Compositions, methods and uses

Abstract

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

Description

[0001] This invention relates to pyrolysis oils and related methods and uses. Specifically, this invention relates to additives for improving the physical properties (especially flowability) of compositions containing plastic pyrolysis oils. Particularly, this invention relates to lowering the pour point of compositions containing pyrolysis oils.

[0002] Pyrolysis oil is a fluid directly generated from the pyrolysis of waste, such as plastic waste, biomass (e.g., agricultural waste, forestry waste), waste cooking oil, algae waste, waste 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., rubber from tires), polyacrylates, and polyacrylonitrile.

[0003] The organic liquids produced by the pyrolysis of plastics and other waste materials are very dark in color, have an unpleasant odor, and are unstable. These liquids may also easily gel at low or medium temperatures, making them difficult to handle and process.

[0004] Pyrolysis oil can be used as a feedstock for chemical processing, such as in the production of polymers like polyethylene. It can also be used as a feedstock for fractionators to produce distillate oil fractions, and as a feedstock for secondary refining processes (such as fluidized bed catalytic cracking units (FCCU)). Pyrolysis oil can also be used for fuel oil production. Using pyrolysis oil to produce polymers is a more sustainable alternative to using crude oil feedstocks.

[0005] Due to the poor stability and processing performance of pyrolysis oil, especially its use may be limited, for example, during cooling during transportation or storage.

[0006] Pyrolysis oils, especially those derived from plastics, can also have relatively high pour points, which can impair their flow properties and use at low to medium or even high temperatures. These pyrolysis oils contain waxy molecules of saturated alkanes produced during pyrolysis. As the temperature of the pyrolysis oil decreases (e.g., during storage), these waxy molecules begin to crystallize and precipitate, eventually forming a three-dimensional network of aggregated wax crystals, thus impairing the oil's free flow. At a certain temperature, pyrolysis oil completely gels and no longer flows in liquid form. This temperature is called the oil's gel point or freeze point. The temperature at which the oil just before it completely gels, while still exhibiting surface motion, is called the oil's pour point. Lowering the pour point of a liquid, even at medium to relatively low temperatures, can improve its handling and processing. This can be important from a safety perspective during on-site handling and storage. Pyrolysis oils typically have relatively low flash points (e.g., 100℉). Applying external heat to improve flowability if the oil is not handled properly near its flash point poses a safety risk. Therefore, given the relatively high pour point of pyrolysis oils, it is desirable to lower the pour point of such pyrolysis oils to facilitate their handling, storage, and safety, thereby enhancing their value and their use, for example, as blending components in fuel oils and as feedstocks in chemical processes.

[0007] The inventors have discovered that certain compounds having C30 (or higher) groups as defined herein, when used alone, can effectively lower the pour point of compositions containing pyrolysis oils. The inventors have also discovered that such additives can enhance the ability of similar polymer additives without C30 groups to lower the pour point of compositions containing pyrolysis oils.

[0008] According to a first aspect of the invention, a composition is provided comprising pyrolysis oil and one or more of the following as additives: (a) an aldehyde-alkylphenol copolymer and / or an aldehyde-alkylphenol-polyamine copolymer, wherein the alkylphenol of the copolymer comprises an alkyl group having at least 30 carbon atoms; and (b) The reaction product of an alcohol and / or amine with an α-olefin and an olefinic unsaturated carboxylic acid ester compound, wherein the α-olefin and / or alcohol and / or amine has at least 30 carbon atoms.

[0009] Suitably, additives (a) and / or (b) act as pour point inhibitors in the composition of the first aspect. A pour point inhibitor is an additive capable of lowering the pour point of a composition (i.e., the composition comprising pyrolysis oil described above) to maintain the fluidity of the composition at lower temperatures. The "pour point" of a liquid is defined as the lowest temperature at which the liquid pours, flows, or exhibits 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 compositions of the present invention is determined using a method modified according to ASTM D97.

[0010] A first aspect of the invention relates to a composition comprising pyrolysis oil. This pyrolysis oil can be obtained by pyrolyzing any type of waste. The composition and properties of the oil will depend on the type of pyrolysis waste and the pyrolysis conditions. For example, the pyrolysis oil can be obtained from pyrolysis waste (e.g., plastic waste, agricultural waste, forestry waste, waste cooking oil, algae waste, waste tires, or waste rubber).

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

[0012] In some embodiments, the pyrolysis oil of the composition of the first aspect may be a 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 the pyrolysis equipment without purification or further processing.

[0015] Suitable, the pyrolysis oil (without additives) has a baseline pour point of at least 30°C, and suitablely at least 40°C.

[0016] Suitable, the pyrolysis oil contains 3 to 30% by weight of n-alkanes. In some embodiments, the pyrolysis oil contains 15 to 30% by weight of n-alkanes, suitablely 20 to 27% by weight.

[0017] A suitable pyrolysis oil contains at least 30% by weight of C9-C18 n-alkanes. A suitable pyrolysis oil contains 30% to 50% by weight of C9-C18 n-alkanes.

[0018] A suitable pyrolysis oil contains at least 25% by weight of C20-C30 n-alkanes. A suitable pyrolysis oil contains 25% to 35% by weight of C20-C30 n-alkanes.

[0019] A suitable pyrolysis oil contains at least 10% by weight of C30-C40 n-alkanes. A suitable pyrolysis oil contains 10% to 20% by weight of C30-C40 n-alkanes.

[0020] A suitable pyrolysis oil contains at least 5% by weight of C40+ n-alkanes. A suitable pyrolysis oil contains 5% to 10% by weight of C40+ n-alkanes.

[0021] Suitable, the n-alkanes in the pyrolysis oil comprise 30 to 50 wt% of C9-C18 n-alkanes, 25 to 35 wt% of C20-C30 n-alkanes, 10 to 20 wt% of C30-C40 n-alkanes and 5 to 10 wt% of C40+ n-alkanes, based on the total weight of the n-alkanes 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, which includes plastic pyrolysis oil and middle distillate fuel oil.

[0024] Middle distillate fuel oils can include petroleum-based fuel oils, particularly middle distillate fuel oils. These middle distillate fuel oils typically boil in the range of 110°C to 500°C, for example, 150°C to 400°C. Middle distillate fuel oils can include atmospheric or vacuum distillate oils, cracked gas oils, or blends of any proportion of straight-run and refinery feedstocks (e.g., thermally cracked and / or catalytically cracked and hydrocracking distillates).

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

[0026] Middle distillate fuel oils may contain renewable fuels, such as biofuel compositions or biodiesel compositions.

[0027] Middle distillate fuel oils may include first-generation biodiesel. First-generation biodiesel contains esters, such as vegetable oils, animal fats, and waste edible 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 oil, waste edible oil, hydrogenated vegetable oil, or any mixture thereof) with alcohols (usually monohydric alcohols) in the presence of a catalyst.

[0028] Middle distillate fuel oils may include second-generation biodiesel. Second-generation biodiesel is derived from renewable sources such as vegetable oils and animal fats, and is typically processed in refineries using hydrotreating processes such as the H-Bio process developed by Petrobras. Second-generation biodiesel can 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 marketed by ConocoPhillips as Renewable Diesel and by Neste as NExBTL.

[0029] The middle distillate fuel oil used in this invention may include third-generation biodiesel. Third-generation biodiesel utilizes gasification and Fischer-Tropsch synthesis technologies, including those known as BTL (biomass-to-liquid) fuels. Third-generation biodiesel is not significantly different from some second-generation biodiesel, but its goal is to fully utilize the entire plant (biomass), thereby broadening the feedstock base.

[0030] Middle distillate fuel oil may contain blends of any one or all of the above-mentioned diesel fuel oils.

[0031] In some embodiments, the middle distillate fuel oil may be a blended diesel fuel containing biodiesel. In such blends, biodiesel may be present in amounts 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, middle distillate fuel oil may contain secondary fuels, such as ethanol. However, middle distillate fuel oil compositions are preferably ethanol-free.

[0033] Middle distillate fuel oils may contain relatively high sulfur content, for example, greater than 0.05% by weight, such as 0.1% by weight or 0.2% by weight.

[0034] However, in a preferred embodiment, the middle distillate fuel oil has a sulfur content of up to 0.05% by weight, more preferably up to 0.035% by weight, and especially up to 0.015% by weight. Fuels with even lower levels of sulfur are also suitable, for example, fuels with less than 50 ppm by weight, preferably less than 20 ppm by weight, such as fuels with 10 ppm by weight or less of sulfur.

[0035] Middle distillate fuel oils may contain various metallic substances. This could be due to contamination of the fuel during manufacturing, storage, transportation, or use, or due to contamination of fuel additives. Metallic substances may also be intentionally added to fuels. For example, transition metals are sometimes added as fuel-carried catalysts, such as to improve the performance of diesel particulate filters.

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

[0037] Other metallic substances may also exist as contaminants, for example, through corrosion of metal and metal oxide surfaces by acidic substances present in the fuel or from lubricating oils. During use, fuels such as diesel fuel frequently come into contact with metal surfaces, such as in vehicle refueling systems, fuel tanks, and fuel transport vehicles. Typically, metallic 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] Besides the metal contaminants that may be present in middle distillate fuel oils, metal-containing substances are sometimes intentionally added to fuels. For example, as is known in the art, metal-containing fuel-carried catalysts can be added to assist in the regeneration of particulate filters.

[0039] Metal contaminants, depending on their source, may exist as insoluble particles or as soluble compounds or complexes. Metal-containing fuel-carrying catalysts are typically soluble compounds or complexes or colloidal substances.

[0040] In some embodiments, the middle distillate fuel oil may contain a metallic substance comprising a fuel-carrying catalyst. Preferably, the fuel-carrying catalyst comprises one or more metals selected from iron, cerium, platinum, manganese, and Group I and Group II metals (e.g., calcium and strontium). Most preferably, the fuel-carrying catalyst comprises a metal selected from iron and cerium.

[0041] In some embodiments, the middle distillate fuel oil may contain zinc-containing metallic substances. Zinc may be present in amounts of 0.01 to 50 ppm, preferably 0.05 to 5 ppm, more preferably 0.1 to 1.5 ppm.

[0042] The composition of the first aspect comprises one or more of the following: (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 / or (b) The reaction product of an alcohol and / or amine with an α-olefin and an olefinic unsaturated carboxylic acid ester compound, wherein the α-olefin and / or alcohol and / or amine has at least 30 carbon atoms.

[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 an aldehyde-alkylphenol-polyamine copolymer, wherein the alkylphenol of the copolymer comprises an alkyl group having at least 30 carbon atoms.

[0047] Surprisingly, the inventors have discovered that copolymers containing alkylphenols (wherein the alkyl group of the alkylphenol has at least 30 carbon atoms) can advantageously lower the pour point of liquid compositions containing pyrolysis oils. In contrast, such copolymers in which the alkylphenol comprises an alkyl group having fewer than 30 carbon atoms have been found to fail to significantly lower the pour point of said compositions containing pyrolysis oils.

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

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

[0050] Preferably, the aldehyde used to prepare the aldehyde-alkylphenol or aldehyde-alkylphenol-polyamine copolymer is selected from formaldehyde or its reactive equivalents, such as paraformaldehyde, C2 to C4 alkylphenol, etc. 10 Aldehydes and aromatic aldehydes, such as benzaldehyde. Preferably, formaldehyde or its reactive equivalents are used as the aldehyde component to prepare aldehyde-alkylphenol or aldehyde-alkylphenol-polyamine copolymers. Therefore, preferred aldehyde-alkylphenol copolymers are copolymers 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 for additive (a) are copolymers of formaldehyde, alkylphenol, and polyamine. Such aldehyde-alkylphenol-polyamine copolymers can be formed by the methods disclosed in EP2197991A2 and US9528074B2, which are incorporated herein by reference.

[0052] Preferably, the alkylphenol is monosubstituted with an alkyl group, preferably at the para position. The preferred alkyl group has 30 to 50 carbon atoms, more preferably 30 to 40 carbon atoms. Such alkylphenols can be prepared by reacting phenol with an alkene containing the aforementioned number of carbon atoms.

[0053] It will be understood that such alkylphenols may contain mixtures of compounds having alkyl groups with varying chain lengths. Therefore, the alkylphenol monomers used to form aldehyde-alkylphenol copolymers (and alkylphenol subunits of aldehyde-alkylphenol copolymers) may contain some alkyl groups having fewer than 30 carbon atoms. However, most of these alkyl groups contain at least 30 carbon atoms. For example, preferably at least 50% by weight of the alkyl group in the alkylphenol monomer (and preferably at least 50% by weight of the alkylphenol-derived subunits in the aldehyde-alkylphenol or aldehyde-alkylphenol-polyamine copolymer) is an alkyl group having at least 30 carbon atoms, preferably at least 75% by weight, at least 80% by weight, or at least 82% by weight.

[0054] Suitably, at least 50% by weight of the alkylphenol monomer (and suitably at least 50% by weight of the alkylphenol-derived subunit of the aldehyde-alkylphenol or aldehyde-alkylphenol-polyamine copolymer) has an alkyl group containing 30 to 40 carbon atoms, suitably at least 75% by weight, at least 80% by weight or at least 82% by weight.

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

[0056] In some embodiments, the alkylphenol monomer (and therefore the alkylphenol subunit in the aldehyde-alkylphenol or aldehyde-alkylphenol-polyamine copolymer) is a polyisobutylene (PIB)-substituted phenol. Therefore, in these embodiments, the alkyl group mentioned above is PIB.

[0057] Polyisobutylene (PIB) substituted phenols comprise hydrocarbon chains having the following repeating units: Polyisobutylene is prepared by the addition polymerization of isobutylene ((CH3)2C=CH2). Each molecule of the resulting polymer will contain a single olefin moiety.

[0058] Conventional polyisobutylene and so-called “highly reactive” polyisobutylene are suitable for preparing the additives of the present invention (a). Hereinafter, highly reactive polyisobutylene is defined as having at least 50% (preferably 70% or more) of terminal olefin double bonds that are vinylidene, as described in EP0565285. Particularly preferred polyisobutylenes are those having greater than 80 mol% and at most 100% terminal vinylidene, such as those described in EP1344785, which is incorporated herein by reference.

[0059] Methods for preparing polyalkylene-substituted phenols, such as polyisobutylene-substituted phenols, are known to those skilled in the art and include the methods described in EP831141, which are incorporated herein by reference.

[0060] The PIB substituents preferably have a number average molecular weight of 400 to 1,000, suitably 400 to 600 or 420 to 560.

[0061] In some preferred embodiments, additive (a) is an aldehyde-alkylphenol copolymer having structure (I) or (II): Where R is an alkyl group having at least 30 carbon atoms, and n is at least 1.

[0062] Preferably, n is 2 to 12, more preferably 5 to 10 or 5 to 7.

[0063] Preferably, R is a C30-C60 alkyl group, more preferably a C30-C50 alkyl group or a C30-C40 alkyl group.

[0064] As described above, alkylphenols may contain mixtures of compounds having alkyl groups with varying chain lengths, and may also contain some alkyl groups having fewer than 30 carbon atoms. However, the R groups present in the additives suitably have at least 50% by weight having at least 30 carbon atoms, suitably at least 75% by weight, at least 80% by weight, or at least 82% by weight.

[0065] Preferably, at least 50% by weight of the R groups present in the additive are C30-C50 alkyl groups, more preferably C30-C40 alkyl groups. Preferably, at least 75% by weight, at least 80% by weight, or at least 82% by weight of the R groups in the additive are C30-C50 alkyl groups, more preferably C30-C40 alkyl groups.

[0066] Preferably, the aldehyde-alkylphenol copolymer of additive (a) has a molecular weight of 3,000 to 20,000, suitably 4,000 to 10,000, and preferably 5,000 to 7,000.

[0067] Other suitable aldehyde-alkylphenol copolymers applicable herein include compounds of formula (I), wherein the terminal phenolic group is further functionalized, for example by reaction with a fatty acid or amine and an aldehyde via a Mannich reaction. Compounds of this type are described, for example, in US2007 / 221539, which is incorporated herein by reference.

[0068] 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 component has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and most preferably 2 to 3 carbon atoms. Most preferably, the polyamine is a polyethylene polyamine.

[0069] Preferably, the polyamine has 2 to 15 nitrogen atoms, more preferably 2 to 10 nitrogen atoms, and even more preferably 2 to 8 nitrogen atoms.

[0070] In a particularly preferred embodiment, the polyamine has the formula R 1 R 2 NCHR 3 CHR 4 NR 5 R 6 , where R 1 R 2 R 3 R 4 R 5 and R 6 Each is independently selected from hydrogen and optionally substituted alkyl, alkenyl, alkynyl, aryl, alkylaryl, or aralkyl substituents. Therefore, the polyamine used to form the additive preferably includes optionally substituted ethylenediamine residues.

[0071] Preferably, R 1 and R 2 At least one of them is hydrogen, preferably R 1 and R 2 Both are hydrogen.

[0072] Preferably, R 1 R 2 R 5 and R 6 At least two of them are hydrogen.

[0073] Preferably, R 3 and R 4 At least one of them is hydrogen. In some preferred embodiments, R 3 and R 4 Both are hydrogen. In some implementations, R 3 It is hydrogen, and R 4 It is an alkyl group, such as C1 to C4 alkyl groups, especially methyl.

[0074] Preferably, R 5 and R 6 At least one of them is an optionally substituted alkyl, alkenyl, alkynyl, aryl, alkylaryl or aralkyl substituent.

[0075] In which R 1 R 2 R 3 R 4 R 5 and R 6 In at least one embodiment that is not hydrogen, each group is independently selected from optionally substituted alkyl, alkenyl, alkynyl, aryl, alkylaryl, or aralkyl moieties. Preferably, each group is independently selected from hydrogen and optionally substituted C(1-6) alkyl moieties.

[0076] In the particularly preferred compounds, R 1 R 2 R 3 R 4 and R 5 Each is hydrogen, and R 6 The substituted group can be an alkyl, alkenyl, alkynyl, aryl, alkylaryl, or aralkyl substituent. R is preferred. 6 The C(1-6) alkyl moiety is optionally substituted.

[0077] Such an alkyl moiety may be substituted with one or more groups selected from hydroxyl, amino (especially unsubstituted amino; -NH-, -NH2), sulfonyl, sulphoxy, C(1-4)alkoxy, nitro, halogen (especially chlorine or fluorine) and mercapto.

[0078] One or more heteroatoms, such as O, N or S, may be incorporated into the alkyl chain to form ethers, amines or thioethers.

[0079] In some implementations, the substituent R 1 R 2 R 3 R 4 R 5 or R 6 It is hydroxy-C(1-4)alkyl and amino-C(1-4)alkyl, especially HO-CH2-CH2- and H2N-CH2-CH2-.

[0080] Suitablely, polyamines include only amine functional groups, or amine and alcohol functional groups.

[0081] The polyamine may be selected, for example, from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentethylenehexamine, hexethyleneheptamine, heptaethyleneoctamine, 1,2-propanediamine, 2-(2-amino-ethylamino)ethanol, and N... 1 N 1 - bis(2-aminoethyl)ethylenediamine (N(CH2CH2NH2)3). The polyamine most preferably comprises tetraethylenepentamine, or especially ethylenediamine.

[0082] Commercially available polyamine sources typically contain mixtures of isomers and / or oligomers, and products prepared from these commercially available mixtures fall within the scope of this invention.

[0083] In such embodiments, where additive (a) is an aldehyde-alkylphenol-polyamine copolymer, the copolymer is suitably formaldehyde in monomeric form; wherein the alkylphenol is an alkylphenol having at least 30 carbon atoms; and selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentethylenehexamine, hexethyleneheptamine, heptaethyleneoctamine, 1,2-propanediamine, 2-(2-amino-ethylamino)ethanol, and N... 1 N 1 The reaction product of bis(2-aminoethyl)ethylenediamine (N(CH2CH2NH2)3) as a polyamine.

[0084] (b) Reaction products of alcohols and / or amines with α-olefin-olefin unsaturated carboxylic acid ester copolymers In some embodiments, the composition of the first aspect comprises an additive (b), which is a reaction product of an alcohol and / or amine with an α-olefin and an olefinic unsaturated carboxylic acid ester compound, wherein the α-olefin and / or alcohol and / or amine has at least 30 carbon atoms.

[0085] Therefore, the copolymer of additive (b) contains groups having at least 30 carbon atoms, which are derived from α-olefins or alcohols and / or amines.

[0086] Additive (b) may be considered to comprise subunits derived from α-olefins, subunits derived from olefinic unsaturated carboxylic acid esters, and moieties derived from subunits derived from alcohols and / or amines and unsaturated carboxylic acid esters. Such moieties derived from alcohols and / or amines and unsaturated carboxylic acid esters can be any group formed by the reaction of an alcohol and / or amine with a carboxylic acid ester group of the subunit derived from the olefinic unsaturated carboxylic acid ester. For example, the moieties derived from alcohols and / or amines and unsaturated carboxylic acid esters can be ester groups, amide groups, imide groups, or amine salt groups, or mixtures thereof. Preferably, the moieties derived from alcohols and / or amines are ester groups and / or amide groups.

[0087] Surprisingly, the inventors have discovered that copolymers in which the α-olefin groups used to form the copolymer have at least 30 carbon atoms can advantageously reduce the pour point of liquid compositions containing pyrolysis oil. In contrast, such copolymers containing alkyl subunits having fewer than 30 carbon atoms or containing a low proportion of alkyl subunits having at least 30 carbon atoms have been found to fail to significantly reduce the pour point of said compositions containing pyrolysis oil.

[0088] The same advantages can be obtained by providing an embodiment having a group having at least 30 carbons by reacting an alcohol or amine with a copolymer of α-olefins and olefinic unsaturated carboxylic acid esters.

[0089] Suitablely, the copolymer of additive (b) is the reaction product of α-olefins and olefinic unsaturated carboxylic acid esters in monomeric form; wherein the reaction product is further reacted to form ester or amide derivatives.

[0090] In embodiments in which the α-olefin has at least 30 carbon atoms, the α-olefin suitably has 30 to 50 carbon atoms, preferably 30 to 40 carbon atoms.

[0091] It will be understood that such α-olefins can contain mixtures of compounds with different chain lengths / carbon number ranges. Therefore, the α-olefin monomers forming the copolymer of additive (b), and the α-olefin-derived subunits of the copolymer, can contain some α-olefins having fewer than 30 carbon atoms.

[0092] In some embodiments, the α-olefin is a mixture of α-olefin compounds, wherein 10 to 90 wt% of the α-olefin compounds have at least 30 carbon atoms, suitably wherein 20 to 50 wt% of the α-olefin compounds have at least 30 carbon atoms.

[0093] The α-olefin used to form the copolymer of additive (b) may be provided by commercially available α-olefin products, such as a commercially available mixture of α-olefin compounds having at least 30 carbon atoms, suitably most of which have at least 30 carbon atoms. The α-olefin may be provided by a mixture of more than one commercially available α-olefin product, such as a mixture of a first commercially available α-olefin mixture having at least 30 carbon atoms and a second commercially available α-olefin mixture having fewer than 30 carbon atoms. Such a second commercially available α-olefin mixture may comprise or consist of C24-28, C20-24, or C26-28 α-olefin compounds or mixtures thereof.

[0094] In such an embodiment, the first and second commercially available α-olefin products can be mixed in a suitable proportion to provide a mixture of α-olefin compounds, wherein 10 to 90 wt% of the α-olefin compound has at least 30 carbon atoms, suitably wherein 20 to 50 wt% of the α-olefin compound has at least 30 carbon atoms.

[0095] In some embodiments, most of the α-olefins contain at least 30 carbon atoms. For example, preferably at least 50% by weight of the α-olefin monomer (and preferably the α-olefin-derived subunit of the copolymer of additive (b)) has at least 30 carbon atoms, suitably at least 75% by weight, at least 80% by weight, or at least 82% by weight.

[0096] Suitably, at least 50% by weight of the α-olefin monomer (and suitably, the α-olefin-derived subunit of the copolymer) has 30 to 40 carbon atoms, suitably at least 75% by weight, at least 80% by weight, or at least 82% by weight.

[0097] Preferably, the α-olefin monomer (and suitable copolymer α-olefin-derived subunits) has a number average molecular weight of 400 to 1,000, suitablely 400 to 600 or 420 to 560.

[0098] In some embodiments, the α-olefin monomer (and therefore the α-olefin-derived subunits of the copolymer) is polyisobutylene (PIB). Thus, in such embodiments, the aforementioned α-olefin-derived subunits are PIB subunits. Suitable PIBs are as described in Additive (a) above.

[0099] The PIB monomers (and subunits) preferably have a number average molecular weight of 400 to 1,000, suitably 400 to 600 or 420 to 560.

[0100] In embodiments where the alcohol and / or amine have at least 30 carbon atoms, the α-olefin may also contain at least 30 carbon atoms and may be as defined above. Alternatively, the α-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 α-olefin may be linear or branched.

[0101] The olefinic unsaturated carboxylic acid ester 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, maleimide and N-alkyl, N-aryl and N-alkylaryl maleimide, phthalic anhydride, citraconic anhydride, citraconic anhydride and N-alkyl, N-aryl and N-alkylaryl citraconic anhydride or combinations thereof.

[0102] Preferably, the olefinically unsaturated carboxylic acid ester compound is maleic anhydride. Therefore, the copolymer of additive (b) suitably comprises maleic acid-derived subunits and α-olefin-derived subunits. In such embodiments, the copolymer of additive (b) may be referred to as an ester or amide derivative of an α-olefin maleic anhydride copolymer (which may be referred to as an OMAC ester or amide). Preferably, additive (b) is an ester derivative of an α-olefin maleic anhydride copolymer (which may be referred to as an OMAC ester).

[0103] The copolymer of additive (b) is suitably an alternating copolymer, and its preparation is as follows: first, maleic anhydride is reacted with an α-olefin to generate OMAC, followed by reaction of OMAC with an alcohol and / or amine, which is partially derivatized from the maleic anhydride into an ester, amide, imide, or amine salt. Methods of carrying out such reactions are well known to those skilled in the art and are described, for example, in US4240916, US3560456, and US4151069, which are incorporated herein by reference.

[0104] OMAC is suitably prepared by reacting maleic anhydride with the α-olefin as defined above in a molar ratio of 3:1 to 1:3, preferably 2:1 to 1:2, more preferably 1.5:1 to 1:1.5, for example about 1:1.

[0105] Preferably, the α-olefin has the above-mentioned number of carbon atoms. A mixture of α-olefins can be used.

[0106] Suitable ester, amide, imide, or amine salt derivatives of copolymers of α-olefins and olefinically unsaturated carboxylic acid esters are formed by reacting the carboxylic acid ester moiety of the olefinically unsaturated carboxylic acid ester subunit in the copolymer with a suitable alcohol or amine. Such alcohols and amines are suitably C12-C50, C12-C40, C12-C28, C16-C24, and preferably C18-C22. Therefore, the copolymer of additive (b) suitably comprises 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. Suitable alcohols or amines are linear. The alcohol or amine may be saturated, unsaturated, or a mixture of both.

[0107] In an embodiment where additive (b) is a reaction product of an amine with an α-olefin and an olefinically unsaturated carboxylic acid ester compound, the amine may be a monoamine, a diamine, or a polyamine. The polyamine may be as defined above.

[0108] In some embodiments, copolymers of α-olefins and olefinically unsaturated carboxylic acid esters are reacted with alcohols or amines having at least 30 carbon atoms, suitably 30 to 50 carbon atoms, or 30 to 40 carbon atoms.

[0109] Such alcohols or amines may contain mixtures of compounds with different numbers of carbon atoms. Alcohols or amines may contain compounds having fewer than 30 carbon atoms. However, a suitable minimum of 50% by weight of the alcohol or amine used to prepare the additive has at least 30 carbon atoms, suitablely at least 75% by weight, at least 80% by weight, or at least 82% by weight.

[0110] Preferably, the alcohol or amine has a number average molecular weight of 400 to 1,000, suitably 400 to 600 or 420 to 560.

[0111] Preferably, the carboxylic acid ester portion of the olefinic unsaturated carboxylic acid ester compound reacts with a C12-C50 alcohol, a C12-C40 alcohol, a C12-C28 alcohol, suitably a C16-C24 alcohol, and preferably a C18-C22 alcohol. Therefore, the copolymer of additive (b) suitably includes a C12-C28 ester portion, preferably a C16-C24 or C18-C22 ester portion.

[0112] In embodiments in which the α-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.

[0113] In some embodiments in which the α-olefin comprises an α-olefin compound having at least 30 carbon atoms, the alcohol and / or amine may 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®.

[0114] In some embodiments where the α-olefin comprises an α-olefin compound having at least 30 carbon atoms, the alcohol and / or amine may be a mixture primarily comprising an alcohol compound having 20 carbon atoms. For example, such an alcohol mixture may comprise at least 40% by weight of an alcohol compound having 20 carbon atoms, suitably about 50% by weight.

[0115] In embodiments in which the α-olefin has fewer than 30 carbon atoms (e.g., 12 to 28 carbon atoms), the alcohol or amine has at least 30 carbon atoms, suitably 30 to 50 carbon atoms or 30 to 40 carbon atoms, as defined above.

[0116] In some embodiments, the α-olefin has at least 30 carbon atoms, as defined above, and the alcohol or amine has at least 30 carbon atoms, as defined above.

[0117] The reaction products of copolymers of alcohols and / or amines with α-olefins and olefinic unsaturated carboxylic acid esters are suitably prepared by reacting the copolymers with alcohols and / or amines as defined above in molar ratios of 0.1:1 to 1:2, 0.5:1 to 1:1.5, preferably 1.1:1 to 1:1.1.

[0118] Suitably, the reaction product of the copolymer of alcohol and / or amine with α-olefin and olefin unsaturated carboxylic acid ester compounds is prepared by reacting the copolymer of α-olefin and olefin unsaturated carboxylic acid ester compounds with 0.5 to 1.5 molar equivalents of alcohol and / or amine (based on the amount of olefin unsaturated carboxylic acid ester monomer used to form the copolymer). In some embodiments, 0.5 to 1.0 molar equivalents of alcohol and / or amine (based on the amount of olefin unsaturated carboxylic acid ester monomer used) are reacted with the copolymer.

[0119] In some embodiments, the copolymer of additive (b) is a C12-C28 ester or amide of an α-olefin maleic anhydride copolymer, wherein the α-olefin-derived subunit has at least 30 carbon atoms. Preferably, the copolymer of additive (b) is a C12-C28 ester of an α-olefin maleic anhydride copolymer, wherein the α-olefin maleic anhydride copolymer comprises an α-olefin-derived subunit having at least 30 carbon atoms. Suitably, at least 30 wt%, at least 40 wt%, or at least 50 wt% of the α-olefin compound used to form the copolymer is a C30-C40 α-olefin. Thus, at least 30 wt%, at least 40 wt%, or at least 50 wt% of the α-olefin-derived subunit of the copolymer has 30 to 40 carbon atoms.

[0120] In some embodiments, the copolymer of additive (b) is the reaction product of an α-olefin maleic anhydride copolymer and 0.5 to 1.5 molar equivalents of an alcohol, suitably 0.5 to 1.0 molar equivalents based on the amount of maleic anhydride monomer used to form the copolymer.

[0121] Suitably, the copolymer of additive (b) is the reaction product of an α-olefin maleic anhydride copolymer and 0.5 to 1.5 molar equivalents (based on the amount of maleic anhydride monomer used to form the copolymer) of a C12-C28 alcohol, wherein the α-olefin maleic anhydride copolymer is formed by reacting maleic anhydride with an α-olefin, said α-olefin comprising at least 30 wt%, at least 40 wt%, or at least 50 wt% of an α-olefin having at least 30 carbon atoms, suitably 30 to 40 carbon atoms.

[0122] Preferably, the additive (b) has a molecular weight of 4,000 to 30,000, 6,000 to 20,000, or 6,000 to 12,000.

[0123] When present, additives (a) and / or (b) 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.

[0124] 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.

[0125] When the additives (a) and / or (b) are present, they are preferably included in the composition of the first aspect in an amount of 100 to 10,000 ppm, 200 to 3,000 ppm, 350 to 3,000 ppm or 400 to 2,500 ppm.

[0126] In embodiments where both (a) and (b) are present, the total amount of additives (a) and (b) present in the composition is suitably as described above.

[0127] In this specification, any reference to ppm refers to parts per million by volume.

[0128] The additive may also contain a carrier or a diluent. Therefore, the additive can be added to the composition in the form of an additive composition comprising one or more additives and said carrier or diluent. Preferred carriers and diluents are aromatic compounds, especially C464. 10 Alkyl naphthalene.

[0129] In some embodiments, the composition of the first aspect can be used as a middle distillate fuel oil. Therefore, the composition may contain one or more additional additives, such as those commonly found in diesel fuels. These additives include, for example, antioxidants, dispersants, detergents, metal deactivating compounds, wax antisettling agents, cold flow improvers, cetane number improvers, demisters, stabilizers, demulsifiers, defoamers, corrosion inhibitors, lubricity improvers, dyes, markers, combustion improvers, metal deactivating agents, odor masking agents, drag reducers, and conductivity improvers. Suitable examples of each of these types of additives are known to those skilled in the art.

[0130] Surprisingly, it was found that the inclusion of additives (a) and / or (b) can lower the pour point of compositions containing pyrolysis oil. The pour point of such compositions is suitably lowered by at least 5°C, at least 10°C, at least 15°C, or at least 20°C compared to similar compositions containing pyrolysis oil without additives (a) and (b) (i.e., compositions containing pyrolysis oil without additives). Such compositions containing pyrolysis oil without additives suitably do not contain other pour point inhibitors. Such compositions containing pyrolysis oil without additives may contain other additives, such as antioxidants, such as component (d) defined below.

[0131] (c) Other additives In some embodiments, the composition of the first aspect comprises an additional additive (c) selected from one or more of the following: (c1) Aldehyde-alkylphenol copolymers and / or aldehyde-alkylphenol-polyamine copolymers, wherein the alkylphenol of the copolymer comprises an alkyl group having fewer than 30 carbon atoms; and (c2) The reaction products of alcohols and / or amines with copolymers of α-olefins and olefinic unsaturated carboxylic acid esters, wherein the α-olefins, alcohols and amines (when present) have fewer than 30 carbon atoms.

[0132] The inventors have discovered that a combination of an additional additive (c) not containing the aforementioned group having at least 30 carbon atoms and an additive (a) or (b) containing a group having at least 30 carbon atoms can further reduce the pour point of the composition containing pyrolysis oil according to the first aspect of the invention. This combination has a synergistic effect in reducing the pour point of the composition containing pyrolysis oil.

[0133] For the avoidance of doubt, neither additive (C1) nor additive (C2) should contain significant amounts of compounds comprising alkyl or alkyl chains having 30 or more carbon atoms. Such additives are typically obtained in mixture form and may contain some compounds comprising alkyl or alkyl chains having at least 30 carbon atoms. However, the alkyl or alkyl chains present in the additive are suitably less than 50% by weight having at least 30 carbon atoms, suitably less than 25% by weight, less than 10% by weight, or less than 5% by weight. Additive (C1) and / or additive (C2) are suitably substantially free of alkyl or alkyl chains having 30 or more carbon atoms.

[0134] In embodiments where additive (c) is additive (c1) an aldehyde-alkylphenol copolymer and / or an aldehyde-alkylphenol-polyamine copolymer, the copolymer is suitably a reaction product of an aldehyde, an alkylphenol and optionally a polyamine in monomer form, wherein the alkyl group of the alkylphenol has fewer than 30 carbon atoms.

[0135] The alkyl group of the alkylphenol in 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 can be straight-chain or branched.

[0136] In embodiments where additive (c) is additive (c2), the additive is suitably an ester, amide, imide, or amine salt derivative of a copolymer of an α-olefin and an olefinically unsaturated carboxylic acid ester compound. Additive (c2) is suitably formed by reacting the carboxylic acid ester moiety of the olefinically unsaturated carboxylic acid ester subunit of the copolymer with a suitable alcohol or amine.

[0137] The α-olefin used to form the additive (C2) 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 α-olefin can be straight-chain or branched.

[0138] The olefinic unsaturated carboxylic acid ester compound used to form additive (c2) is suitably defined as above for additive (b).

[0139] The alcohol and / or amine used to form additive (c2) is suitably a C12-C28 alcohol or amine, or a mixture thereof, suitably a C16-C24 alcohol or amine, preferably a C18-C22 alcohol or amine. Therefore, the copolymer of additive (c2) suitably 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. Suitably, the alcohol or amine is linear. The alcohol or amine may be saturated, unsaturated, or a mixture of both.

[0140] In such embodiments that include additional additive (c), the ratio of the total amount of additive (a) and / or (b) present in the composition to the amount of additive (c) present is suitably 2:1 to 1:3, suitably 1.5:1 to 1:2, and suitably 1:1 to 1:1.6.

[0141] (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.

[0142] The antioxidants applicable to this article include phenolic antioxidants and amino antioxidants.

[0143] Suitable amino antioxidants include aromatic amines, hindered amines, N-oxides, polyalkylene polyamines; and polyisobutylene-substituted succinimides.

[0144] Suitable aromatic amines include diaminobenzene and alkylated diaminobenzene, especially dialkylated and trialkylated diaminobenzene, such as p-phenylenediamine, 3,5-diethyltoluene-2,4-diamine; 3,5-diethyltoluene-2,2-diamine; 2,4,6-triethylphenyl-2,6-diamine alkylated diphenylamine; diphenylamine and alkylated diphenylamine, such as N,N-diphenyl-1,4-phenylenediamine; and naphthylamines, such as N-phenyl-1-naphthylamine and N-phenyl-2-naphthylamine.

[0145] Suitable hindered amines include aliphatic secondary and tertiary amines, such as dimethylcyclohexylamine and diethylhydroxylamine.

[0146] Suitable N-oxides include TEMPO and its derivatives.

[0147] Polyisobutylene-substituted succinimides are known to those skilled in the art, and their use as antioxidants is described, for example, in WO2009 / 016400.

[0148] In some implementations, (d) is a phenolic antioxidant.

[0149] In some embodiments, the composition of the first aspect comprises amino-based antioxidants and phenolic antioxidants.

[0150] Any suitable phenolic antioxidant may be used. Suitable antioxidants are known to those skilled in the art.

[0151] Phenolic antioxidant compounds are any compounds that include a phenolic moiety (i.e., a benzene ring substituted with a hydroxyl group). These compounds can be very simple, such as phenylene glycol, alkyl-substituted phenols, or glycerols. Alternatively, phenolic antioxidants can be part of a more complex molecule. It may contain two phenolic moieties, for example, see the compounds disclosed in US 2006 / 0219979.

[0152] The phenolic antioxidant compounds suitable for use in this invention include those of formula (III): Where R 1 Selected from optionally substituted alkyl or alkenyl, aryl, aralkyl; ester, carboxylic acid, aldehyde, ketone, ether, alcohol, amine or amide; R 2 and R 3 It is independently selected from hydrogen, optionally substituted alkyl or alkenyl, aryl, ester, ketone, aldehyde, carboxylic acid, ether, alcohol, amine or amide; and n is an integer from 1 to 5.

[0153] Preferably, R 1 It is an alkyl group, preferably having 1 to 9 carbon atoms, and can be straight-chain or branched. Preferably, R 1 Selected from methyl, ethyl, isopropyl, and tert-butyl. R 1 and R 2 They can co-form cyclic substituents, which can be alkyl or aryl. R 2 and R 3 Preferably, it is hydrogen or an alkyl group having 1 to 9 carbon atoms. Preferably, R 2 and R 3 It is independently selected from hydrogen, methyl, ethyl, tert-butyl, and isopropyl. Preferably, n is 1, 2, or 3.

[0154] The phenolic antioxidant compounds preferably used in this invention are substituted benzene compounds having one or more hydroxyl substituents. Examples include tert-butylhydroquinone (TBHQ or MTBHQ), 2,5-di-tert-butylhydroquinone (DTBHQ), pyrogallol, pyrogcatechol, 2,6-di-tert-butyl-4-methylphenol (BHT), 2,6-di-tert-butylphenol, propyl gallate, and tert-butylcatechol.

[0155] One phenolic antioxidant particularly preferred in this article is 2,6-di-tert-butylphenol. However, those skilled in the art will understand that commercial sources of this compound typically comprise mixtures of mono-tert-butylphenol, tert-butylphenol, and tri-tert-butylphenol.

[0156] The antioxidant (d), when present, 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.

[0157] The 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, when present.

[0158] In a preferred embodiment, the composition of the first aspect comprises 100 to 1,000 ppm, preferably 250 to 750 ppm, of an antioxidant (d) and 100 to 10,000 ppm, preferably 400 ppm to 2,500 ppm, of an additive (a) and / or (b).

[0159] According to a second aspect of the invention, a method for lowering the pour point of a composition comprising pyrolysis oil is provided, the method comprising adding one or more additives selected from the group consisting of: (a) An aldehyde-alkylphenol copolymer, wherein the alkylphenol of the copolymer comprises an alkyl group having at least 30 carbon atoms; and (b) The reaction product of an alcohol and / or amine with an α-olefin and an olefinic unsaturated carboxylic acid ester compound, wherein the α-olefin and / or alcohol and / or amine has at least 30 carbon atoms.

[0160] The additives (a) and (b) used in the method of the second aspect may have any suitable characteristics and advantages described with respect to the first aspect.

[0161] The composition containing pyrolysis oil used in the method of the second aspect may have any suitable features and advantages described with respect to the first aspect.

[0162] The composition containing pyrolysis oil used in the method of the second aspect may contain component (d) an antioxidant as defined with respect to the first aspect.

[0163] According to a third aspect of the invention, there is a use for lowering the pour point of a composition comprising pyrolysis oil, wherein said one or more additives are selected from: (a) an aldehyde-alkylphenol copolymer and / or an aldehyde-alkylphenol-polyamine copolymer, wherein the alkylphenol of the copolymer comprises an alkyl group having at least 30 carbon atoms; and (b) The reaction product of an alcohol and / or amine with an α-olefin and an olefinic unsaturated carboxylic acid ester compound, wherein the α-olefin and / or alcohol and / or amine has at least 30 carbon atoms.

[0164] The additives (a) and (b) used in this third aspect may have any suitable characteristics and advantages described with respect to the first aspect.

[0165] The composition containing pyrolysis oil used in this third aspect may have any suitable features and advantages described with respect to the first aspect.

[0166] The composition containing pyrolysis oil used in the third aspect may contain component (d) an antioxidant as defined with respect to the first aspect.

[0167] The method of the second aspect or the use of the third aspect suitably lowers 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 suitably relative to similar compositions containing pyrolysis oil without additives (a) and (b) (i.e., compositions containing pyrolysis oil without additives). Such compositions containing pyrolysis oil without additives suitably do not contain other pour point inhibitors. Such compositions containing pyrolysis oil without additives may contain other additives, such as antioxidants, as defined in component (d) above.

[0168] The second aspect of the method or the third aspect of the use may also provide the composition with one or more of the following: - Reduce discoloration during storage; - Reduce sedimentation; - Reduce the formation of colloids and particles; - Improve filtration; and - Further improve low-temperature performance.

[0169] Such further improvements in low-temperature performance can be achieved by lowering the cloud point, slowing down the viscosity change with temperature, and / or reducing the viscosity of the composition at or near the pour point of the unadulterated fluid.

[0170] In the method of the second aspect or the use of the third aspect, additives (a) and / or (b) may be added to the composition containing the pyrolysis oil at any time, including during the process itself. It is preferred to add (one or more) of the additives as soon as possible after oil synthesis, and preferably before the oil is cooled.

[0171] The method and application of the present invention reduce the pour point of compositions containing pyrolysis oil.

[0172] Preferably, the method and use of the present invention lower the pour point of the composition containing plastic pyrolysis oil.

[0173] The methods and uses of the present invention can also improve the stability of compositions containing pyrolysis oil.

[0174] The method and application of the present invention can improve the stability of compositions containing plastic pyrolysis oil.

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

[0176] The method and use of the present invention can improve the storage stability of compositions containing plastic pyrolysis oil.

[0177] Improved storage stability appropriately leads to reduced oil degradation during storage. This can be observed in several ways.

[0178] In some implementation schemes, improved stability can reduce settlement.

[0179] In some implementations, improved stability can reduce or prevent an increase in viscosity.

[0180] In some implementations, improved stability can provide improved filterability, especially after storage.

[0181] In some embodiments, improved stability can provide improved low-temperature properties of compositions containing pyrolysis oil.

[0182] In some embodiments, the purpose of the third aspect is to lower the pour point of a composition comprising pyrolysis oil and additive (c), wherein additive (c) is as defined with respect to the first aspect.

[0183] In such an implementation, additive (c) is suitably selected from one or more of the following: (c1) Aldehyde-alkylphenol copolymers and / or aldehyde-alkylphenol-polyamine copolymers, wherein the alkylphenol of the copolymer comprises an alkyl group having fewer than 30 carbon atoms; and (c2) The reaction products of alcohols and / or amines with copolymers of α-olefins and olefinic unsaturated carboxylic acid esters, wherein the α-olefins, alcohols and amines (when present) have fewer than 30 carbon atoms.

[0184] In such embodiments, additive (c) is suitably additive (c2) as defined above.

[0185] Therefore, this third aspect of the invention provides the use of one or more of additives (a) and (b) in combination with one or more of additives (c1) and (c2) for reducing the pour point of a composition containing pyrolysis oil. Suitably, this use relates to the use of one or more of additives (a) and (b) in combination with one or more additives (c2) for reducing the pour point of a composition containing pyrolysis oil.

[0186] In these embodiments, the use may involve synergistically reducing the pour point of a composition containing pyrolysis oil by combining additive (a) and / or additive (b) with additive (c1) and / or additive (c2). Suitably, the use involves synergistically reducing the pour point of a composition containing pyrolysis oil by combining additive (a) and / or additive (b) with additive (c2).

[0187] According to a fourth aspect of the invention, there is a use for one or more additives selected from the group consisting of [a group consisting of] additive (c) in a composition containing pyrolysis oil to improve the pour point inhibition properties of the additive (c). (a) an aldehyde-alkylphenol copolymer and / or an aldehyde-alkylphenol-polyamine copolymer, wherein the alkylphenol of the copolymer comprises an alkyl group having at least 30 carbon atoms; and (b) The reaction product of an alcohol and / or amine with an α-olefin and an olefinic unsaturated carboxylic acid ester compound, wherein the α-olefin and / or alcohol and / or amine has at least 30 carbon atoms; The additive (c) is as defined with respect to the first aspect.

[0188] In such an implementation, additive (c) is selected from one or more of the following: (c1) Aldehyde-alkylphenol copolymers and / or aldehyde-alkylphenol-polyamine copolymers, wherein the alkylphenol of the copolymer comprises an alkyl group having fewer than 30 carbon atoms; and (c2) The reaction products of alcohols and / or amines with copolymers of α-olefins and olefinic unsaturated carboxylic acid esters, wherein the α-olefins, alcohols and amines (when present) have fewer than 30 carbon atoms.

[0189] Suitable additive (c) is the reaction product of (c2) alcohols and / or amines with α-olefins and olefinic unsaturated carboxylic acid esters, wherein the α-olefins, alcohols and amines (when present) have fewer than 30 carbon atoms.

[0190] The additives (a) and (b) used in this third aspect may have any suitable characteristics and advantages described in relation to the first aspect.

[0191] Additive (c) is suitably as defined with respect to the first aspect.

[0192] The composition containing pyrolysis oil used in this fourth aspect may have any suitable features and advantages described with respect to the first aspect.

[0193] The composition containing pyrolysis oil used in the fourth aspect may contain component (d) an antioxidant as defined with respect to the first aspect.

[0194] The fourth aspect of use suitably lowers 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 suitably relative to similar compositions 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 antioxidants, such as component (d) as defined above.

[0195] The invention will now be further described with reference to the following non-limiting embodiments. Example

[0196] additive Additive composition A is a commercially available composition comprising an aldehyde-alkylphenol copolymer conforming to the definition of additive (a) above and the solvent Solvesso 150. The additive is formed from formaldehyde and alkylphenol, wherein the alkylphenol is a mixture of compounds having an alkyl group containing at least 30 carbon atoms. The additive is a linear polymer with a relatively high number average molecular weight of 5,000 to 7,000. The amount of the aldehyde-alkylphenol copolymer present in additive composition A (by weight of the active component) is 48-52% by weight.

[0197] Additive composition B comprises an OMAC ester conforming to the definition of additive (b) above. This additive is formed by reacting an α-olefin compound having at least 30 carbon atoms, comprising at least 82% by weight, with maleic anhydride to generate an α-olefin-maleic anhydride copolymer. The 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 (by weight of the active component) is 70-75% by weight.

[0198] Additive composition C comprises an OMAC ester conforming to the definition of additive (b) above. Additive composition C is formed by reacting an α-olefin comprising about 50% by weight of a commercially available 'C30+' α-olefin compound and about 50% by weight of a C24-C28 α-olefin with maleic anhydride to form an α-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 (by weight of the active component) is 75-80% by weight.

[0199] Comparative additive composition D is a commercially available composition comprising an aldehyde-alkylphenol copolymer and the solvent Solvesso 150. The copolymer is formed from formaldehyde and alkylphenols, wherein the alkylphenols are a mixture of compounds having C24-C28 alkyl groups. The amount of the aldehyde-alkylphenol copolymer present in this composition (weight %) is 48-52%.

[0200] The comparative additive composition E is an OMAC ester formed by reacting a C24-C28 α-olefin with maleic anhydride to generate an α-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 (weight %) is 75-80% of the active component.

[0201] The comparative additive composition F is a commercially available OMAC ester, formed by reacting a C24-28 α-olefin with maleic anhydride, followed by esterification with 0.5-1.0 mol of a C18-22 fatty alcohol (relative to the maleic anhydride monomer). The amount of OMAC ester present in the composition (weight %) is 75-80% by weight.

[0202] The comparative additive composition G is a commercially available OMAC ester, which is formed by reacting a C20-24 α-olefin with maleic anhydride, followed by esterification with 0.5-1.0 mol of a C18-22 fatty alcohol (relative to the maleic anhydride monomer). The amount of OMAC ester present in the composition (weight %) of the active component is 70-75% by weight.

[0203] The comparative additive composition H is a commercially available polyalkylated phenol additive. The amount of additive present in the composition (weight %) of the active component is approximately 50% by weight.

[0204] Additive composition I comprises an OMAC ester conforming to the definition in additive (b) above. Additive composition I is formed by reacting an α-olefin comprising about 30% by weight of a commercially available 'C30+' α-olefin product and about 70% by weight of a C24-C28 α-olefin product with maleic anhydride to form an α-olefin-maleic anhydride copolymer. This copolymer is then esterified with an alcohol in a molar equivalent relative to the maleic anhydride monomer used to obtain the additive. The alcohol is a mixture of C16-C26 straight-chain fatty alcohols comprising about 50% by weight of a C20 alcohol. The amount of OMAC ester present in additive composition I (by weight of the active component) is 70-75% by weight.

[0205] pyrolysis oil In the following examples and comparative compositions, additives were added to plastic-derived pyrolysis oils having the following specifications. nature method result unit Acid value (inflection point) ASTM D664 (Method A) <0.05 mg KOH / g <![CDATA[60 o API under F]]> ASTM D4052 43.5 <![CDATA[ o API]]> <![CDATA[60 / 60 o Relative density (SG) at F ASTM D4052 0.8085 <![CDATA[15 o Density at C]]> ASTM D4052 808.1 <![CDATA[kg / m 3 ]]> <![CDATA[60 o C(140 o Kinematic viscosity at F) ASTM D445 3.922 cSt <![CDATA[100 o C(212 o Kinematic viscosity at F) ASTM D445 2.03 cSt HT GC determination of the boiling range distribution of residual samples IBP 99 <![CDATA[ o F]]> <![CDATA[LSR (IBP - 150 o F)]]> 0.99 %(m / m) <![CDATA[RFD (150 o F - 365 o F)]]> 24.18 %(m / m) <![CDATA[Kerosene (365 o F - 450 o F)]]> 8.72 %(m / m) <![CDATA[Diesel (450 o F - 600 o F]]> 15.93 %(m / m) <![CDATA[AGO (600 o F - 670 o F)]]> 6.47 %(m / m) <![CDATA[LVGO (670 o F - 1000 o F)]]> 34.38 %(m / m) <![CDATA[Vacresid (1000+ o F)]]> 9.33 %(m / m) Pour point ASTM D97 54 <![CDATA[ o C]]>

[0206] Examples and Comparative Compositions Group 1 The following examples and comparative compositions were formed by mixing the additive into the pyrolysis oil as defined above at the stated dosage.

[0207] Example 1 contains the above-mentioned pyrolysis oil and 2,000 ppm (by volume) of additive A.

[0208] Example 1b contains the above-mentioned pyrolysis oil and 1,000 ppm (by volume) of additive A.

[0209] Example 1c contains the above-mentioned pyrolysis oil and 500 ppm (by volume) of additive A.

[0210] Example 2 contains the above-mentioned pyrolysis oil and 2,000 ppm (by volume) of additive B.

[0211] Example 2b contains the above-mentioned pyrolysis oil and 1,000 ppm (by volume) of additive B.

[0212] Example 3 contains the above-mentioned pyrolysis oil and 2,000 ppm (by volume) of additive C.

[0213] Example 4 comprises the above-mentioned pyrolysis oil and 2,000 ppm (by volume) of additive A and comparative additive composition E in a 1:1 weight ratio.

[0214] Example 5 comprises the above-mentioned pyrolysis oil and 2,000 ppm (by volume) of additive A and comparative additive composition F in a 1:1 weight ratio.

[0215] Example 6 comprises the above-mentioned pyrolysis oil, 2,000 ppm (by volume) of additive B in a 1:1 weight ratio, and comparative additive composition E.

[0216] Comparative Example 1 contains the above-mentioned pyrolysis oil and 2,000 ppm (by volume) of comparative additive D.

[0217] Comparative Example 2 contains the above-mentioned pyrolysis oil and 2,000 ppm (by volume) of comparative additive E.

[0218] Comparative Example 3 comprises the above-mentioned pyrolysis oil and 2,000 ppm (by volume) of comparative additive composition F.

[0219] Comparative Example 4 comprises the above-mentioned pyrolysis oil and 2,000 ppm (by volume) of comparative additive composition G.

[0220] Comparative Example 5 comprises the above-mentioned pyrolysis oil and 2,000 ppm (by volume) of comparative additive composition H.

[0221] Pour point test 1 The pour points of the example compositions containing additive type (a) or (b), the control compositions without additives, and the comparative compositions containing different additives were determined using the ASTM D97 method. A minor modification to the ASTM D97 method was made, and 20 mL samples of basic pyrolysis oil were used in these tests.

[0222] The pour points of the compositions are shown in Table 1 below.

[0223] Table 1 Composition additive Dosage (ppm) Pour point (°C) Comparison blank -- 52 (0) Comparative Example 1 Comparison D 2,000 52 (0) Comparative Example 2 Comparison E 2,000 49 (-3) Comparative Example 3 Comparison F 2,000 52 (0) Comparative Example 4 Comparison with G 2,000 52 (0) Comparative Example 5 Comparison H 2,000 52 (0) Example 1 A 2,000 24 (-28) Example 2 B 2,000 27 (-25) Example 3 C 2,000 35 (-17) Example 4 A+ vs. F 1,000 / 1,000 24 (-28) Example 5 A+ vs. G 1,000 / 1,000 21 (-31) Example 6 B+ compared to F 1,000 / 1,000 24 (-28)

[0224] The change in pour point of the composition compared to the control is given in parentheses after the pour point.

[0225] Different dosage levels of additives A and B in the pyrolysis oil were also tested separately—500 ppm (Example 1c), 1,000 ppm (Examples 1b / 2b), and 2,000 ppm (Examples 1 / 2). The results are shown in Table 2 below.

[0226] Table 2 Composition additive Dosage (ppm) Pour point (°C) Comparison blank -- 52 (0) Example 1 A 2,000 24 (-28) Example 1b A 1,000 32 (-20) Example 1c A 500 38 (-14) Example 2 B 2,000 27 (-25) Example 2b B 1,000 38 (-14)

[0227] The results showed that the compositions of the present invention (Examples 1, 1b, 1c, 2, 2b, 3, 4, 5, and 6), containing additives of classes (a) and (b) as defined herein (additive compositions A, B, and C), had significantly lower pour points than the control compositions containing only pyrolysis oil without additives and the comparative compositions containing additives without significant amounts of C30+ alkyl chains. The pour points of the compositions of Examples 1-6 were 14 to 31°C lower than the control and comparative compositions. The results of Examples 4-6 also showed that the combination of additives of classes (a) and (b) with OMAC ester additives that do not contain groups having more than 30 carbon atoms and do not have pour point inhibiting activity when used alone has a synergistic effect.

[0228] Such a reduction in the pour point of the compositions of the present invention is expected to provide significant advantages for the treatment and use of such pyrolysis oils (e.g., pyrolysis oils derived from plastic waste). This could facilitate the use of such pyrolysis oils in the production of fuels and chemical feedstocks, thereby providing a beneficial use for plastic waste to reduce the amount of such waste entering landfills or polluting the ocean. Therefore, such potential improvements to pyrolysis oils are expected to result in significant overall environmental benefits.

[0229] Examples and Comparative Compositions Group 2 The following examples and comparative compositions were prepared by mixing the additives into waste plastic pyrolysis oil at specified dosages. The waste plastic pyrolysis oil was another commercially produced waste plastic pyrolysis oil from the United States, and was conditioned at 160℉.

[0230] Example 2.1 comprises the above-mentioned pyrolysis oil and 1,000 ppm (by volume) of additive I.

[0231] Example 2.2 comprises the above-mentioned pyrolysis oil and 1,000 ppm (by volume) of additive A.

[0232] Example 2.3 comprises the above-mentioned pyrolysis oil and 1,500 ppm (by volume) of additive A.

[0233] Example 2.4 comprises the above-mentioned pyrolysis oil and 2,000 ppm (by volume) of additive I.

[0234] Example 2.5 comprises the above-mentioned pyrolysis oil and 2,000 ppm (by volume) of additive C.

[0235] Example 2.6 comprises the above-mentioned pyrolysis oil and 2,000 ppm (by volume) of additive A.

[0236] Comparative Example 2.1 comprises the above-mentioned pyrolysis oil and 1,000 ppm (by volume) of comparative additive E.

[0237] Comparative Example 2.2 comprises the above-mentioned pyrolysis oil and 1,000 ppm (by volume) of comparative additive F.

[0238] Comparative Example 2.3 contains the above-mentioned pyrolysis oil and 2,000 ppm (by volume) of comparative additive E.

[0239] Comparative Example 2.4 contains the above-mentioned pyrolysis oil and 2,000 ppm (by volume) of comparative additive F.

[0240] Pour point test 2 Using the modified method described in ASTM D97 above, the pour points of the second group of example compositions containing additive type (a) or (b), as well as the control compositions without additives and the comparative compositions containing different additives, were determined.

[0241] The pour points of the compositions are shown in Table 3 below.

[0242] Table 3 Composition additive Dosage (ppm) Pour point (°C) Comparison blank -- 46.1 (0) Comparative Example 2.1 Comparison E 1,000 46.1 (0) Comparative Example 2.2 Comparison F 1,000 40.6 (-5.5) Example 2.1 I 1,000 32.2 (-13.9) Example 2.2 A 1,000 23.9 (-22.2) Example 2.3 A 1,500 21.1 (-25.0) Comparative Example 2.3 Comparison E 2,000 46.1 (0) Comparative Example 2.4 Comparison F 2,000 40.6 (-5.5) Example 2.4 I 2,000 29.4 (-16.7) Example 2.5 C 2,000 29.4 (-16.7) Example 2.6 A 2,000 21.1 (-25.0)

[0243] The change in pour point of the composition compared to the control is given in parentheses after the pour point.

[0244] These results indicate that the pour points of the compositions of the present invention (Examples 2.1-2.6) containing additives of types (a) and (b) as defined herein (additive compositions A, C, and I) are significantly lower than those of the control compositions containing only pyrolysis oil without additives and the comparative compositions containing additives without significant amounts of C30+ alkyl chains. The pour points of the compositions of Examples 2.1-2.6 are 13 to 25°C lower than those of the control and comparative compositions.

[0245] As described above with respect to Example Group 1, such a reduction in pour point of the compositions of the present invention in Example Group 2 is expected to provide significant advantages for the treatment and use of such pyrolysis oils (e.g., pyrolysis oils derived from plastic waste). This could facilitate the utilization of such pyrolysis oils in the production of fuels and chemical feedstocks, thereby providing a beneficial use for plastic waste to reduce the amount of such waste entering landfills or polluting the ocean. Therefore, the potential improvements to such pyrolysis oils are expected to yield significant overall environmental benefits.

[0246] Although some preferred embodiments have been shown and described, those skilled in the art will understand that various changes and modifications can be made without departing from the scope of the invention as defined by the appended claims.

[0247] Throughout this specification, the terms "comprising" or "including" mean comprising the specified (one or more) components, but do not exclude the presence of other components. The terms "consistent primarily of" or "essentially of" mean comprising the specified components, but excluding other components, except for substances present as impurities, unavoidable substances present due to the processes used to prepare these components, and components added for purposes other than achieving the technical effects of the invention. Generally, when referring to a composition, a composition consisting primarily of one group 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.

[0248] The terms “composed of” or “consisting of” mean that the specified components are included, but not the addition of other components.

[0249] Where appropriate, depending on the context, the use of the terms “including” or “comprising” may also be understood to encompass or include the meaning of “consistent with” or “essentially composed of”, and may also be understood to include the meaning of “composed of” or “formed by”.

[0250] To avoid ambiguity, the amount of a component in the composition is described as % by weight, which indicates the weight percentage of the specified component relative to the total composition referred to.

[0251] The optional features described herein can be used individually or in combination where appropriate, particularly in combination as described in the appended claims. The optional features of each aspect or exemplary embodiment of the invention described herein should also be understood to be applicable to any other aspect or exemplary embodiment of the invention where appropriate. In other words, those skilled in the art reading this specification should consider the optional features of each exemplary embodiment of the invention to be interchangeable and combinable between different exemplary embodiments.

[0252] Please note all papers and documents that were submitted at the same time as or before this specification and made publicly available together with this specification, and the contents of all such papers and documents are incorporated herein by reference.

[0253] All features disclosed in this specification (including any appended claims and drawings) and / or all steps of any disclosed method or process may be combined in any combination, unless at least some of these features and / or steps are mutually exclusive combinations.

[0254] Unless otherwise expressly stated, each feature disclosed in this specification (including any accompanying claims and drawings) may be replaced by an alternative feature having the same, equivalent, or similar purpose. Therefore, unless otherwise expressly stated, each disclosed feature is merely one example of a general series of equivalent or similar features.

[0255] This invention is not limited to the details of the foregoing embodiments(s). This invention covers any novel feature or any novel combination thereof disclosed in this specification (including any appended claims and drawings), or any novel step or any novel combination thereof in any disclosed method or process step.

Claims

1. A composition comprising pyrolysis oil and one or more of the following as additives: (a) an aldehyde-alkylphenol copolymer and / or an aldehyde-alkylphenol-polyamine copolymer, wherein the alkylphenol of the copolymer comprises an alkyl group having at least 30 carbon atoms; and (b) The reaction product of an alcohol and / or amine with an α-olefin and an olefinic unsaturated carboxylic acid ester compound, wherein the α-olefin and / or alcohol and / or amine has at least 30 carbon atoms.

2. The composition according to claim 1, wherein the pyrolysis oil is plastic pyrolysis oil.

3. The composition according to claim 1 or claim 2, wherein 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; wherein the aldehyde-alkylphenol copolymer has structure (I) or (II): Where R is an alkyl group having at least 30 carbon atoms, and n is at least 1.

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

5. The composition according to claim 3 or claim 4, wherein at least 50% by weight of the R group present in the additive is a C30-C40 alkyl group.

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

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

8. The composition according to claim 1 or claim 2, wherein the additive is (b) a reaction product of a copolymer of an alcohol and / or amine with an α-olefin and an olefinic unsaturated carboxylic acid ester compound, wherein the α-olefin and / or alcohol and / or amine has at least 30 carbon atoms, and wherein the olefinic unsaturated carboxylic acid ester compound is maleic anhydride.

9. The composition according to claim 8, wherein the additive is a reaction product of a copolymer of an alcohol having at least 30 carbon atoms with an α-olefin and an olefinic unsaturated carboxylic acid ester compound.

10. The composition according to claim 9, wherein the α-olefin has fewer than 30 carbon atoms.

11. The composition according to claim 8, wherein the additive is a C12-C28 ester of a copolymer of an α-olefin and an olefinic unsaturated carboxylic acid ester compound, wherein the α-olefin has at least 30 carbon atoms.

12. The composition according to any one of claims 8, 9 or 11, wherein 10 to 90 wt% of the α-olefin compound used to form the copolymer has at least 30 carbon atoms, preferably wherein 20 to 50 wt% of the α-olefin compound has at least 30 carbon atoms.

13. The composition according to any one of claims 8, 9, 11 or 12, wherein at least 50% by weight of the α-olefin compound used to form the copolymer is a C30-C40 α-olefin.

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

15. The composition according to any one of claims, comprising (c) an additional additive selected from one or more of the following: (c1) Aldehyde-alkylphenol copolymers and / or aldehyde-alkylphenol-polyamine copolymers, wherein the alkylphenol of the copolymer comprises an alkyl group having fewer than 30 carbon atoms; and (c2) The reaction product of an alcohol and / or amine with a copolymer of an α-olefin and an olefinic unsaturated carboxylic acid ester compound, wherein the α-olefin, alcohol and amine, when present, have fewer than 30 carbon atoms.

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

17. The composition according to any one of the preceding claims, comprising: (d) Antioxidants.

18. The composition according to claim 17, wherein the antioxidant in (d) is a phenolic antioxidant selected from tert-butylhydroquinone (TBHQ or MTBHQ), 2,5-di-tert-butylhydroquinone (DTBHQ), pyrogallol, pyrogcatechol, 2,6-di-tert-butyl-4-methylphenol (BHT), 2,6-di-tert-butylphenol, propyl gallate, and tert-butylcatechol.

19. The composition according to claim 17, wherein (d) the antioxidant comprises an amino antioxidant selected from aromatic amines, hindered amines, N-oxides, polyalkylene polyamines and polyisobutylene-substituted succinimides.

20. A method for lowering the pour point of a composition comprising pyrolysis oil, the method comprising adding one or more additives selected from the group consisting of: (a) an aldehyde-alkylphenol copolymer and / or an aldehyde-alkylphenol-polyamine copolymer, wherein the alkylphenol of the copolymer comprises an alkyl group having at least 30 carbon atoms; and (b) The reaction product of an alcohol and / or amine with an α-olefin and an olefinic unsaturated carboxylic acid ester compound, wherein the α-olefin and / or alcohol and / or amine has at least 30 carbon atoms.

21. Use of one or more additives for lowering the pour point of a composition comprising pyrolysis oil, wherein said one or more additives are selected from: (a) an aldehyde-alkylphenol copolymer and / or an aldehyde-alkylphenol-polyamine copolymer, wherein the alkylphenol of the copolymer comprises an alkyl group having at least 30 carbon atoms; and (b) The reaction product of an alcohol and / or amine with an α-olefin and an olefinic unsaturated carboxylic acid ester compound, wherein the α-olefin and / or alcohol and / or amine has at least 30 carbon atoms.

22. The method or use according to claim 20 or claim 21, wherein the composition comprising pyrolysis oil contains one or more additives (c); Additive (c) is selected from one or more of the following: (c1) Aldehyde-alkylphenol copolymers and / or aldehyde-alkylphenol-polyamine copolymers, wherein the alkylphenol of the copolymer comprises an alkyl group having fewer than 30 carbon atoms; and (c2) The reaction product of an alcohol and / or amine with a copolymer of an α-olefin and an olefinic unsaturated carboxylic acid ester compound, wherein the α-olefin, alcohol and amine, when present, have fewer than 30 carbon atoms.

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

24. The method or use according to any one of claims 20 to 23, wherein it provides one or more of the following: - Reduce discoloration during storage; - Reduce sedimentation; - Reduce the formation of colloids and particles; - Improve filtration; and - Further improve low-temperature performance.

25. Use of one or more additives selected from the following for improving the pour point inhibition properties of additive (c) in a composition containing pyrolysis oil: (a) an aldehyde-alkylphenol copolymer and / or an aldehyde-alkylphenol-polyamine copolymer, wherein the alkylphenol of the copolymer comprises an alkyl group having at least 30 carbon atoms; and (b) The reaction product of an alcohol and / or amine with an α-olefin and an olefinic unsaturated carboxylic acid ester compound, wherein the α-olefin and / or alcohol and / or amine has at least 30 carbon atoms; Additive (c) is selected from one or more of the following: (c1) Aldehyde-alkylphenol copolymers and / or aldehyde-alkylphenol-polyamine copolymers, wherein the alkylphenol of the copolymer comprises an alkyl group having fewer than 30 carbon atoms; and (c2) The reaction product of an alcohol and / or amine with a copolymer of an α-olefin and an olefinic unsaturated carboxylic acid ester compound, wherein the α-olefin, alcohol and amine, when present, have fewer than 30 carbon atoms.

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