Compositions, methods and uses

Abstract

A composition comprising pyrolysis oil and, as additives, one or more of the following: (a) an antioxidant; and (b) a stabilizing additive selected from the group consisting of: (i) an alkoxylated amine compound; (ii) an aldehyde-alkylphenol copolymer; (iii) a quaternary ammonium salt, and mixtures thereof. Methods and uses for improving the stability of a composition comprising pyrolysis oil by adding one or more of the additives to the composition are also provided.

Description

[0001] The present invention relates to pyrolysis oils and methods and uses related thereto. In particular, the present invention relates to additives for improving the stability of compositions comprising plastic pyrolysis oils.

[0002] Pyrolysis oil is a liquid produced by the pyrolysis of waste, such as plastic waste, biomass (such as agricultural waste, forestry waste, waste cooking oil and algae waste). Examples of waste plastics that can produce plastic pyrolysis oil by pyrolysis include polyethylene, polypropylene, polystyrene, polyethylene terephthalate (PET) and rubber (such as from tires). The organic liquid produced by the pyrolysis of plastics and other waste materials has a very dark color, an unpleasant smell, and is unstable. However, there is a strong desire to find the purposes of these oils to avoid these wastes being sent to landfills or polluting the ocean.

[0003] Pyrolysis oils can be used as feedstock for chemical processing, for example to produce polymers such as polyethylene. They can also be used for fuel oil. Using pyrolysis oil to produce polymers is a sustainable alternative to using crude oil feedstock.

[0004] The use of pyrolysis oil is limited due to its poor stability, especially when cooled, for example during transport or storage. This can be due to oxidation of oxygen- or nitrogen-containing substances present in the oil. However, it is also believed that the deposition of particulate matter in large amounts of oil is also a problem.

[0005] Pyrolysis oils may optionally be hydrotreated or cracked before subsequent use. Such processes may increase their stability. Alternatively, they may be treated with chemical additives to improve their stability.

[0006] The present inventors have discovered that certain compounds are effective in reducing precipitation and / or improving stability of compositions comprising pyrolysis oil.

[0007] According to a first aspect of the present invention, there is provided a composition comprising pyrolysis oil and one or more of the following as additives:

[0008] (a) antioxidants; and

[0009] (b) a stabilizing additive selected from the group consisting of (i) alkoxylated amine compounds; (ii) aldehyde-alkylphenol copolymers; and mixtures thereof.

[0010] In some aspects, the stabilizing additive (b) may be (iii) a quaternary ammonium salt. Therefore, according to another aspect of the present invention, there is provided a composition comprising pyrolysis oil and one or more of the following as additives:

[0011] (a) antioxidants; and

[0012] (b) a stabilizing additive selected from the group consisting of (i) alkoxylated amine compounds; (ii) aldehyde-alkylphenol copolymers; (iii) quaternary ammonium salts; and mixtures thereof.

[0013] A first aspect of the present invention relates to a composition comprising pyrolysis oil. Pyrolysis oil can be obtained by pyrolysis of any type of waste. The components of the oil and its characteristics will depend on the type of pyrolysis waste and the pyrolysis conditions. For example, pyrolysis oil can be obtained by pyrolysis of plastic waste, agricultural waste, forestry waste, waste cooking oil and algae waste.

[0014] Preferably, the pyrolysis oil comprises plastic pyrolysis oil. Plastic pyrolysis oil can be obtained by pyrolysis of any type of plastic. For example, pyrolysis oil can be obtained by pyrolysis of waste tires.

[0015] Preferred plastic pyrolysis oils are obtained by pyrolysis of one or more polymers selected from polyethylene, polypropylene, PET, rubber and mixtures thereof.

[0016] Preferred plastic pyrolysis oils are obtained by further pyrolysis of one or more polymers selected from polyethylene, polypropylene, PET, rubber, waste tires and mixtures thereof.

[0017] In some embodiments, the pyrolysis oil in the composition of the first aspect may be a hydrotreated pyrolysis oil.

[0018] In some embodiments, the pyrolysis oil in the composition of the first aspect has been treated using a cracking process.

[0019] In a preferred embodiment, the composition of the first aspect comprises pyrolysis oil obtained directly from a pyrolysis plant without purification or further treatment.

[0020] In some embodiments, the composition of the first aspect may include a blended fuel oil comprising plastic pyrolysis oil and one or more fuel oils from hydrocarbon and / or renewable sources.

[0021] In some embodiments, the composition of the first aspect comprises a mixed fuel oil comprising plastic pyrolysis oil and middle distillate fuel oil.

[0022] Middle distillate fuel oils may include petroleum-based fuel oils, especially middle distillate fuel oils. Such distillate fuel oils typically boil in the range of 110° C. to 500° C., such as 150° C. to 400° C. Middle distillate fuel oils may include atmospheric or vacuum distillates, cracked gas oils, or a mixture of any proportion of straight run and refinery streams (e.g., thermal and / or catalytic cracking and hydrocracking fractions).

[0023] Middle distillate fuel oils may include 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) fuels.

[0024] The middle distillate fuel oil may comprise a renewable fuel, such as a biofuel composition or a biodiesel composition.

[0025] Middle distillate fuel oil can comprise first generation biodiesel.First generation biodiesel contains esters of for example vegetable oil, animal fat and waste edible fat.This form of biodiesel can be obtained by transesterifying oil, for example rapeseed oil, soybean oil, safflower oil, palm oil, palm kernel oil, corn oil, peanut oil, cottonseed oil, tallow, coconut oil, medicinal nut oil (jatropha oil), sunflower oil, waste edible oil, hydrogenated vegetable oil or any mixture thereof with alcohol (normally monohydric alcohol) in the presence of a catalyst.

[0026] Middle distillate fuel oils may include second generation biodiesel. Second generation biodiesel is derived from renewable resources such as vegetable oils and animal fats, and is typically processed in refineries, typically using hydroprocessing (e.g., the H-Bio process developed by Petrobras). Second generation biodiesel may be similar in properties and quality to petroleum-based fuel oil streams, such as renewable diesel produced from vegetable oils, animal fats, etc., and is sold by ConocoPhillips as Renewable Diesel and by Neste as NExBTL.

[0027] The middle distillate fuel oil used in the present invention may include 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 much different from some second generation biodiesel, but is intended to utilize whole plants (biomass), thereby expanding the feedstock base.

[0028] Middle distillate fuel oils may contain mixtures of any or all of the above diesel fuel oils.

[0029] In some embodiments, the middle distillate fuel oil can be a mixed diesel fuel comprising biodiesel. In such mixtures, biodiesel can exist in an amount of, for example, up to 0.5%, up to 1%, up to 2%, up to 3%, up to 4%, up to 5%, up to 10%, up to 20%, up to 30%, up to 40%, up to 50%, up to 60%, up to 70%, up to 80%, up to 90%, up to 95% or up to 99%.

[0030] In some embodiments, the middle distillate fuel oil may contain a secondary fuel, such as ethanol. Preferably however the diesel fuel composition does not contain ethanol.

[0031] Middle distillate fuel oils may contain a relatively high sulphur content, for example greater than 0.05 wt%, such as 0.1 wt% or 0.2 wt%.

[0032] In a preferred embodiment, however, the middle distillate fuel oil has a sulfur content of at most 0.05 wt.-%, more preferably at most 0.035 wt.-%, in particular at most 0.015 wt.-%. Fuels with even lower sulfur contents are also suitable, for example fuels containing less than 50 wt.-ppm, preferably less than 20 wt.-ppm, for example 10 wt.-ppm or less sulfur.

[0033] Various metal species may be present in middle distillate fuel oils. This may be due to contamination of the fuel during manufacture, storage, transport or use, or due to contamination of fuel additives. Metal species may also be added to the fuel intentionally. For example, transition metals are sometimes added as fuel-borne catalysts, for example to improve the performance of diesel particulate filters.

[0034] In a preferred embodiment, the middle distillate fuel oil used in the present invention contains sodium and / or calcium. Preferably, they contain sodium. Sodium and / or calcium are generally present in an amount totaling 0.01 to 50 ppm, preferably 0.05 to 5 ppm, preferably 0.1 to 2 ppm, for example 0.1 to 1 ppm.

[0035] Other metal-containing species may also be present as contaminants, for example, by corrosion of metal and metal oxide surfaces by acidic species present in the fuel or from lubricating oils. During use, fuels (e.g., diesel fuels) often come into contact with metal surfaces, for example, in vehicle refueling systems, fuel tanks, fuel transportation devices, etc. Typically, metal-containing contaminants may include transition metals, such as zinc, iron, and copper; other Group I or Group II metals and other metals, such as lead.

[0036] In addition to the metal-containing contaminants that may be present in middle distillate fuel oils, there are also situations where metal-containing materials may be intentionally added to the fuel. For example, as is known in the art, a metal-containing fuel-borne catalyst material may be added to aid in the regeneration of a particulate filter.

[0037] Metal-containing contaminants may be in the form of insoluble particulate matter or soluble compounds or complexes, depending on their source. Metal-containing fuel-borne catalysts are generally soluble compounds or complexes or colloidal substances.

[0038] In some embodiments, the middle distillate fuel oil may contain a metal-containing substance including a fuel-borne catalyst. Preferably, the fuel-borne catalyst comprises one or more metals selected from iron, cerium, platinum, manganese, Group I and Group II metals (e.g., calcium and strontium). Most preferably, the fuel-borne catalyst comprises a metal selected from iron and cerium.

[0039] In some embodiments, the middle distillate fuel oil may contain metal-containing species including zinc. Zinc may be present in an amount of 0.01 to 50 ppm, preferably 0.05 to 5 ppm, more preferably 0.1 to 1.5 ppm.

[0040] The composition of the first aspect comprises one or more of (a) an antioxidant and (b) a stabilizing additive.

[0041] In some embodiments, the composition of the first aspect comprises (a) an antioxidant. There may be a mixture of two or more antioxidants.

[0042] In some embodiments, the composition of the first aspect comprises (b) a stabilizing additive.

[0043] In some embodiments, the composition of the first aspect comprises (a) an antioxidant and (b) a stabilizing additive.

[0044] The stabilizing additive may include (i) an alkoxylated amine compound, (ii) an aldehyde-alkylphenol copolymer, or a mixture thereof.

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

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

[0047] In some preferred embodiments, the composition of the first aspect comprises (b) a stabilizing additive comprising (i) an alkoxylated amine compound and (ii) an aldehyde-alkylphenol copolymer.

[0048] In some embodiments, the composition of the first aspect comprises (a) an antioxidant and (b) a stabilizing additive, the stabilizing additive comprising (i) an alkoxylated amine compound.

[0049] In some embodiments, the composition of the first aspect comprises (a) an antioxidant and (b) a stabilizing additive, the stabilizing additive comprising (ii) an aldehyde-alkylphenol copolymer.

[0050] In some preferred embodiments, the composition of the first aspect comprises (a) an antioxidant and (b) a stabilizing additive comprising (i) an alkoxylated amine compound and (ii) an aldehyde-alkylphenol copolymer.

[0051] In some embodiments, the composition of the first aspect comprises (b) a stabilizing additive comprising one or more (iii) quaternary ammonium salts.

[0052] In some preferred embodiments, the composition of the first aspect comprises (b) a stabilizing additive comprising (i) an alkoxylated amine compound and one or more (iii) quaternary ammonium salts.

[0053] In some preferred embodiments, the composition of the first aspect comprises (b) a stabilizing additive comprising (ii) an aldehyde-alkylphenol copolymer and one or more (iii) quaternary ammonium salts.

[0054] In some embodiments, the composition of the first aspect comprises (a) an antioxidant and (b) a stabilizing additive comprising one or more (iii) quaternary ammonium salts.

[0055] In some preferred embodiments, the composition of the first aspect comprises (a) an antioxidant and (b) a stabilizing additive comprising (i) an alkoxylated amine compound and one or more (iii) quaternary ammonium salts.

[0056] In some preferred embodiments, the composition of the first aspect comprises (a) an antioxidant and (b) a stabilizing additive comprising (ii) an aldehyde-alkylphenol copolymer and one or more (iii) quaternary ammonium salts.

[0057] In some preferred embodiments, the composition of the first aspect comprises (a) an antioxidant and (b) a stabilizing additive comprising (i) an alkoxylated amine compound, (ii) an aldehyde-alkylphenol copolymer and one or more (iii) quaternary ammonium salts.

[0058] Antioxidants suitable for use herein include phenolic antioxidants and amino antioxidants.

[0059] Suitable amino antioxidants include aromatic amines, hindered amines, N-oxides, polyalkylene polyamines; and polyisobutylenyl substituted succinimides.

[0060] 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.

[0061] Suitable hindered amines include primary and secondary aliphatic amines such as dimethylcyclohexylamine and diethylhydroxylamine.

[0062] Suitable N-oxides include TEMPO and its derivatives.

[0063] Polyisobutenyl-substituted succinimides are known to the person skilled in the art and their use as antioxidants is described, for example, in WO 2009 / 016400.

[0064] Preferably, the composition of the first aspect comprises a phenolic antioxidant.

[0065] In some embodiments, the composition of the first aspect comprises an amino antioxidant and a phenolic antioxidant.

[0066] Any suitable phenolic antioxidant may be used. Suitable antioxidants will be known to those skilled in the art.

[0067] By phenolic antioxidant compounds, we mean any compound containing a phenolic moiety (i.e. a benzene ring substituted with a hydroxyl group). This can be a very simple compound, such as benzene glycol, an alkyl-substituted phenol or benzenetriol. Alternatively, the phenolic antioxidant can be part of a more complex molecule. It can include two phenolic moieties, for example, see the compounds disclosed in US2006 / 0219979.

[0068] Phenolic antioxidant compounds suitable for use in the present invention include those of formula (I):

[0069]

[0070] 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 is independently selected from hydrogen, an optionally substituted alkyl or alkenyl group, an aryl group, an ester group, a ketone, an aldehyde, a carboxylic acid, an ether, an alcohol, an amine or an amide; and n is an integer from 1 to 5.

[0071] Preferably, 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, R 2 and R 3 is independently selected from hydrogen, methyl, ethyl, tert-butyl and isopropyl. Preferably, n is 1, 2 or 3.

[0072] 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), pyrogalol, pyrocatechol, 2,6-di-tert-butyl-4-methylphenol (BHT), 2,6-di-tert-butylphenol, propyl gallate and tert-butylcatechol.

[0073] 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.

[0074] In some embodiments, the antioxidant is a reaction product of an acylating agent derived from a carboxylic acid and an amine. These compounds may also be collectively referred to herein as acylated nitrogen compounds. Such additives may be additionally or alternatively defined as stabilizing additives. Therefore, the reaction product of an acylating agent derived from a carboxylic acid as defined herein and an amine may provide an additive type (a) antioxidant or an additive type (b) stabilizing additive in the composition comprising pyrolysis oil of the first aspect.

[0075] Therefore, in another aspect, the present invention may provide a composition comprising pyrolysis oil and one or more of the following as additives:

[0076] (a) antioxidants; and

[0077] (b) a stabilizing additive selected from: (i) alkoxylated amine compounds; (ii) aldehyde-alkylphenol copolymers; (iii) quaternary ammonium salts; (iv) reaction products of carboxylic acid derived acylating agents as defined herein and amines; and mixtures thereof.

[0078] Suitable acylated nitrogen-containing compounds can be prepared by reacting a carboxylic acid acylating agent with an amine and are known to those skilled in the art. Suitable carboxylic acid acylating agents are hydrocarbyl-substituted acylating agents.

[0079] As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary sense, which is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include:

[0080] (i) hydrocarbon groups, i.e., aliphatic (which may be saturated or unsaturated, straight chain or branched, e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic (including aliphatic and alicyclic substituted aromatic) substituents, as well as cyclic substituents in which the ring is completed by another part of the molecule (e.g., two substituents together form a ring);

[0081] (ii) substituted hydrocarbon groups, i.e. substituents containing non-hydrocarbon groups which, in the context of the present invention, do not alter the predominantly hydrocarbon nature of the substituent (e.g., halogenated (e.g., chloro, fluoro or bromo), hydroxyl, alkoxy (e.g., C 1 To C 4 alkoxy), ketone, acyl, cyano, thiol, amino, amide, nitro, nitroso, sulfoxide, nitro and carboxyl);

[0082] (iii) heterosubstituents, i.e., substituents which, in the context of the present invention, although having predominantly hydrocarbon character, contain atoms other than carbon in a ring or chain which would otherwise consist of carbon atoms. Heteroatoms include sulfur, oxygen, nitrogen, and include substituents such as pyridyl, furyl, thienyl and imidazolyl. In general, no more than two, preferably no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; usually, no non-hydrocarbon substituent will be present in the hydrocarbyl group.

[0083] The preferred hydrocarbyl substituted acylating agent is polyisobutenyl succinic anhydride.These compounds are commonly referred to as "PIBSA" and are well known to those skilled in the art.

[0084] In such an embodiment, the antioxidant is suitably a polyisobutenyl-substituted succinimide.

[0085] Conventional polyisobutylenes and so-called "highly reactive" polyisobutylenes are suitable for use in the present invention. Highly reactive polyisobutylenes in this context are defined 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 0565285. Particularly preferred polyisobutylenes are those having greater than 80 mol % and up to 100 mol % of terminal vinylidene groups, such as those described in US Pat. No. 7291758. Preferred polyisobutylenes have the preferred molecular weight (Mn) ranges as generally described above for the hydrocarbyl substituents.

[0086] Particularly preferred PIBSAs are those having a PIB molecular weight (Mn) of 300 to 2800, preferably 450 to 2300, more preferably 500 to 1300.

[0087] In a preferred embodiment, the reaction product of a carboxylic acid derived acylating agent and an amine includes at least one primary or secondary amine group.

[0088] Preferred acylated nitrogen compounds for use herein are prepared by reacting a polyisobutylene-substituted succinic acid derived acylating agent (e.g., anhydrides, acids, esters, etc.) with a mixture of ethylene polyamines having from 2 to about 9 amino nitrogen atoms, preferably from about 2 to about 8 nitrogen atoms and from about 1 to about 8 ethylene groups per ethylene polyamine, wherein the polyisobutylene substituent has a number average molecular weight (Mn) of from 170 to 2800. These acylated nitrogen compounds are suitably formed by reacting an acylating agent:amino compound molar ratio of from 10:1 to 1:10, preferably from 5:1 to 1:5, more preferably from 2:1 to 1:2, and most preferably from 2:1 to 1:1. In particularly preferred embodiments, the acylated nitrogen compound is formed by reacting an acylating agent to an amino compound in a molar ratio of from 1.8:1 to 1:1.2, preferably from 1.6:1 to 1:1.2, more preferably from 1.4:1 to 1:1.1, and most preferably from 1.2:1 to 1:1. Acylated amino compounds of this type and their preparation are well known to the person skilled in the art and are described, for example, in EP 0 565 285 and US Pat. No. 5,925,151.

[0089] In some preferred embodiments, the composition comprises a compound formed by the reaction of an acylating agent derived from a polyisobutylene-substituted succinic acid and a polyethylene polyamine. Suitable compounds are described, for example, in WO2009 / 040583.

[0090] In a preferred embodiment, the reaction product of a carboxylic acid-derived acylating agent and an amine (b) comprises the reaction product of a polyisobutylene-substituted succinic acid or succinic anhydride and a polyethylene polyamine selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, and mixtures and isomers thereof; wherein the polyisobutylene substituent has a number average molecular weight of 500 to 2000, preferably 600 to 1000.

[0091] The composition of the first aspect may comprise a stabilizing additive selected from (i) an alkoxylated amine compound, (ii) an aldehyde-alkylphenol copolymer, or a mixture thereof.

[0092] The so-called stabilizing additive refers to a component that improves the stability of the pyrolysis oil composition (for example, its storage stability or oxidation stability), or a component that helps disperse solids, waxes or high molecular weight colloids in the pyrolysis oil. Suitable stabilizing additives can be referred to as dispersants in the art.

[0093] The composition may comprise any alkoxylated amine compound. This is meant to include any compound containing an amine functional group that has been reacted with at least one alkylene oxide moiety.

[0094] In a preferred embodiment, the alkoxylated amine compound contains more than one alkylene oxide residue.

[0095] Suitable alkylene oxide residues include ethylene oxide residues, propylene oxide residues, butylene oxide residues and mixtures thereof.

[0096] Preferably, the alkoxylated amine compound comprises ethylene oxide residues, propylene oxide residues, or mixtures thereof.

[0097] Preferably, the alkoxylated amine compound is an alkoxylated amine, an alkoxylated diamine or an alkoxylated polyamine.

[0098] 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.

[0099] R is preferably ethylene, propylene or butylene. R can be n-propylene or n-butylene or isopropylene or isobutylene. For example, R can be -CH 2 CH 2 -、-CH 2 CH(CH 3 )-、-CH 2 C(CH 3 ) 2 、-CH(CH 3 )CH(CH 3 )-or-CH 2 CH(CH 2 CH 3 )-.

[0100] R may comprise a mixture of isomers. For example, when R is propylene, the polyol may comprise -CH 2 CH(CH 3 )- and -CH(CH 3 )CH 2 -part.

[0101] Each R may be the same or different. R may include a mixture of different groups such as ethylene, propylene or butylene units. In such an embodiment, block copolymer units are preferred.

[0102] Preferably, R is ethylene and / or propylene. More preferably, R is -CH 2 CH 2 - or -CH(CH 3 )CH 2 -.

[0103] In some preferred embodiments, the alkoxylated amine compound (i) comprises a mixture of ethylene oxide residues and propylene oxide residues.

[0104] n is at least 1. Preferably, n is from 5 to 1000, preferably from 5 to 500, more preferably from 10 to 400, more preferably from 15 to 300, preferably from 20 to 250, suitably from 30 to 200, preferably from 50 to 150.

[0105] A is the residue of an amine. Suitably A is the residue of an amino group or a polyamino compound having at least one NH group. Suitable amino compounds include primary or secondary monoamines having a hydrocarbon substituent having 1 to 30 carbon atoms or a hydroxy-substituted hydrocarbon substituent having 1 to about 30 carbon atoms.

[0106] Preferably, A is the residue of a polyamine.

[0107] The polyamine may be selected from any compound comprising two or more amine groups. Preferably, the polyamine is a (poly)alkylenepolyamine (which refers to alkylenepolyamines or polyalkylenepolyamines; in each case including diamines, which are within the meaning of "polyamine"). Preferably, the polyamine is a (poly)alkylenepolyamine, wherein 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).

[0108] Preferably, the polyamine has 2 to 15 nitrogen atoms, preferably 2 to 10 nitrogen atoms, more preferably 2 to 8 nitrogen atoms.

[0109] The polyamines may be selected, for example, from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexyleneheptamine, heptaethyleneoctamine, propane-1,2-diamine, 2(2-amino-ethylamino)ethanol, N',N'-bis(2-aminoethyl)ethylenediamine (N(CH 2 CH 2 NH 2 ) 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.

[0110] Most preferably, A is the residue of ethylenediamine.

[0111] In some preferred embodiments, the alkoxylated amine compound (i) comprises a compound of formula (II):

[0112]

[0113]

[0114] 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. The compound 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. to provide a compound of formula (II) wherein the ethylene oxide and propylene oxide residues may be present in any combination and in any order bonded to the nitrogen of the amine group.

[0115] Preferably, a, b, c, d, e, f, g and h are each at least one. Preferably, the sum of a, b, c, d, e, f, g and h is 10 to 500, preferably 20 to 250, more preferably 40 to 200.

[0116] Those skilled in the art will appreciate that the polymer compound of formula (II) is typically in the form of a mixture.

[0117] Some alkoxylated amine compounds suitable for use herein are described in US6838422.

[0118] In some embodiments, the composition of the first aspect may comprise an aldehyde-alkylphenol copolymer.

[0119] Any suitable aldehyde-alkylphenol copolymer may be used and such compounds will be known to those skilled in the art.

[0120] Preferably, the aldehyde used to prepare the aldehyde-alkylphenol copolymer is selected from formaldehyde or its reactive equivalents, such as paraformaldehyde, C 2 To C 10 Aldehydes and aromatic aldehydes, such as benzaldehyde.

[0121] Preferred aldehyde-alkylphenol copolymers are copolymers of formaldehyde and alkylphenol. Preferably, the phenol is monosubstituted by 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.

[0122] In some embodiments, the alkylphenol is a polyisobutylene (PIB) substituted phenol.

[0123] The polyisobutenyl (PIB) substituted phenols include a hydrocarbyl chain having the following repeating units:

[0124]

[0125] Polyisobutylene is a kind of isobutylene ((CH 3 ) 2 C=CH 2 Each molecule of the resulting polymer will contain a single olefin moiety.

[0126] Conventional polyisobutenes and so-called "highly reactive" polyisobutenes are suitable for preparing the additive (ii) of the present invention. Highly reactive polyisobutenes in this context are defined 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 0565285. Particularly preferred polyisobutenes are polyisobutenes having more than 80 mol % and up to 100% of terminal vinylidene groups, such as those described in EP 1344785.

[0127] 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.

[0128] 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.

[0129] In some embodiments, the phenol may include a PIB substituent having an average molecular weight of up to 2800, preferably up to 2600, such as up to 2500 or up to 2400.

[0130] 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.

[0131] In some embodiments, the phenol may include a PIB substituent having an average molecular weight of 200 to 600.

[0132] In some embodiments, the phenol may include a PIB substituent having an average molecular weight of 500 to 1000.

[0133] In some embodiments, the phenol may include a PIB substituent having an average molecular weight of 700 to 1300.

[0134] In some embodiments, the phenol may include a PIB substituent having an average molecular weight of 1000 to 2000.

[0135] In some embodiments, the phenol may include a PIB substituent having an average molecular weight of 1700 to 2600 (eg, 2000 to 2500).

[0136] In some preferred embodiments, the aldehyde-alkylphenol copolymer has structure (III) or (IV):

[0137]

[0138]

[0139] wherein R is hydrogen or alkyl and n is at least 1.

[0140] Preferably, n is 2 to 12, preferably 5 to 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.

[0141] Those skilled in the art will appreciate that aldehyde-alkylphenol copolymers can be prepared from monomer mixtures, particularly compounds wherein R comprises a mixture of alkyl groups. Other aldehyde-alkylphenol copolymers suitable for use herein include compounds of formula (III) wherein the terminal phenol group is further functionalized, for example by reacting with a fatty acid or an amine and an aldehyde via a Mannich reaction. For example, compounds of this type are described in US 2007 / 221539.

[0142] 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.

[0143] In some embodiments, the composition of the first aspect comprises one or more (iii) quaternary ammonium salts as an additive.

[0144] Preferably, the quaternary ammonium salt additive is the reaction product of a compound including a tertiary amine group and a quaternizing agent.

[0145] Any suitable quaternizing agent may be used. The quaternizing agent may suitably be selected from esters and non-esters.

[0146] Suitable quaternizing agents include esters of carboxylic acids, dialkyl sulfates, benzyl halides, hydrocarbyl substituted carbonates, hydrocarbyl substituted epoxides (optionally in combination with an acid), alkyl halides, alkyl sulfonates, sultones, hydrocarbyl substituted phosphates, hydrocarbyl substituted borates, alkyl nitrites, alkyl nitrates, hydroxides, N-oxides, chloroacetic acid or salts thereof, or mixtures thereof.

[0147] In some preferred embodiments, the quaternizing agents used to form the quaternary ammonium salt additives of the present invention are esters.

[0148] Preferred ester quaternizing agents are compounds of formula (XI):

[0149]

[0150] wherein R is an optionally substituted alkyl, alkenyl, aryl or alkaryl group, and R 1 is a C1 to C22 alkyl, aryl or alkaryl group. The compound of formula (XI) is suitably an ester of a carboxylic acid capable of reacting with a tertiary amine to form a quaternary ammonium salt.

[0151] Suitable quaternizing agents include esters of carboxylic acids having a pKa of 3.5 or less.

[0152] The compound of formula (XI) is preferably an ester of a carboxylic acid selected from substituted aromatic carboxylic acids, α-hydroxycarboxylic acids and polycarboxylic acids.

[0153] In some preferred embodiments, the compound of formula (XI) is an ester of a substituted aromatic carboxylic acid, and thus R is a substituted aryl group.

[0154] Preferably, R is a substituted aryl group having 6 to 10 carbon atoms, preferably phenyl or naphthyl, most preferably phenyl. R is suitably substituted with one or more selected from alkoxycarbonyl, nitro, cyano, hydroxyl, SR 5 or NR 5 R 6 The group substituted. 5 and R 6 Each may be hydrogen or an optionally substituted alkyl, alkenyl, aryl or alkoxycarbonyl group. 5 and R 6 Each is hydrogen or an optionally substituted C1 to C22 alkyl group, preferably hydrogen or a C1 to C16 alkyl group, preferably hydrogen or a C1 to C10 alkyl group, more preferably hydrogen or a C1 to C4 alkyl group. Preferably, R 5 is hydrogen and R 6 is hydrogen or C1 to C4 alkyl. Most preferably, R 5 and R 6 Preferably, R is one or more selected from hydroxyl, alkoxycarbonyl, nitro, cyano and NH 2 In some embodiments, R may be an aryl substituted with a hydroxyl group and a alkyl group, such as an alkyl group, such as described in EP2631283.

[0155] Preferably, R is a monosubstituted aryl. Preferably, R is an ortho-substituted aryl. Suitably, R is selected from OH, NH 2 、NO 2 Preferably, R is OH or NH 2 Preferably, R is 2-hydroxyphenyl.

[0156] Preferably, R 1is an alkyl group, an aralkyl group or an alkaryl group. 1 It may be a C1 to C16 alkyl group, preferably a C1 to C10 alkyl group, and suitably a C1 to C8 alkyl group. 1 It may be a C7 to C16 aralkyl or alkaryl group, preferably a C7 to C10 aralkyl or alkaryl group. 1 It can be methyl, ethyl, propyl, butyl, pentyl, benzyl or an isomer thereof. 1 is benzyl or methyl. Most preferably, R 1 It is methyl.

[0157] Particularly preferred compounds of formula (XI) are lower alkyl esters of salicylic acid, such as methyl salicylate, ethyl salicylate, n-propyl salicylate and isopropyl salicylate, and butyl salicylate, preferably methyl salicylate.

[0158] In some embodiments, the compound of formula (XI) is an ester of an α-hydroxycarboxylic acid. In such embodiments, the compound has the following structure:

[0159]

[0160] Where R 7 and R 8 are the same or different and are each selected from hydrogen, alkyl, alkenyl, aralkyl or aryl. Compounds of this type suitable for use herein are described in EP1254889.

[0161] Examples of compounds of formula (XI) in which RCOO is an α-hydroxycarboxylic acid residue include methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl and allyl esters of 2-hydroxyisobutyric acid; methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl and allyl esters of 2-hydroxy-2-methylbutyric acid; methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl and allyl esters of 2-hydroxy-2-ethylbutyric acid; methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl and allyl esters of lactic acid; and methyl, ethyl, propyl, butyl, pentyl, hexyl, allyl, benzyl and phenyl esters of glycolic acid. Among them, the preferred compound is methyl 2-hydroxyisobutyrate.

[0162] In some embodiments, the compound of formula (XI) is an ester of a polycarboxylic acid. In this definition, it refers to a carboxylic acid including dicarboxylic acids and having more than two acid moieties. In such embodiments, RCOO preferably exists in the form of an ester, that is, one or more additional acid groups present in the group R are in esterified form. However, embodiments in which not all acid groups are esterified are also within the scope of the present invention. Mixed esters of polycarboxylic acids may also be used. Preferred esters are C1 to C4 alkyl esters.

[0163] The ester quaternizing agent may be selected from the group consisting of diesters of oxalic acid, diesters of phthalic acid, diesters of maleic acid, diesters of malonic acid or diesters of citric acid.An especially preferred compound of formula (XI) is dimethyl oxalate.

[0164] In a preferred embodiment, the compound of formula (XI) is an ester of a carboxylic acid having a pKa of less than 3.5. In such embodiments where the compound comprises more than one acid group, it refers to the first dissociation constant.

[0165] The ester quaternizing agent can be selected from esters of carboxylic acids, wherein the carboxylic acids are selected from one or more of the following: oxalic acid, phthalic acid, salicylic acid, maleic acid, malonic acid, citric acid, nitrobenzoic acid, aminobenzoic acid, 2,4,6-trihydroxybenzoic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, acetylenedicarboxylic acid, glutaconic acid, muconic acid, citraconic acid, mesaconic acid, itaconic acid, tartronic acid, mesooxalic acid, tartaric acid, oxaloacetic acid, dioxosuccinic acid, α-hydroxyglutaric acid, biphenylcarboxylic acid and 2,6-naphthalene dicarboxylic acid.

[0166] The ester quaternizing agent may be selected from esters of carboxylic acids selected from one or more of oxalic acid, phthalic acid, salicylic acid, maleic acid, malonic acid, citric acid, nitrobenzoic acid, aminobenzoic acid and 2,4,6-trihydroxybenzoic acid.

[0167] Preferred ester quaternizing agents include dimethyl oxalate, methyl 2-nitrobenzoate and methyl salicylate.

[0168] In some preferred embodiments, the quaternizing agent used to form the quaternary ammonium salt additive of the present invention is an ester selected from dimethyl oxalate, methyl 2-nitrobenzoate and methyl salicylate, preferably dimethyl oxalate and methyl salicylate.

[0169] Suitable non-ester quaternizing agents include dialkyl sulfates, benzyl halides, hydrocarbyl substituted carbonates, hydrocarbyl substituted epoxides (optionally in combination with an acid), alkyl halides, alkyl sulfonates, sultones, hydrocarbyl substituted phosphates, hydrocarbyl substituted borates, alkyl nitrites, alkyl nitrates, hydroxides, N-oxides, chloroacetic acid or salts thereof, or mixtures thereof.

[0170] Preferred non-ester quaternizing agents include dialkyl sulfates, benzyl halides, hydrocarbyl substituted carbonates, hydrocarbyl substituted epoxides in combination with acids, alkyl halides, alkyl sulfonates, sultones, hydrocarbyl substituted phosphates, hydrocarbyl substituted borates, N-oxides, chloroacetic acid or its salts, or mixtures thereof.

[0171] In some embodiments, quaternary ammonium salts can be prepared from, for example, alkyl or benzyl halides (especially chlorides), followed by ion exchange reactions to provide different anions as part of the quaternary ammonium salt. Such methods can be suitable for preparing quaternary ammonium hydroxides, alkoxides, nitrites or nitrates.

[0172] Suitable alkyl halides for use herein include chlorides, bromides and iodides.

[0173] Suitable benzyl halides include chlorides, bromides and iodides. The phenyl group may be optionally substituted, for example by one or more alkyl or alkenyl groups, particularly when a chloride is used. A preferred compound is benzyl bromide.

[0174] Suitable dialkyl sulfates for use herein as quaternizing agents include those having an alkyl group having from 1 to 10, preferably from 1 to 4, carbon atoms in the alkyl chain. The preferred compound is dimethyl sulfate.

[0175] Suitable alkyl-substituted carbonates can include two alkyls, which can be identical or different. Each alkyl can contain 1 to 50 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, suitably 1 to 5 carbon atoms. Preferably, the alkyl or each alkyl is an alkyl. Preferred compounds of this type include diethyl carbonate and dimethyl carbonate.

[0176] Suitable hydrocarbyl substituted epoxides have the formula:

[0177]

[0178] Where R 1 , R 2 , R 3 and R 4 Each is independently hydrogen or a hydrocarbyl group having 1 to 50 carbon atoms. Examples of suitable epoxides include ethylene oxide, propylene oxide, butylene oxide, styrene oxide and stilbene oxide. Hydrocarbyl epoxides are used in combination with acids as quaternizing agents.

[0179] In some embodiments, the compound comprising a tertiary amine group also includes an acid functional group. In these embodiments, if an epoxide is used as a quaternizing agent, there is no need to add a separate acid. However, in other embodiments, an acid such as acetic acid may be used.

[0180] Particularly preferred epoxide quaternizing agents are propylene oxide and styrene oxide, optionally in combination with an additional acid.

[0181] Suitable alkyl sulfonates include those having 1 to 20, preferably 1 to 10, more preferably 1 to 4 carbon atoms.

[0182] Suitable sultones include propane sultone and butane sultone.

[0183] Suitable hydrocarbyl-substituted phosphates include monoalkyl phosphates, dialkyl phosphates, trialkyl phosphates and O,O-dialkyl dithiophosphates.Preferred alkyl groups have from 1 to 12 carbon atoms.

[0184] Suitable hydrocarbyl-substituted borate groups include alkyl borates having from 1 to 12 carbon atoms.

[0185] Preferred alkyl nitrites and alkyl nitrates have 1 to 12 carbon atoms.

[0186] Preferably, the non-ester quaternizing agent is selected from dialkyl sulfates, benzyl halides, hydrocarbyl substituted carbonates, hydrocarbyl substituted epoxides optionally in combination with an additional acid, chloroacetic acid or its salts, and mixtures thereof.

[0187] Particularly preferred non-ester quaternizing agents for use herein are hydrocarbyl-substituted epoxides in combination with acids. These may include embodiments in which a separate acid is provided or embodiments in which the acid is provided by a quaternized tertiary amine compound. Preferably, the acid is provided by a quaternized tertiary amine molecule.

[0188] Preferred quaternizing agents for use herein include dimethyl oxalate, methyl 2-nitrobenzoate, methyl salicylate, chloroacetic acid or its salts, and styrene oxide or propylene oxide (optionally in combination with an additional acid).

[0189] In some embodiments, mixtures of two or more quaternizing agents may be used.

[0190] To form the quaternary ammonium salt additive, a quaternizing agent is reacted with a compound containing a tertiary amine group.

[0191] Any suitable compound containing a tertiary amine group may be used.

[0192] The compound comprising at least one tertiary amine group may be selected from:

[0193] (1) The reaction product of a hydrocarbyl-substituted acylating agent and a compound containing at least one tertiary amine group and a primary amine, secondary amine or alcohol group;

[0194] (2) Mannich reaction products containing tertiary amine groups;

[0195] (3) a polyalkylene-substituted amine having at least one tertiary amine group; and

[0196] (4) Simple alkylamines and alkanolamines.

[0197] Examples of quaternary ammonium salts and methods for their preparation are described in the following patents: US2008 / 0307698, US2008 / 0052985, US2008 / 0113890, and US2013 / 031827.

[0198] The preparation of some suitable quaternary ammonium salt additives is described in WO2006 / 135881, US2020 / 0024536 and WO2011 / 095819, wherein the compound containing at least one tertiary amine group is of type (1).

[0199] US 2008 / 0052985 describes the preparation of quaternary ammonium salts of type (2) in which the compound comprises at least one tertiary amine group.

[0200] The preparation of quaternary ammonium salt additives in which the compound comprising at least one tertiary amine group is of type (3) is described, for example, in US 2008 / 0113890.

[0201] For example, the preparation of some suitable quaternary ammonium salt additives is described in WO 2016 / 016641, wherein the compound containing at least one tertiary amine group is of type (4).

[0202] Other suitable quaternary ammonium salts include quaternized terpolymers such as those described in US2011 / 0258917; quaternized copolymers such as those described in US2011 / 0315107; and acid-free quaternized nitrogen compounds disclosed in US2012 / 0010112.

[0203] In some embodiments, the present invention does not encompass acid-free quaternized nitrogen compounds. In preferred embodiments, the quaternary ammonium salt additives of the present invention include a single anion and a single cation.

[0204] In some embodiments, the quaternary ammonium compound used in the present invention is the quaternization reaction product of a fatty acid (eg, oleic acid) and dimethylaminopropylamine.

[0205] Other suitable quaternary ammonium compounds for use in the present invention include the quaternary ammonium compounds described in the applicant's co-pending applications WO2011 / 095819, WO2013 / 017889, WO2015 / 011506, WO2015 / 011507, WO2016 / 016641 and WO2017 / 017454.

[0206] Preferably, additive (iii) comprises a quaternary ammonium salt which is the quaternary reaction product of a hydrocarbyl-substituted succinic acid derived acylating agent and a compound capable of reacting with said acylating agent and comprising a tertiary amine group.

[0207] Preferably, the hydrocarbyl-substituted acylating agent is a hydrocarbyl-substituted succinic acid derived acylating agent.

[0208] For the avoidance of doubt, reference to a quaternized reaction product is intended to refer to a reaction product comprising a tertiary amine which has then been quaternized to form a quaternary ammonium group. The quaternary ammonium salt additive is formed by the reaction of a quaternizing agent with a hydrocarbyl-substituted succinic acid derived acylating agent and a compound capable of reacting with the acylating agent and containing a tertiary amine group.

[0209] Suitable hydrocarbyl-substituted succinic acid derived acylating agents and methods for their preparation are well known in the art. For example, a common method for preparing hydrocarbyl-substituted succinic acid acylating agents is by reacting maleic anhydride with an olefin via a chlorination route or a thermal route (the so-called "ene" reaction).

[0210] The example of alkyl substituent group comprises n-octyl, n-decyl, n-dodecyl, tetrapropylene, n-octadecyl, oleyl, chlorooctadecyl, triacontyl etc.The alkyl substituent group can be made by the homopolymer or interpolymer (for example copolymer, terpolymer) of monoolefin and diolefin (for example ethylene, propylene, butane-1, isobutylene, butadiene, isoprene, 1-hexene, 1-octene etc.) with 2 to 10 carbon atoms.Preferably, these olefins are 1-monoolefins.Or, substituent group can be made by other sources, for example monomer high molecular weight olefin (for example 1-tetradecene), aliphatic petroleum fractions, for example paraffin and its cracking analog, white oil, synthetic olefin (for example produced by Ziegler-Natta process) (for example poly (ethylene) grease) and other sources well known to persons skilled in the art.If necessary, any unsaturation in the substituent group can be reduced or eliminated by hydrogenation according to procedures known in the art.

[0211] Preferably, the hydrocarbyl substituents are 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.

[0212] The hydrocarbyl substituent of the succinic acid derived acylating agent preferably contains at least 10 carbon atoms, more preferably at least 12 carbon atoms, 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 to 2800, for example 250 to 1500, preferably 500 to 1500, and more preferably 500 to 1100. An Mn of 700 to 1300 is particularly preferred.

[0213] The skilled artisan will be familiar with standard techniques for measuring number average molecular weight, for example by vapour pressure osmometry, end group titration, proton NMR, boiling point elevation, freeze suppression (cryometry) and GPC (gel permeation chromatography).

[0214] The hydrocarbyl-substituted succinic acid derived acylating agent may comprise a mixture of compounds. For example, a mixture of compounds having different hydrocarbyl substituents may be used.

[0215] The preferred hydrocarbyl substituent is polyisobutylene. Such compounds are known to those skilled in the art.

[0216] The preferred hydrocarbyl-substituted succinic acid derived acylating agent is polyisobutenyl succinic anhydride. These compounds are commonly referred to as "PIBSA" and are well known to those skilled in the art.

[0217] Conventional polyisobutylenes and so-called "highly reactive" polyisobutylenes are suitable for use in the present invention. Suitable highly reactive polyisobutylenes are as defined above.

[0218] Other preferred hydrocarbyl groups include those having internal olefins, such as those described in applicant's published application WO2007 / 015080.

[0219] As used herein, internal olefins refer to any olefins containing primarily non-alpha double bonds, i.e., beta or higher olefins. Preferably, such materials are substantially entirely beta olefins or higher olefins, e.g., containing less than 10% by weight of alpha olefins, more preferably less than 5% by weight or less than 2% by weight. Typical internal olefins include Neodene 1518IO available from Shell.

[0220] 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.

[0221] The preferred hydrocarbyl substituted succinic acid derived acylating agent for preparing additive (iii) of the present invention is polyisobutenyl substituted succinic anhydride or PIBSA. Particularly preferred PIBSAs are those having a PIB molecular weight (Mn) of 300 to 2800, preferably 450 to 2300, more preferably 500 to 1300.

[0222] Hydrocarbyl-substituted succinic acid derived acylating agents are suitably prepared by reacting maleic anhydride with an olefin (e.g. polyisobutylene). The product obtained (e.g. PIBSA) still contains double bonds. Maleic anhydride is present as the succinic acid moiety in the resulting molecule. The initial product is a monomaleated PIBSA.

[0223] The monomaleated PIBSA may have structure (A) or (B):

[0224]

[0225] The double bond in the monomaleated product can react with another molecule of maleic anhydride to form a bismaleated PIBSA having structure (C) or (D):

[0226]

[0227] Thus, a hydrocarbyl group substituted with more than one succinic acid moiety may be provided.

[0228] Those skilled in the art will appreciate that the additive used in the present invention will typically comprise a mixture of compounds and will be prepared from a mixture of monomaleated and bismaleated PIBSA.PIBSA can be defined according to its level of bismaleation.

[0229] One way in which the bismaleylation level can be determined is by calculating the average number of succinic acid moieties per molecule of acylating agent.

[0230] Monomaleated PIBSA contains one succinic acid moiety per molecule.

[0231] Bismaleated PIBSA contains two succinic acid moieties per molecule.

[0232] A mixture comprising monomaleated PIBSA and bismaleated PIBSA in a 1:1 molar ratio contained an average of 1.5 succinic acid moieties per PIBSA molecule.

[0233] The average number of succinic acid moieties per molecule of acylating agent is sometimes referred to in the art as the "P value."

[0234] Suitably, the quaternary ammonium salt additive is prepared from a hydrocarbyl-substituted succinic acid derived acylating agent containing an average of 1 to 2 succinic acid moieties per molecule.

[0235] In some preferred embodiments, the present invention may involve the use of quaternary ammonium salts derived from hydrocarbyl-substituted acylating agents comprising an average of at least 1.2 succinic acid moieties per molecule.

[0236] Those skilled in the art will appreciate that a single molecule cannot have 1.2 succinic acid moieties. By at least 1.2 succinic acid moieties is meant the average number of succinic acid moieties per molecule of acylating agent, equal to the sum of all succinic acid moieties present in the sample divided by the total number of acylating agent molecules having one or more succinic acid moieties present in the sample.

[0237] Preferably, the hydrocarbyl-substituted succinic acid derived acylating agent comprises an average of at least 1.21 succinic acid moieties per molecule, more preferably an average of at least 1.22 succinic acid moieties per molecule.

[0238] In some embodiments, the hydrocarbyl-substituted succinic acid derived acylating agent may comprise at least 1.23 or at least 1.24 succinic acid moieties per molecule.

[0239] In some embodiments, the hydrocarbyl-substituted succinic acid derived acylating agent may comprise at least 1.25, at least 1.26, or at least 1.27 succinic acid moieties per molecule.

[0240] In some embodiments, the hydrocarbyl-substituted succinic acid derived acylating agent may comprise at least 1.28, at least 1.29, or at least 1.30 succinic acid moieties per molecule.

[0241] The term succinic acid moiety is intended to include succinic acid residues in the form of the diacid or the anhydride.

[0242] The hydrocarbyl-substituted succinic acid derived acylating agent is reacted with a compound capable of reacting with the acylating agent and comprising a tertiary amine group. The tertiary amine group is quaternized to provide a quaternary ammonium salt additive.

[0243] Examples of suitable compounds capable of reacting with a hydrocarbyl-substituted succinic acid-derived acylating agent and containing a tertiary amine group may include, but are not limited to: N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, N,N-dimethylaminoethylamine. Nitrogen- or oxygen-containing compounds capable of condensing with an acylating agent and also having a tertiary amino group may also include aminoalkyl-substituted heterocyclic compounds, such as 1-(3-aminopropyl)imidazole and 4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-diamino-N-methyldipropylamine, and 3'3-aminobis(N,N-dimethylpropylamine). Other types of nitrogen- or oxygen-containing compounds having tertiary amino groups that can condense with an acylating agent include alkanolamines, including but not limited to triethanolamine, trimethanolamine, N,N-dimethylaminopropanol, N,N-dimethylaminoethanol, N,N-diethylaminopropanol, N,N-diethylaminoethanol, N,N-diethylaminobutanol, N,N,N-tris(hydroxyethyl)amine, N,N,N-tris(hydroxymethyl)amine, N,N,N-tris(aminoethyl)amine, N,N-dibutylamino Propylamine and N,N,N'-trimethyl-N'-hydroxyethyl-bisaminoethyl ether; N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine; N-(3-dimethylaminopropyl)-N,N-diisopropanolamine; N'-(3-(dimethylamino)propyl)-N,N-dimethyl 1,3-propanediamine; 2-(2-dimethylaminoethoxy)ethanol, N,N,N'-trimethylaminoethylethanolamine and 3-(2-(dimethylamino)ethoxy)propylamine.

[0244] Preferably, the compound capable of reacting with the hydrocarbyl-substituted succinic acid derived acylating agent and comprising a tertiary amine group is an amine of formula (XII) or (XIII):

[0245]

[0246] Where R 2 and R 3 are the same or different alkyl, alkenyl, aryl, alkaryl or aralkyl groups having 1 to 22 carbon atoms; X is a bond or an optionally substituted alkylene group having 1 to 20 carbon atoms; n is 0 to 20; m is 1 to 5; and R 4 is hydrogen or C 1 To C 22 alkyl.

[0247] When the compound of formula (XII) is used, R 4 Preferably hydrogen or C 1 To C 16 Alkyl, preferably C 1 To C 10 Alkyl, more preferably C 1 To C 6 Alkyl. When R 4 When R is an alkyl group, it may be straight chain or branched. For example, it may be substituted with hydroxyl or alkoxy substituents. Preferably, R 4 More preferably, R 4 is selected from hydrogen, methyl, ethyl, propyl, butyl and isomers thereof. Most preferably, R 4 For hydrogen.

[0248] When a compound of formula (XIII) is used, m is preferably 2 or 3, most preferably 2; n is preferably 0 to 15, preferably 0 to 10, more preferably 0 to 5. Most preferably, n is 0 and the compound of formula (XIII) is an alcohol.

[0249] Preferably, a hydrocarbyl-substituted acylating agent is reacted with a diamine compound of formula (XII).

[0250] R 2 and R 3 are the same or different alkyl, alkenyl, aryl, alkaryl or aralkyl groups having 1 to 22 carbon atoms. 2 and R 3 can be linked together to form a ring structure, such as a piperidine, imidazole or morpholine moiety. 2 and R 3 Together they may form an aromatic and / or heterocyclic moiety. 2 and R 3It may be a branched alkyl or alkenyl group. Each may be substituted, for example, with hydroxy or alkoxy substituents.

[0251] Preferably, R 2 and R 3 Each independently is C 1 To C 16 Alkyl, preferably C 1 To C 10 Alkyl. 2 and R 3 R may independently be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl or any isomer of these groups. 2 and R 3 Each independently is C 1 To C 4 Preferably, R 2 Preferably, R 3 It is methyl.

[0252] X is a bond or an optionally substituted alkylene group having 1 to 20 carbon atoms. In a preferred embodiment, when X is an alkylene group, the group can be straight chain or branched. The alkylene group can contain a cyclic structure therein. It can be optionally substituted, for example, by a hydroxyl or alkoxy substituent. In some embodiments, X can include heteroatoms within the alkylene chain, for example, X can include an ether functional group.

[0253] X is preferably an alkylene group having 1 to 16 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, for example 2 to 6 carbon atoms or 2 to 5 carbon atoms. In some preferred embodiments, X is an unsubstituted alkylene group. Most preferably, X is ethylene, propylene or butylene, especially propylene.

[0254] Examples of compounds of formula (XII) suitable for use herein include 1-aminopiperidine, 1-(2-aminoethyl)piperidine, 1-(3-aminopropyl)-2-piperidin, 1-methyl-(4-methylamino)piperidine, 4-(1-pyrrolidinyl)piperidine, 1-(2-aminoethyl)pyrrolidine, 2-(2-aminoethyl)-1-methylpyrrolidine, N,N-diethylethylenediamine, N,N-dimethylethylenediamine, N,N-dibutylethylenediamine, N,N-diethyl-1,3-diaminopropane, N,N-dimethyl-1,3-diaminopropane, N,N,N'-trimethylethylenediamine, N,N-dimethyl-N'-ethylethylenediamine, N,N-diethyl-N'-methylethylenediamine, N,N,N'-trimethylethylenediamine, ethylethylenediamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, 3-dibutylaminopropylamine, N,N,N'-trimethyl-1,3-propylenediamine, N,N,2,2-tetramethyl-1,3-propylenediamine, 2-amino-5-diethylaminopentane, N,N,N',N'-tetraethyldiethylenetriamine, 3,3'-diamino-N-methyldipropylamine, 3,3'-iminobis(N,N-dimethylpropylamine), 1-(3-aminopropyl)imidazole and 4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-diamino-N-methyldipropylamine, 3,3-aminobis(N,N-dimethylpropylamine), 3-(2-(dimethylamino)ethoxy)propylamine or a combination thereof.

[0255] In some preferred embodiments, the compound of formula (XII) is selected from N,N-dimethyl-1,3-diaminopropane, N,N-diethyl-1,3-diaminopropane, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dibutylethylenediamine, 3-(2-(dimethylamino)ethoxy)propylamine, or a combination thereof.

[0256] Examples of compounds of formula (XIII) suitable for use herein include alkanolamines, including but not limited to triethanolamine, N,N-dimethylaminopropanol, N,N-diethylaminopropanol, N,N-diethylaminobutanol, triisopropanolamine, 1-[2-hydroxyethyl]piperidine, 2-[2-(dimethylamino)ethoxy]-ethanol, N-ethyldiethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, N,N-diethylaminoethanol, N,N-dimethylaminoethanol , 2-dimethylamino-2-methyl-1-propanol, N,N,N'-trimethyl-N'-hydroxyethyl-bisaminoethyl ether; N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine; N-(3-dimethylaminopropyl)-N,N-diisopropanolamine; N'-(3-(dimethylamino)propyl)-N,N-dimethyl-1,3-propanediamine; 2-(2-dimethylaminoethoxy)ethanol and N,N,N'-trimethylaminoethylethanolamine.

[0257] In some preferred embodiments, the compound of formula (XIII) is selected from triisopropanolamine, 1-[2-hydroxyethyl]piperidine, 2-[2-(dimethylamino)ethoxy]-ethanol, N-ethyldiethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, N,N-diethylaminoethanol, N,N-dimethylaminoethanol, 2-dimethylamino-2-methyl-1-propanol, or a combination thereof.

[0258] A particularly preferred compound of formula (XII) is N,N-dimethyl-1,3-diaminopropane (dimethylaminopropylamine).

[0259] When the compound of formula (XIII) reacts with a succinic acylating agent, the resulting product is a succinate. 4 When the succinic acid acylating agent reacts with a compound of formula (XII) (wherein R 4 When the reaction is carried out with 2-H-butyl 2-nitropropene (not hydrogen), the product obtained is an amide

[0260] To form the quaternary ammonium salt additive (iii), a hydrocarbyl-substituted succinic acid derived acylating agent is reacted with a compound capable of reacting with the acylating agent and containing a tertiary amine group. The reaction product is then quaternized by reaction with a quaternizing agent.

[0261] The reaction product of the acylating agent and the compound comprising a tertiary amine group is preferably reacted with at least one molar equivalent of quaternizing agent per mole of tertiary amine groups present in the reaction product.

[0262] In some embodiments, the reaction product of the acylating agent and the compound comprising a tertiary amine group may be reacted with more than one molar equivalent of a quaternizing agent per mole of tertiary amine groups present in the reaction product, preferably at least 1.2 molar equivalents of quaternizing agent per mole of tertiary amine groups, more preferably at least 1.5 molar equivalents of quaternizing agent, suitably at least 1.7 molar equivalents of quaternizing agent, for example at least 1.9 molar equivalents of quaternizing agent.

[0263] In some embodiments, the reaction product of the acylating agent and the compound containing a tertiary amine group may be reacted with two or more molar equivalents of quaternizing agent per mole of tertiary amine groups present in the reaction product, preferably at least 2.1 molar equivalents of quaternizing agent.

[0264] In some embodiments, the reaction product of an acylating agent and a compound comprising a tertiary amine group is reacted with more than 2.2 molar equivalents of quaternizing agent per mole of tertiary amine groups present in the reaction product, e.g., 2.3 to 4 molar equivalents, 2.3 to 3 molar equivalents, or 2.3 to 2.7 or 2.5 to 3 molar equivalents.

[0265] To form some preferred quaternary ammonium salt additives of the present invention, a compound of formula (XI) is reacted with a compound formed by reacting a hydrocarbyl-substituted acylating agent and an amine of formula (XII) or (XIII).

[0266] The compound of formula (XII) or formula (XIII) is as described above.

[0267] Preferably, the amine of formula (XII) or (XIII) is reacted with a hydrocarbyl-substituted succinic acid derived acylating agent such as succinic acid or succinic anhydride.

[0268] Suitably about one equivalent of amine is added per succinic acid moiety present in the acylating agent.Thus, the proportion of amine used will generally depend on the average number of succinic acid moieties present per molecule of the acylating agent.

[0269] Preferred quaternary ammonium salts for use herein can be formed by reacting methyl salicylate, dimethyl oxalate or propylene oxide, optionally in combination with an acid, with the reaction product of polyisobutylene-substituted succinic anhydride and dimethylaminopropylamine having a PIB molecular weight (Mn) of 700 to 1300. Mixtures of two or more such quaternary ammonium salts can be used.

[0270] The quaternary ammonium salt preferably used herein is a quaternary ammonium salt of the reaction product of a polyisobutylene-substituted succinic anhydride having a PIB molecular weight (Mn) of 700 to 1300 and dimethylaminopropylamine.

[0271] Particularly preferred quaternary ammonium salts for use herein are formed from methyl salicylate or dimethyl oxalate reacted with the reaction product of a polyisobutylene-substituted succinic anhydride having a PIB molecular weight (Mn) of 700 to 1300 and dimethylaminopropylamine.

[0272] In a preferred embodiment, the polyisobutylene-substituted succinic anhydride comprises an average of at least 1.2 succinic acid moieties per molecule.

[0273] When an antioxidant is present, it is preferably comprised in the composition of the first aspect in an amount of at least 10 ppm, preferably at least 20 ppm, more preferably at least 50 ppm, for example at least 70 ppm.

[0274] When an antioxidant is present, it may be included in the composition of the first aspect in an amount of up to 10000 ppm, preferably up to 5000 ppm, more preferably up to 2000 ppm, for example up to 1000 ppm.

[0275] When a stabilizing additive is present, it is preferably comprised in the composition of the first aspect in an amount of at least 10 ppm, preferably at least 20 ppm, more preferably at least 50 ppm, for example at least 70 ppm.

[0276] When present, a stabilizing additive may be included in the composition of the first aspect in an amount of up to 10000 ppm, preferably up to 5000 ppm, more preferably up to 2000 ppm, for example up to 1000 ppm.

[0277] When an alkoxylated amine compound is present it is preferably comprised in the composition of the first aspect in an amount of at least 5 ppm, preferably at least 10 ppm, more preferably at least 20 ppm, for example at least 40 ppm.

[0278] 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 1500 ppm, for example up to 800 ppm.

[0279] When the aldehyde-alkylphenol copolymer is present it is preferably comprised in the composition of the first aspect in an amount of at least 5 ppm, preferably at least 10 ppm, more preferably at least 20 ppm, for example at least 30 ppm.

[0280] 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.

[0281] In this specification, any reference to ppm refers to parts per million by weight.

[0282] In a preferred embodiment, the stabilizing additive (b) comprises 1 part by weight of the alkoxylated amine compound (i) and 0.5 to 2.5 parts by weight of the aldehyde-alkylphenol copolymer.

[0283] The stabilizing additive may also include a carrier or diluent. Preferred carriers and diluents are aromatic hydrocarbon compounds, especially C 10 Alkyl naphthalene.

[0284] In a preferred embodiment, the composition of the first aspect comprises 100 to 1000 ppm, preferably 250 to 750 ppm of an antioxidant and / or 100 to 1000 ppm, preferably 250 to 750 ppm of a stabilizing additive selected from (i) an alkoxylated amine compound; (ii) an aldehyde-alkylphenol copolymer; and mixtures thereof.

[0285] In a preferred embodiment, the composition of the first aspect comprises 100 to 1000 ppm, preferably 250 to 750 ppm of an antioxidant and / or 0 to 500 ppm, preferably 100 to 300 ppm of an alkoxylated amine compound and / or 0 to 500 ppm, preferably 100 to 300 ppm of an aldehyde-alkylphenol copolymer.

[0286] In a preferred embodiment, the composition of the first aspect comprises 50 to 500 ppm, preferably 125 to 325 ppm, of one or more quaternary ammonium salts, suitably wherein the quaternary ammonium salt is a polyisobutylene-substituted succinimide ammonium salt, for example a quaternary ammonium salt of the reaction product of a polyisobutylene-substituted succinic anhydride having a PIB molecular weight (Mn) of 700 to 1300 and dimethylaminopropylamine.

[0287] In a preferred embodiment the composition of the first aspect comprises from 200 to 400 ppm, preferably from 275 to 375 ppm, of a polyisobutenyl substituted succinimide, for example the reaction product of a polyisobutenyl substituted succinic acid or succinic anhydride and a polyethylene polyamine, suitably selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine and mixtures and isomers thereof; suitably tetraethylenepentamine; suitably wherein the polyisobutenyl substituent has a number average molecular weight of between 500 and 2000, preferably 600 to 1000.

[0288] In some embodiments, the composition of the first aspect can be used as middle distillate fuel oil.Therefore, said composition can include one or more other additives, for example common additives in diesel fuel.These include for example antioxidant, dispersant, detergent, metal deactivation compound, wax anti-settling agent, cold flow improver, cetane number improver, demister, stabilizer, demulsifier, defoamer, corrosion inhibitor, lubricity improver, dye, marker, combustion improver, metal deactivator, odor masking agent, drag reducer and conductivity improver.The example of the respective suitable amount of these types of additives will be known to those skilled in the art.

[0289] Surprisingly, it has been found that the addition of (a) an antioxidant; and / or (b) a stabilizing additive selected from (i) an alkoxylated amine compound, (ii) an aldehyde-alkylphenol copolymer, or a mixture thereof, improves the storage stability of a composition comprising pyrolysis oil.

[0290] According to a second aspect of the present invention, there is provided a method for improving the stability of a composition comprising pyrolysis oil, the method comprising adding to the composition one or more additives selected from the group consisting of:

[0291] (a) antioxidants; and

[0292] (b) a stabilizing additive selected from the group consisting of (i) alkoxylated amine compounds; (ii) aldehyde-alkylphenol copolymers; and mixtures thereof.

[0293] According to another aspect of the present invention, there is provided a method for improving the stability of a composition comprising pyrolysis oil, the method comprising adding to the composition one or more additives selected from the group consisting of:

[0294] (a) antioxidants; and

[0295] (b) a stabilizing additive selected from the group consisting of (i) alkoxylated amine compounds; (ii) aldehyde-alkylphenol copolymers; (iii) quaternary ammonium salts; and mixtures thereof.

[0296] According to a third aspect of the present invention, there is provided a use of one or more additives selected from the following for improving the stability of a composition comprising pyrolysis oil:

[0297] (a) antioxidants; and

[0298] (b) a stabilizing additive selected from the group consisting of (i) alkoxylated amine compounds; (ii) aldehyde-alkylphenol copolymers; and mixtures thereof.

[0299] According to another aspect of the present invention, there is provided a use of one or more additives selected from the following for improving the stability of a composition comprising pyrolysis oil:

[0300] (a) antioxidants; and

[0301] (b) a stabilizing additive selected from the group consisting of (i) alkoxylated amine compounds; (ii) aldehyde-alkylphenol copolymers; (iii) quaternary ammonium salts; and mixtures thereof.

[0302] 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.

[0303] One or more additives may be added to the composition comprising pyrolysis oil at any time. They are preferably added as soon as possible after the oil is synthesized, preferably before the oil is cooled.

[0304] The method and use of the present invention improves the stability of compositions comprising pyrolysis oil.

[0305] Preferably, the method and use improve the stability of the composition comprising plastic pyrolysis oil.

[0306] Preferably, the method and use improves the storage stability of a composition comprising pyrolysis oil.

[0307] Preferably, the method and use improve the storage stability of the composition comprising plastic pyrolysis oil.

[0308] The improvement in storage stability suitably results in a reduction in oil degradation during storage. This can be observed in a number of ways.

[0309] In some embodiments, the improved stability may provide a reduction in discoloration during storage.

[0310] In some embodiments, the improvement in stability can provide reduced precipitation.

[0311] In some embodiments, the improvement in stability can reduce or prevent an increase in viscosity.

[0312] In some embodiments, the improved stability can reduce the formation of gums and particulates in compositions comprising pyrolysis oil.

[0313] In some embodiments, improved stability can provide improved filterability, particularly after storage.

[0314] In some embodiments, the improved stability can provide improved low temperature performance of compositions comprising pyrolysis oil.

[0315] One method of measuring stability improvement is described in Example 1. In this example, the precipitation of pyrolysis oil over time was collected by filtration. In addition, the residue adhering to the surface of the storage container was also checked.

[0316] Preferably, the method and use according to the invention reduces the formation of insoluble residues in the pyrolysis oil by at least 5 wt.-%, preferably by at least 10 wt.-%, for example by at least 15 wt.-%.

[0317] The invention will now be further described with reference to the following non-limiting examples.

[0318] Embodiment 1:

[0319] 500 mg / L of the following additives were added to plastic pyrolysis oil from commercial sources:

[0320]

[0321] The storage stability of the oils with the additives was compared with the storage stability of the oils without the additives. The compositions were kept at a minimum temperature of 15°C during the 28 day storage period.

[0322] The test involved agitating the jars to ensure all the sediment was dispersed, extracting 500 ml from each jar and filtering through a nitrocellulose filter (0.8 μm). The filter was then dried with 2,2,4-trimethylpentane, a method known to wash away any remaining pyrolysis oil without dissolving the sediment. The weight of the filter before and after was measured to quantify the amount present.

[0323] The results are shown in Table 1, and the filter paper is as shown in Table 1. Figure 1 As shown:

[0324] Table 1.

[0325]

[0326] Embodiment 2:

[0327] The composition was prepared by metering the following additives into the plastic pyrolysis oil:

[0328] Table 2.

[0329] Composition additive Treatment rate (mg / L) C Dispersant 1 250 D Dispersant 1 500 E Antioxidant 1 250 F Antioxidant 1 500

[0330] Dispersant 1 is as defined in Example 1.

[0331] Antioxidant 1 is a phenolic antioxidant comprising at least 75 wt % of 2,6-di-tert-butylphenol and at most 25 wt % of tert-butylphenol and tri-tert-butylphenol.

[0332] After a storage period of four weeks, 500 ml of each fuel was filtered through a nitrocellulose filter (0.8 μm).

[0333] The filter was then washed with 2,2,4-trimethylpentane, a method known to wash away any residual pyrolysis oil without dissolving the deposits, and then dried.

[0334] The weight of the filter paper before and after was measured to quantify the amount of insoluble material present.

[0335] After filtration, the adhering insoluble material remaining in the storage bottle was then dissolved in a tri-solvent (1:1:1 - acetone:toluene:methanol) and transferred to a pre-weighed beaker.

[0336] The solvent was then evaporated and the content of adhering insoluble matter was determined.

[0337] The total amount of insoluble matter recovered from each composition is shown in Table 3:

[0338] Table 3.

[0339]

[0340]

[0341] Embodiment 3:

[0342] A further exemplary composition was prepared by metering the following additives into the plastic pyrolysis oil:

[0343] Table 4.

[0344] Composition additive Treatment rate (mg / L) G Additive 2 250 H Additive 2 500 I Additive 3 500

[0345] Additive 2 is a polyisobutenyl substituted succinimide ammonium salt and was prepared as follows:

[0346] By mixing 700 g (0.7 mol) of polyisobutylene (M n1000) was loaded into a jacketed reactor purged with nitrogen and equipped with an overhead stirrer to prepare polyisobutenyl succinic anhydride (PIBSA). The starting material was heated to 120°C under stirring and the nitrogen flush was repeated. The reaction temperature was raised to 190°C and maleic anhydride (82.4g, 0.84mol, 1.2 equivalents) was loaded within 1 hour. After the temperature of 190°C was maintained for another 1 hour, the temperature was raised to 200-208°C and maintained within this range for 8 hours. Then a vacuum (<30mbar) was applied for 2.5 hours while maintaining the reaction temperature, which reduced the content of residual maleic anhydride to ≤0.05% by weight. The reaction mass was cooled to ≤80°C and then discharged from the reactor.

[0347] The PIBSA prepared as described above was charged into a nitrogen purged jacketed reactor equipped with an overhead stirrer and heated to 120°C. 3-(Dimethylamino)propylamine (DMAPA) (1 equivalent relative to the anhydride groups) was slowly charged, maintaining the reaction temperature between 120-130°C. After stirring at 120°C for another hour, the reaction temperature was raised to 140°C and maintained for 3 hours while distilling water. Methyl salicylate (2.1 equivalents relative to the anhydride groups) was added in one go and heating was continued at 140°C for 10 hours. Prior to discharge from the reactor, the reaction mass was diluted with Aromatic 150 solvent to provide a total solids content of 60 wt%.

[0348] Additive 3 is a polyisobutenyl substituted succinimide and was prepared as follows:

[0349] The reaction apparatus using a 1L jacketed glass reactor was equipped with a Dean Stark condenser, an overhead stirrer, a dropping funnel, and a nitrogen input device. 600 g of PIBSA (HR 750 mw PIB, 0.768 mole) and 483.33 g of Aromatic A150 solvent were transferred to the reactor. The mixture was stirred and heated to 65 ° C to form a uniform liquid. Then tetraethylene pentamine (138.12 g, 0.729 mol) was loaded into the reactor through a dropping funnel within 1 hour. The temperature of the mixture was raised to 135 ° C and maintained for 1 hour to distill water. The temperature of the mixture was then raised to 165 ° C and maintained for 3 hours. After the distillation was completed, the product was cooled and transferred to storage (1208.32 g).

[0350] The storage stability of pyrolysis oil compositions G, H and I was tested as described above for Example 2. The amount of insoluble matter (filtered and adherent) recovered for each composition, including the total amount, is shown in Table 5:

[0351] Table 5.

[0352]

[0353] These results show that the amount of adherent insoluble matter produced by plastic pyrolysis oil during storage is significantly reduced when the additives of the present invention are used. In addition, the results for compositions H and I also show that additives 2 and 3 (treatment rate of 500 mg / l) also significantly reduce the total amount of insoluble matter produced. Therefore, these additives are effective in improving the stability of compositions containing pyrolysis oil.

Claims

1. A composition comprising pyrolysis oil and one or more of the following as additives: (a) antioxidants; and (b) a stabilizing additive selected from the group consisting of: (i) alkoxylated amine compounds; (ii) aldehyde-alkylphenol copolymers; (iii) quaternary ammonium salts, and mixtures thereof.

2. A method for improving the stability of a composition comprising pyrolysis oil, the method comprising adding to the composition one or more additives selected from the group consisting of: (a) antioxidants; and (b) Stabilizing additives selected from the group consisting of (i) alkoxylated amine compounds; (ii) aldehyde-alkylphenol copolymers; (iii) quaternary ammonium salts and mixtures thereof.

3. Use of one or more additives selected from the following for improving the stability of a composition comprising pyrolysis oil: (a) antioxidants; and (b) a stabilizing additive selected from the group consisting of (i) alkoxylated amine compounds; (ii) aldehyde-alkylphenol copolymers; (iii) quaternary ammonium salts, and mixtures thereof.

4. A composition, method or use according to any one of the preceding claims, wherein the pyrolysis oil is a plastic pyrolysis oil.

5. A composition, method or use according to any preceding claim comprising an antioxidant.

6. The composition, method or use of claim 5, wherein the antioxidant is a phenolic antioxidant.

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

8. The composition, method or use of claim 5, wherein the antioxidant is a polyisobutenyl-substituted succinimide.

9. The composition, method or use of any preceding claim, wherein the antioxidant comprises an amino antioxidant.

10. A composition, method or use according to any preceding claim comprising a stabilizing additive.

11. The composition, method or use of claim 10, wherein the stabilizing additive comprises an alkoxylated amine compound.

12. The composition, method or use of claim 11, 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 zero.

13. The composition, method or use of any one of claims 10 to 12, wherein the stabilizing additive comprises an aldehyde-alkylphenol copolymer.

14. The composition, method or use of claim 13, wherein the aldehyde-alkylphenol copolymer has structure (III) or (IV): wherein R is hydrogen or alkyl and n is at least 1.

15. A composition, method or use according to any preceding claim wherein the stabilizing additive comprises (iii) a quaternary ammonium salt.

16. The composition, method or use of claim 15, wherein the quaternary ammonium salt is formed by reacting methyl salicylate or dimethyl oxalate with the reaction product of a polyisobutylene-substituted succinic anhydride having a PIB molecular weight (Mn) of 700 to 1300 and dimethylaminopropylamine.

17. The method or use according to any one of claims 2 to 16, wherein the improvement in stability is an improvement in storage stability.

18. The method or use according to any one of claims 2 to 16, 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 -Improvement of low temperature performance.

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