Compositions, methods and uses

Abstract

A fuel composition comprising a fuel oil having a boiling point distribution in the gasoline range obtained from distillation of pyrolytic oil and one or more of the following as additives: (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 fuel oil having a boiling point distribution in the gasoline range obtained from the distillation of pyrolytic oil, comprising adding to the composition 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 gasoline fuel fraction typically accounts for about half of the distillate obtained from the crude plastic pyrolysis oil.

[0005] Although the fuel obtained from the distillation of crude pyrolysis oil has the same boiling point range as gasoline fuel obtained from fossil 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] Fuels obtained from fractional distillation of plastic pyrolysis oil typically have a much lower proportion of sulfur compounds than those obtained from fractional distillation of crude oil. This means that hydrotreating is not always necessary, and the straight-run fractions can be used directly in internal combustion engines, such as direct injection and spark-ignition engines. However, because the chemical composition of fuels obtained from plastic pyrolysis oil is very different from that of fossil-derived fuels, the stability of these fuels varies.

[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 those formed in mineral fuels.Another major difference is that the olefin content of the fuel obtained by pyrolysis oil may be significantly higher than the fuel obtained by mineral oil.The fuel obtained from mineral oil contains olefins at the most 5 % by weight usually, wherein butylene and propylene are the main olefin components.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 such fuel, it is necessary to provide stabilizing additive to guarantee that they meet required standard, particularly ASTM D4814 and EN 228.

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

[0010] According to a first aspect of the present invention, there is provided a fuel composition comprising a fuel oil obtained from the distillation of a pyrolysis oil having a boiling point distribution in the gasoline range 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 fuel obtained from the distillation of a pyrolysis oil having a boiling point distribution in the gasoline range.

[0012] Pyrolysis oil can be obtained from the pyrolysis of any type of waste. The composition and properties of the pyrolysis oil, as well as the fraction of distillates obtained from it, 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 by pyrolysis of one or more polymers selected from 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 fuel oil obtained from the distillation of a pyrolysis oil, preferably a plastic pyrolysis oil. Suitably, the distillate fuel oil boils in the range of 30-225°C, preferably 35-200°C.

[0016] Fuel oil obtained from the distillation of pyrolysis oil (also known as naphtha) having a boiling point distribution in the gasoline range may be referred to herein as pyrolysis oil gasoline fraction.

[0017] The fuel composition of the present invention is suitable for use as gasoline fuel oil. Preferably, the fuel composition complies with ASTM D4814 and EN228.

[0018] The pyrolysis oil gasoline fraction may optionally be hydrotreated and / or treated using a cracking process.However, due to the generally low aromatics and sulfur content of the fuel oil obtained from pyrolysis oil, straight run distillates may be used.

[0019] In some embodiments, the fuel composition of the first aspect comprises a straight run distillate having a boiling point distribution in the gasoline range obtained directly from the distillation of pyrolysis oil without further processing.

[0020] It can be considered that fuel composition of the present invention comprises fuel component and additive component (a) and / or (b), wherein said fuel component comprises pyrolysis oil gasoline distillate.In some embodiments, the fuel component of fuel composition is basically composed of pyrolysis oil gasoline distillate.Therefore, fuel composition can be by or basically composed of pyrolysis oil gasoline distillate and additive component (a) and / or (b).

[0021] In some embodiments, the fuel component of the fuel composition can be a blended fuel component, which comprises a pyrolysis oil gasoline distillate, preferably a plastic pyrolysis oil gasoline distillate, and one or more other fuel components, for example one or more other fuel oil components with a boiling point range within the gasoline range, which are obtained from minerals and / or renewable resources. The fuel component obtained from other synthetic sources can also be included. Alcohol can also be present.

[0022] In such embodiments, the fuel component suitably comprises at least 1% by volume, suitably at least 10% by volume, at least 20% by volume, at least 50% by volume, at least 80% by volume or at least 90% by volume of the pyrolysis oil gasoline distillate. Suitably, the fuel component accounts for at most 100% by volume of the pyrolysis oil gasoline distillate, at most 99% by volume of the pyrolysis oil gasoline distillate, at most 95% by volume or at most 90% by volume. Suitably, the fuel component comprises 1-100% by volume of the pyrolysis oil gasoline distillate, suitably 1-99% by volume, 10-99% by volume or 50-99% by volume of the pyrolysis oil gasoline distillate.

[0023] In such embodiments, the fuel component of the fuel composition may comprise a petroleum-based fuel oil, particularly a gasoline fuel oil. Such gasoline fuel oils typically boil in the range of 30 to 225° C., for example, 35 to 200° C. The gasoline fuel oil may comprise an atmospheric distillate or a vacuum distillate, a cracked gas oil, or a blend of straight run and refinery streams (e.g., thermally and / or catalytically cracked and hydrocracked distillates) in any proportion.

[0024] The fuel component of the fuel composition may comprise from 0 to 99 volume % of such gasoline fuel oil, from 1 to 99 volume %, from 1 to 90 volume % or from 1 to 50 volume % gasoline fuel oil.

[0025] The term "gasoline" refers to a liquid fuel for spark-ignition engines (typically or preferably containing primarily or exclusively C4-C12 hydrocarbons) and meeting international gasoline specifications such as ASTM D-4814 and EN228.

[0026] In such an embodiment, the fuel component of the fuel composition may comprise an oxygen-containing component, such as an alcohol or an ether. Suitable oxygen-containing components may be selected from methanol, ethanol, butanol, methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), preferably ethanol.

[0027] The fuel component may comprise 0 to 85 vol% of such oxygen-containing component, 1 to 85 vol%, 1 to 50 vol%, 1 to 20 vol% or 5 to 15 vol% of such oxygen-containing component, suitably ethanol.

[0028] In some embodiments, the fuel component of the fuel composition of the present invention may comprise 1 to 99 volume % pyrolysis oil gasoline fraction, 1 to 99 volume % gasoline fuel oil and 1 to 85 volume % oxygenated component, suitably ethanol.

[0029] In such embodiments, the fuel component suitably comprises 1-20% by volume ethanol.

[0030] The fuel component of the fuel composition of the present invention may comprise 50 to 99 volume % of pyrolysis oil gasoline fraction, 1 to 50 volume % of gasoline fuel oil and 1 to 20 volume % of an oxygenated component, suitably ethanol.

[0031] Fuel composition of the present invention comprises pyrolysis oil gasoline distillate.This component of fuel composition comprises olefin.Preferably, pyrolysis oil gasoline distillate comprises at least 10 weight % olefin, at least 20 weight % olefin, at least 30 weight % or at least 40 weight % olefin.Preferably, pyrolysis oil gasoline distillate comprises at most 70 weight % olefin, at most 65 weight % olefin or at most 60 weight % olefin.Pyrolysis oil gasoline distillate preferably comprises 10-65 weight % olefin, preferably 30 weight %-60 weight % or 40-60 weight % olefin.According to the method for ASTM D1319, suitably measure the olefin content of pyrolysis oil gasoline distillate.Contained olefin in the pyrolysis oil gasoline distillate suitably comprises propylene and butylene.

[0032] 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.

[0033] The fuel composition of the first aspect comprises one or more of (a) an antioxidant and (b) a stabilizing additive.

[0034] In some embodiments, the composition of the first aspect comprises (a) an antioxidant. A mixture of two or more antioxidants may be present.

[0035] In some embodiments, the composition of the first aspect comprises (b) a stabilizing additive.

[0036] In some embodiments, the composition of the first aspect comprises (a) an antioxidant and (b) a stabilizing additive.

[0037] The stabilizing additive may comprise (x) an alkoxylated amine compound, (y) an aldehyde-alkylphenol copolymer, (z) an acylated nitrogen compound, or a mixture thereof.

[0038] In some embodiments, the composition of the first aspect comprises (b) a stabilizing additive comprising (x) an alkoxylated amine compound.

[0039] In some embodiments, the composition of the first aspect comprises (b) a stabilizing additive comprising (y) an aldehyde-alkylphenol copolymer.

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

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

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

[0046] In some embodiments, the composition of the first aspect comprises (a) an antioxidant and (b) a stabilizing additive comprising (y) an aldehyde-alkylphenol copolymer.

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

[0049] 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.

[0050] 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.

[0051] 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.

[0052] Suitable antioxidants for use herein include phenolic antioxidants and nitrogen-containing antioxidants.

[0053] In some preferred embodiments, the fuel composition of the first aspect comprises a phenolic antioxidant.

[0054] In some embodiments, the fuel composition of the first aspect comprises a nitrogen-containing antioxidant and a phenolic antioxidant.

[0055] Any suitable phenolic antioxidant may be used. Suitable antioxidants will be known to those skilled in the art.

[0056] 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.

[0057] Phenolic antioxidant compounds suitable for use in the present invention include those of formula (I): where R 1 is 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] Suitable nitrogen-containing antioxidants include aromatic amines, hindered amines, N-oxides, polyalkylene polyamines, phenylenediamines, substituted hydroxylamines, and mixtures thereof.

[0062] 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.

[0063] Suitable hindered amines include aliphatic secondary and tertiary amines, such as dimethylcyclohexylamine and diethylhydroxylamine.

[0064] Suitable N-oxides include (2,2,6,6-tetramethylpiperidin-1-yl)oxy (TEMPO) and its derivatives.

[0065] Preferably, the one or more nitrogen-containing antioxidants (a) are selected from: (i) Phenylenediamine; (ii) substituted hydroxylamines; and (iii) mixtures thereof.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] Component (i) may comprise a mixture of compounds and / or a mixture of isomers.

[0070] The preferred substituted hydroxylamine compound (ii) for use herein is a compound of formula R2NOH, wherein each R is independently hydrogen or an optionally substituted hydrocarbyl group. Preferably, each R is an optionally substituted hydrocarbyl group. Each R may be the same or different. Preferably, each R is the same.

[0071] 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.

[0072] Preferably component (ii) comprises diethylhydroxylamine.

[0073] Component (ii) may comprise a mixture of compounds and / or a mixture of isomers.

[0074] In some embodiments, the fuel composition of the first aspect includes (i) phenylenediamine.

[0075] In some embodiments, the fuel composition of the first aspect includes (ii) a substituted hydroxylamine.

[0076] In some embodiments, the fuel composition of the first aspect comprises (i) a phenylenediamine and (ii) a substituted hydroxylamine.

[0077] 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.

[0078] 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.

[0079] In some embodiments, the composition of the first aspect may comprise (x) an alkoxylated amine compound.

[0080] 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.

[0081] In a preferred embodiment, the alkoxylated amine compound includes more than one alkylene oxide residue.

[0082] Suitable alkylene oxide residues include ethylene oxide residues, propylene oxide residues, butylene oxide residues, and mixtures thereof.

[0083] Preferably, the alkoxylated amine compound comprises ethylene oxide residues, propylene oxide residues, or mixtures thereof.

[0084] Preferably, the alkoxylated amine compound is an alkoxylated amine, an alkoxylated diamine or an alkoxylated polyamine.

[0085] 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.

[0086] 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)-.

[0087] 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.

[0088] 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.

[0089] Preferably, R is ethylene and / or propylene. More preferably, R is -CH2CH2- or -CH(CH3)CH2-.

[0090] In some preferred embodiments, the alkoxylated amine compound (i) comprises a mixture of ethylene oxide residues and propylene oxide residues.

[0091] 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.

[0092] 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.

[0093] Preferably, A is the residue of a polyamine.

[0094] 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).

[0095] Preferred polyamines have 2 to 15 nitrogen atoms, preferably 2 to 10 nitrogen atoms, more preferably 2 to 8 nitrogen atoms.

[0096] 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.

[0097] Most preferably A is the residue of ethylenediamine.

[0098] 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.

[0099] 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.

[0100] The skilled person will appreciate that the polymeric compound of formula (II) is typically in the form of a mixture.

[0101] Some suitable alkoxylated amine compounds for use herein are described in US Pat. No. 6,838,422.

[0102] In some embodiments, the composition of the first aspect may comprise (y) an aldehyde-alkylphenol copolymer.

[0103] Any suitable aldehyde-alkylphenol copolymer may be used, and such compounds are known to those skilled in the art.

[0104] 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.

[0105] 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.

[0106] In some embodiments, the alkylphenol is a polyisobutenyl (PIB) substituted phenol.

[0107] Polyisobutenyl (PIB) substituted phenols include a hydrocarbyl chain having the following repeating units: 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.

[0108] 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.

[0109] 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.

[0110] 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.

[0111] 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.

[0112] In some embodiments, the phenol may include a PIB substituent having an average molecular weight of 400 to 2500, preferably 500 to 1500, suitably 550 to 1300.

[0113] In some embodiments, the phenol may include a PIB substituent having an average molecular weight of 200 to 600.

[0114] In some embodiments, the phenol may include a PIB substituent having an average molecular weight of 500 to 1000.

[0115] In some embodiments, the phenol may include a PIB substituent having an average molecular weight of 700 to 1300.

[0116] In some embodiments, the phenol may include a PIB substituent having an average molecular weight of 1000 to 2000.

[0117] In some embodiments, the phenol may include a PIB substituent having an average molecular weight of 1700 to 2600, such as 2000 to 2500.

[0118] 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.

[0119] 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.

[0120] 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.

[0121] 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.

[0122] In some embodiments, the composition of the first aspect may comprise (z) an acylated nitrogen compound.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] Suitable hydrocarbyl-substituted acylating agents and methods for their preparation are well known in the art.

[0127] 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.

[0128] 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.

[0129] 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.

[0130] 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.

[0131] 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.

[0132] A preferred hydrocarbyl-based substituent is polyisobutylene. Such compounds are known to those skilled in the art.

[0133] 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.

[0134] 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.

[0135] Other preferred hydrocarbyl groups include those having internal olefins, for example as described in applicant's published application WO 2007 / 015080.

[0136] 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.

[0137] 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.

[0138] 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 450-2300, more preferably 500-1300.

[0139] 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.

[0140] 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.

[0141] 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.

[0142] 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, and each R 3 As defined above, and y is 2 to 8.

[0143] 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.

[0144] Preferred amines are polyethylene polyamines, including ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, and mixtures and isomers thereof.

[0145] 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.

[0146] 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.

[0147] 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.

[0148] Component (z) may comprise a mixture of two or more acylated nitrogen compounds.

[0149] 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.

[0150] A suitable method for measuring the molecular weight distribution of an additive is GPC using polystyrene standards.

[0151] 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.

[0152] In some preferred embodiments, the fuel compositions of the present invention further comprise a metal deactivating compound.

[0153] 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.

[0154] Preferred metal deactivating compounds are those of formula (VI): where R 1 、R 2 and 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.

[0155] A particularly preferred metal deactivator is N,N'-disalicylic acid-1,2-diaminopropane and has the formula shown in formula (VII): Another preferred metal deactivation compound is shown in formula (VIII): The composition of the first application of the invention comprises a fuel oil obtained from the distillation of pyrolysis oil having a boiling point distribution in the gasoline range and one or more additives.

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

[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 resources, 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 included 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 pyrolysis oil gasoline fraction. In some embodiments, the antioxidant may be present in an amount of at least 50 ppm, calculated as a proportion of the pyrolysis oil gasoline fraction.

[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 the pyrolysis oil gasoline fraction.

[0160] When present, the antioxidant is preferably included 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 pyrolysis oil gasoline fraction.

[0161] When present, the stabilizing additive is preferably included 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 pyrolysis oil gasoline fraction. In some embodiments, the stabilizing additive may be present in an amount of at least 50 ppm, calculated as a proportion of the pyrolysis oil gasoline fraction.

[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 the pyrolysis oil gasoline fraction.

[0163] When present, the stabilizing additive is preferably included 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 pyrolysis oil gasoline fraction.

[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 the pyrolysis oil gasoline fraction. In some embodiments, the alkoxylated amine compound may be present in an amount of at least 50 ppm, calculated as a proportion of the pyrolysis oil gasoline fraction.

[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 the pyrolysis oil gasoline fraction.

[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 pyrolysis oil gasoline fraction.

[0167] When present, the aldehyde-alkylphenol copolymer is preferably included 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 pyrolysis oil gasoline fraction. In some embodiments, the aldehyde-alkylphenol copolymer may be present in an amount of at least 50 ppm, calculated as a proportion of the pyrolysis oil gasoline fraction.

[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 the pyrolysis oil gasoline fraction.

[0169] When present, the aldehyde-alkylphenol copolymer is preferably included 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 pyrolysis oil gasoline fraction.

[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 the pyrolysis oil gasoline fraction. In some embodiments, the acylated nitrogen compound may be present in an amount of at least 50 ppm, calculated as a proportion of the pyrolysis oil gasoline fraction.

[0171] When present, the acylated nitrogen 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 700 ppm, calculated as a proportion of the pyrolysis oil gasoline fraction.

[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 pyrolysis oil gasoline fraction.

[0173] When present, the metal deactivating compound is preferably included 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 the pyrolysis oil gasoline fraction.

[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 the pyrolysis oil gasoline fraction.

[0175] When present, the metal deactivating compound is preferably included 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 pyrolysis oil gasoline fraction.

[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 1-500 ppm, preferably 20-150 ppm, of an antioxidant; 1-500 ppm, preferably 20-150 ppm, of an acylated nitrogen compound; and 1-250 ppm, preferably 1-100 ppm, of a metal deactivating compound, calculated as a proportion of the pyrolysis oil gasoline fraction.

[0179] Preferably, the composition of the present invention comprises 1 to 500 ppm, preferably 20 to 150 ppm, of polyisobutenyl succinimide; 1 to 500 ppm, preferably 20 to 150 ppm, of a phenylenediamine compound; and 1 to 250 ppm, preferably 1 to 100 ppm, of a metal deactivating compound, calculated as a proportion of the pyrolysis oil gasoline fraction.

[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 present invention comprises 1-500 ppm, preferably 20-150 ppm, of polyisobutenylsuccinimide; 10-500 ppm, preferably 20-150 ppm, of N,N'-di-sec-butyl-p-phenylenediamine; and 1-250 ppm, preferably 1-100 ppm, of N,N'-disalicylic acid-1,2-propylenediamine, calculated as a proportion of the pyrolysis oil gasoline fraction.

[0182] The stabilizing additive may also include 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, based on the proportion of the pyrolysis oil gasoline fraction, the stabilizing additive being selected from the group consisting of (x) alkoxylated amine compounds; (y) aldehyde-alkylphenol copolymers; (z) acylated nitrogen compounds and mixtures thereof.

[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 the pyrolysis oil gasoline fraction.

[0185] The fuel compositions used in the present invention may contain one or more additional additives conventionally added to gasoline, such as other detergents, dispersants, antioxidants, anti-icing agents, metal deactivators, lubricity additives, friction modifiers, defogging agents, corrosion inhibitors, dyes, markers, octane improvers, anti-valve seat depression additives, stabilizers, demulsifiers, defoamers, odor masking agents, conductivity improvers, and carrier fluids.

[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 distillate fuel oil having a boiling point range in the gasoline range obtained by distillation of 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 fuel oil having a boiling point distribution in the gasoline range obtained by 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 a fuel composition comprising a fuel oil having a boiling point distribution in the gasoline range obtained by distillation of a pyrolysis oil.

[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 fuel oils having a boiling point distribution in the gasoline range obtained from the distillation of pyrolysis oils.

[0192] Preferably, the method and use improve the stability of a fuel composition comprising a fuel oil having a boiling point distribution in the gasoline range obtained by distillation of plastic pyrolysis oil.

[0193] Preferably, the method and use improves the storage stability of a fuel composition comprising a fuel oil having a boiling point distribution in the gasoline range obtained from the distillation of a pyrolysis oil.

[0194] Preferably, the method and use improve the storage stability of a fuel composition comprising a fuel oil having a boiling point distribution in the gasoline range obtained by distillation of plastic pyrolysis oil.

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

[0196] In some embodiments, the improved 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 pyrolysis oil gasoline fractions.

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

[0201] In some embodiments, the improved stability can provide improved low temperature properties of fuel compositions comprising the pyrolysis oil gasoline fraction.

[0202] In some embodiments, the methods and uses of the present invention improve the stability of fuel compositions as measured by ASTM D525.

[0203] ASTM D525 is a standard test for determining the stability of gasoline fuels under accelerated oxidation conditions using the induction period method.

[0204] In some embodiments, the methods and uses of the present invention improve the stability of fuel compositions as measured by ASTM D873.

[0205] ASTM D873 is a standard test used to determine the tendency of fuels to form gums and deposits under accelerated aging conditions.

[0206] In some embodiments, the methods and uses of the present invention improve the stability of fuel compositions as measured by ASTM D381.

[0207] ASTM D381 is a test method for measuring the colloid content of the presence of aviation fuel, motor gasoline or other volatile distillates. ASTM D381 measures the residual material remaining after gasoline volatilizes at high temperatures in the presence of air. The evaporated residue is commonly referred to as "unwashed colloid" in the industry. However, fuel additives (such as those described herein) can be added to gasoline to improve fuel quality. The active components in these fuel additives do not evaporate under the D381 test conditions, so they contribute to the concentration of unwashed colloid. In order to eliminate the impact of the ultimate concentration of the colloid measured in the test, the evaporated colloid is rinsed with a solvent (normal heptane), dried under air, and then the remaining residue is reweighed. This residue is called "washed colloid", and it only reflects the true concentration of the polymer colloid formed in the test fuel and the residual solvent insoluble matter present in the fuel.

[0208] Test Methods ASTM D525, ASTM D873, and ASTM D381 are standard test methods known to those skilled in the art.

[0209] The invention will now be further described with reference to the following non-limiting examples.

[0210] Example 1 Two fuel oils with boiling point distribution in the gasoline range were tested, obtained from pyrolysis oils of different plastics.

[0211] Fuel I has the following properties: Element concentration P 15 ND<10.52ppm S 16 29.92ppm Cl 17 253ppm K 19 0.69ppm Ca 20 ND<0.21ppm V 23 ND<0.05ppm Cr 24 ND<0.03ppm Mn 25 0.22ppm Fe 26 1.32ppm Co 27 0.03ppm Ni 28 ND<0.02ppm Cu 29 ND<0.03ppm Zn 30 ND<0.06ppm Fuel 1 had an olefin content of 47.2 wt% as measured by ASTM D1319.

[0212] Fuel II has the following properties: Element concentration P 15 ND<10.52ppm S 16 29.92ppm Cl 17 253ppm K 19 0.69ppm Ca 20 ND<0.21ppm V 23 ND<0.05ppm Cr 24 ND<0.03ppm Mn 25 0.22ppm Fe 26 1.32ppm Co 27 0.03ppm Ni 28 ND<0.02ppm Cu 29 ND<0.03ppm Zn 30 ND<0.06ppm Fuel II had an olefin content of 55.0 wt% as measured by ASTM D1319.

[0213] The following additive compositions were prepared: Additive Composition A PIBSI X is a polyisobutenyl succinimide obtained by the condensation reaction of polyisobutenyl succinic anhydride derived from polyisobutene having an Mn of about 750 with a mixture of polyethylene polyamines having an average composition close to that of tetraethylene pentamine.

[0214] Additive Composition B The imidazoline component is provided by the reaction product of fatty acids and polyethylene polyamines including diethylenetriamine (DETA).

[0215] Additive Composition C Additive Composition D The 2,6-di-tert-butylphenol used in the above composition contains at least 75% by weight of 2,6-di-tert-butylphenol and at most 25% by weight of tert-butylphenol and tri-tert-butylphenol.

[0216] Example 2 The additive composition of Example 1 was added to fuel oils I and II in the amounts specified in Table 1. The stability of the resulting fuel compositions was evaluated using the methods of ASTM D525, ASTM D873, and ASTM D381. The results are shown in Table 2: Table 1 Table 2 These results demonstrate that additive compositions AD disclosed herein can improve the stability of gasoline fuel compositions derived from pyrolysis oil (pyrolysis oil gasoline fractions) as measured by the methods of ASTM D525, ASTM D873, and ASTM D381.

[0217] With respect to the ASTM D525 test results, each of the tested fuels containing one of the additive compositions AD showed an increase in the time it took for the fuel oil to degrade under the accelerated oxidation conditions tested, compared to the base fuel oil without the additive. These results demonstrate that the additive compositions disclosed herein can improve the resistance of pyrolysis oil gasoline fractions to oxidative degradation and, therefore, improve the stability of the fuel oil.

[0218] ASTM D873 test results show that compared to the base fuel without the additive, the test fuel containing one of the additive compositions AD formed less gum and sediment under accelerated aging conditions. These results indicate that the additive composition disclosed herein can reduce gum formation in pyrolysis oil gasoline distillate and thus improve the stability of the fuel oil.

[0219] With respect to the ASTM D381 test results, each of the tested fuels containing one of the additive compositions AD showed a reduction in the amount of gum in the fuel oil compared to the fuel oil containing no additive. These results indicate that the additive compositions disclosed herein can reduce gum formation in pyrolysis oil gasoline fractions and, therefore, improve the stability of the fuel oil.

[0220] Example 3 Additive Composition A of Example 1 was further tested for its stability enhancing properties in fuel oils III-VI. Fuel oils III-VI have a boiling point distribution in the gasoline range and are obtained from plastic pyrolysis oils. Fuel oils III-VI have the composition / boiling point range shown in Table 3 below: Table 3 Additive composition A was added to fuel oils III-VI in the amounts specified in Table 4 and tested against the corresponding base fuel oils without the additive. The stability of the resulting fuel compositions was evaluated using the methods of ASTM D525 and ASTM D381. The results are shown in Table 4: Table 4 Preferably, the fuel oil treated with the additive composition produces a result of 240 minutes or greater in the ASTM D525 test and a result of about 5 mg / 100 ml or less in the ASTM D381 test, or values close to these levels, to demonstrate particularly effective stabilization of the test fuel oil.

[0221] These results demonstrate that the additive compositions disclosed herein can improve the stability of gasoline fuel compositions derived from pyrolysis oil (pyrolysis oil gasoline fractions) as measured by ASTM D525 and ASTM D381.

[0222] With respect to the ASTM D525 test results, each of the tested fuels containing Additive Composition A showed an increase in the time it took for the fuel oil to degrade under the accelerated oxidation conditions tested, compared to the fuel oil that did not contain the additive. These results demonstrate that the additive compositions disclosed herein can improve the resistance of pyrolysis oil gasoline fractions to oxidative degradation and, therefore, improve the stability of the fuel oil.

[0223] With respect to the ASTM D381 test results, each of the tested fuels containing Additive Composition A showed a reduction in the quality of gums in the fuel oil compared to the fuel oil without the additive. These results indicate that the additive compositions disclosed herein can reduce the formation of gums in pyrolysis oil gasoline fractions and, therefore, improve the stability of the fuel oil.

Claims

1. A fuel composition comprising a fuel oil obtained from the distillation of a pyrolysis oil having a boiling point distribution in the gasoline range 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 for improving the stability of a fuel composition comprising a fuel oil having a boiling point distribution in the gasoline range 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) an alkoxylated amine compound; (y) an aldehyde-alkylphenol copolymer; (z) an acylated nitrogen compound; and mixtures thereof; To improve the stability of a fuel composition comprising a fuel oil having a boiling point distribution in the gasoline range obtained by distillation of a pyrolysis oil.

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 fuel oil comprises at least 10 wt% olefins.

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 6, 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; -Reduction in the formation of colloids and particles; - Improved filterability; and - Improved low temperature performance.

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