[0068] Preferably, each R is an optionally substituted alkyl or alkenyl group, preferably having 1 to 12 carbon atoms, suitably 1 to 10 or 1 to 8 carbon atoms, for example 1 to 6, preferably 1 to 4 carbon atoms. Preferably, each R is an alkyl group. Each R may be a substituted alkyl group, for example a hydroxy-substituted alkyl group. Preferably, each R is an unsubstituted alkyl group or a hydroxyalkyl group. More preferably, each R is an unsubstituted alkyl group. The alkyl chain may be straight or branched. Preferably, each R is selected from methyl, ethyl, propyl and butyl, including isomers thereof. Most preferably, each R is ethyl.

[0069] Preferably component (ii) comprises diethylhydroxylamine.

[0070] Component (ii) may comprise a mixture of compounds and / or a mixture of isomers.

[0071] In some embodiments, the fuel composition of the first aspect includes (i) phenylenediamine.

[0072] In some embodiments, the fuel composition of the first aspect includes (ii) a substituted hydroxylamine.

[0073] In some embodiments, the fuel composition of the first aspect comprises (i) a phenylenediamine and (ii) a substituted hydroxylamine.

[0074] The fuel composition of the first aspect may comprise (b) a stabilizing additive selected from (x) an alkoxylated amine compound, (y) an aldehyde-alkylphenol copolymer, (z) an acylated nitrogen compound, or a mixture thereof.

[0075] Stabilizing additives refer to components that improve the stability of a fuel composition, such as its storage or oxidative stability, or that aid in the dispersion of solids, waxes or high molecular weight gums within the fuel composition. Suitable stabilizing additives are known in the art as dispersants.

[0076] In some embodiments, the composition of the first aspect may comprise (x) an alkoxylated amine compound.

[0077] The fuel composition may include any alkoxylated amine compound. This means any compound comprising an amine functionality that has been reacted with at least one alkylene oxide moiety.

[0078] In a preferred embodiment, the alkoxylated amine compound includes more than one alkylene oxide residue.

[0079] Suitable alkylene oxide residues include ethylene oxide residues, propylene oxide residues, butylene oxide residues, and mixtures thereof.

[0080] Preferably, the alkoxylated amine compound comprises ethylene oxide residues, propylene oxide residues, or mixtures thereof.

[0081] Preferably, the alkoxylated amine compound is an alkoxylated amine, an alkoxylated diamine or an alkoxylated polyamine.

[0082] Some preferred alkoxylated amine compounds for use herein have the formula A-(RO) n -H, wherein A is the residue of an amine, and RO is the residue of an alkylene oxide, and n is at least 1.

[0083] R is preferably ethylene, propylene or butylene. R can be n-propylene or n-butylene or isopropylene or isobutylene. For example, R can be -CH2CH2-, -CH2CH(CH3)-, -CH2C(CH3)2, -CH(CH3)CH(CH3)- or -CH2CH(CH2CH3)-.

[0084] R may comprise a mixture of isomers. For example, when R is propylene, the polyol may comprise the moieties -CH2CH(CH3)- and -CH(CH3)CH2- in any order within the chain.

[0085] Each R may be the same or different. R may comprise a mixture of different groups, such as ethylene, propylene or butylene units. In such an embodiment, block copolymer units are preferred.

[0086] Preferably, R is ethylene and / or propylene. More preferably, R is -CH2CH2- or -CH(CH3)CH2-.

[0087] In some preferred embodiments, the alkoxylated amine compound (i) comprises a mixture of ethylene oxide residues and propylene oxide residues.

[0088] n is at least 1. Preferably n is 5-1000, preferably 5-500, more preferably 10-400, more preferably 15-300, preferably 20-250, suitably 30-200, preferably 50-150.

[0089] A is the residue of an amine. Suitably, A is the residue of an amino compound or a polyamino compound having at least one NH group. Suitable amino compounds include primary or secondary monoamines having a hydrocarbon substituent having from 1 to 30 carbon atoms or a hydroxy-substituted hydrocarbon substituent having from 1 to about 30 carbon atoms.

[0090] Preferably, A is the residue of a polyamine.

[0091] The polyamine may be selected from any compound comprising two or more amine groups. Preferably, the polyamine is a (poly)alkylenepolyamine (which means alkylenepolyamine or polyalkylenepolyamine; in each case including diamine within the meaning of "polyamine"). Preferably, the polyamine is a (poly)alkylenepolyamine in which the alkylene component has 1 to 6, preferably 1 to 4, most preferably 2 to 3 carbon atoms. Most preferably, the polyamine is a (poly)ethylenepolyamine (i.e., ethylenepolyamine or polyethylenepolyamine).

[0092] Preferred polyamines have 2 to 15 nitrogen atoms, preferably 2 to 10 nitrogen atoms, more preferably 2 to 8 nitrogen atoms.

[0093] The polyamines can, for example, be chosen from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexethyleneheptamine, heptaethyleneoctamine, propane-1,2-diamine, 2(2-amino-ethylamino)ethanol, N',N'-bis(2-aminoethyl)ethylenediamine (N(CH2CH2NH2)3), diphenyl 4,4'-diamine, diaminonaphthalene, phenylenediamine, xylenediamine, 1,2-diaminopropane and 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane and 1,6-diaminohexane.

[0094] Most preferably A is the residue of ethylenediamine.

[0095] In some preferred embodiments, the alkoxylated amine compound (x) comprises a compound of formula (II): wherein EO represents an ethylene oxide residue, PO represents a propylene oxide residue, and at least one of a, b, c, d, e, f, g, and h is not 0. Compounds of formula (II) can be prepared by reacting ethylenediamine with ethylene oxide and propylene oxide (when both are present) in any combination and in any order, i.e., so as to provide compounds of formula (II) in which the ethylene oxide and propylene oxide residues may be present in any combination and in any order of bonding to the nitrogen of the amine group.

[0096] Preferably, a, b, c, d, e, f, g and h are each at least 1. Preferably, the sum of a, b, c, d, e, f, g and h is from 10 to 500, preferably from 20 to 250, more preferably from 40 to 200.

[0097] The skilled person will appreciate that the polymeric compound of formula (II) is typically in the form of a mixture.

[0098] Some suitable alkoxylated amine compounds for use herein are described in US Pat. No. 6,838,422.

[0099] In some embodiments, the composition of the first aspect may comprise (y) an aldehyde-alkylphenol copolymer.

[0100] Any suitable aldehyde-alkylphenol copolymer may be used, and such compounds are known to those skilled in the art.

[0101] Preferably, the aldehyde used to prepare the aldehyde-alkylphenol copolymer is selected from formaldehyde or its reactive equivalents, such as paraformaldehyde, C2-C 10 Aldehydes and aromatic aldehydes, such as benzaldehyde.

[0102] Preferred aldehyde-alkylphenol copolymers are copolymers of formaldehyde and alkylphenol. Preferably, the phenol is monosubstituted with an alkyl group, preferably in the para position. Preferred alkyl groups have 1 to 40 carbon atoms, preferably 2 to 36 carbon atoms, more preferably 4 to 30 carbon atoms, for example 6 to 24 carbon atoms.

[0103] In some embodiments, the alkylphenol is a polyisobutenyl (PIB) substituted phenol.

[0104] Polyisobutenyl (PIB) substituted phenols include a hydrocarbyl chain having the following repeating units: .

[0105] Poly(isobutylene) is prepared by the addition polymerization of isobutylene (CH3)2C=CH2. Each molecule of the resulting polymer will contain a single olefin moiety.

[0106] Conventional polyisobutenes and so-called "highly reactive" polyisobutenes are suitable for preparing the additive (y) of the present invention. Highly reactive polyisobutenes are defined herein as polyisobutenes in which at least 50%, preferably 70% or more, of the terminal olefinic double bonds are of the vinylidene type as described in EP 0 565 285. Particularly preferred polyisobutenes are those having greater than 80 mol % and up to 100 mol % of terminal vinylidene groups, such as those described in EP 1 344 785.

[0107] Methods for preparing polyalkylene-substituted phenols, such as polyisobutylene-substituted phenols, are known to those skilled in the art and include the method described in EP831141.

[0108] The hydrocarbyl substituent of the PIB substituent preferably has an average molecular weight of from 200 to 3000. Preferably, it has a molecular weight of at least 225, suitably at least 250, preferably at least 275, suitably at least 300, for example at least 325 or at least 350. In some embodiments, the hydrocarbyl substituent of component (c) has an average molecular weight of at least 375, preferably at least 400, suitably at least 475, for example at least 500.

[0109] In some embodiments, the phenol may include a PIB substituent having an average molecular weight of at most 2800, preferably at most 2600, eg, at most 2500 or at most 2400.

[0110] In some embodiments, the phenol may include a PIB substituent having an average molecular weight of 400 to 2500, such as 450 to 2400, preferably 500 to 1500, suitably 550 to 1300.

[0111] In some embodiments, the phenol may include a PIB substituent having an average molecular weight of 200 to 600.

[0112] In some embodiments, the phenol may include a PIB substituent having an average molecular weight of 500 to 1000.

[0113] In some embodiments, the phenol may include a PIB substituent having an average molecular weight of 700 to 1300.

[0114] In some embodiments, the phenol may include a PIB substituent having an average molecular weight of 1000 to 2000.

[0115] In some embodiments, the phenol may include a PIB substituent having an average molecular weight of 1700 to 2600, such as 2000 to 2500.

[0116] In some preferred embodiments, the aldehyde-alkylphenol copolymer (y) has structure (III) or (IV): wherein R is hydrogen or alkyl and n is at least 1.

[0117] Preferably, n is 2-12, preferably 5-9; and R is C3-C24-alkyl, preferably C4-C12-alkyl, in particular isononyl, isobutyl or pentyl, C6-C12-aryl or -hydroxyaryl or C7-C12-aralkyl.

[0118] As will be appreciated by those skilled in the art, aldehyde-alkylphenol copolymers can be prepared from mixtures of monomers, particularly compounds wherein R comprises a mixture of alkyl groups. Additional suitable aldehyde-alkylphenol copolymers for use herein include compounds of formula (III) wherein the terminal phenol group is further functionalized, for example by reaction with a fatty acid or an amine and an aldehyde via a Mannich reaction. Compounds of this type are described, for example, in US 2007 / 221539.

[0119] Preferably, the aldehyde-alkylphenol copolymer has a number average molecular weight of 500 to 20,000, preferably 1,000 to 10,000, more preferably 1,500 to 5,000, for example 2,000 to 3,500.

[0120] In some embodiments, the composition of the first aspect may comprise (z) an acylated nitrogen compound.

[0121] Suitable acylated nitrogen compounds (z) can be prepared by reacting a carboxylic acid acylating agent with an amine and are known to those skilled in the art. In such compounds, the acylating agent is linked to the amino compound via an imino, amido, amidine or acyloxyammonium bond.

[0122] Preferred acylated nitrogen-containing compounds are hydrocarbyl substituted. The hydrocarbyl substituent may be in the carboxylic acid acylating agent-derived portion of the molecule or in the amine-derived portion of the molecule, or both. However, it is preferably in the acylating agent portion. One preferred class of acylated nitrogen-containing compounds suitable for use in the present invention is those formed by reacting an acylating agent having a hydrocarbyl substituent of at least 8 carbon atoms with a compound containing at least one primary or secondary amine group.

[0123] The acylating agent may be a mono- or polycarboxylic acid (or a reactive equivalent thereof), such as a substituted succinic, phthalic or propionic acid or anhydrides thereof.

[0124] Suitable hydrocarbyl-substituted acylating agents and methods for their preparation are well known in the art.

[0125] Examples of hydrocarbyl-based substituents containing at least 8 carbon atoms are n-octyl, n-decyl, n-dodecyl, tetrapropenyl, n-octadecyl, oleyl, chlorooctadecyl, triacontyl, and the like. Hydrocarbyl-based substituents can be made from homopolymers or interpolymers (e.g., copolymers, terpolymers) of mono- and di-olefins having 2 to 10 carbon atoms, such as ethylene, propylene, butene-1, isobutylene, butadiene, isoprene, 1-hexene, 1-octene, and the like. Preferably, these olefins are 1-mono-olefins.

[0126] As used herein, the term "hydrocarbyl" refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly aliphatic hydrocarbon character.

[0127] The hydrocarbyl-based substituents are preferably predominantly saturated, that is, they contain no more than one carbon-carbon unsaturated bond for every ten carbon-carbon single bonds present. Most preferably, they contain no more than one carbon-carbon non-aromatic unsaturated bond for every 50 carbon-carbon bonds present.

[0128] The hydrocarbyl substituent in such an acylating agent preferably contains at least 10, more preferably at least 12, for example at least 30 or at least 40 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) of 170-2800, for example 250-1500, preferably 500-1500, and more preferably 500-1100. An Mn of 700 to 1300 is particularly preferred. In a particularly preferred embodiment, the hydrocarbyl substituent has a number average molecular weight of 700-1000, preferably 700-850, for example 750.

[0129] The carboxylic acid-derived acylating agent may comprise a mixture of compounds. For example, a mixture of compounds having different hydrocarbyl substituents may be used. In some embodiments, the acylating agent may have more than one hydrocarbyl substituent. In such embodiments, each hydrocarbyl substituent may be the same or different.

[0130] A preferred hydrocarbyl-based substituent is polyisobutylene. Such compounds are known to those skilled in the art.

[0131] The 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.

[0132] Conventional polyisobutylenes and so-called "highly reactive" polyisobutylenes are suitable for use in the present invention. Highly reactive polyisobutylenes are defined herein as polyisobutylenes in which at least 50%, preferably 70% or more, of the terminal olefinic double bonds are of the vinylidene type as described in EP 0 565 285. Particularly preferred polyisobutylenes are those having greater than 80 mol % and up to 100 mol % terminal vinylidene groups, such as those described in US Pat. No. 7 291 758. Preferred polyisobutylenes generally have the preferred molecular weight ranges for the hydrocarbyl substituents as described above.

[0133] Other preferred hydrocarbyl groups include those having internal olefins, for example as described in applicant's published application WO 2007 / 015080.

[0134] As used herein, internal olefins refer to any olefin containing primarily non-alpha double bonds, i.e., beta or higher olefins. Preferably, such materials are essentially entirely beta or higher olefins, e.g., containing less than 10% by weight alpha olefins, more preferably less than 5% by weight or less than 2% by weight. Typical internal olefins include Neodene 151810 available from Shell.

[0135] Internal olefins are sometimes referred to as isomerized olefins and can be prepared from alpha olefins by isomerization processes known in the art, or can be obtained from other sources. The fact that they are also referred to as internal olefins reflects that they do not necessarily have to be prepared by isomerization.

[0136] Preferred carboxylic acid derived acylating agents are polyisobutenyl substituted succinic anhydrides or PIBSAs. Particularly preferred PIBSAs are those having a PIB molecular weight (Mn) of 300-2800, preferably 400-2300, more preferably 500-1300.

[0137] The carboxylic acid derived acylating agent reacts with an amine. Suitably, it reacts with a primary or secondary amine. Some examples of suitable amines will now be described.

[0138] Amine compounds useful for reaction with the acylating agent include polyalkylene polyamines of the following general formula: where R 3 are each independently selected from a hydrogen atom, a hydrocarbon group, or a hydroxy-substituted hydrocarbon group containing up to about 30 carbon atoms, provided that at least one R 3 is a hydrogen atom, n is an integer from 1 to 10 and U is a C1-18 alkylene group. 3 Each is independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl and isomers thereof. 3 U is preferably a C1-4 alkylene group, and most preferably an ethylene group.

[0139] Other useful amines include heterocyclic substituted polyamines, including hydroxyalkyl substituted polyamines, wherein the polyamine is as described above and the heterocyclic substituent is selected from nitrogen-containing aliphatic and aromatic heterocycles such as piperazine, imidazoline, pyrimidine, morpholine and derivatives thereof.

[0140] Other useful amines for reaction with the acylating agent include aromatic polyamines of the general formula: Ar is an aromatic nucleus of 6 to 20 carbon atoms, each R 3 As defined above, and y is 2 to 8.

[0141] Specific examples of polyalkylene polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, tris(trimethylene)tetramine, pentaethylenehexamine, hexaethyleneheptamine, 1,2-propylenediamine, and mixtures thereof. Other commercially available materials comprising complex mixtures of polyamines may also be used. For example, higher ethylene polyamines may optionally contain all or some of the above, in addition to higher boiling fractions containing 8 or more nitrogen atoms. Specific examples of hydroxyalkyl-substituted polyamines include N-(2-hydroxyethyl)ethylenediamine, N,N'-bis(2-hydroxyethyl)ethylenediamine, N-(3-hydroxybutyl)tetramethylenediamine, and the like. Specific examples of heterocyclic substituted polyamines (2) are N-2-aminoethylpiperazine, N-2 and N-3 aminopropylmorpholine, N-3 (dimethylamino)propylpiperazine, 2-heptyl-3-(2-aminopropyl)imidazoline, 1,4-bis(2-aminoethyl)piperazine, 1-(2-hydroxyethyl)piperazine, and 2-heptadecanyl-1-(2-hydroxyethyl)imidazoline. Specific examples of aromatic polyamines (3) are various isomeric phenylenediamines, various isomeric naphthalenediamines, and the like.

[0142] Preferred amines are polyethylene polyamines, including ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, and mixtures and isomers thereof.

[0143] In preferred embodiments, the reaction product of a carboxylic acid-derived acylating agent and an amine includes at least one primary or secondary amine group.

[0144] Preferred acylated nitrogen compounds for use herein are prepared by reacting a poly(isobutylene)-substituted succinic acid-derived acylating agent (e.g., anhydride, acid, ester, etc.), wherein the poly(isobutylene) substituent has a number average molecular weight (Mn) of 170 to 2800, with a mixture of ethylene polyamines having 2 to about 9 amino nitrogen atoms, preferably about 2 to about 8 nitrogen atoms per ethylene polyamine and about 1 to about 8 ethylene groups. These acylated nitrogen compounds are suitably formed by reacting an acylating agent:amino compound molar ratio of 10:1 to 1:10, preferably 5:1 to 1:5, more preferably 2:1 to 1:2, and most preferably 2:1 to 1:1. In a particularly preferred embodiment, the acylated nitrogen compound is formed by reacting an acylating agent to an amino compound at a molar ratio of 1.8:1 to 1:1.2, preferably 1.6:1 to 1:1.2, more preferably 1.4:1 to 1:1.1, and most preferably 1.2:1 to 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 EP 0 565 285 and US Pat. No. 5,925,151.

[0145] In a particularly preferred embodiment, the acylated nitrogen-containing additive (i) comprises the reaction product of a polyisobutylene-substituted succinic acid or succinic anhydride with a polyethylene polyamine to form a succinimide detergent. Preferred polyethylene polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, and mixtures and isomers thereof. Suitably, the polyisobutylene substituent of the polyisobutylene-substituted succinic acid or succinic anhydride has a number average molecular weight of 500-2000, preferably 500-1500, more preferably 500-1100, suitably 600-1000, preferably 700-800, for example about 750.

[0146] Component (z) may comprise a mixture of two or more acylated nitrogen compounds.

[0147] In the additive used in the present invention, preferably at least 50% by weight of the additive, preferably at least 70%, more preferably at least 90%, preferably at least 95%, suitably at least 97% of the molecules have a number average molecular weight greater than 400.

[0148] A suitable method for measuring the molecular weight distribution of an additive is GPC using polystyrene standards.

[0149] Those skilled in the art will appreciate that polyisobutylene-substituted succinimide detergent additives typically contain a complex mixture of compounds. Such compounds are typically prepared by reacting polyisobutylene (PIB) with maleic anhydride (MA) to form polyisobutylene-substituted succinic anhydride (PIBSA), which is then reacted with a polyamine (PAM) to form polyisobutylene-substituted succinimide (PIBSI). In the reaction of PIB and MA, more than one MA can react with each PIB, and some unreacted PIB may remain. Each PIBSA molecule can react with one or more PAM molecules as described above. Varying the ratios of the different starting materials and including intermediate purification steps can affect the ratios of the various components of the final additive material.

[0150] In some preferred embodiments, the fuel compositions of the present invention further comprise a metal deactivating compound.

[0151] Any metal deactivating compound known to those skilled in the art may be used and includes, for example, substituted triazole compounds of formula (V) wherein R and R' are independently selected from optionally substituted alkyl or hydrogen. .

[0152] Preferred metal deactivating compounds are those of formula (VI): where R 1 、R 2and R 3 R is independently selected from optionally substituted alkyl or hydrogen, preferably alkyl or hydrogen of 1 to 4 carbon atoms. 1 Preferably, hydrogen, R 2 Preferably, hydrogen, and R 3 It is preferably a methyl group, and n is an integer of 0-5, and most preferably 1.

[0153] A particularly preferred metal deactivator is N,N'-disalicylic acid-1,2-diaminopropane and has the formula (VII): .

[0154] Another preferred metal deactivation compound (VIII): .

[0155] The composition of the first application of the invention comprises a middle distillate fuel oil obtained from the distillation of pyrolysis oil and one or more additives.

[0156] The composition may further comprise one or more fuel oils obtained from hydrocarbon and / or renewable sources.

[0157] In embodiments where the fuel composition comprises a blended fuel comprising a fuel oil obtained from the distillation of a pyrolysis oil and one or more additional fuel oils obtained from hydrocarbon and / or renewable sources, such fuels are typically blended shortly before distribution. The component fuels are typically stored separately prior to blending, and thus the present invention can suitably stabilize the fuel oil obtained from the distillation of a pyrolysis oil during storage.

[0158] When present, the antioxidant is preferably contained in the composition of the first aspect in an amount of at least 1 ppm, preferably at least 2 ppm, more preferably at least 5 ppm or at least 10 ppm, calculated as a proportion of the middle distillate fuel oil obtained from the distillation of the pyrolysis oil. In some embodiments, the antioxidant may be present in an amount of at least 50 ppm, calculated as a proportion of the middle distillate fuel oil obtained from the distillation of the pyrolysis oil.

[0159] When present, the antioxidant may be included in the composition of the first aspect in an amount of at most 10000 ppm, preferably at most 5000 ppm, more preferably at most 2000 ppm, for example at most 1000 ppm, calculated as a proportion of middle distillate fuel oil obtained from distillation of pyrolysis oil.

[0160] When present, the antioxidant is preferably contained in the composition of the first aspect in an amount of from 1 to 1000, preferably from 2 to 500 ppm, calculated as a proportion of the middle distillate fuel oil obtained from the distillation of the pyrolysis oil.

[0161] When present, the stabilizing additive is preferably contained in the composition of the first aspect in an amount of at least 1 ppm, preferably at least 2 ppm, more preferably at least 5 ppm, for example at least 10 ppm, calculated as a proportion of the middle distillate fuel oil obtained from the distillation of the pyrolysis oil. In some embodiments, the stabilizing additive may be present in an amount of at least 50 ppm, calculated as a proportion of the middle distillate fuel oil obtained from the distillation of the pyrolysis oil.

[0162] When present, the stabilising additive may be included in the composition of the first aspect in an amount of at most 10000 ppm, preferably at most 5000 ppm, more preferably at most 1000 ppm, for example at most 700 ppm, calculated as a proportion of middle distillate fuel oil obtained from distillation of pyrolysis oil.

[0163] When present, the stabilizing additive is preferably contained in the composition of the first aspect in an amount of from 1 to 1000, preferably from 2 to 500 ppm, calculated as a proportion of the middle distillate fuel oil obtained from the distillation of the pyrolysis oil.

[0164] When present, the alkoxylated amine compound is preferably contained in the composition of the first aspect in an amount of at least 1 ppm, preferably at least 2 ppm, more preferably at least 5 ppm, for example at least 10 ppm, calculated as a proportion of a middle distillate fuel oil obtained from the distillation of a pyrolysis oil. In some embodiments, the alkoxylated amine compound may be present in an amount of at least 50 ppm, calculated as a proportion of a middle distillate fuel oil obtained from the distillation of a pyrolysis oil.

[0165] When present, the alkoxylated amine compound may be included in the composition of the first aspect in an amount of up to 7000 ppm, preferably up to 3000 ppm, more preferably up to 1000 ppm, for example up to 500 ppm, calculated as a proportion of middle distillate fuel oil obtained from distillation of pyrolysis oil.

[0166] When present, the alkoxylated amine compound is preferably contained in the composition of the first aspect in an amount of from 1 to 1000, preferably from 2 to 500 ppm, calculated as a proportion of the middle distillate fuel oil obtained from the distillation of pyrolysis oil.

[0167] When present, the aldehyde-alkylphenol copolymer (when present) is preferably contained in the composition of the first aspect in an amount of at least 1 ppm, preferably at least 2 ppm, more preferably at least 5 ppm, for example at least 10 ppm, calculated as a proportion of the middle distillate fuel oil obtained from the distillation of the pyrolysis oil. In some embodiments, the aldehyde-alkylphenol copolymer may be present in an amount of at least 50 ppm, calculated as a proportion of the middle distillate fuel oil obtained from the distillation of the pyrolysis oil.

[0168] When present, the aldehyde-alkylphenol copolymer may be included in the composition of the first aspect in an amount of up to 5000 ppm, preferably up to 3000 ppm, more preferably up to 1000 ppm, for example up to 700 ppm, calculated as a proportion of middle distillate fuel oil obtained from distillation of pyrolysis oil.

[0169] When present, the aldehyde-alkylphenol copolymer is preferably comprised in the composition of the first aspect in an amount of from 1 to 1000, preferably from 2 to 500 ppm, calculated as a proportion of middle distillate fuel oil obtained from the distillation of pyrolysis oil.

[0170] When present, the acylated nitrogen compound is preferably contained in the composition of the first aspect in an amount of at least 1 ppm, preferably at least 2 ppm, more preferably at least 5 ppm, for example at least 10 ppm, calculated as a proportion of a middle distillate fuel oil obtained from the distillation of a pyrolysis oil. In some embodiments, the acylated nitrogen compound may be present in an amount of at least 50 ppm, calculated as a proportion of a middle distillate fuel oil obtained from the distillation of a pyrolysis oil.

[0171] When present, the acylated nitrogen compound may be included in the composition of the first aspect in an amount of up to 5000 ppm, preferably up to 3000 ppm, more preferably up to 1000 ppm, for example up to 700 ppm, calculated as a proportion of middle distillate fuel oil obtained from distillation of pyrolysis oil.

[0172] When present, the acylated nitrogen compound is preferably contained in the composition of the first aspect in an amount of from 1 to 1000, preferably from 2 to 500 ppm, calculated as a proportion of the middle distillate fuel oil obtained from the distillation of the pyrolysis oil.

[0173] When present, the metal deactivating compound is preferably comprised in the composition of the first aspect in an amount of at least 0.1 ppm, preferably at least 0.25 ppm, more preferably at least 0.5 ppm, for example at least 1 ppm, calculated as a proportion of middle distillate fuel oil obtained from distillation of pyrolysis oil.

[0174] When present, the metal deactivating compound may be included in the composition of the first aspect in an amount of at most 5000 ppm, preferably at most 3000 ppm, more preferably at most 1000 ppm, for example at most 500 ppm, calculated as a proportion of middle distillate fuel oil obtained from distillation of pyrolysis oil.

[0175] When present, the metal deactivating compound is preferably contained in the composition of the first aspect in an amount of from 0.1 to 1000, preferably from 1 to 100 ppm, calculated as a proportion of the middle distillate fuel oil obtained from the distillation of the pyrolysis oil.

[0176] In this specification any reference to ppm is parts per million by weight.

[0177] In a preferred embodiment, the composition of the present invention comprises an antioxidant, an acylated nitrogen compound, and a metal deactivating compound.

[0178] Preferably, the composition of the present invention comprises 1 to 500 ppm, preferably 20 to 150 ppm, of an antioxidant; 1 to 500 ppm, preferably 20 to 150 ppm, of an acylated nitrogen compound; and 1 to 250 ppm, preferably 1 to 100 ppm, of a metal deactivating compound.

[0179] Preferably, the composition of the invention comprises from 1 to 500 ppm, preferably from 20 to 150 ppm, of polyisobutenylsuccinimide; from 1 to 500 ppm, preferably from 20 to 150 ppm, of a phenylenediamine compound; and from 1 to 250 ppm, preferably from 1 to 100 ppm, of a metal deactivating compound, calculated as a proportion of a middle distillate fuel oil obtained from the distillation of pyrolysis oil.

[0180] In a particularly preferred embodiment, the composition of the present invention comprises polyisobutenyl succinimide; N,N'-di-sec-butyl-p-phenylenediamine and N,N'-disalicylic acid-1,2-propylenediamine.

[0181] In a particularly preferred embodiment, the composition of the invention comprises 1 to 500 ppm, preferably 20 to 150 ppm, of polyisobutenylsuccinimide; 10 to 500 ppm, preferably 20 to 150 ppm, of N,N'-di-sec-butyl-p-phenylenediamine; and 1 to 250 ppm, preferably 1 to 100 ppm, of N,N'-disalicylic acid-1,2-propylenediamine, calculated as a proportion of the middle distillate fuel oil obtained by distillation of pyrolysis oil.

[0182] The stabilizing additive may also contain a carrier or diluent. Preferred carriers and diluents are aromatic compounds, especially C 10 Alkyl naphthalene.

[0183] In a preferred embodiment, the composition of the first aspect comprises from 1 to 1000 ppm, preferably from 2 to 500 ppm, of an antioxidant and / or from 1 to 1000 ppm, preferably from 2 to 500 ppm, of a stabilizing additive selected from (x) alkoxylated amine compounds; (y) aldehyde-alkylphenol copolymers; (z) acylated nitrogen compounds and mixtures thereof, calculated as a proportion of middle distillate fuel oil obtained from the distillation of pyrolysis oil.

[0184] In a preferred embodiment, the composition of the first aspect comprises 1 to 1000 ppm, preferably 2 to 500 ppm, of an antioxidant and / or 1 to 1000 ppm, preferably 2 to 500 ppm, of an alkoxylated amine compound and / or 1 to 1000 ppm, preferably 2 to 500 ppm, of an aldehyde-alkylphenol copolymer and / or 1 to 1000 ppm, preferably 2 to 500 ppm, of an acylated nitrogen compound, calculated as a proportion of a middle distillate fuel oil obtained from the distillation of pyrolysis oil.

[0185] The fuel composition of the first aspect is a middle distillate fuel oil.Therefore, the fuel composition may comprise one or more other additives, for example common those in diesel fuel.These comprise for example antioxidant, dispersant, washing composition, metal deactivation compound, wax anti-settling agent, cold flow improver, cetane number improver, mist remover, stabilizing agent, demulsifier, defoamer, corrosion inhibitor, lubricity improver, dyestuff, marker, combustion improver, metal deactivator, odor masking agent, drag reducer and conductivity improver.The example of each suitable amount in the additive of these types is well known by persons skilled in the art.

[0186] Surprisingly, it has been found that the inclusion of (a) an antioxidant; and / or (b) a stabilizing additive selected from (x) an alkoxylated amine compound, (y) an aldehyde-alkylphenol copolymer, (z) an acylated nitrogen compound, or mixtures thereof, improves the storage stability of a fuel composition comprising a middle distillate fuel oil obtained from the distillation of a pyrolysis oil.

[0187] According to a second aspect of the present invention, there is provided a method for improving the stability of a fuel composition comprising a middle distillate fuel oil obtained from the distillation of a pyrolysis oil, the method comprising adding to the fuel composition one or more additives selected from the group consisting of: (a) antioxidants; and (b) a stabilizing additive selected from the group consisting of (x) alkoxylated amine compounds; (y) aldehyde-alkylphenol copolymers; (z) acylated nitrogen compounds; and mixtures thereof.

[0188] According to a third aspect of the present invention, there is provided a use of one or more additives selected from the group consisting of: (a) antioxidants; and (b) a stabilizing additive selected from the group consisting of (x) alkoxylated amine compounds; (y) aldehyde-alkylphenol copolymers; (z) acylated nitrogen compounds, and mixtures thereof; To improve the stability of fuel compositions comprising middle distillate fuel oils obtained from the distillation of pyrolysis oils.

[0189] Preferred features of the second and third aspects are as defined in relation to the first aspect.Further preferred features of the invention will now be described.

[0190] One or more additives may be added to the fuel composition at any time.

[0191] The method and use of the present invention improve the stability of compositions comprising middle distillate fuel oils obtained from the distillation of pyrolysis oils.

[0192] Preferably, the method and use improves the stability of a fuel composition comprising a middle distillate fuel oil obtained from the distillation of plastic pyrolysis oil.

[0193] Preferably, the method and use improves the storage stability of a fuel composition comprising a middle distillate fuel oil obtained from the distillation of a pyrolysis oil.

[0194] Preferably, the method and use improves the storage stability of a fuel composition comprising a middle distillate fuel oil obtained from the distillation of plastic pyrolysis oil.

[0195] The improvement in storage stability suitably results in a reduction in degradation of the oil on storage. This can be observed in a number of ways.

[0196] In some embodiments, the increased stability can provide reduced discoloration upon storage.

[0197] In some embodiments, the improved stability can provide reduced sedimentation.

[0198] In some embodiments, the improvement in stability can reduce or prevent an increase in viscosity.

[0199] In some embodiments, the improved stability can reduce the formation of gums and particulates in fuel compositions comprising middle distillate fuel oils obtained from the distillation of pyrolysis oils.

[0200] In some embodiments, the improved stability can provide improved filterability, particularly after storage.

[0201] In some embodiments, the improvement in stability can provide improvements in the low temperature properties of compositions comprising middle distillate fuel oils obtained from the distillation of pyrolysis oils.

[0202] Preferably, the methods and uses of the present invention improve the stability of the fuel composition as measured by ASTM D6468.

[0203] ASTM D6468 is a standard used to measure the high-temperature stability of middle distillate fuels under aging conditions. In this test, the fuel is aged at high temperature and then filtered through a filter pad. The light reflectance of the filter pad is measured to estimate the amount of filterable insoluble matter in the fuel sample. The lower the reflectance, the more filterable insoluble sediment the fuel sample contains, and therefore the lower the fuel sample's stability after aging.

[0204] The invention will now be further described with reference to the following non-limiting examples.

[0205] Example 1 Two middle distillate fuel oils obtained from the pyrolysis oils of different plastics were tested.

[0206] Fuel I has the following properties: element concentration P 15 14.10ppm S 16 19.62ppm Cl 17 54.81ppm K 19 0.50ppm Ca 20 ND<0.21ppm V 23 ND<0.05ppm Cr 24 12.15ppm Mn 25 0.35ppm Fe 26 5.77ppm Co 27 0.08ppm Ni 28 ND<0.02ppm Cu 29 ND<0.03ppm Zn 30 ND<0.06ppm

[0207] Fuel II has the following properties: element concentration P 15 10.79ppm S 16 30.55ppm Cl 17 190ppm K 19 0.40ppm Ca 20 ND<0.21ppm V 23 ND<0.04ppm Cr 24 ND<0.03ppm Mn 25 0.17ppm Fe 26 3.72ppm Co 27 0.06ppm Ni 28 ND<0.02ppm Cu 29 0.18ppm Zn 30 0.35ppm

[0208] The following additive compositions were prepared: Additive Composition A Components Weight % active PIBSI X 16.8 N,N'-di-sec-butyl-p-phenylenediamine 20 N,N'-disalicylic acid-1,2-propylenediamine 7.5 Aromatic solvents margin

[0209] PIBSI X is a polyisobutenyl succinimide obtained by the condensation reaction of polyisobutylene succinic anhydride derived from polyisobutylene having an Mn of about 750 with a mixture of polyethylene polyamines having an average composition close to that of tetraethylene pentamine.

[0210] Additive Composition B Components Weight % active PIBSI X 9 N,N'-di-sec-butyl-p-phenylenediamine 15 imidazoline 18 Diethylhydroxylamine 25 Aromatic solvents margin

[0211] The imidazoline component is provided by the reaction product of fatty acids and polyethylene polyamines including diethylenetriamine (DETA).

[0212] Additive Composition C Components Weight % active PIBSI X 60 Aromatic solvents margin

[0213] Additive Composition D Components Weight % active N,N'-disalicylic acid-1,2-propylenediamine 2.25 2,6-di-tert-butylphenol 58.75 N,N-di-sec-butyl-1,4-phenylenediamine 39

[0214] Additive Composition E Components Weight % active Dodecylphenol resin Y 50 Aromatic solvents margin

[0215] Dodecylphenol resin Y is a formaldehyde dodecylphenol polymer having a number average molecular weight of 4,500 to 5,000.

[0216] Additive Composition F Additive composition F is a commercially available polyisobutenyl succinimide containing 30-70 wt% of an aromatic hydrocarbon solvent.

[0217] Example 2 The additive composition of Example 1 was added to fuel oils I and II, and the stability of the resulting fuel compositions was evaluated using the method of ASTM D6468. The results are shown in Table 1: Table 1 Composition fuel additive Treatment rate (mg / L) Accelerated stability, % reflectance (ASTM D6468) 1 I none 53.8 2 I A 524 80.3 3 II none 30.2 4 II A 500 81.1 5 II B 500 56.9 6 II C 500 82.6 7 II D 500 38.7 8 II E 500 46.2 9 II F 500 52.6

[0218] Each test fuel containing the additive composition disclosed herein exhibited increased light reflectance from the filter pad used to filter the sample, compared to the corresponding filter pad used to filter the unadulterated base fuel, which corresponded to lower sediment formation in the sample during the test, and thus increased stability. These results demonstrate that the additive composition disclosed herein can improve the stability of middle distillate fuel oils obtained from the distillation of pyrolysis oils, as measured by the method of ASTM D6468.

Claims

1. A fuel composition comprising a middle distillate fuel oil obtained from the distillation of a pyrolysis oil and one or more of the following as additives: (a) antioxidants; and (b) a stabilizing additive selected from the group consisting of (x) alkoxylated amine compounds; (y) aldehyde-alkylphenol copolymers; (z) acylated nitrogen compounds; and mixtures thereof.

2. A method of improving the stability of a fuel composition comprising a middle distillate fuel oil obtained from the distillation of a pyrolysis oil, the method comprising adding to the composition one or more additives selected from the group consisting of: (a) antioxidants; and (b) a stabilizing additive selected from the group consisting of (x) an alkoxylated amine compound; (y) an aldehyde-alkylphenol copolymer; (z) an acylated nitrogen compound; and mixtures thereof.

3. Use of one or more additives selected from the following: (a) antioxidants; and (b) a stabilizing additive selected from the group consisting of (x) alkoxylated amine compounds; (y) aldehyde-alkylphenol copolymers; (z) acylated nitrogen compounds; and mixtures thereof; To improve the stability of fuel compositions comprising middle distillate fuel oils obtained from the distillation of pyrolysis oils.

4. A fuel composition, method or use according to any preceding claim, wherein the pyrolysis oil is a plastic pyrolysis oil.

5. A fuel composition, method or use according to any preceding claim wherein the middle distillate fuel oil comprises paraffins and at least 50 wt% of the paraffinic compounds present have at least 18 carbons.

6. A fuel composition, method or use according to any preceding claim, wherein the fuel composition comprises an antioxidant (a).

7. The fuel composition, method or use of claim 6, wherein the antioxidant is a phenolic antioxidant.

8. The fuel composition, method or use of claim 7, wherein the phenolic antioxidant is selected from the group consisting of tert-butylhydroquinone (TBHQ or MTBHQ), 2,5-di-tert-butylhydroquinone (DTBHQ), pyrogallol, pyrocatechol, 2,6-di-tert-butyl-4-methylphenol (BHT), 2,6-di-tert-butylphenol, propyl gallate and tert-butylcatechol.

9. A fuel composition, method or use according to any preceding claim, wherein the antioxidant comprises a nitrogen-containing antioxidant.

10. A fuel composition, method or use according to any one of the preceding claims, wherein the fuel composition comprises one or more nitrogen-containing antioxidants selected from: (i) Phenylenediamine; (ii) substituted hydroxylamines; and (iii) mixtures thereof.

11. The fuel composition, method or use of claim 10, wherein the fuel composition comprises a phenylenediamine of the formula: where R 1 、R 2 、R 3 、R 4 、R 5 、R 6 and R 7 are independently selected from hydrogen, optionally substituted alkyl, alkenyl, aryl, alkaryl or aralkyl, ester, carboxylic acid, aldehyde, ketone, ether, alcohol, amine or amide.

12. A fuel composition, method or use according to claim 10 or claim 11, wherein the fuel composition comprises a compound of formula R2NOH, wherein each R is independently hydrogen or an optionally substituted hydrocarbyl group.

13. A fuel composition, method or use according to any preceding claim, wherein the fuel composition comprises a stabilising additive (b).

14. The fuel composition, method or use of claim 13, wherein the stabilizing additive comprises (x) an alkoxylated amine compound.

15. The fuel composition, method or use of claim 14, wherein the alkoxylated amine compound comprises a compound of formula (II): wherein EO represents an ethylene oxide residue, PO represents a propylene oxide residue, and at least one of a, b, c, d, e, f, g, and h is not 0.

16. The fuel composition, method or use of any one of claims 13 to 15, wherein the stabilizing additive comprises (y) an aldehyde-alkylphenol copolymer.

17. The fuel composition, method or use of claim 16, wherein the aldehyde-alkylphenol copolymer has structure (III) or (IV): wherein R is hydrogen or alkyl and n is at least 1.

18. The fuel composition, method or use of any one of claims 13 to 17, wherein the stabilizing additive comprises (z) an acylated nitrogen compound.

19. The fuel composition, method or use of claim 18, wherein the fuel composition comprises an acylated nitrogen compound (z) which is the reaction product of a polyisobutylene-substituted succinic acid or succinic anhydride and a polyethylene polyamine.

20. A fuel composition, method or use according to any preceding claim, wherein the fuel composition comprises a metal deactivator.

21. The method or use according to any one of claims 2 to 20, wherein the improvement in stability is an improvement in storage stability.

22. The method or use according to any one of claims 2 to 21, which provides one or more of the following: -Reduction of discoloration during storage; - Reduced sedimentation; - Reduced formation of colloids and particles; - Improved filterability; and - Improved low temperature performance.

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