Compositions, methods and uses

Abstract

A composition comprising pyrolysis oil and, as an additive, one or more of: (a) an aldehyde-alkylphenol copolymer and / or an aldehyde-alkylphenol-polyamine copolymer, wherein the alkylphenol of the copolymer contains an alkyl group having at least 30 carbon atoms; and (b) a reaction product of an alcohol and / or an amine with a copolymer of an alpha-olefin and an ethylenically unsaturated carboxylate compound, wherein the alpha-olefin and / or alcohol and / or amine has at least 30 carbon atoms. Also disclosed are a method for reducing the pour point of a composition comprising pyrolysis oil, and the use of the additive described above for reducing the pour point of a composition comprising pyrolysis oil.

Description

[Technical Field]

[0001] The present invention relates to pyrolysis oils and related methods and uses. In particular, the present invention relates to additives for improving the physical properties, especially the flowability, of compositions containing plastic pyrolysis oils. The present invention is particularly directed to lowering the pour point of compositions containing pyrolysis oils. [Background technology]

[0002] Pyrolysis oil is a fluid produced directly from the pyrolysis of waste materials, such as plastic waste, biomass, such as agricultural waste, forestry waste, waste cooking oil, algae waste, used tires, or waste 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), polyacrylate, and polynitrile.

[0003] Organic liquids produced by the pyrolysis of plastics and other waste materials have a very dark color, an unpleasant odor, and are unstable. Such liquids may also have a tendency to gel at low or moderate temperatures, and therefore may be impractical to handle and process.

[0004] Pyrolysis oil can be used as a feedstock for chemical processing, for example, in the production of polymers such as polyethylene. Pyrolysis oil can also be used as a feedstock to fractionators that can produce distillate cuts, and can be used as a feedstock to secondary refinery process units such as fluid catalytic cracking units (FCCUs). Pyrolysis oil can also be used in fuel oil. The use of pyrolysis oil to produce polymers represents a more sustainable alternative to the use of crude oil feedstocks in polymer production.

[0005] The utilization of pyrolysis oil can be limited due to its poor stability and poor handling characteristics, particularly with respect to cooling during transport or storage, for example.

[0006] Pyrolysis oils, especially those derived from plastics, can also have relatively high pour points, which impair their flow properties and their use at low to moderate or even high temperatures. Such pyrolysis oils contain saturated paraffinic wax-like molecules generated during pyrolysis. These wax-like molecules begin to crystallize and deposit as the temperature of the pyrolysis oil decreases, for example, during storage, eventually forming a three-dimensional network of aggregated wax crystals that impair the oil's free flow. At a certain temperature, the pyrolysis oil completely gels and no longer flows as a liquid. This temperature is known as the oil's gel point or freezing point. The temperature of the oil just before complete gelation, at which the oil still exhibits surface movement, is known as the oil's pour point. If the pour point of the liquid could be lowered, this would improve the handling and processing of the liquid at moderate or even relatively low temperatures. This can be important from a safety standpoint when handling and storing in the field. Pyrolysis oils have relatively low flash points (e.g., 100 o F). If the oil has insufficient handleability near its flash point, applying heat externally to improve flowability poses a safety risk. Therefore, due to the relatively high pour point of pyrolysis oils, in order to increase their value and use them, for example, as blending components in fuel oils and as feedstocks for chemical processes, it may be desirable to lower the pour point of such pyrolysis oils to facilitate their handleability, storage, and safety. Summary of the Invention [Means for solving the problem]

[0007] The inventors have found that certain compounds having a C30 (or higher) group as defined herein, when used alone, effectively depress the pour point of compositions containing pyrolysis oils. The inventors have further found that such additives can improve the ability of similar polymer additives that do not have a C30 group to depress the pour point of compositions containing pyrolysis oils. DETAILED DESCRIPTION OF THE INVENTION

[0008] According to a first aspect of the present invention, a pyrolysis oil and, as an additive, (a) aldehyde-alkylphenol copolymers and / or aldehyde-alkylphenol-polyamine copolymers, wherein the alkylphenol of the copolymer comprises an alkyl group having at least 30 carbon atoms; and (b) Reaction products of alcohols and / or amines with copolymers of alpha-olefins and ethylenically unsaturated carboxylate compounds, wherein the alpha-olefins and / or alcohols and / or amines have at least 30 carbon atoms. and one or more of:

[0009] Preferably, additives (a) and / or (b) act as pour point depressants in the composition of this first aspect. Pour point depressant is meant to refer to an additive that can depress the pour point of a composition (i.e., the above-referenced composition containing pyrolysis oil) to maintain the composition's fluidity at low temperatures. The "pour point" of a liquid is defined as the lowest temperature at which the liquid will pour, flow, or exhibit surface motion under a specific set of conditions. Standard methods for measuring the pour point of liquid compositions include ASTM D97, D5853-11, D5950-14, and D5949-10. Preferably, the pour point of the composition of the present invention is determined using a modified method of ASTM D97.

[0010] A first aspect of the present invention relates to a composition comprising pyrolysis oil. The pyrolysis oil can be obtained from the pyrolysis of any type of waste. The components of the oil and its properties depend on the type of pyrolysis waste and the pyrolysis conditions. For example, the pyrolysis oil can be obtained from the pyrolysis of waste, such as plastic waste, agricultural waste, forestry waste, waste cooking oil, algae waste, used tires, or waste rubber.

[0011] Preferably, the pyrolysis oil comprises plastic pyrolysis oil. Suitable plastic pyrolysis oils can be obtained from the pyrolysis of any type of plastic. Preferred plastic pyrolysis oils are obtained from the pyrolysis of one or more polymers selected from polyethylene, polypropylene, PET, rubber, polyacrylate, polynitrile, and mixtures thereof.

[0012] In some embodiments, the pyrolysis oil of the composition of the first aspect may be hydrotreated pyrolysis oil.

[0013] In some embodiments, the pyrolysis oil of the composition of the first aspect has undergone a cracking process.

[0014] In a preferred embodiment, the composition of the first aspect comprises pyrolysis oil obtained directly from a pyrolysis plant without purification or further treatment.

[0015] Preferably the pyrolysis oil (if not added) has a baseline pour point of at least 30°C, preferably at least 40°C.

[0016] Preferably, the n-paraffin content of the pyrolysis oil is 3 to 30 wt%. In some embodiments, the n-paraffin content of the pyrolysis oil is 15 to 30 wt%, preferably 20 to 27 wt%.

[0017] Preferably, at least 30 wt% of the n-paraffin compounds in the pyrolysis oil are C9-C18 n-paraffins. Preferably, 30-50 wt% of the n-paraffin compounds in the pyrolysis oil are C9-C18 n-paraffins.

[0018] Preferably, at least 25 wt% of the n-paraffin compounds in the pyrolysis oil are C20-C30 n-paraffins. Preferably, 25-35 wt% of the n-paraffin compounds in the pyrolysis oil are C20-C30 n-paraffins.

[0019] Preferably, at least 10 wt% of the n-paraffin compounds in the pyrolysis oil are C30-C40 n-paraffins. Preferably, 10-20 wt% of the n-paraffin compounds in the pyrolysis oil are C30-C40 n-paraffins.

[0020] Preferably, at least 5 wt% of the n-paraffin compounds in the pyrolysis oil are C40+ n-paraffins. Preferably, 5 to 10 wt% of the n-paraffin compounds in the pyrolysis oil are C40+ n-paraffins.

[0021] Preferably, the n-paraffin compounds in the pyrolysis oil comprise 30-50 wt% C9-C18 n-paraffins, 25-35 wt% C20-C30 n-paraffins, 10-20 wt% C30-C40 n-paraffins, and 5-10 wt% C40+ n-paraffins based on the total weight of n-paraffins present in the pyrolysis oil.

[0022] In some embodiments, the composition of the first aspect may comprise a blended fuel oil comprising plastic pyrolysis oil and one or more fuel oils derived from hydrocarbon and / or renewable sources.

[0023] In some embodiments, the composition of the first aspect comprises a blended fuel oil comprising plastic pyrolysis oil and a middle distillate fuel oil.

[0024] Middle distillate fuel oils may include petroleum-based fuel oils, especially middle distillate fuel oils. Such middle distillate fuel oils generally boil within the range of 110° C. to 500° C., for example, 150° C. to 400° C. Middle distillate fuel oils may include atmospheric or vacuum fractions, cracked gas oils, or blends of straight run and refinery streams in any proportion, such as thermal and / or catalytic cracked and hydrocracked fractions.

[0025] Middle distillate fuel oils can include non-renewable Fischer-Tropsch fuels, such as those described as gas-to-liquid (GTL) fuels, coal-to-liquid (CTL) fuels, and oil sands-to-liquid (OTL) fuels.

[0026] The middle distillate fuel oil may comprise a renewable fuel, for example a biofuel composition or a biodiesel composition.

[0027] Middle distillate fuel oils can include first-generation biodiesel, which contains, for example, esters of vegetable oils, animal fats, and used cooking fats. This form of biodiesel can be obtained by transesterification of oils, such as rapeseed oil, soybean oil, safflower oil, palm oil, palm kernel oil, corn oil, peanut oil, cottonseed oil, tallow, coconut oil, jatropha oil, sunflower seed oil, used cooking oil, hydrogenated vegetable oil, or any mixture thereof, with an alcohol, usually a monoalcohol, in the presence of a catalyst.

[0028] Middle distillate fuel oils can include second-generation biodiesel, which is derived from renewable resources such as vegetable oils and animal fats and is often processed in refineries, often using hydroprocessing such as the H-Bio process developed by Petrobras. Second-generation biodiesel can be similar in properties and quality to renewable diesel produced from petroleum-based fuel oil streams, such as vegetable oils, animal fats, etc., and sold by ConocoPhillips as Renewable Diesel and by Neste as NExBTL.

[0029] The middle distillate fuel oil used in the present invention may include third-generation biodiesel, which utilizes gasification and Fischer-Tropsch technology, including what is described as biomass-to-liquid (BTL) fuel. Third-generation biodiesel is not significantly different from some second-generation biodiesels, but aims to utilize whole plants (biomass), thereby broadening the feedstock base.

[0030] The middle distillate fuel oil may contain a blend of any or all of the above diesel fuel oils.

[0031] In some embodiments, the middle distillate fuel oil may be a blended diesel fuel containing biodiesel. In such a blend, the biodiesel may be present 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%.

[0032] In some embodiments, the middle distillate fuel oil may contain a secondary fuel, such as ethanol, however, the middle distillate fuel oil composition preferably does not contain ethanol.

[0033] Middle distillate fuel oils may contain relatively high sulphur contents, for example above 0.05% by weight, such as 0.1% or 0.2%.

[0034] However, in a preferred embodiment, the middle distillate fuel oil has a sulphur content of at most 0.05 wt%, more preferably at most 0.035 wt%, especially at most 0.015%. Fuels containing even lower levels of sulphur are also suitable, for example fuels containing less than 50 ppm by weight, preferably less than 20 ppm, for example 10 ppm or less.

[0035] Various metal species can be present in middle distillate fuel oils. This can result from contamination of the fuel during production, storage, transportation, or use, or from contamination of fuel additives. Metal species can also be intentionally added to the fuel. For example, transition metals are sometimes added as fuel-borne catalysts, for example, to improve the performance of diesel particulate filters.

[0036] In a preferred embodiment, the middle distillate fuel oil used in the present invention contains sodium and / or calcium. Preferably, the middle distillate fuel oil contains sodium. The sodium and / or calcium are typically present in a total amount of from 0.01 to 50 ppm, preferably from 0.05 to 5 ppm, preferably from 0.1 to 2 ppm, for example from 0.1 to 1 ppm.

[0037] Other metal-containing species may also be present as contaminants, for example, due to corrosion of metal and metal oxide surfaces by acidic species present in the fuel or derived from the lubricating oil. During use, fuels such as diesel fuel routinely come into contact with metal surfaces, for example, in vehicle fuel delivery systems, fuel tanks, fuel transport vehicles, 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.

[0038] In addition to the metal-containing contaminants that may be present in middle distillate fuel oils, there are situations in which metal-containing species may be intentionally added to the fuel. For example, as is known in the art, metal-containing fuel-based catalytic species may be added to aid in the regeneration of particulate traps.

[0039] Depending on their source, metal-containing contaminants can be in the form of insoluble particulates or soluble compounds or complexes. Metal-containing fuel-based catalysts are often soluble compounds or complexes, or colloidal species.

[0040] In some embodiments, the middle distillate fuel oil may contain a metal-containing species containing fuel catalyst. Preferably, the fuel catalyst contains one or more metals selected from iron, cerium, platinum, manganese, Group I and Group II metals, such as calcium and strontium. Most preferably, the fuel catalyst contains a metal selected from iron and cerium.

[0041] In some embodiments, the middle distillate fuel oil may include metal-containing species including zinc, which may be present in an amount of from 0.01 to 50 ppm, preferably from 0.05 to 5 ppm, more preferably from 0.1 to 1.5 ppm.

[0042] The composition of the first aspect comprises: (a) aldehyde-alkylphenol copolymers and / or aldehyde-alkylphenol-polyamine copolymers, wherein the alkylphenol of the copolymer contains an alkyl group having at least 30 carbon atoms; and / or (b) Reaction products of alcohols and / or amines with copolymers of alpha-olefins and ethylenically unsaturated carboxylate compounds, wherein the alpha-olefins and / or alcohols and / or amines have at least 30 carbon atoms. Includes one or more of the following.

[0043] In some embodiments, the composition of the first aspect comprises (a) as an additive.

[0044] In some embodiments, the composition of the first aspect comprises (b) as an additive.

[0045] In some embodiments, the composition of the first aspect comprises (a) and (b) as additives.

[0046] (a) Aldehyde-Alkylphenol / Aldehyde-Alkylphenol-Polyamine Copolymer In some embodiments, the composition of the first aspect comprises an additive (a) an aldehyde-alkylphenol and / or aldehyde-alkylphenol-polyamine copolymer, wherein the alkylphenol of the copolymer comprises an alkyl group having at least 30 carbon atoms.

[0047] The present inventors have surprisingly found that copolymers containing alkyl phenols in which the alkyl group has at least 30 carbon atoms can advantageously reduce the pour point of liquid compositions containing pyrolysis oil. In comparison, such copolymers in which the alkyl phenol of the copolymer contains an alkyl group with fewer than 30 carbon atoms have been found to be ineffective in significantly reducing the pour point of such compositions containing pyrolysis oil.

[0048] In embodiments where additive (a) is an aldehyde-alkylphenol copolymer, the copolymer is preferably the reaction product of, as monomers, an aldehyde and an alkylphenol, wherein the alkyl group of the alkylphenol has at least 30 carbon atoms. The aldehyde-alkylphenol copolymer can be considered to comprise subunits derived from the alkylphenol and subunits derived from the aldehyde.

[0049] In embodiments where additive (a) is an aldehyde-alkylphenol-polyamine copolymer, the copolymer is preferably a reaction product of an aldehyde, an alkylphenol, and a polyamine as monomers, where the alkyl group of the alkylphenol has at least 30 carbon atoms. The aldehyde-alkylphenol-polyamine copolymer can be considered to contain subunits derived from the alkylphenol, subunits derived from the aldehyde, and subunits derived from the polyamine. Such copolymers are sometimes referred to as Mannich resins, formed by a Mannich polymerization reaction.

[0050] Preferably, the aldehyde used to prepare the aldehyde-alkylphenol or aldehyde-alkylphenol-polyamine copolymer is formaldehyde or its reactive equivalent, e.g., paraformaldehyde, C2-C 10 The aldehyde is selected from aldehydes and aromatic aldehydes, such as benzaldehyde. Preferably, formaldehyde or its reactive equivalent is used as the aldehyde component for preparing the aldehyde-alkylphenol or aldehyde-alkylphenol-polyamine copolymer. Therefore, the preferred aldehyde-alkylphenol copolymer is a copolymer of formaldehyde and alkylphenol. Such aldehyde-alkylphenol copolymers can be prepared by the methods disclosed in US9518184 and US9068128, which are incorporated herein by reference.

[0051] Suitable aldehyde-alkylphenol-polyamine copolymers of additive (a) are copolymers of formaldehyde, alkylphenols and polyamines. Such aldehyde-alkylphenol-polyamine copolymers can be formed by the methods disclosed in EP 2197991 A2 and US 9528074 B2, which are incorporated herein by reference.

[0052] Preferably, the alkylphenol is monosubstituted with an alkyl group, preferably in the para position. Preferred alkyl groups have 30 to 50 carbon atoms, preferably 30 to 40 carbon atoms. Such alkylphenols can be prepared by reacting phenol with an olefin containing the above-mentioned number of carbon atoms.

[0053] It will be recognized that such alkylphenols may contain a mixture of compounds having alkyl groups of a range of chain lengths. Thus, the alkylphenol monomers that form the aldehyde-alkylphenol copolymer (and thus are the alkylphenol subunits of the aldehyde-alkylphenol copolymer) may contain some alkyl groups having fewer than 30 carbon atoms. However, the majority of the alkyl groups contain at least 30 carbon atoms. For example, preferably, at least 50 wt% of the alkyl groups of the alkylphenol monomers (and preferably at least 50 wt% of the alkylphenol-derived subunits of the aldehyde-alkylphenol or aldehyde-alkylphenol-polyamine copolymer), suitably at least 75 wt%, at least 80 wt%, or at least 82 wt%, have alkyl groups having at least 30 carbon atoms.

[0054] Preferably, at least 50 wt% of the alkylphenol monomers (and preferably at least 50 wt% of the alkylphenol-derived subunits of the aldehyde-alkylphenol or aldehyde-alkylphenol-polyamine copolymer), preferably at least 75 wt%, at least 80 wt%, or at least 82 wt% have alkyl groups having 30 to 40 carbon atoms.

[0055] Preferably, the alkyl group of the alkylphenol monomer (and preferably the alkylphenol-derived subunit of the aldehyde-alkylphenol or aldehyde-alkylphenol-polyamine copolymer) has a number average molecular weight of 400 to 1,000, preferably 400 to 600.

[0056] In some embodiments, the alkylphenol monomer (and thus the alkylphenol subunit of the aldehyde-alkylphenol or aldehyde-alkylphenol-polyamine copolymer) is a polyisobutenyl (PIB)-substituted phenol. Thus, in such embodiments, the alkyl group referred to above is PIB.

[0057] Polyisobutenyl (PIB) substituted phenols contain hydrocarbyl chains with the following repeating units: [ka]

[0058] Poly(isobutene) is prepared by the addition polymerization of isobutene (CH3)2C=CH2. Each molecule of the resulting polymer contains a single alkene moiety.

[0059] Conventional polyisobutenes and so-called "highly reactive" polyisobutenes are suitable for use in preparing the additive (a) of the present invention. In this context, highly reactive polyisobutenes 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 0 565 285. Particularly preferred polyisobutenes are those having more than 80 mol% and up to 100% terminal vinylidene groups, such as those described in EP 1 344 785, which is incorporated herein by reference.

[0060] Methods for preparing polyalkylene-substituted phenols, such as polyisobutene-substituted phenols, are known to those skilled in the art and include those described in EP 831141, which is incorporated herein by reference.

[0061] The PIB substituent preferably has a number average molecular weight of 400-1,000, and more preferably 400-600 or 420-560.

[0062] In some preferred embodiments, additive (a) has structure (I) or (II): [ka] JPEG2026506009000003.jpg66170, where R is an alkyl group having at least 30 carbon atoms and n is at least 1. The aldehyde-alkylphenol copolymer has the formula:

[0063] Preferably, n is 2-12, preferably 5-10 or 5-7.

[0064] Preferably, R is a C30-C60 alkyl group, preferably a C30-C50 alkyl group or a C30-C40 alkyl group.

[0065] As noted above, the alkylphenol may contain a mixture of compounds having alkyl groups of a range of chain lengths and may contain some alkyl groups having fewer than 30 carbon atoms. However, preferably at least 50 wt%, preferably at least 75 wt%, at least 80 wt%, or at least 82 wt% of the R groups present in the additive have at least 30 carbon atoms.

[0066] Preferably, at least 50 wt% of the R groups present in the additive are C30-C50 alkyl groups, preferably C30-C40 alkyl groups. Preferably, at least 75 wt%, at least 80 wt%, or at least 82 wt% of the R groups present in the additive are C30-C50 alkyl groups, preferably C30-C40 alkyl groups.

[0067] Preferably, the aldehyde-alkylphenol copolymer of additive (a) has a molecular weight in the range of 3,000 to 20,000, suitably 4,000 to 10,000, preferably 5,000 to 7,000.

[0068] Further suitable aldehyde-alkylphenol copolymers for use herein include compounds of formula (I) in which the terminal phenolic groups have been further functionalized, for example, by reaction of a fatty acid or an amine with an aldehyde via a Mannich reaction. Compounds of this type are described, for example, in US 2007 / 221539, which is incorporated herein by reference.

[0069] In embodiments where additive (a) is an aldehyde-alkylphenol-polyamine copolymer, the polyamine is suitably an amine having at least two amino groups and 2 to 22 carbon atoms. In such embodiments, the polyamine may be a polyalkylene polyamine. Preferably, the polyamine is a polyalkylene polyamine in which the alkylene moiety has 1 to 6, preferably 1 to 4, and most preferably 2 to 3 carbon atoms. Most preferably, the polyamine is a polyethylene polyamine.

[0070] Preferably, the polyamine has 2 to 15 nitrogen atoms, preferably 2 to 10 nitrogen atoms, more preferably 2 to 8 nitrogen atoms.

[0071] In a particularly preferred embodiment, the polyamine has the formula R 1 R 2 NCHR 3 CHR 4 NR 5 R 6 (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 wherein each is independently selected from hydrogen, and optionally substituted alkyl, alkenyl, alkynyl, aryl, alkylaryl, or arylalkyl substituents. Thus, the polyamine used to form the additive preferably comprises optionally substituted ethylenediamine residues.

[0072] Preferably, R 1 and R 2At least one of R is hydrogen. 1 and R 2 Both are hydrogen.

[0073] Preferably, R 1 , R 2 , R 5 and R 6 At least two of are hydrogen.

[0074] Preferably, R 3 and R 4 In some preferred embodiments, at least one of R 3 and R 4 Each of R is hydrogen. 3 is hydrogen and R 4 is alkyl, for example a C1-C4 alkyl group, especially methyl.

[0075] Preferably, R 5 and R 6 At least one of is an optionally substituted alkyl, alkenyl, alkynyl, aryl, alkylaryl, or arylalkyl substituent.

[0076] R 1 , R 2 , R 3 , R 4 , R 5 and R 6 In embodiments where at least one of is not hydrogen, each is independently selected from an optionally substituted alkyl, alkenyl, alkynyl, aryl, alkylaryl, or arylalkyl moiety. Preferably, each is independently selected from hydrogen and an optionally substituted C(1-6)alkyl moiety.

[0077] In particularly preferred compounds, R 1 , R 2 , R 3 , R 4 and R 5 is hydrogen, and R 6is an optionally substituted alkyl, alkenyl, alkynyl, aryl, alkylaryl, or arylalkyl substituent. Preferably, R 6 is an optionally substituted C(1-6) alkyl moiety.

[0078] Such alkyl moieties may be substituted with one or more groups selected from hydroxyl, amino (especially unsubstituted amino; -NH-, -NH2), sulfo, sulfoxy, C(1-4)alkoxy, nitro, halo (especially chloro or fluoro), and mercapto.

[0079] One or more heteroatoms, such as O, N or S, may be incorporated into the alkyl chain to provide ethers, amines or thioethers.

[0080] In some embodiments, the substituent R 1 , R 2 , R 3 , R 4 , R 5 or R 6 are hydroxy-C(1-4)alkyl and amino-C(1-4)alkyl, especially HO-CH2-CH2- and H2N-CH2-CH2-.

[0081] Preferably, the polyamine contains only amine functionality or amine and alcohol functionality.

[0082] Polyamines include, for example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, propane-1,2-diamine, 2(2-amino-ethylamino)ethanol, and N 1 , N 1 -bis(2-aminoethyl)ethylenediamine (N(CH2CH2NH2)3). Most preferably, the polyamine comprises tetraethylenepentamine or especially ethylenediamine.

[0083] Commercially available sources of polyamines typically contain mixtures of isomers and / or oligomers, and products prepared from these commercially available mixtures are within the scope of this invention.

[0084] In those embodiments in which additive (a) is an aldehyde-alkylphenol-polyamine copolymer, the copolymer preferably comprises, as monomers, formaldehyde; an alkylphenol in which the alkyl group of the alkylphenol has at least 30 carbon atoms; and ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, propane-1,2-diamine, 2(2-amino-ethylamino)ethanol, and N 1 ,N 1 -bis(2-aminoethyl)ethylenediamine (N(CH2CH2NH2)3).

[0085] (b) Reaction products of alcohols and / or amines with α-olefin-ethylenically unsaturated carboxylate copolymers In some embodiments, the composition of the first aspect comprises additive (b) a reaction product of an alcohol and / or amine with a copolymer of an alpha-olefin and an ethylenically unsaturated carboxylate compound, wherein the alpha-olefin and / or alcohol and / or amine have at least 30 carbon atoms.

[0086] The copolymer of additive (b) therefore comprises groups with at least 30 carbon atoms derived either from an alpha-olefin or from an alcohol and / or an amine.

[0087] Additive (b) can be considered to include moieties derived from subunits derived from alpha-olefins, subunits derived from ethylenically unsaturated carboxylate compounds, and subunits derived from alcohols and / or amines and unsaturated carboxylate compounds. Such moieties derived from subunits derived from alcohols and / or amines and unsaturated carboxylate compounds can be any group obtained by reacting an alcohol and / or amine with a carboxylate group of a subunit derived from an ethylenically unsaturated carboxylate compound. For example, the moieties derived from subunits derived from alcohols and / or amines and unsaturated carboxylate compounds can be esters, amides, imides, or amine bases, or mixtures thereof. Preferably, the moieties derived from alcohols and / or amines are ester and / or amide groups.

[0088] The present inventors have surprisingly found that copolymers in which the alpha-olefin groups used to form the copolymer have at least 30 carbons can advantageously reduce the pour point of liquid compositions containing pyrolysis oil. In comparison, copolymers containing alkyl subunits having fewer than 30 carbon atoms or containing a low proportion of alkyl subunits having at least 30 carbons have been found to be ineffective in significantly reducing the pour point of such compositions containing pyrolysis oil.

[0089] The same advantage can be obtained by embodiments in which a group having at least 30 carbons is provided by an alcohol or amine that is reacted with the copolymer of an alpha-olefin and an ethylenically unsaturated carboxylate compound.

[0090] Preferably, the copolymer of additive (b) is a reaction product of an alpha-olefin and an ethylenically unsaturated carboxylate compound as monomers; said reaction product is further reacted to form an ester or amide derivative.

[0091] In embodiments in which the alpha-olefin has at least 30 carbon atoms, the alpha-olefin suitably has from 30 to 50 carbon atoms, preferably from 30 to 40 carbon atoms.

[0092] It will be appreciated that such alpha-olefins may comprise a mixture of compounds having a range of different chain lengths / number of carbon atoms. Thus, the alpha-olefin monomers forming the copolymer of additive (b), and therefore the alpha-olefin derived subunits of the copolymer, may contain some alpha-olefins having less than 30 carbon atoms.

[0093] In some embodiments, the alpha-olefin is a mixture of alpha-olefin compounds, wherein 10-90 wt% of the alpha-olefin compounds have at least 30 carbon atoms, and preferably 20-50 wt% of the alpha-olefin compounds have at least 30 carbon atoms.

[0094] The alpha-olefins used to form the copolymer of additive (b) can be provided by commercially available alpha-olefin products, for example, by a commercially available alpha-olefin mixture containing alpha-olefin compounds having at least 30 carbon atoms, preferably a majority of alpha-olefin compounds having at least 30 carbon atoms. The alpha-olefins can be provided by a mixture of two or more commercially available alpha-olefin products, for example, a mixture of a first commercially available alpha-olefin mixture containing alpha-olefin compounds having at least 30 carbon atoms and a second commercially available alpha-olefin mixture containing alpha-olefin compounds having less than 30 carbon atoms. Such a second commercially available alpha-olefin mixture can comprise or consist of C24-28, C20-24, or C26-28 alpha-olefin compounds or mixtures thereof.

[0095] In such an embodiment, the first and second commercially available alpha-olefin products may be mixed in a ratio suitable to result in a mixture of alpha-olefin compounds in which 10 to 90 wt % of the alpha-olefin compounds have at least 30 carbon atoms, preferably in which 20 to 50 wt % of the alpha-olefin compounds have at least 30 carbon atoms.

[0096] In some embodiments, the majority of the alpha-olefins contain at least 30 carbon atoms. For example, preferably at least 50 wt%, suitably at least 75 wt%, at least 80 wt%, or at least 82 wt% of the alpha-olefin monomers (and preferably the alpha-olefin derived subunits of the copolymer of additive (b)) have at least 30 carbon atoms.

[0097] Preferably, at least 50 wt%, preferably at least 75 wt%, at least 80 wt%, or at least 82 wt% of the alpha-olefin monomers (and preferably the alpha-olefin derived subunits of the copolymer) have 30 to 40 carbon atoms.

[0098] Preferably, the alpha-olefin monomers (and suitably the alpha-olefin derived subunits of the copolymer) have a number average molecular weight of 400 to 1,000, suitably 400 to 600, or 420 to 560.

[0099] In some embodiments, the alpha-olefin monomer (and thus the alpha-olefin-derived subunits of the copolymer) is polyisobutenylene (PIB). Thus, the alpha-olefin-derived subunits referred to above are PIB subunits in such embodiments. Suitable PIBs are as described above for additive (a).

[0100] The PIB monomer (and subunits) preferably have a number average molecular weight of 400 to 1,000, suitably 400 to 600, or 420 to 560.

[0101] In embodiments in which the alcohol and / or amine have at least 30 carbon atoms, the alpha-olefin may also contain at least 30 carbon atoms and may be as defined above. Alternatively, the alpha-olefin may have 12 to 28 carbon atoms, preferably 16 to 28 carbon atoms, 18 to 26 carbon atoms, or most preferably 20 to 24 carbon atoms. The alpha-olefin may be linear or branched.

[0102] The ethylenically unsaturated carboxylate compound used to prepare the copolymer of additive (b) may be selected from fumaric acid, maleic anhydride, maleic acid, (meth)acrylic acid, itaconic anhydride or itaconic acid, maleimides and N-alkyl, N-aryl and N-alkaryl maleimides, phthalic anhydride, citraconic anhydride, citraconic imide and N-alkyl, N-aryl and N-alkaryl citraconic imides, or combinations thereof.

[0103] Preferably, the ethylenically unsaturated carboxylate compound is maleic anhydride. Accordingly, the copolymer of additive (b) suitably comprises subunits derived from maleic acid and subunits derived from an alpha-olefin. In such an embodiment, the copolymer of additive (b) may be referred to as an ester or amide derivative of an alpha-olefin maleic anhydride copolymer (which may be referred to as an OMAC ester or amide). Preferably, additive (b) is an ester derivative of an alpha-olefin maleic anhydride copolymer (which may be referred to as an OMAC ester).

[0104] The copolymer of additive (b) is preferably an alternating copolymer, first prepared by reacting maleic anhydride with an alpha-olefin to form OMAC, which is subsequently derivatized by reaction with an alcohol and / or an amine to form an ester, amide, imide, or amine salt from the maleic anhydride moiety. Means for carrying out such reactions are well known to those skilled in the art and are described, for example, in US 4,240,916, US 3,560,456, and US 4,151,069, which are incorporated herein by reference.

[0105] OMAC is suitably prepared by reacting maleic anhydride with an alpha-olefin as defined above in a molar ratio of from 3:1 to 1:3, preferably from 2:1 to 1:2, more preferably from 1.5:1 to 1:1.5, for example about 1:1.

[0106] Preferably, the alpha-olefin has the number of carbon atoms mentioned above. Mixtures of alpha-olefins may be used.

[0107] Suitable ester, amide, imide, or amine salt derivatives of the copolymer of an alpha-olefin and an ethylenically unsaturated carboxylate compound are formed by reacting the carboxylate moiety of the ethylenically unsaturated carboxylate subunit of the copolymer with a suitable alcohol or amine. Such alcohols and amines are preferably C12-C50 alcohols and amines, C12-C40 alcohols or amines, C12-C28 alcohols or amines, preferably C16-C24 alcohols or amines, and preferably C18-C22 alcohols or amines. Thus, the copolymer of additive (b) preferably contains a C12-C50 ester, amide, imide, or amine salt moiety, preferably a C16-C24 or C18-C22 ester, amide, imide, or amine salt moiety. The alcohol or amine may be branched or linear. Preferably, the alcohol or amine is linear. The alcohol or amine may be saturated, unsaturated, or a mixture of both.

[0108] In embodiments in which additive (b) is the reaction product of an amine with a copolymer of an alpha-olefin and an ethylenically unsaturated carboxylate compound, the amine may be a monoamine, diamine, or polyamine. The polyamine may be as defined above.

[0109] In some embodiments, the copolymer of an alpha-olefin and an ethylenically unsaturated carboxylate compound is reacted with an alcohol or amine having at least 30 carbon atoms, preferably 30 to 50 carbon atoms or 30 to 40 carbon atoms.

[0110] Such alcohols or amines may contain a mixture of compounds having different numbers of carbon atoms. The alcohols or amines may include compounds having fewer than 30 carbon atoms. However, preferably at least 50 wt%, preferably at least 75 wt%, at least 80 wt%, or at least 82 wt% of the alcohols or amines used to prepare the additive have at least 30 carbon atoms.

[0111] Preferably, the alcohol or amine has a number average molecular weight of 400-1,000, and more preferably 400-600 or 420-560.

[0112] Preferably, the carboxylate moiety of the ethylenically unsaturated carboxylate compound is reacted with a C12-C50 alcohol, a C12-C40 alcohol, a C12-C28 alcohol, suitably a C16-C24 alcohol, preferably a C18-C22 alcohol. Accordingly, the copolymer of additive (b) suitably comprises a C12-C28 ester moiety, preferably a C16-C24 or C18-C22 ester moiety.

[0113] In embodiments in which the alpha-olefin has at least 30 carbon atoms, the alcohol and / or amine is suitably a C12-C28 alcohol or amine, suitably a C16-C24 alcohol or amine, preferably a C18-C22 alcohol or amine.

[0114] In some embodiments where the alpha-olefin comprises an alpha-olefin compound having at least 30 carbon atoms, the alcohol and / or amine can be a mixture of alcohol compounds having at least 20 carbon atoms (which may be referred to as "C20+ alcohols"). Such C20+ alcohols are commercially available as Alfol® and Nafol®.

[0115] In some embodiments where the alpha-olefin comprises an alpha-olefin compound having at least 30 carbon atoms, the alcohol and / or amine may be a mixture of alcohol compounds comprising primarily alcohol compounds having 20 carbon atoms. For example, such a mixture of alcohols may comprise at least 40 wt %, preferably approximately 50 wt %, of alcohol compounds having 20 carbon atoms.

[0116] In embodiments where the alpha-olefin has fewer than 30 carbon atoms, e.g., 12 to 28 carbon atoms, the alcohol or amine, as defined above, has at least 30 carbon atoms, preferably 30 to 50 carbon atoms, or 30 to 40 carbon atoms.

[0117] In some embodiments, the alpha-olefin, as defined above, has at least 30 carbon atoms, and the alcohol or amine, as defined above, has at least 30 carbon atoms.

[0118] The reaction product of an alcohol and / or amine with a copolymer of an alpha-olefin and an ethylenically unsaturated carboxylate compound is suitably prepared by reacting the copolymer, as defined above, with an alcohol and / or amine in a molar ratio of from 0.1:1 to 1:2, from 0.5:1 to 1:1.5, preferably from 1.1:1 to 1:1.1.

[0119] Preferably, the reaction product of the alcohol and / or amine with the copolymer of an alpha-olefin and an ethylenically unsaturated carboxylate compound is prepared by reacting the copolymer of an alpha-olefin and an ethylenically unsaturated carboxylate compound with 0.5 to 1.5 molar equivalents of the alcohol and / or amine relative to the amount of ethylenically unsaturated carboxylate monomer used to form the copolymer. In some embodiments, 0.5 to 1.0 molar equivalents of the alcohol and / or amine relative to the amount of ethylenically unsaturated carboxylate monomer used are reacted with the copolymer.

[0120] In some embodiments, the copolymer of additive (b) is a C12-C28 ester or amide of an alpha-olefin maleic anhydride copolymer, wherein the alpha-olefin derived subunits have at least 30 carbon atoms. Preferably, the copolymer of additive (b) is a C12-C28 ester of an alpha-olefin maleic anhydride copolymer, wherein the alpha-olefin maleic anhydride copolymer comprises alpha-olefin derived subunits having at least 30 carbon atoms. Suitably, at least 30 wt%, at least 40 wt%, or at least 50 wt% of the alpha-olefin compounds used to form the copolymer are C30-C40 alpha-olefins. Thus, at least 30 wt%, at least 40 wt%, or at least 50 wt% of the alpha-olefin derived subunits of the copolymer have 30 to 40 carbon atoms.

[0121] In some embodiments, the copolymer of additive (b) is the reaction product of an alpha-olefin maleic anhydride copolymer with 0.5 to 1.5 molar equivalents, preferably 0.5 to 1.0 molar equivalents, of alcohol relative to the amount of maleic anhydride monomer used to form the copolymer.

[0122] Preferably, the copolymer of additive (b) is the reaction product of an alpha-olefin maleic anhydride copolymer with 0.5 to 1.5 molar equivalents of a C12-C28 alcohol relative to the amount of maleic anhydride monomer used to form the copolymer, the alpha-olefin maleic anhydride copolymer being formed by reacting maleic anhydride with an alpha-olefin comprising at least 30 wt%, at least 40 wt%, or at least 50 wt% of an alpha-olefin having at least 30 carbon atoms, preferably 30 to 40 carbon atoms.

[0123] Preferably, additive (b) has a molecular weight in the range of 4,000 to 30,000, 6,000 to 20,000, or 6,000 to 12,000.

[0124] Additives (a) and / or (b), when present, are preferably included 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 100 ppm. Suitably, additives (a) and / or (b) are present in an amount of at least 200 ppm, at least 300 ppm, at least 400 ppm, or at least 500 ppm.

[0125] Suitably, additives (a) and / or (b), when present, are preferably included in the composition of the first aspect in an amount of up to 10,000 ppm, preferably up to 5,000 ppm, more preferably up to 3,000 ppm, up to 2,500 ppm, or up to 2,000 ppm.

[0126] Additives (a) and / or (b), when present, are preferably included in the composition of the first aspect in an amount of from 100 to 10,000 ppm, from 200 to 3,000 ppm, from 350 to 3,000 ppm, or from 400 ppm to 2,500 ppm.

[0127] In embodiments in which both (a) and (b) are present, the combined amounts of additives (a) and (b) present in the composition are preferably as described above.

[0128] All references to ppm herein are parts per million by volume.

[0129] The additive may also include a carrier or diluent. Thus, the additive may be added to the composition as an additive composition comprising the additive and the carrier or diluent. Preferred carriers and diluents are aromatic hydrocarbon compounds, especially C 10 It is an alkylnaphthalene.

[0130] In some embodiments, the composition of the first aspect may be used as a middle distillate fuel oil. Accordingly, the composition may contain one or more additional additives, such as those commonly found in diesel fuels. These include, for example, antioxidants, dispersants, detergents, metal deactivating compounds, wax anti-settling agents, cold flow improvers, cetane improvers, dehazers, stabilizers, demulsifiers, antifoam agents, corrosion inhibitors, lubricity improvers, dyes, markers, combustion improvers, metal deactivators, odor masking agents, drag reducers, and conductivity improvers. Examples of suitable amounts of each of these types of additives will be known to those skilled in the art.

[0131] It has been surprisingly found that the inclusion of additives (a) and / or (b) reduces the pour point of compositions containing pyrolysis oil. The pour point reduction of such compositions is preferably at least 5°C, at least 10°C, at least 15°C, or at least 20°C compared to a similar composition containing pyrolysis oil but not containing additives (a) and (b) (i.e., a composition containing pyrolysis oil but no additives). Such compositions containing pyrolysis oil but no additives preferably do not contain other pour point depressants. Such compositions containing pyrolysis oil but no additives may contain other additives, such as component (d), defined below, e.g., antioxidants.

[0132] (c) Further additives In some embodiments, the composition of this first aspect comprises: (c1) aldehyde-alkylphenol copolymers and / or aldehyde-alkylphenol-polyamine copolymers, wherein the alkylphenol of the copolymer contains an alkyl group having less than 30 carbon atoms; and (c2) Reaction products of alcohols and / or amines with copolymers of alpha-olefins and ethylenically unsaturated carboxylate compounds, where the alpha-olefins, alcohols, and amines, if present, have less than 30 carbon atoms. and further additives (c) selected from one or more of:

[0133] The inventors have found that the pour point of compositions of this first aspect of the invention containing pyrolysis oil can be further reduced by combining the further additive (c) not containing a group having at least 30 carbon atoms discussed above with additive (a) or (b) containing a group having at least 30 carbon atoms, and this combination can have a synergistic effect in reducing the pour point of said compositions containing pyrolysis oil.

[0134] For the avoidance of doubt, preferably, neither additive (c1) nor additive (c2) contains significant amounts of compounds containing alkyl groups or alkyl chains having 30 or more carbon atoms. Such additives are often obtained as mixtures and may contain some compounds having alkyl groups or alkyl chains having at least 30 carbon atoms. However, preferably, less than 50 wt%, preferably less than 25 wt%, less than 10 wt%, or less than 5 wt% of the alkyl groups or alkyl chains present in the additive have at least 30 carbon atoms. Preferably, additive (c1) and / or additive (c2) are substantially free of alkyl groups or alkyl chains having 30 or more carbon atoms.

[0135] In the embodiment where additive (c) is additive (c1) an aldehyde-alkylphenol copolymer and / or an aldehyde-alkylphenol-polyamine copolymer, the copolymer is preferably the reaction product of, as monomers, an aldehyde, an alkylphenol and, optionally, a polyamine, wherein the alkyl group of the alkylphenol has less than 30 carbon atoms.

[0136] The alkyl group of the alkylphenol of additive (c1) suitably has 12 to 28 carbon atoms, preferably 16 to 28 carbon atoms, 18 to 26 carbon atoms, or most preferably 20 to 24 carbon atoms. The alkyl group may be linear or branched.

[0137] In embodiments where additive (c) is additive (c2), the additive is preferably an ester, amide, imide, or amine salt derivative of a copolymer of an alpha-olefin and an ethylenically unsaturated carboxylate compound. Additive (c2) is preferably formed by reacting the carboxylate moieties of the ethylenically unsaturated carboxylate subunits of the copolymer with a suitable alcohol or amine.

[0138] The alpha-olefins used to form additive (c2) suitably have from 12 to 28 carbon atoms, preferably from 16 to 28 carbon atoms, from 18 to 26 carbon atoms, or most preferably from 20 to 24 carbon atoms. The alpha-olefins may be linear or branched.

[0139] The ethylenically unsaturated carboxylate compound used to form additive (c2) is preferably as defined above for additive (b).

[0140] The alcohol and / or amine used to form additive (c2) is preferably a C12-C28 alcohol or amine, or a mixture thereof, preferably a C16-C24 alcohol or amine, preferably a C18-C22 alcohol or amine. Accordingly, the copolymer of additive (c2) preferably comprises a C12-C28 ester, amide, imide, or amine salt moiety, preferably a C16-C24 or C18-C22 ester, amide, imide, or amine salt moiety. The alcohol or amine may be branched or linear. Preferably, the alcohol or amine is linear. The alcohol or amine may be saturated, unsaturated, or a mixture of both.

[0141] In such embodiments comprising a further additive (c), the ratio of the total amount of additives (a) and / or (b) present in the composition to the amount of additive (c) present is preferably from 2:1 to 1:3, preferably from 1.5:1 to 1:2, preferably from 1:1 to 1:1.6.

[0142] (d) antioxidants In some embodiments, the composition of the first aspect comprises (d) an antioxidant. A mixture of two or more antioxidants may be present.

[0143] Suitable antioxidants for use herein include phenolic antioxidants and amino antioxidants.

[0144] Suitable amino antioxidants include aromatic amines, hindered amines, N-oxides, polyalkylene polyamines; and polyisobutenyl-substituted succinimides.

[0145] Suitable aromatic amines include diaminobenzenes and alkylated diaminobenzenes, especially di- and tri-alkylated 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; diphenylamine and alkylated diphenylamines, such as N,N-diphenyl-1,4-phenylenediamine; and naphthylamines, such as N-phenyl-1-naphthylamine and N-phenyl-2-naphthylamine.

[0146] Suitable hindered amines include secondary and tertiary aliphatic amines, such as dimethylcyclohexylamine and diethylhydroxylamine.

[0147] Suitable N-oxides include TEMPO and its derivatives.

[0148] Polyisobutenyl-substituted succinimides are known to those skilled in the art and their use as antioxidants is described, for example, in WO 2009 / 016400.

[0149] In some embodiments, (d) is a phenolic antioxidant.

[0150] In some embodiments, the composition of the first aspect comprises amino and phenolic antioxidants.

[0151] Any suitable phenolic antioxidant may be used. Suitable antioxidants will be known to those skilled in the art.

[0152] Phenolic antioxidant compounds are meant to include any compound containing a phenol moiety, i.e., a benzene ring substituted with a hydroxyl group. They may be very simple compounds, such as benzenediols, alkyl-substituted phenols, or benzenetriols. Alternatively, the phenolic antioxidant may be part of a more complex molecule, which may contain two phenol moieties, see, for example, the compounds disclosed in US 2006 / 0219979.

[0153] Phenolic antioxidant compounds suitable for use in the present invention include those of formula (III): [ka] (In the formula, R 1 is selected from an optionally substituted alkyl or alkenyl group, an aryl group, an aralkyl group; an ester, a carboxylic acid, an aldehyde, a ketone, an ether, an alcohol, an amine, or an amide; R 2 and R 3 are 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. Examples include:

[0154] Preferably, R 1 is preferably an alkyl group having 1 to 9 carbon atoms, and may be linear or branched. 1 is selected from methyl, ethyl, isopropyl, and tertiary butyl. 1 and R 2 may be taken together to form a cyclic substituent that is either alkyl or aryl. 2 and R 3 is preferably hydrogen or an alkyl group having 1 to 9 carbon atoms. 2 and R 3is independently selected from hydrogen, methyl, ethyl, tertiary butyl, and isopropyl. Preferably, n is 1, 2, or 3.

[0155] Preferred phenolic antioxidant compounds for use in the present invention are substituted benzene compounds having one or more hydroxy substituents, such as 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.

[0156] One particularly preferred phenolic antioxidant for use herein is 2,6-di-tert-butyl-phenol, although those skilled in the art will recognize that commercial sources of this compound often comprise mixtures containing mono-, tert-, and tri-tert-butyl-phenol.

[0157] When present, antioxidant (d) is preferably included 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.

[0158] When present, antioxidant (d) may be included in the composition of the first aspect in an amount of up to 10,000 ppm, preferably up to 5,000 ppm, more preferably up to 2,000 ppm, for example up to 1,000 ppm.

[0159] In a preferred embodiment, the composition of the first aspect comprises 100 to 1,000 ppm, preferably 250 to 750 ppm of (d) antioxidant, and 100 to 10,000 ppm, preferably 400 ppm to 2,500 ppm of additives (a) and / or (b).

[0160] According to a second aspect of the present invention, there is provided a method for reducing the pour point of a composition comprising pyrolysis oil, comprising the steps of: (a) an aldehyde-alkylphenol copolymer, wherein the alkylphenol of the copolymer comprises an alkyl group having at least 30 carbon atoms; and (b) Reaction products of alcohols and / or amines with copolymers of alpha-olefins and ethylenically unsaturated carboxylate compounds, wherein the alpha-olefins and / or alcohols and / or amines have at least 30 carbon atoms. In one embodiment, a method is provided that includes adding to the composition one or more additives selected from:

[0161] The additives (a) and (b) used in the method of this second aspect may have any of the suitable features and advantages described in relation to the first aspect.

[0162] The composition comprising pyrolysis oil used in the method of this second aspect may have any of the suitable features and advantages described in relation to the first aspect.

[0163] The pyrolysis oil-containing composition used in the method of this second aspect may also include component (d) an antioxidant as defined in relation to the first aspect.

[0164] According to a third aspect of the present invention, there is provided the use of one or more additives to depress the pour point of a composition comprising a pyrolysis oil, the one or more additives comprising: (a) aldehyde-alkylphenol copolymers and / or aldehyde-alkylphenol-polyamine copolymers, wherein the alkylphenol of the copolymer comprises an alkyl group having at least 30 carbon atoms; and (b) Reaction products of alcohols and / or amines with copolymers of alpha-olefins and ethylenically unsaturated carboxylate compounds, wherein the alpha-olefins and / or alcohols and / or amines have at least 30 carbon atoms. The use is provided, wherein the

[0165] The additives (a) and (b) used in this third aspect may have any of the suitable features and advantages described in relation to the first aspect.

[0166] The pyrolysis oil-containing composition used in this third aspect may have any of the suitable features and advantages described in relation to the first aspect.

[0167] The pyrolysis oil-containing composition used in this third aspect may also include component (d) an antioxidant as defined in relation to the first aspect.

[0168] The method of the second aspect or the use of the third aspect preferably results in a depression of the pour point of the composition by at least 5°C, at least 10°C, at least 15°C, or at least 20°C. Such a depression is preferably relative to a similar composition comprising pyrolysis oil but without additives (a) and (b) (i.e., a composition comprising pyrolysis oil and no additives). Such compositions comprising pyrolysis oil and no additives preferably do not contain other pour point depressants. Such compositions comprising pyrolysis oil and no additives may contain other additives, such as component (d) as defined above, for example, antioxidants.

[0169] The method of the second aspect or the use of the third aspect may also comprise adding to the composition: - Reduced discoloration during storage; - Reduced sedimentation; - Reduced gum and grain formation; - Improved filterability; and - Further improvement of low temperature characteristics This may result in one or more of the following:

[0170] Such further low temperature property improvements may be a lowering of the cloud point, a reduction in viscosity change with temperature, and / or a reduction in the viscosity of the composition at or near the pour point of the unadditized fluid.

[0171] In the method of the second aspect or the use of the third aspect, the additives (a) and / or (b) can be added to the composition comprising the pyrolysis oil at any time, including during the process. It is preferred that the additives are added as soon as possible after synthesis of the oil, preferably before the oil cools.

[0172] The methods and uses of the present invention reduce the pour point of compositions containing pyrolysis oil.

[0173] Preferably, the methods and uses of the present invention reduce the pour point of compositions containing plastic pyrolysis oil.

[0174] The methods and uses of the present invention may also improve the stability of compositions containing pyrolysis oil.

[0175] The methods and uses of the present invention may improve the stability of compositions containing plastic pyrolysis oil.

[0176] The methods and uses of the present invention may improve the storage stability of compositions containing pyrolysis oil.

[0177] The methods and uses of the present invention may improve the storage stability of compositions containing plastic pyrolysis oil.

[0178] Improved storage stability preferably results in reduced deterioration of the oil during storage, which can be observed in several ways.

[0179] In some embodiments, improved stability may result in reduced precipitation.

[0180] In some embodiments, improved stability may reduce or prevent viscosity buildup.

[0181] In some embodiments, improved stability may result in improved filterability, especially after storage.

[0182] In some embodiments, the improved stability may result in improved low temperature properties of compositions including the pyrolysis oil.

[0183] In some embodiments, the use of this third aspect is to reduce the pour point of a composition comprising pyrolysis oil and additive (c), where additive (c) is as defined in relation to the first aspect.

[0184] In such an embodiment, additive (c) is preferably (c1) aldehyde-alkylphenol copolymers and / or aldehyde-alkylphenol-polyamine copolymers, wherein the alkylphenol of the copolymer contains an alkyl group having less than 30 carbon atoms; and (c2) Reaction products of alcohols and / or amines with copolymers of alpha-olefins and ethylenically unsaturated carboxylate compounds, where the alpha-olefins, alcohols, and amines, if present, have less than 30 carbon atoms. The compound is selected from one or more of the following:

[0185] In such an embodiment, additive (c) is preferably additive (c2) as defined above.

[0186] This third aspect of the invention may therefore provide the use of one or more of additives (a) and (b) in combination with one or more of additives (c1) and (c2) to depress the pour point of a composition comprising a pyrolysis oil. Preferably, the use comprises one or more of additives (a) and (b) in combination with one or more of additives (c2) to depress the pour point of a composition comprising a pyrolysis oil.

[0187] In such an embodiment, the use may include a synergistic depression of the pour point of the composition comprising the pyrolysis oil, provided by the combination of additive (a) and / or additive (b) with additive (c1) and / or additive (c2). Preferably, the use includes a synergistic depression of the pour point of the composition comprising the pyrolysis oil, provided by the combination of additive (a) and / or additive (b) with additive (c2).

[0188] According to a fourth aspect of the present invention, there is provided a composition for improving the pour point depressing performance of additive (c) in a composition comprising pyrolysis oil, (a) aldehyde-alkylphenol copolymers and / or aldehyde-alkylphenol-polyamine copolymers, wherein the alkylphenol of the copolymer comprises an alkyl group having at least 30 carbon atoms; and (b) Reaction products of alcohols and / or amines with copolymers of alpha-olefins and ethylenically unsaturated carboxylate compounds, wherein the alpha-olefins and / or alcohols and / or amines have at least 30 carbon atoms. The use of one or more additives selected from There is provided a use wherein the additive (c) is as defined in relation to the first aspect.

[0189] In such an embodiment, additive (c) is (c1) aldehyde-alkylphenol copolymers and / or aldehyde-alkylphenol-polyamine copolymers, wherein the alkylphenol of the copolymer contains an alkyl group having less than 30 carbon atoms; and (c2) Reaction products of alcohols and / or amines with copolymers of alpha-olefins and ethylenically unsaturated carboxylate compounds, where the alpha-olefins, alcohols, and amines, if present, have less than 30 carbon atoms. The compound is selected from one or more of the following:

[0190] Preferably, additive (c) is (c2) a reaction product of an alcohol and / or amine with a copolymer of an alpha-olefin and an ethylenically unsaturated carboxylate compound, where the alpha-olefin, alcohol and amine, if present, have less than 30 carbon atoms.

[0191] The additives (a) and (b) used in this third aspect may have any of the suitable features and advantages described in relation to the first aspect.

[0192] Additive (c) is suitably as defined in relation to the first aspect.

[0193] The pyrolysis oil-containing composition used in this fourth aspect may have any of the suitable features and advantages described in relation to the first aspect.

[0194] The pyrolysis oil-containing composition used in this fourth aspect may also include component (d) an antioxidant as defined in relation to the first aspect.

[0195] Use of the fourth aspect preferably results in a reduction in the pour point of the composition by at least 5° C., at least 10° C., at least 15° C., or at least 20° C. Such a reduction is preferably relative to a similar composition comprising pyrolysis oil and additive (c) but not additives (a) and (b). Such compositions comprising pyrolysis oil and additive (c) may contain other additives such as component (d) as defined above, for example antioxidants.

[0196] The invention will now be further described with reference to the following non-limiting examples.

[0197] [Example] additives Additive composition A is Solvesso 150, a commercially available composition comprising an aldehyde-alkylphenol copolymer according to the definition of additive (a) above and a solvent. The additive is formed from formaldehyde and an alkylphenol, where the alkylphenol is a mixture of compounds having an alkyl group with at least 30 carbon atoms. The additive is a linear polymer having a relatively high number average molecular weight of 5,000-7,000. The amount of aldehyde-alkylphenol copolymer present in additive composition A (wt% active ingredient) was 48-52 wt%.

[0198] Additive Composition B contains an OMAC ester according to the definition of additive (b) described above. This additive is formed by reacting an alpha-olefin containing at least 82 wt% of an alpha-olefin compound having at least 30 carbon atoms with maleic anhydride to form an alpha-olefin maleic anhydride copolymer. This copolymer is then esterified with 1.0 molar equivalent of a C18-C22 alcohol relative to the maleic anhydride monomer used to obtain the additive. The amount of OMAC ester present in Additive Composition B (wt% actives) was 70-75 wt%.

[0199] Additive composition C includes an OMAC ester according to the definition of additive (b) described above. Additive composition C is formed by reacting alpha olefins, including approximately 50 wt% of a commercially available "C30+" alpha olefin compound and approximately 50 wt% of a C24-C28 alpha olefin, with maleic anhydride to form an alpha-olefin maleic anhydride copolymer. This copolymer is then esterified with 1.0 molar equivalent of a C18-C22 alcohol relative to the maleic anhydride monomer used to obtain the additive. The amount of OMAC ester present in additive composition C (wt% actives) was 75-80 wt%.

[0200] Comparative additive composition D is Solvesso 150, a commercially available composition comprising an aldehyde-alkylphenol copolymer and a solvent. The copolymer is formed from formaldehyde and an alkylphenol, where the alkylphenol is a mixture of compounds having C24-C28 alkyl groups. The amount of aldehyde-alkylphenol copolymer present in the composition (wt% active ingredient) was 48-52 wt%.

[0201] Comparative additive composition E is an OMAC ester formed by reacting a C24-C28 alpha olefin with maleic anhydride to form an alpha-olefin maleic anhydride copolymer. This copolymer is then esterified with 1.0 molar equivalent of a C18-C22 alcohol relative to the maleic anhydride monomer used to obtain the additive. The amount of OMAC ester present in the composition (wt% active) was 75-80 wt%.

[0202] Comparative additive composition F is a commercially available OMAC ester formed by reacting a C24-28 alpha-olefin with maleic anhydride, followed by esterification with 0.5 to 1.0 moles of a C18-22 fatty alcohol (relative to the maleic anhydride monomer). The amount of OMAC ester present in the composition (wt% active) was 75-80 wt%.

[0203] Comparative additive composition G is a commercially available OMAC ester formed by reacting a C20-24 alpha-olefin with maleic anhydride, followed by esterification with 0.5 to 1.0 moles of a C18-22 fatty alcohol (relative to the maleic anhydride monomer). The amount of OMAC ester present in the composition (wt% active) was 70-75 wt%.

[0204] Comparative additive composition H is a commercially available polyalkylated phenol additive. The amount of additive present in the composition (wt% active ingredient) was approximately 50 wt%.

[0205] Additive composition I contains an OMAC ester conforming to the definition of additive (b) described above. Additive composition I is formed by reacting alpha-olefins, including approximately 30 wt% of a commercially available "C30+" alpha-olefin product and approximately 70 wt% of a C24-C28 alpha-olefin product, with maleic anhydride to form an alpha-olefin maleic anhydride copolymer. This copolymer is then esterified with 0.5 to 1.0 molar equivalents of alcohol, relative to the maleic anhydride monomer used, to obtain the additive. The alcohol is a mixture of C16-C26 linear fatty alcohols, including approximately 50 wt% of a C20 alcohol. The amount of OMAC ester present in additive composition I (wt% actives) was 70-75 wt%.

[0206] pyrolysis oil In the following example and comparative example compositions, the additives were added to a plastic-derived pyrolysis oil having the following specifications: [Table 1]

[0207] Example and Comparative Example Composition Set 1 The following example and comparative example compositions were formed by mixing the indicated additives in the indicated dosage amounts into the pyrolysis oil defined above. Example 1 contained the pyrolysis oil described above and 2,000 ppm (by volume) of Additive A. Example 1b contained the pyrolysis oil described above and 1,000 ppm (by volume) of Additive A. Example 1c contained the pyrolysis oil described above and 500 ppm (by volume) of Additive A. Example 2 contained the pyrolysis oil described above and 2,000 ppm (by volume) of Additive B. Example 2b contained the pyrolysis oil described above and 1,000 ppm (by volume) of Additive B. Example 3 contained the pyrolysis oil described above and 2,000 ppm (by volume) of Additive C. Example 4 contained the pyrolysis oil described above and 2,000 ppm (by volume) of Additive A and Comparative Additive Composition E in a 1:1 weight ratio. Example 5 contained the pyrolysis oil described above and 2,000 ppm (by volume) of Additive A and Comparative Additive Composition F in a 1:1 weight ratio. Example 6 contained the pyrolysis oil described above and 2,000 ppm (by volume) of Additive B and Comparative Additive Composition E in a 1:1 weight ratio. Comparative Example 1 contained the pyrolysis oil described above and 2,000 ppm (by volume) of Comparative Additive D. Comparative Example 2 contained the pyrolysis oil described above and 2,000 ppm (by volume) of Comparative Additive E. Comparative Example 3 contained the pyrolysis oil described above and 2,000 ppm (by volume) of Comparative Additive Composition F. Comparative Example 4 contained pyrolysis oil and 2,000 ppm (by volume) of Comparative Additive Composition G described above. Comparative Example 5 contained the pyrolysis oil described above and 2,000 ppm (by volume) of Comparative Additive Composition H.

[0208] Pour Point Test 1 The ASTM D97 method was used to determine the pour points of example compositions containing additive type (a) or (b), as well as an unadded control and comparative compositions containing different additives. As a slight modification to the ASTM D97 method, 20 ml samples of the base pyrolysis oil were used in these tests.

[0209] The pour points of the compositions are shown in Table 1 below. [Table 2]

[0210] The change in pour point of the composition compared to the control is shown in parentheses after the pour point.

[0211] Additives A and B were also tested in separate tests at different dosage levels of 500 ppm (Example 1c), 1,000 ppm (Example 1b / 2b), and 2,000 ppm (Example 1 / 2) in pyrolysis oil. The results are shown in Table 2 below. [Table 3]

[0212] The results show that compositions of the present invention (Examples 1, 1b, 1c, 2, 2b, 3, 4, 5, and 6) containing type (a) and (b) additives (additive compositions A, B, and C) as defined herein significantly reduce pour points compared to unadded control compositions containing only pyrolysis oil and comparative compositions containing additives that do not contain significant amounts of C30+ alkyl chains. The pour points of the compositions of Examples 1-6 were 14-31°C lower than the control and comparative compositions. The results of Examples 4-6 also demonstrate the synergistic effect of combining type (a) and (b) additives with OMAC ester additives that do not contain groups with more than 30 carbon atoms and have no pour-reducing activity when used alone.

[0213] Such a reduction in the pour point of these compositions of the present invention is expected to provide significant advantages in the handling and use of such pyrolysis oils, such as those derived from plastic waste. This can facilitate the utilization of such pyrolysis oils in the production of fuels and chemical feedstocks, and can therefore provide beneficial use for plastic waste, reducing the amount of such waste that ends up in landfills or pollutes the oceans. Thus, such potential improvements to pyrolysis oils are expected to provide significant benefits to the environment as a whole.

[0214] Example and Comparative Composition Set 2 The following example and comparative example compositions were formed by mixing the indicated additives in the indicated dosage amounts into waste plastic pyrolysis oil, which was a commercially produced, different waste plastic pyrolysis oil sourced in the United States and conditioned at 160°F.

[0215] Example 2.1 contained the pyrolysis oil described above and 1,000 ppm (by volume) of Additive I. Example 2.2 contained the pyrolysis oil described above and 1,000 ppm (by volume) of Additive A. Example 2.3 contained the pyrolysis oil described above and 1,500 ppm (by volume) of Additive A. Example 2.4 contained the pyrolysis oil described above and 2,000 ppm (by volume) of Additive I. Example 2.5 contained the pyrolysis oil described above and 2,000 ppm (by volume) of Additive C. Example 2.6 contained the pyrolysis oil described above and 2,000 ppm (by volume) of Additive A. Comparative Example 2.1 contained the pyrolysis oil described above and 1,000 ppm (by volume) of Comparative Additive E. Comparative Example 2.2 contained the pyrolysis oil described above and 1,000 ppm (by volume) of Comparative Additive F. Comparative Example 2.3 contained the pyrolysis oil described above and 2,000 ppm (by volume) of Comparative Additive E. Comparative Example 2.4 contained the pyrolysis oil described above and 2,000 ppm (by volume) of Comparative Additive F.

[0216] Pour Point Test 2 Using the modified ASTM D97 method described above, the pour points of the example compositions of Set 2 containing additive type (a) or (b) were determined, along with the pour points of an unadded control and comparative compositions containing different additives.

[0217] The pour points of the compositions are shown in Table 3 below. [Table 4]

[0218] The change in pour point of the composition compared to the control is shown in parentheses after the pour point.

[0219] These results demonstrate that compositions of the present invention (Examples 2.1-2.6) containing Type (a) and (b) additives (Additive Compositions A, C, and I) as defined herein, reduce pour points significantly more than either the unadded control composition containing only pyrolysis oil or the comparative composition containing an additive that does not contain significant amounts of C30+ alkyl chains. The pour points of the compositions of Examples 2.1-2.6 were 13-25°C lower than the control and comparative compositions.

[0220] As noted above for Example Set 1, such a reduction in the pour point of these compositions of the present invention in Example Set 2 is expected to provide significant advantages in the handling and use of such pyrolysis oils, such as plastic waste-derived pyrolysis oils. This can facilitate the utilization of such pyrolysis oils in the production of fuels and chemical feedstocks, thus providing beneficial use of plastic waste and reducing the amount of such waste that ends up in landfills or pollutes the oceans. Thus, such potential improvements to pyrolysis oils are expected to provide significant benefits to the environment overall.

[0221] While several preferred embodiments have been shown and described, those skilled in the art will recognize that various changes and modifications can be made therein without departing from the scope of the invention as defined in the appended claims.

[0222] Throughout this specification, the terms "comprising" or "comprises" mean including the specified components but not excluding the presence of other components. The terms "consisting essentially of" or "consists essentially of" mean including the specified components but excluding other components except for materials present as impurities, unavoidable materials present as a result of the process used to produce the components, and components added for purposes other than achieving the technical effects of the invention. Typically, when referring to a composition, a composition consisting essentially of a set of components will contain less than 5% by weight, typically less than 3% by weight, and more typically less than 1% by weight of unspecified components.

[0223] The terms "consisting of" or "consists of" mean including the specified components, but excluding the addition of other components.

[0224] Where appropriate and always depending on the context, use of the words "comprises" or "comprising" can also be interpreted to include or include the meaning of "consists essentially of" or "consisting essentially of" and can also be interpreted to include the meaning of "consists of" or "consisting of."

[0225] For the avoidance of doubt, when the amount of an ingredient in a composition is stated in wt%, this means the weight percent of the specified ingredient in relation to the total composition being referenced.

[0226] Any features described herein may be used either individually or in combination with one another as appropriate, particularly in the combinations set forth in the appended claims. Any feature of each aspect or exemplary embodiment of the present invention described herein will also be read as being applicable to any other aspect or exemplary embodiment of the present invention, where appropriate. In other words, those skilled in the art who read this specification will consider any feature of each exemplary embodiment of the present invention to be interchangeable and combinable between different exemplary embodiments.

[0227] Attention is directed to all articles and documents filed contemporaneously with or prior to this application in connection with this application, and all articles and documents open to public inspection herewith, and the contents of all such articles and documents are incorporated herein by reference.

[0228] All of the features disclosed in this specification (including any accompanying claims and drawings), and / or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations in which at least some of such features and / or steps are mutually exclusive.

[0229] Each feature disclosed in this specification (including any accompanying claims and drawings), unless expressly stated otherwise, may be replaced by alternative features serving the same, equivalent, or similar purpose. Thus, unless expressly stated otherwise, each feature disclosed is only one example of a generic series of equivalent or similar features.

[0230] The invention is not limited to the details of the foregoing embodiments, and extends to any novel one or any novel combination of features disclosed in this specification (including any accompanying claims and drawings), or any novel one or any novel combination of steps of any method or process so disclosed.

Claims

1. Pyrolysis oil and, as an additive, (a) aldehyde-alkylphenol copolymers and / or aldehyde-alkylphenol-polyamine copolymers, wherein the alkylphenol of the copolymer comprises an alkyl group having at least 30 carbon atoms; and (b) reaction products of alcohols and / or amines with copolymers of alpha-olefins and ethylenically unsaturated carboxylate compounds, wherein the alpha-olefins and / or the alcohols and / or amines have at least 30 carbon atoms; and one or more of:

2. The composition of claim 1 , wherein the pyrolysis oil is a plastic pyrolysis oil.

3. The additive is (a) an aldehyde-alkylphenol copolymer, wherein the alkylphenol of the copolymer comprises an alkyl or alkenyl group having at least 30 carbon atoms; and the aldehyde-alkylphenol copolymer has structure (I) or (II): 【Chemistry 1】 【change】 wherein R is an alkyl group having at least 30 carbon atoms and n is at least 1.

3. The composition of claim 1 or 2, wherein

4. The composition of claim 3, wherein n is 5 to 10.

5. 5. The composition of claim 3 or 4, wherein at least 50 wt% of the R groups present in the additive are C30-C40 alkyl groups.

6. 10. The composition of claim 1 or 5, wherein the additive is (a) an aldehyde-alkylphenol-polyamine copolymer, the alkylphenol of the copolymer comprising an alkyl or alkenyl group having at least 30 carbon atoms.

7. The composition of any one of claims 3 to 6, wherein the additive (a) has a molecular weight in the range of 3,000 to 20,000.

8. 3. The composition of claim 1 or 2, wherein the additive is (b) a reaction product of an alcohol and / or an amine with a copolymer of an alpha-olefin and an ethylenically unsaturated carboxylate compound, wherein the alpha-olefin and / or the alcohol and / or amine have at least 30 carbon atoms, and the ethylenically unsaturated carboxylate compound is maleic anhydride.

9. 9. The composition of claim 8, wherein the additive is a reaction product of an alcohol having at least 30 carbon atoms and a copolymer of an alpha-olefin and an ethylenically unsaturated carboxylate compound.

10. The composition of claim 9, wherein the alpha-olefin has less than 30 carbon atoms.

11. 9. The composition of claim 8, wherein the additive is a C12-C28 ester of a copolymer of an alpha-olefin and an ethylenically unsaturated carboxylate compound, said alpha-olefin having at least 30 carbon atoms.

12. 12. The composition of any of claims 8, 9 and 11, wherein 10 to 90 wt% of the alpha-olefin compounds used to form the copolymer have at least 30 carbon atoms, preferably 20 to 50 wt% of the alpha-olefin compounds have at least 30 carbon atoms.

13. 13. The composition of any of claims 8, 9, 11 and 12, wherein at least 50 wt% of the alpha-olefin compounds used to form the copolymer are C30-C40 alpha-olefins.

14. The composition according to any one of claims 8 to 13, wherein the additive (b) has a molecular weight in the range of 4,000 to 30,000.

15. (c1) aldehyde-alkylphenol copolymers and / or aldehyde-alkylphenol-polyamine copolymers, wherein the alkylphenol of the copolymer comprises an alkyl group having less than 30 carbon atoms; and (c2) Reaction products of alcohols and / or amines with copolymers of alpha-olefins and ethylenically unsaturated carboxylate compounds, wherein the alpha-olefins, the alcohols, and the amines, if present, have less than 30 carbon atoms.

15. The composition according to any one of claims 1 to 14, comprising a further additive (c) selected from one or more of:

16. The composition of any preceding claim, wherein the additive is present in the composition in an amount of from 100 to 3,000 ppm.

17. (d) antioxidants The composition of any one of claims 1 to 16, comprising:

18. 18. The composition of claim 17, wherein the (d) antioxidant is a phenolic antioxidant selected from 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-butyl-phenol, propyl gallate, and tert-butylcatechol.

19. 18. The composition of claim 17, wherein (d) the antioxidant comprises an amino-based antioxidant selected from aromatic amines, hindered amines, N-oxides, polyalkylene polyamines; and polyisobutenyl-substituted succinimides.

20. 1. A method for reducing the pour point of a composition comprising pyrolysis oil, comprising: (a) aldehyde-alkylphenol copolymers and / or aldehyde-alkylphenol-polyamine copolymers, wherein the alkylphenol of the copolymer comprises an alkyl group having at least 30 carbon atoms; and (b) reaction products of alcohols and / or amines with copolymers of alpha-olefins and ethylenically unsaturated carboxylate compounds, wherein the alpha-olefins and / or the alcohols and / or amines have at least 30 carbon atoms; The method further comprising the step of adding to the composition one or more additives selected from:

21. 1. Use of one or more additives to depress the pour point of a composition comprising a pyrolysis oil, the one or more additives comprising: (a) aldehyde-alkylphenol copolymers and / or aldehyde-alkylphenol-polyamine copolymers, wherein the alkylphenol of the copolymer comprises an alkyl group having at least 30 carbon atoms; and (b) reaction products of alcohols and / or amines with copolymers of alpha-olefins and ethylenically unsaturated carboxylate compounds, wherein the alpha-olefins and / or the alcohols and / or amines have at least 30 carbon atoms; The above-mentioned use, wherein the above-mentioned use is selected from the group consisting of:

22. The composition comprising pyrolysis oil comprises one or more additives (c); The additive (c) is (c1) aldehyde-alkylphenol copolymers and / or aldehyde-alkylphenol-polyamine copolymers, wherein the alkylphenol of the copolymer comprises an alkyl group having less than 30 carbon atoms; and (c2) Reaction products of alcohols and / or amines with copolymers of alpha-olefins and ethylenically unsaturated carboxylate compounds, wherein the alpha-olefins, the alcohols, and the amines, if present, have less than 30 carbon atoms.

22. The method or use according to claim 20 or 21, selected from one or more of:

23. 23. The method or use of any of claims 20 to 22, wherein the pour point depression of the composition is at least 10°C.

24. - Reduced discolouration during storage; - reduced sedimentation; - reduced gum and particulate formation; - improved filterability; and - Further improvement of low-temperature properties The method or use according to any one of claims 20 to 23, wherein the method or use results in one or more of the following:

25. To improve the pour point depressing performance of additive (c) in a composition containing pyrolysis oil, (a) aldehyde-alkylphenol copolymers and / or aldehyde-alkylphenol-polyamine copolymers, wherein the alkylphenol of the copolymer comprises an alkyl group having at least 30 carbon atoms; and (b) reaction products of alcohols and / or amines with copolymers of alpha-olefins and ethylenically unsaturated carboxylate compounds, wherein the alpha-olefins and / or the alcohols and / or amines have at least 30 carbon atoms; The use of one or more additives selected from The additive (c) is (c1) aldehyde-alkylphenol copolymers and / or aldehyde-alkylphenol-polyamine copolymers, wherein the alkylphenol of the copolymer comprises an alkyl group having less than 30 carbon atoms; and (c2) Reaction products of alcohols and / or amines with copolymers of alpha-olefins and ethylenically unsaturated carboxylate compounds, wherein the alpha-olefins, the alcohols, and the amines, if present, have less than 30 carbon atoms. The above uses are selected from one or more of the following:

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