Emulsion formulations of alpha-olefin maleic anhydride copolymers as crude oil paraffin inhibitors

Abstract

The invention relates to highly stable emulsion formulations of alpha-olefin maleic anhydride copolymers comprising biosurfactants and nonionic surfactants. The invention also relates to a method for producing said formulations, compositions thereof and uses as crude oil paraffin inhibitors and pour point depressants.

Description

202400230 Foreign Filings 1EMULSION FORMULATIONS OF ALPHA-OLEFIN MALEIC ANHYDRIDE COPOLYMERS AS CRUDE OIL PARAFFIN INHIBITORSTECHNICAL FIELD OF THE INVENTIONThe invention relates to highly stable emulsion formulations of alpha-olefin maleic anhydride copolymers comprising a biosurfactant and a nonionic surfactant. The invention also relates to a method for producing said formulations, compositions thereof and uses as crude oil paraffin inhibitors and pour point depressants.BACKGROUND OF THE INVENTIONAlpha-olefin maleic anhydride copolymers (OMACs) are particularly effective as crude oil pour point depressants and cold flow improvers.The pour point of an oil is the temperature below which the oil loses its flow characteristics. It is defined as the minimum temperature in which the oil has the ability to pour down from a beaker. Pour point depressants are additives added to oils or fuels to increase their flowability at low temperatures. These compounds are indispensable in many fields where it is important to keep fluids flowing even when temperatures drop. Paraffin inhibitors are used to reduce wax deposition and improve the flow properties of waxy crude oils.A major drawback of using alpha-olefin maleic anhydride copolymers in oilfield applications is the poor handling properties. The materials are solid at room temperature and often require heating in excess of 50 °C to melt the polymer.Alternatively, alpha-olefin maleic anhydride copolymers may be dissolved in solvents such as xylene, toluene, and solvent naphtha. Solution-based alternatives contain low percentages of active ingredients and require the use of low flashpoint solvents which introduce further safety considerations.For this reason, emulsion formulations, particularly those where the polymer is dispersed in an aqueous continuous phase, are of interest in oilfield applications. Emulsion formulations enable higher actives content than solution-based alternatives and provide handling benefits (increased pumpability, lower solidification points) that are important for end-users in the oilfield.Polymeric emulsions can be generated in situ\na emulsion polymerization or by postsynthetic emulsification wherein a premade polymer is dispersed in liquid media. A postsynthetic emulsification refers to a process where a polymer is synthesized prior to the dispersing and emulsification step.US5851429A describes a method for generating dispersions of pourpoint depressants which are solid at room temperature.US20200283692A1 describes a method for postsynthetic emulsification of cold flow improvers using the202400230 Foreign Filings 2salt of an ether carboxylic acid and a nonionic surfactant. Their work shows that utilizing high shear methods to decrease particle size improves the long-term stability of emulsions.WO2023025636A1 describes methods of postsynthetic emulsification of pour point depressants in an aqueous phase using anionic surfactants including sulfonate, sulfate, phosphonate, or phosphate groups.However, there remains a need to develop highly stable emulsion formulations of alpha-olefin maleic anhydride copolymers, with lower viscosity at temperatures below 0 °C, and performance benefits as crude oil paraffin inhibitors and pour point depressants.BRIEF SUMMARY OF THE INVENTIONThe invention relates to an emulsion formulation of alpha-olefin maleic anhydride copolymer comprising a biosurfactant and a nonionic surfactant according to the claims.It has now been found that by combining an alpha-olefin maleic anhydride copolymer, a nonionic surfactant and a biosurfactant to form an emulsion formulation, enhanced stability of the formulation could be achieved. The stability of the system is contingent on the inclusion of a biosurfactant.Postsynthetic emulsification provides enhanced tunability, enabling a broader range of polymer compositions, including blends of polymers, to be emulsified using the same surfactant system and similar reaction conditions. Emulsions according to the invention exhibit can be formulated with a smaller amount of surfactant in comparison to state-of-the-art emulsions.Moreover, the formulations of the invention have lower viscosity at subzero temperatures than known formulations and provide significant performance benefits as crude oil paraffin inhibitors and pour point depressants. The low viscosity of dispersions is critical for the intended application (oilfield chemicals) because meeting this requirement enables the formulation to be pumped at lower temperatures than the existing state of the art. Therefore, the formulation of the invention can be used in colder climates (such as lower than -40 °C) where there are limited chemical solutions available.A second aspect of the present invention is a method of preparing the emulsion formulation according to the present invention.A third aspect of the present invention is a crude oil composition comprising the emulsion formulation according to the present invention and a crude oil.A fourth aspect of the present invention is the use of the emulsion formulation of the invention as crude oil paraffin inhibitors and pour point depressants, wherein the emulsion formulation of the invention is added to crude oil.202400230 Foreign Filings 3The present invention is also directed to a method of treating a crude oil with an emulsion formulation as defined herein to enhance the cold flow properties of the crude oil, wherein the emulsion formulation is added to the crude oil.DETAILED DESCRIPTION OF THE INVENTIONThe present invention relates to an emulsion formulation comprising a carrier medium and the following components:a) 5 to 50 % by weight of one or more alpha-olefin maleic anhydride copolymers, based on the total weight of the emulsion formulationb) 1 to 5 % by weight of one or more nonionic surfactant, based on the total weight of the emulsion formulation,c) 0.1 to 5% by weight one or more biosurfactant, based on the total weight of the emulsion formulation.Within the context of the present invention, the term “one or more” means one compound (such as one polymer) or more than one compound (such as a mixture of polymers).The inventive emulsion formulations exhibit higher stability, lower viscosity at subzero temperatures, and performance benefits as crude oil paraffin inhibitors and pour point depressants.In particular, the emulsions formulation of the invention can be formulated with a smaller amount of surfactant in comparison to state-of-the-art emulsions. Dynamic viscosity of the emulsion formulations at temperatures below 0°C is preferably lower than 2 Pa*s.The low viscosity is critical for the intended application (oilfield chemicals) because meeting this requirement enables the formulation to be pumped at lower temperatures than the existing state of the art. The emulsions of the invention could be used in colder climates (such as lower than -40 °C).The emulsions of the invention preferably have dynamic viscosity at -20°C below 1.0 Pa*s, preferably below 0.7 Pa*s, measured according to the method described in the experimental part below.Alpha olefin maleic anhydride copolymers (OMAC - component a))The amount of alpha-olefin maleic anhydride copolymers in the emulsion formulation is from 5 to 50 % by weight of the total formulation, preferably from 10 to 40 % by weight of the total formulation, more preferably from 15 to 35 % by weight of the total formulation.Preferably, the alpha-olefin maleic anhydride copolymer a) is prepared by polymerizing a monomer composition comprising202400230 Foreign Filings 4i) from 10 to 70 % by weight of monomers selected from alkyl maleate compound of Formula (I), maleimide compound of Formula (II) or a mixture thereof, based on the total weight of the alpha-olefin maleic anhydride copolymer,"wherein R in Formula (I) and Formula (II) is a linear or branched alkyl group having from 10 to 40 carbon atoms; andii) from 30 to 90 % by weight of one or more non-functionalized alpha-olefin of formula (III), based on the total weight of the alpha-olefin maleic anhydride copolymer,wherein R2 is a linear alkyl group having from 8 to 40 carbon atoms, preferably from 10 to 40 carbon atoms, more preferably from 10 to 35 carbon atoms.Within the context of the present invention, the monomer composition corresponds to the total amount of monomers to prepare the alpha-olefin maleic anhydride copolymer.More preferably, the alpha-olefin maleic anhydride copolymer a) is a prepared by polymerizing a monomer composition comprisingi) 10 to 70 % of alkyl maleate compound of Formula (I), based on the total weight of the copolymer, andii) 30 to 90 % by weight of one or more non-functionalized alpha-olefin of formula (III), based on the total weight of the copolymer.202400230 Foreign Filings 5Preferably R in Formula (I) and Formula (II) is a linear or branched alkyl group having from 10 to 40 carbon atoms, more preferably from 12 to 30 carbon atoms.Preferably R2 in Formula (III) is a linear alkyl group having from 10 to 40 carbon atoms, more preferably from 10 to 35 carbon atoms.The content of alkyl maleate i) in the copolymer is preferably from 20 to 50 % by weight, more preferably from 25 to 40% by weight, based on the total weight of the copolymer.The content of alpha-olefin ii) in the copolymer is preferably from 50 to 80 % by weight, more preferably 60 to 75 % by weight, based on the total weight of the copolymer.In one embodiment the OMAC is a polymer prepared by polymerizing a monomer composition comprising C18-C22 alkyl maleate and C20-C32 non-functionalized alpha-olefin.In another embodiment, the OMAC is a polymer prepared by polymerizing a monomer composition comprising C18-C22 alkyl maleate and C20-C24 non-functionalized alpha-olefin.In a further embodiment, the OMAC is a polymer prepared by polymerizing a monomer composition comprising C18-C22 alkyl maleate and C10-C18 non-functionalized alpha-olefin.A copolymer is a polymer formed from two or more different types of monomers linked in a polymeric chain.Preferably, the OMAC is selected from the group consisting of a polymer prepared by polymerizing a monomer composition comprising C18-C22 alkyl maleate and C20-C32 non-functionalized alpha-olefin, a polymer prepared by polymerizing a monomer composition comprising C18-C22 alkyl maleate and C20-C24 non-functionalized alpha-olefin, a polymer prepared by polymerizing a monomer composition comprising C18-C22 alkyl maleate and C10-C18 non-functionalized alpha-olefin, or a mixture thereof.As used herein, the term “maleate” refers to esters of maleic acid. The term “alkyl maleate” refers to esters of maleic acid and aliphatic alcohols. The alkyl maleate described herein are characterized by the number of carbon atoms in the alkyl chain derived from the alcohol.For example, the term “C18-C22 alkyl maleate” refers to esters of maleic acid and linear or branched alcohols having 18 to 22 carbon atoms. The term encompasses individual maleic esters with an alcohol of a particular length, and likewise a mixture of maleic esters with alcohols of different lengths. Likewise, the term “C20-C24 alkyl maleate” refers to esters of maleic acid with linear or branched alkyl chain having 20 to 24 carbon atoms. The term encompasses individual maleic esters with an alcohol of a particular length, and likewise mixtures of maleic esters with alcohols of different lengths.202400230 Foreign Filings 6Alpha-olefin is compound made up of hydrogen and carbon that contains one or more pairs of carbon atoms linked by a double bond. As used herein, the term C1-C40 olefin, C10-C18 olefin or C20-C32 olefin refers to an olefin comprising a linear, branched or cyclic residue with 1 to 40 carbon atoms, 10 to 18 carbon atoms or 20 to 32 carbon atoms, respectively.As an optional component, the monomer composition to prepare the alpha-olefin maleic anhydride copolymer may contain further monomer iii), or a mixture thereof.Preferably, these monomers iii) are selected from the list consisting of:hydroxyalkyl (meth)acrylates, preferably hydroxyalkyl (meth)acrylates selected from 3-hydroxypropyl (meth)acrylate, 3,4-dihydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2 hydroxypropyl (meth)acrylate, 2,5-dimethyl-1 ,6-hexanediol (meth)acrylate, 1,10 decanediol (meth)acrylate;aminoalkyl (meth)acrylates and aminoalkyl (meth)acrylamides, preferably aminoalkyl (meth)acrylates and aminoalkyl (meth)acrylamides selected from N-(3-dimethyl-aminopropyl)methacrylamide, 3-diethylami nopentyl (meth)acrylate, 3-dibutyl-aminohexadecyl (meth)acrylate; nitriles of (meth)acrylic acid and other nitrogen-containing (meth)acrylates, preferably nitriles of (meth)acrylic acid and other nitrogen-containing (meth)acrylates selected from N- (methacryloyloxyethyl)diisobutylketimine, N-(methacryloyloxyethyl)dihexadecyl-ketimine, (meth)acryloylamidoacetonitrile, 2-methacryloyloxyethylmethylcyanamide, cyanomethyl (meth)acrylate;aryl (meth)acrylates like benzyl (meth)acrylate or phenyl (meth)acrylate, where the acryl residue in each case can be unsubstituted or substituted up to four times;carbonyl-containing (meth)acrylates, preferably carbonyl-containing (meth)acrylates selected from 2- carboxyethyl (meth)acrylate, carboxymethyl (meth)acrylate, N-methyacryloyloxy)-formamide, acetonyl (meth)acrylate, N-methacryloyl-2 pyrrolidinone, N-(2-methyacryloxyoxyethyl)-2- pyrrolidinone, N-(3-methacryloyloxy-propyl)-2-pyrrolidinone, N-(2-methyacryloyloxypentadecyl(- 2-pyrrolidinone, N-(3 methacryloyloxyheptadecyl-2-pyrrolidinone;(meth)acrylates of ether alcohols, preferably (meth)acrylates of ether alcohols selected from tetrahydrofurfuryl (meth)acrylate, methoxyethoxyethyl (meth)acrylate, 1 -butoxypropyl (meth)acrylate, cyclohexyloxyethyl (meth)acrylate, propoxyethoxyethyl (meth)acrylate, benzyloxyethyl (meth)acrylate, furfuryl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-ethoxy-2- ethoxyethyl (meth)acrylate, 2-methoxy-2-ethoxypropyl (meth)acrylate, ethoxylated (meth)acrylates, 1 -ethoxybutyl (meth)acrylate, methoxyethyl (meth)acrylate, 2-ethoxy-2-ethoxy- 2-ethoxyethyl (meth)acrylate, esters of (meth)acrylic acid and methoxy polyethylene glycols; (meth)acrylates of halogenated alcohols, preferably (meth)acrylates of halogenated alcohols selected from 2,3-dibromopropyl (meth)acrylate, 4 bromophenyl (meth)acrylate, 1 ,3-dichloro-2-propyl (meth)acrylate, 2-bromoethyl (meth)acrylate, 2-iodoethyl (meth)acrylate, chloromethyl (meth)acrylate;oxiranyl (meth)acrylate, preferably oxiranyl (meth)acrylate selected from 2, 3-epoxybutyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 10,11 epoxyundecyl (meth)acrylate, 2,3-202400230 Foreign Filings 7epoxycyclohexyl (meth)acrylate, oxiranyl (meth)acrylates such as 10,11 -epoxyhexadecyl (meth)acrylate, glycidyl (meth)acrylate;phosphorus-, boron- and / or silicon-containing (meth)acrylates, preferably phosphorus-, boron- and / or silicon-containing (meth)acrylates selected from 2-(dimethyl-phosphato)propyl (meth)acrylate, 2-(ethylphosphito)propyl (meth)acrylate, 2 dimethylphosphinomethyl (meth)acrylate, dimethylphosphonoethyl (meth)acrylate, diethylmethacryloyl phosphonate, dipropylmethacryloyl phosphate, 2 (dibutylphosphono)ethyl (meth)acrylate, 2,3- butylenemethacryloylethyl borate, methyldiethoxymethacryloylethoxysiliane, diethylphosphatoethyl (meth)acrylate;sulfur-containing (meth)acrylates, preferably sulfur-containing (meth)acrylates selected from ethylsulfinylethyl (meth)acrylate, 4-thio-cyanatobutyl (meth)acrylate, ethylsulfonylethyl (meth)acrylate, thiocyanatomethyl (meth)acrylate, methylsulfinylmethyl (meth)acrylate, bis(methacryloyloxyethyl) sulfide;heterocyclic (meth)acrylates, preferably heterocyclic (meth)acrylates selected from 2-(1- imidazolyl)ethyl (meth)acrylate, oxazolidinylethyl (meth)acrylate, N-methacryloylmorpholine and 2-(4-morpholinyl)ethyl (meth)acrylate;fumaric acid and fumaric acid derivatives, preferably mono- and diesters of fumaric acid;vinyl halides, preferably vinyl halides selected from vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride;vinyl esters, preferably vinyl acetate;vinyl monomers containing aromatic groups, preferably vinyl monomers containing aromatic groups selected from styrene, substituted styrenes with an alkyl substituent in the side chain, such as alpha-methylstyrene and alpha-ethylstyrene, substituted styrenes with an alkyl substituent on the ring such as vinyltoluene and p-methylstyrene, halogenated styrenes such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes; heterocyclic vinyl compounds, preferably heterocyclic vinyl compounds selected from 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1- vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N- vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, vinylfuran, vinylthiophene, vinylthiolane, vinylthiazoles and hydrogenated vinylthiazoles, vinyloxazoles and hydrogenated vinyloxazoles;vinyl and isoprenyl ethers;methacrylic acid and acrylic acid, or a mixture thereof.As used herein, the term “(meth)acrylate” refers to esters of acrylic and methacrylic acid, and to mixtures thereof. The term “alkyl (meth)acrylate” refers to esters of (meth)acrylic acid and aliphatic alcohols. The alkyl (meth)acrylates described herein are characterized by the number of carbon atoms in the alkyl chain derived from the alcohol.202400230 Foreign Filings 8The proportion of monomers (iii) in the monomer composition can vary depending on the use and property profile of the OMAC. Preferably, the content of monomer iii) in the monomer composition to prepare the alpha-olefin maleic anhydride copolymer is in the range from 0 to 20 % by weight, preferably from 0 to 15 % by weight, more preferably from 0.1 to 15 % by weight, based on the total weight of the monomer composition.Preferably, the amounts of monomers (i), (ii) and (iii) sum up from 95 to 100 % by weight, more preferably sum up to 100 % by weight, based on the total weight of the monomer composition of the OMAC.Preferably, the weight-average molecular weight of the alpha-olefin maleic anhydride copolymer a) is from 5,000 to 300,000 g / mol, preferably from 7,000 to 150,000 g / mol even more preferably from 8,000 to 80,000 g / mol and most preferably from 8,000 to 30,000 g / mol, determined by gel permeation chromatography using poly(methyl-methacrylate) calibration standards (GPC method as described in more detail in the experimental section below).Preparation of olefin-co-ester of maleic acid and olefin-co-imide-derivative of maleic acid are well known in the art and described in literature such as in US10738138B2 and US4192930.Olefin-co-ester of maleic acid polymer: These polymers include a combination of one or more olefins and an ester of maleic acid or a maleic acid derivative such as citraconic acid, nadic acid. Such polymers can be made by copolymerizing an unsaturated ester of maleic anhydride (or a derivative thereof) with one or more alpha-olefins or by reacting an alcohol (a hydroxyl-bearing moiety) with a copolymer of maleic anhydride (or a derivative thereof) and one or more alpha-olefins.R” represents the alkyl group from the alcohol or hydroxy bearing moiety used to create the ester of maleic anhydride. Depending on the esterification conversion, the R” group may appear once or twice in the maleic anhydride derivative portion of the polymer.The term alkyl maleate refers to esters of maleic acid or a maleic acid derivative. The structure is represented by Formula (I).“C18-C22 alkyl maleate” refers to esters of maleic acid or a maleic acid derivative where the alkyl chain length is 18-22 carbon atoms. The esterification of the maleic anhydride can be partial or full and R in Formula (I) is a linear or branched alkyl group having from 18 to 22 carbon atoms.Olefin-co-imide-derivative of maleic acid polymers: These polymers are a combination of one or more olefins and an N-alkyl, N-aryl, or N-alkaryl maleimide or maleimide derivative. Such polymers may be made by copolymerizing an unsaturated imide with one or more alpha-olefins or reacting an amine with a copolymer of maleic anhydride (or a derivative thereof) and one or more alpha-olefins.202400230 Foreign Filings 9The term alkyl maleimide refers to derivatives of the reaction of maleic anhydride and ammonia or an amine derivative. The structure is represented by Formula (II).“C18-C22 alkyl maleimide” refers to refers to derivatives of the reaction of maleic anhydride and ammonia or an amine derivative. The imidization of the maleic anhydride can be partial or full and R in Formula (II) is a linear or branched alkyl group having from 18 to 22 carbon atoms.The OMAC can be obtained by free-radical polymerization and related processes, for example ATRP (Atom Transfer Radical Polymerization), RAFT (Reversible Addition Fragmentation Chain Transfer) or NMP processes (nitroxide-mediated polymerization). More preferably, the polymers b) of the invention are prepared by free-radical polymerization.Customary free-radical polymerization is described, inter alia, in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition. In general, a polymerization initiator is used for this purpose. The usable initiators include the azo initiators widely known in the technical field, such as 2,2’-azo-bis-isobutyronitrile (AIBN), 2,2’-azo-bis-(2-methylbutyronitrile) (AMBN) and 1 ,1-azobiscyclohexanecarbonitrile, and also peroxy compounds such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert-butyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, ketone peroxide, tert-butyl peroctoate, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl-peroxybenzoate, tert-butyl-peroxyisopropylcarbonate, 2,5-bis(2-ethylhexanoy|-,peroxy)-2,5-dimethylhexane, tert-butyl-peroxy-2-ethylhexanoate, tert-butyl-peroxy-3,5,5-trimethylhexanoate, dicumyl peroxide, 1 ,1-bis(tert-butyl-peroxy)cyclohexane, 1 ,1-bis(tert-butyl-peroxy)-3,3,5-trimethylcyclohexane, cumyl hydroperoxide, tert-butyl-hydroperoxide, bis(4-tert-butylcyclohexyl) peroxydicarbonate, or a mixture of two or more of the aforementioned compounds with one another, and mixtures of the aforementioned compounds with compounds which have not been mentioned but can likewise form free radicals. Preferred initiator for the preparation of OMAC is tert-butyl-peroxy-2-ethylhexanoate.Furthermore, a chain transfer agent can be used. It is well-known in the art that a good way to control the molecular weight of a polymer chain is to use chain transfer agents during the polymerization synthesis. Chain transfer agents are molecules with a weak chemical bond which facilitate the chain transfer reaction. During the chain transfer reaction, the radical of the polymer chain abstracts a hydrogen from the chain transfer agent, resulting in the formation of a new radical on the sulfur atom of the chain transfer agent capable of further propagation. Common chain transfer agents are organic compounds comprising -SH groups such as n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, butylthiol glycolate, and octylthiol glycolate. A preferred chain transfer agent is selected from n-dodecyl mercaptan, tert-dodecyl mercaptan or a mixture thereof, most preferably n-dodecyl mercaptan.Preferably, the monomer mixture to prepare the OMAC of the present invention may comprise 0.05 to 7 % by weight, preferably 0.05 to 5 % by weight and more preferably 0.1 to 1 % by weight of initiator based on the total weight of the monomer composition to prepare the OMAC. The amount of chain transfer agents to202400230 Foreign Filings 10prepare the OMAC is in the range of 0 to 5 % by weight, preferably 0.01 to 5 % by weight and more preferably 0.05 to 4 % by weight, based on the total weight of the monomer composition.The polymerization may be carried out at standard pressure, reduced pressure or elevated pressure. The polymerization temperature is not critical. Conventionally the polymerization temperature may be in the range of 0 °C to 200 °C, preferably 0 °C to 140 °C, and more preferably 60 °C to 130 °C.The polymerization may be carried out with or without solvent. The term solvent is to be understood here in a broad sense. The polymerization is preferably carried out in a nonpolar solvent. These include hydrocarbon solvents, for example aromatic solvents such as toluene, benzene and xylene, saturated hydrocarbons, for example cyclohexane, heptane, octane, nonane, decane, dodecane, which may also be present in branched form, or a mixture thereof, such as naphtha. These solvents may be used individually and as a mixture. Particularly preferred solvents are mineral oils, diesel fuels of mineral origin, naphthenic solvents, natural vegetable and animal oils, biodiesel fuels and synthetic oils (e.g. ester oils such as dinonyl adipate), or a mixture thereof.Nonionic surfactant b)In the context of the present invention, the term “surfactant” is understood to mean organic substances having interface-active properties that can reduce the surface tension of water. Surface tension is typically determined by tensiometers such as the DuNouy ring method.Nonionic surfactants, which are preferred for the present invention, are similar materials in which the polar functionality is not provide by an anionic or cationic group, but by a neutral polar group such as typically an alcohol, amine, ether, ester, ketone, or amide function. Typical nonionic surfactants include polyoxyethylenated alkylphenols such as polyoxyethylenated p-nonylphenol, p-octylphenol, or p-dodecylphenol, polyoxyethylenated straight-chain alcohols derived from coconut oil, tallow, or synthetic materials including oleyl derivatives; polyoxyethylenated polyoxypropylene glycols (block copolymers of ethylene oxide and propylene oxide), typically having molecular weights of 1000 to 30,000 g / mol; polyethylene glycol; polyoxyethylenated mercaptans; long-chain carboxylic acid esters including glyceryl and polyglyceryl esters of natural fatty acids, propylene glycol esters, sorbitol esters, polyoxyethylenated sorbitol esters, polyoxyethylene glycol esters, and polyoxyethylenated fatty acids; alkanolamine "condensates" e.g. the condensates made by reaction of methyl or triglyceride esters of fatty acids with equimolar or twice equimolar amounts of alkanolamine; tertiary acetylenic glycols; polyoxyethylenated silicones, prepared by reaction of a reactive silicone intermediate with a capped allyl polyalkylene oxide such as propylene oxide or mixed ethylene oxide / propylene oxide copolymer; N-alkylpyrrolidones, and alkylpolyglycosides (long chain acetals of polysaccharides).Preferably the nonionic surfactants are alcohol ethoxylates.202400230 Foreign Filings 11Alcohol ethoxylates according to the present invention can be branched or linear and contain an ethylene oxide chain attached to a branched or linear alcohol. These compounds act as surfactants when used in an emulsion formulation.Preferably, the alcohol ethoxylate is branched or linear and contains an ethylene oxide chain attached to a branched or linear alcohol of Formula R(OC2H4)nOH, wherein R is an aliphatic hydrocarbyl radical containing from 6 to 16 carbon atoms, preferably 8 to 14 carbon atoms, and wherein n ranges from 1 to 20, preferably from 7 to 15.Preferably, the alcohol ethoxylate has an average of 1 to 20 ethylene oxide groups with a Hydrophilic Lipophilic Balance (HLB) value of from 8 to 18 measured with the Griffin method (see detailed measurement method in the experimental part below).Examples of alcohol ethoxylates are the ethoxylated alcohol product from Evonik, TOMADOL® 91-2.5, containing an average of 2.7 ethylene oxide groups with an HLB value of 8.5 (with the formula R(OC2H4)nOH wherein R is an aliphatic hydrocarbyl radical containing from 9 to 11 carbon atoms and with an average value of n being 2.7), the ethoxylated alcohol product from Evonik, TOMADOL® 91-6, containing an average of 6 ethylene oxide groups with an HLB value of 12.4 (with the formula R(OC2H4)nOH wherein R is an aliphatic hydrocarbyl radical containing from 9 to 11 carbon atoms and with an average value of n being 6); or secondary alcohol ethoxylates, such as Tergitol™ 15-S-7 containing an average of 7 ethylene oxide groups with an HLB value of 12.1 (with the formula R(OC2H4)nOH wherein R is a secondary aliphatic hydrocarbyl radical containing from 12 to 14 carbon atoms and with an average value of n being 7) and Tergitol™ 15-S-15 containing an average of 15 ethylene oxide groups with an HLB value of 15.4 (with the formula R(OC2H4)nOH wherein R is a secondary aliphatic hydrocarbyl radical containing from 12 to 14 carbon atoms and with an average value of n being 15).The amount of nonionic surfactant in the emulsion formulation is from 1 to 5 % by weight of the total formulation, preferably from 1.5 to 4 % by weight of the total formulation, more preferably from 2 to 4 % by weight of the total emulsion formulation.Biosurfactant c)Preferably, the biosurfactant is selected from the group consisting of rhamnolipids, sophorolipids, glucolipids, cellulose lipids, mannosylerythritol lipids and trehalose lipids or a mixture thereof, preferably rhamnolipids, sophorolipids and glucolipids or a mixture thereof, most preferably sophorolipids.Within the context of the present invention, “biosurfactants” are understood as meaning all glycolipids produced by fermentation. The term “biosurfactant” also covers glycolipids that are chemically or enzymatically modified after fermentation, as long as structurally a glycolipid remains. Raw materials for producing the biosurfactants that can be used are carbohydrates, in particular sugars such as e.g. glucose202400230 Foreign Filings 12and / or lipophilic carbon sources such as fats, oils, partial glycerides, fatty acids, fatty alcohols, long-chain saturated or unsaturated hydrocarbons.The biosurfactants can be produced e.g. as in EP 0499434, US 7,985,722, WO 03 / 006146, JP 60183032, DE 19648439, DE 19600743, JP 01 304034, CN 1337439, JP 2006 274233, KR 2004033376, JP 2006 083238, JP 2006 070231 , WO 03 / 002700, FR 2740779, DE 2939519, US 7,556,654, FR 2855752, EP 1445302, JP 2008062179 and JP 2007 181789 or the documents cited therein. Suitable biosurfactants can be acquired e.g. from Soliance, France.Preferably the biosurfactant is selected from rhamnolipids, preferably mono-, di- or polyrhamnolipids, glucolipids, preferably mono-, di- or polyglucolipids, sophorolipids, preferably mono-, di- or polysophorolipids and combination thereof. Most preferred biosurfactants are sophorolipids.The term "rhamnolipids" in the context of the present invention preferably is understood to mean particularly compounds of the general Formula (IV), and salts thereof:Formula (IV)whereinmRL = 2, 1 or 0,nRL = 1 or 0,R1RLand R2RL= mutually independently, identical or different, organic residues having 2 to 24, preferably 5 to 13 carbon atoms, in particular optionally branched, optionally substituted, particularly hydroxysubstituted, optionally unsaturated, in particular optionally mono-, bi- or tri-unsaturated alkyl residues, preferably those selected from the group consisting of pentenyl, heptenyl, nonenyl, undecenyl and tridecenyl and (CH2)o-CH3 wherein o = 1 to 23, preferably 4 to 12.If nRL = 1 , the glycosidic bond between the two rhamnose units is preferably in the a-configuration. The optically active carbon atoms of the fatty acids are preferably present as R-enantiomers (e.g. (R)-3-{(R)-3-[2-O-(a-L-rhamnopyranosyl)-a-L-rhamnopyranosyl]oxydecanoyl}oxydecanoate).202400230 Foreign Filings 13The term "mono-rhamnolipid" in the context of the present invention is understood to mean compounds of the general formula (I) or salts thereof, where nRL = 0. The term "di-rhamnolipid" in the context of the present invention is understood to mean compounds of the general formula (IV) or salts thereof, where nRL = 1.Distinct rhamnolipids are abbreviated according to the following nomenclature:"diRL-CXCY" are understood to mean di-rhamnolipids of the general formula (IV), in which one of the residues R1RLand R2RL= (CH2)o-CH3 where o = X-4 and the remaining residue R1or R2= (CH2)o-CH3 where o = Y-4."monoRL-CXCY" are understood to mean mono-rhamnolipids of the general formula (IV), in which one of the residues R1RLand R2RL= (CH2)o-CH3 where o = X-4 and the remaining residue R1RLor R2RL= (CH2)o-CH3 where 0 = Y-4.The nomenclature used therefore does not distinguish between "CXCY" and "CYCX".For rhamnolipids where mRL=0, monoRL-CX or diRL-CX is used accordingly.If one of the abovementioned indices X and / or Y is provided with ":Z", this signifies that the respective residue R1RLand / or R2RLis equal to an unbranched, unsubstituted hydrocarbon residue having X-3 or Y-3 carbon atoms having Z double bonds.Methods for preparing the relevant rhamnolipids are disclosed, for example, in EP2786743 and EP2787065.Rhamnolipids applicable in the context of the present invention can also be produced by fermentation of Pseudomonas, especially Pseudomonas aeruginosa, which are preferably non genetically modified cells, a technology already disclosed in the eighties, as documented e.g. in EP0282942 and DE4127908. Rhamnolipids produced in Pseudomonas aeruginosa cells which have been improved for higher rhamnolipid titres by genetical modification can also be used in the context of the instant invention; such cells have for example been disclosed by Lei et al. in Biotechnol Lett. 2020 Jun;42(6):997-1002.In the context of the present invention, the term “sophorolipids” preferably is understood as meaning compounds of the general Formulae (Va) and (Vb), and salts thereof:202400230 Foreign Filings 14)whereinR1SL= H or CO-CH3,R2SL= H or CO-CH3,R3si_ =adivalent organic moiety which comprises 6 to 32 carbon atoms and which is unsubstituted or substituted by hydroxyl functions, is unbranched and optionally comprises one to three double or triple bonds,R4SL= H, CH3 or a monovalent organic radical which comprises 2 to 10 carbon atoms and which is unsubstituted or substituted by hydroxyl functions, which is unbranched and which optionally comprises one to three double or triple bonds, andnSL = 1 orO.202400230 Foreign Filings 15Sophorolipids may be used in accordance with the invention in their acid form or their lactone form.Preferred compositions according to the present invention comprise a sophorolipid, in which the ratio by weight of lactone form to acid form is in the range of 20:80 to 80:20, especially preferably in the ranges of 30:70 to 40:60.To determine the content of sophorolipids in the acid or lactone form in a formulation, refer to EP1411111B1 , page 8, paragraph

[0053] ,In connection with the present invention, the term “glucolipids” preferably is understood as meaning compounds of the general formula (III) and salts thereof,whereinmGL = 1 or 0,R1GLand R2GL= independently of one another identical or different organic radical having 2 to 24 carbon atoms, in particular optionally branched, optionally substituted, in particular hydroxy-substituted, optionally unsaturated, in particular optionally mono-, di- or tri unsaturated, alkyl radical, preferably one selected from the group consisting of pentenyl, heptenyl, nonenyl, undecenyl and tridecenyl and (CH2)o-CH3 where o = 1 to 23, preferably 4 to 12.Distinct glucolipids are abbreviated according to the following nomenclature:“GL-CXCY” is understood as meaning glucolipids of the general formula (VI) in which one of the radicals R1GLand R2GL= (CH2)o-CH3 where o = X-4 and the remaining radical R1GLor R2GL= (CH2)o-CH3 where o = Y-4.The nomenclature used thus does not differentiate between “CXCY” and “CYCX”.If one of the aforementioned indices X and / or Y is provided with “:Z”, then this means that the respective radical R1GLand / or R2GL= an unbranched, unsubstituted hydrocarbon radical with X-3 or Y-3 carbon atoms having Z double bonds.202400230 Foreign Filings 16Methods for production of glucolipids can be carried out as described in WO2019154970.The amount of biosurfactant in the emulsion formulation is from 0.1 to 5 % by weight of the total formulation, preferably from 0.2 to 3 % by weight of the total formulation, more preferably from 0.3 to 1% by weight of the total emulsion formulation.Carrier MediumWithin the context of the present invention, the term “carrier medium” refers to a liquid in the formulations.The amount of carrier medium in the emulsion formulation corresponds to the remaining amount to be added in the emulsion formulation to reach 100% by weight, after having included all components a), b), c) and optional components (such as components d) and e) described below), based on the total weight of the emulsion formulation.Thus, the amount of carrier medium is chosen to reach 100 % by weight of the total weight ofthe emulsion formulation, after having included all components a), b), c) and any other optional components (such as components d) and e)) in the emulsion formulation.The carrier medium is preferably selected from the group consisting of water, organic solvent, water miscible alcohol or a mixture thereof, more preferably water, hydrocarbon, glycols, and glycol ethers, even more preferably water, glycols and naphtha, most preferably water and ethylene glycol and optionally naphtha.Preferably, the carrier medium is a mixture of water and ethylene glycol, wherein the weight ratio of water to ethylene glycol is from 40:60 to 60:40.More preferably, the carrier medium is a mixture of water, ethylene glycol and an aromatic solvent. The amount of aromatic solvent is preferably from 0 to 20 % by weight, more preferably from 0.1 to 15 % by weight, even more preferably from 0.5 to 10 % by weight, most preferably from 1 to 5 % by weight, of the emulsion formulation.Polyalkyl (meth)acrylate polymer (optional component d)Preferably, the emulsion formulation according to the invention may also further comprise a polyalkyl (meth)acrylate polymer d).The polyalkyl(meth)acrylate polymer d) is prepared by polymerizing a monomer composition comprising from 50 to 100 % by weight of one or more alkyl (meth)acrylate monomers having a linear, branched or cyclic carbon chain of 8 to 30 carbon atoms, based on the total weight of the monomer composition, and202400230 Foreign Filings 17wherein the polyalkyl(meth)acrylate polymer has a weight-average molecular weight from 5,000 to 600,000 g / mol.Within the context of the present invention, the monomer composition corresponds to the total amount of monomers to prepare the polyalkyl(meth)acrylate polymer.The weight-average molecular weight of the polyalkyl(meth)acrylate polymer is determined by gel permeation chromatography using poly(methyl-methacrylate) calibration standards (see detailed method in the experimental section below).The amount of polyalkyl(meth)acrylate polymer in the emulsion formulation is preferably from 0 to 30 % by weight or less, more preferably from 1 to 25 % by weight even more preferably from 5 to 20 % by weight, based on the total weight of the emulsion formulation.According to another preferred embodiment of the invention, the polyalkyl(meth)acrylate polymer d) is a Ca-Cso polyalkylacrylate polymer prepared by polymerizing a monomer composition comprising C8-C30 acrylate monomers; oris a Cs-Cso polyalkyl(meth)acrylate polymer prepared by polymerizing a monomer composition comprising from 40 to 80 %, preferably from 50 to 80 % by weight of Cs-Cso acrylate and from 20 to 60 % by weight, preferably from 20 to 50 % by weight of Cs-Cso methacrylate, based on the total weight of the monomer composition; oris a mixture of both.According to a preferred embodiment of the invention, the polyalkyl(meth)acrylate polymer d) is a polyalkylacrylate polymer made by polymerizing C12-C22 alkyl acrylate monomers. In this embodiment, the polyalkyl(meth)acrylate polymer a) is formed from C12-C22 acrylate monomers. Most preferably, the polyalkylacrylate polymer a) is polybehenylacrylate.According to the present invention, the weight-average molecular weight of the polyalkyl(meth)acrylate polymer is from 5,000 to 600,000 g / mol, preferably from 8,000 to 550,000 g / mol, more preferably from 10,000 to 500,000 g / mol, determined by gel permeation chromatography using poly(methyl-methacrylate) calibration standards (GPC method as described in more detail in the experimental section below).The polyalkyl(meth)acrylate polymer d) can be prepared by free-radical polymerization and related processes, for example ATRP (Atom Transfer Radical Polymerization), RAFT (Reversible Addition Fragmentation Chain Transfer) or NMP processes (nitroxide-mediated polymerization). More preferably, the PAMA d) are prepared by free-radical polymerization. Customary free-radical polymerization is described, inter alia, in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition.202400230 Foreign Filings 18Other additives of the emulsion formulation (optional component e)According to another preferred aspect of the invention, the emulsion formulation may further comprise some additives e) selected from the list consisting of pH regulators, pH buffers, inorganic salts, antioxidants, preservatives, corrosion inhibitors or metal deactivators.If present in the formulation, the amount of additives e) is preferably 5% by weight or less, more preferably from 0.1 to 5% by weight, and even more preferably from 0.2 to 2% by weight, based on the total weight of the emulsion formulation.Method for preparing the emulsion formulationsEmulsification is the process of dispersing one immiscible liquid (the dispersed phase) into another liquid (the continuous phase) to form a stable emulsion. This process involves the use of emulsifiers, which are surfactant molecules that lower the interfacial tension between the two liquids and stabilize the resulting mixture.The term "emulsion” in the context of the present invention refers to a mixture of surfactant-based chemical agents that disperse and suspend visually or light microscopically identifiable polymer aggregates that are not precipitating, but instead remain dispersed or suspended in bulk fluids. Indeed, to keep oil flowing and not depositing in downhole or flowlines, it is essential to avoid solid or gel sediments which are unsuitable for further processing on a large industrial scale.The present invention relates to a method for preparing the emulsion formulation described above, the method comprising mixing the alpha-olefin maleic anhydride copolymers, preferably melted, with a nonionic alcohol ethoxylate, a biosurfactant and a carrier medium, and if present, any further additional components of the emulsion formulation (such as the polyalkyl(meth)acrylate polymer d) and / or other additives e)).The heated components, particularly if they are in a liquid (melted or dissolved) state are mixed to ensure dispersion. This mixing can be conducted under high shear or cavitation conditions.In the context of the present invention, the term "high shear mixing" preferably means mixing at high stir rate of at least 1 ,000 rpm, preferably at least 10,000 rpm, and more preferably at least 20,000 rpm.The mixing can also be conducted under cavitation conditions, which are also considered to be “high shear mixing conditions” as described in US5851429. Cavitation generally involves formation of microscopic bubbles within a liquid, which expand under the influence of ultrasonic energy and thereafter implode with an intense shearing action. Devices capable of producing a sufficiently high shear or cavitation conditions include a Sonicator.RTM., a high intensity ultrasonic processor, in which high frequency electrical voltage (e.g., 20 kHz) is converted to mechanical vibration energy which is directed into a liquid sample by means of a probe. Also included are high shear dispersers (such as Dispersator.RTM.) in which a high-speed rotor202400230 Foreign Filings 19is held in close clearance to a fixed stator, creating an environment of extremely high shear due to the mechanical and hydraulic forces as the fluid passes into the rotor and is expelled at high velocity through the stator, or a Microfluidizer.RTM. (from Microfluidics Inti. Inc.) in which two high pressure streams interact at high velocities in defined micro-channels, whereby shear, impact, and cavitation forces typically produce submicron particles.Preferably, the mixing of all components of the emulsion formulation is made preferably at a temperature above 30°C. More preferably, the temperature is preferably below 80°C. The temperature to which the emulsion formulation is to be heated depends on the melting, solubility, and volatility characteristics of the materials employed.Preferably, the mixing step is of at least 30 minutes to allow efficient mixing of all components in the emulsion formulation.Usually, the heated mixture is then cooled to a temperature at which the waxy material is substantially insoluble and would normally exist in a solid or semisolid state, while maintaining the conditions mixing. The resulting mixture is a stable emulsion.Due to the preparation process according to the invention, a highly stable formulation can be obtained supported by the emulsifier component mixture of nonionic surfactant b) and biosurfactant c).Postsynthetic emulsification provides enhanced tunability, enabling a broader range of polymer compositions, including blends of polymers, to be emulsified using the same surfactant system and similar reaction conditions. In the present invention, the term “postsynthetic emulsification” refers to a process where a polymer is synthesized prior to the dispersing and emulsification step.Crude oil compositionThe present invention is further directed to a crude oil composition comprising the emulsion formulation as described above and a crude oil. All preferred characteristics of the emulsion formulation described above apply for the crude oil composition.Preferably, the crude oil composition comprises the emulsion formulation at a concentration of from 0.001 % by weight to 1 % by weight, more preferably of from 0.005 % by weight to 0.8 % by weight, even more preferably of 0.005 % by weight to 0.5 % by weight, of emulsion formulation, based on the total weight of the crude oil composition.Preferably, the crude oil and the emulsion formulation sum up from 90 to 98 % by weight, based on the total weight of the crude oil composition.202400230 Foreign Filings 20In the context of the present invention, the term “crude oil” is defined as the crude oil that contains high amount of long chain paraffin wax (alkanes) compounds, making the crude possess a high pour point and become viscous at temperatures lower than the wax appearance temperature.The crude oil composition according to the invention may further comprise an additive such as scale inhibitors, corrosion inhibitors, oxygen scavengers, biocides, emulsion breakers, antifoam agents, drag reducing agents, hydrate inhibitors, paraffin dispersants, asphaltene control agents, a pour point depressant other than the polymers a) and d), or a mixture thereof.Preferably, the amounts of crude oil, emulsion formulation and additive / s sum up to 90 to 99 % by weight, more preferably sum up to 95 to 98 % by weight, even more preferably sum up to 100 % by weight, based on the total weight of the crude oil composition.The method for preparing the crude oil composition according to the invention preferably comprises the step of mixing the crude oil and the emulsion formulation. More preferably, the method comprises the step of mixing for at least 5, 10, 15, 25 or 30 minutes.The method may also comprise a step of heating the crude oil and the emulsion formulation, preferably to at least 40 °C, even more preferably to at least 50 °C, most preferably to at least 60 °C. The method may comprise heating and mixing the crude oil simultaneously.The method of the present invention is able to reduce the pour point of the crude oil, or to reduce the viscosity of the crude oil, or to achieve both. The resulting crude oil composition is thereby easier to transport and store compared to the crude oil with no emulsion formulation. In addition, no modifications to plant design are required to provide a crude oil having a reduced pour point or viscosity, as this can be achieved by adding the emulsion formulation of the present invention after the crude oil is made.Uses of the emulsion formulationsThe invention also relates to the use of the emulsion formulation of the invention, as described above in detail, as crude oil paraffin inhibitors and pour point depressants, wherein the emulsion formulation is added to the crude oil. In the context of the present invention, the emulsion formulation of the invention is an additive composition which is added to the crude oil.In particular, the present invention relates to a method for treating a crude oil with an emulsion formulation according to the present invention to enhance cold flow properties of the crude oil, wherein the emulsion formulation is added to the crude oil.202400230 Foreign Filings 21In the context of the invention, the term “crude oil composition” refers to the emulsion formulation and crude oil in field applications. Preferably, the treat rate of the emulsion in the crude oil composition is from 0.001 % to 1% by weight, based on the total weight of the crude oil composition.In the context of the present invention, the term “crude oil” is defined as the crude oil that contains high amount of long chain paraffin wax (alkanes) compounds, making the crude possess a high pour point and become viscous at temperatures lower than the wax appearance temperature.EXPERIMENTAL PARTThe invention is further illustrated in detail hereinafter with reference to examples and comparative examples, without any intention to limit the scope of the present invention.AbbreviationsNS1 Tergitol™ 15-S-15 (C12-C14 secondary alcohol ethoxylate, 15 Ethylene Oxide Units) NS2 Tergitol™ 15-S-7 (C12-C14 secondary alcohol ethoxylate, 7 Ethylene Oxide Units) NS3 Tween® 20 (Polyethylene glycol sorbitan monolaurate, Polysorbate 20)ECA ether carboxylic acid (trideceth-7-carboxylic acid)MEG monoethylene glycolMw weight average molecular weightn.m not measuredOMAC alpha-olefin maleic anhydride copolymerPAMA polyalkyl(meth)acrylatePPD Pour Point Depressant51 sophorolipid with a lactone:acid weight ratio of 60:4052 sophorolipid with a lactone:acid weight ratio weight of 40:60ShellSol™A150 Naphtha, C9-C10 aromatic hydrocarbon solventCrude oil characteristicsThe tested crude oil has the characteristic and properties as shown in Table 1 below.Table 1 : Crude oil (1)202400230 Foreign Filings 22PolymersThe respective compositions of the polymer components a) and d) are shown in Table 2 below.Table 2: Monomer compositions of the polymers a) and d) as used in the present inventionEmulsion formulationsIn the examples below, details are provided on how to prepare the different emulsion formulations according to the invention, as well as comparative emulsion formulations. Table 2 below summarizes the compositions of the respective emulsion formulations. The emulsion formulation of Example 7 corresponds to a mixture of PPD1 (OMAC) and PPD2 (PAMA) in a weight ratio of 50:50.Inventive Example 1 :Shellsol A150 (7 g) and polymer (40 g) were combined in a vessel and heated to 80 °C to melt the polymer. Next, a sophorolipid (1 g), Tergitol™ 15-S-15 (5 g), DI water (63 g), and ethylene glycol (65 g) were combined and heated to 80 °C in a separate vessel. After all components were melted, a propeller stirrer was placed in the polymer / oil phase. With moderate stirring, the aqueous solution / surfactant mixture was slowly added to the polymer / oil solution. After the addition was completed, the reaction was maintained at 80 °C with stirring for an additional hour. The mixture was then optionally cooled to 70 °C and homogenized using an UltraTurrax for 2 minutes while maintaining the speed between 14,000 and 21 ,500 rpm. The final solution was filtered through a 125-micrometer paint filter and cooled to room temperature (20°C).Inventive Examples 2-12Inventive examples 2 to 12 were prepared in the same way as Inventive Example 1. However the compositions and weight ratios of the polymer, biosurfactant, nonionic surfactants, and solvents were modified as described in Table 3 to emphasize the robustness of the method. Some examples show an optional additional step where fatty acids and triethanolamine are added to the emulsion after it is formed via the homogenization step. In these examples, the components are added to the mixture and the sample is homogenized at low shear rates (6000 rpm) for an additional 2 minutes prior to the filtration step.Comparative Example 13:Shellsol A150 (14 g) and polymer (40 g) were combined in a vessel and heated to 80 °C to melt the polymer. Next, a solution of ether carboxylic acid (5.4 g oftrideceth-7-carboxylic acid), triethanolamine (1g), Tergitol™202400230 Foreign Filings 2315-S-15 (5g), deionized water (54 g), and ethylene glycol (74 g) were combined and heated to 80 °C in a separate vessel. After all components were melted, a propeller stirrer was placed in the polymer / oil phase. With moderate stirring, the aqueous solution / surfactant mixture was slowly added to the polymer / oil solution. After the addition was completed, the reaction was maintained at 80 °C with stirring for an additional hour. The mixture was then optionally cooled to 70 °C and homogenized using an UltraTurrax for 2 minutes at 21,500 rpm. The final solution was filtered through a 125-micrometer paint filter and cooled to room temperature (20°C).Comparative Examples 14 and 15:Comparative examples 14 and 15 were prepared as comparative example 13, but the amounts shown in Table 3 were used.The comparative examples 13 to 15 do not comprise any biosurfactant.Table 3: Compositions of the emulsion formulations (all amounts given in g)means “not added202400230 Foreign Filings 24Test methods:Pour points were measured according to ASTM D5853.Dynamic viscosity was measured using a Discovery HR20 TA instruments rheometer at the following conditions: - Temp. Ramp: 30 to -40°C- Cooling rate: 1°C / min- Shear rate: 10 1 / s- Sampling interval: 10 s / pt- Geometry: plate / plateIn the present invention, the weight-average molecular weights (Mw) and the number-average molecular weights (Mn) of the polymers a) (PAMA) and d) (OMAC) are determined by gel permeation chromatography (GPC) using poly(methyl-methacrylate) calibration standards according to DIN 55672-1 using the following measurement conditions:Column: the column set consists of a precolumn and 5 SDV columns as disclosed in Table 4:Table 4Instruments: Agilent 1100 Series Pump; PSS SECcurity Inline-Degaser; Agilent 1260 Series Autosampler; Agilent 1100 Series Rl-Detector; Agilent 1260 Series UV-Detector; Techlab column oven;Oven temperature: 35 °C;Standards: poly(methyl-methacrylate) (so called PMMA) calibration standards;Eluent: tetra hydrofuran (THF);Flow rate: 1 mL / min;Injected volume: 100 pL;Detection: Rl at a temperature of 35 °C and UV at a wavelength of 239 nm.The hydrophilic-lipophilic balance (HLB) of a surfactant is a measure of its degree of hydrophilicity or lipophilicity, determined by calculating percentages of molecular weights for the hydrophilic and lipophilic portions of the surfactant molecule. It is measured whit the method of Griffin as described in Griffin, W.C. (1949) Classification of Surface-Active Agents by “HLB”, Journal of Cosmetic Science, 1, 311-326.The centrifuge stability test is commonly employed to test the stability of dispersion products. In a centrifugation test, the sample is subjected to centrifuge for 3 rounds at 2,000 rpm: 20 min, 40 min, and 60 min. After each round, the sample tubes are removed from the centrifuge, inspected, and tilted 90°. The202400230 Foreign Filings 25initial appearance and flow behavior are scored based on the criteria in Table 5. After 3 rounds, the scores from each round are summed, giving a maximum score of 300 points. Samples with higher points are considered more stable.Table 5: Centrifuge Scoring CriteriaThe emulsion formulations of Table 3 were tested using the test methods as described above. In particular, the low temperature properties of the emulsion formulations of Table 3 are summarized below in Table 6, as well as their stability over time (shelf-life) as shown in Table 7 below. The cold flow properties of the emulsion formulations of Table 3 in crude oil are also shown in Table 8.Two additional comparative examples were prepared, which correspond to dilutions of PPD1 of Table 2 in toluene (not emulsion formulations). Comparative example 16 corresponds to a dilution in toluene of 5 wt% PPD 1 , based on the total weight of the dilution. Comparative example 17 corresponds to a dilution in toluene of2.5 wt% PPD 1, based on the total weight of the dilution.Table 6: Low Temperature Properties of the emulsion formulations, as well as of dilutions (Comp16 and Comp17)<<<<<<>Table 7: Sample Stability via Centrifugation (90 days aged)202400230 Foreign Filings 26Table 8: Emulsion formulations cold flow performance in Crude Oil 1Results discussionAs shown in Table 6, the emulsion formulation examples produced with this method have improved dynamic viscosities for subzero temperatures in comparison to the comparative emulsion formulation examples made according to the prior art, which have higher dynamic viscosities for subzero temperatures (see e.g. comparative examples Comp13 and Comp14). The comparative emulsion Compl 5 example made only with nonionic surfactant (without any biosurfactant) solidifies at 20°C. For comparative Compl 6 and Compl 7 examples, the OMAC polymer are only diluted in an organic solvent and do not remain liquid at subzero temperatures.As shown in Table 7, the emulsion according to the invention (inventive example 1) shows a high shelf-life stability since it scores very high even after 90 days. In contrast, the comparative emulsion Compl 4, made according to the teachings of prior art US20200283692A1 shows a lower storage stability with a score of 60 after 90 days.In Table 8, it can be observed that the emulsion formulations according to the present invention advantageously improve the cold flow properties of crude oil by lowering the pour point of the crude oil composition they are added in.The emulsion formulations according to the present invention, synthesized using a dual combination of biosurfactants and nonionic surfactants, advantageously show a high shelf-life stability compared to examples made based on the state-of-the-art. They also advantageously exhibit low dynamic viscosities. The inventive formulations also significantly decrease the pour point of corresponding crude oil compositions.

Claims

202400230 Foreign Filings 27CLAIMS1. An emulsion formulation comprising a carrier medium and the following components:a) 5 to 50 % by weight of one or more alpha-olefin maleic anhydride copolymers, based on the total weight of the emulsion formulationb) 1 to 5 % by weight of one or more nonionic surfactant, based on the total weight of the emulsion formulation,c) 0.1 to 5 % by weight one or more biosurfactant, based on the total weight of the emulsion formulation.

2. The emulsion formulation according to claim 1 , wherein the alpha-olefin maleic anhydride copolymer a) is prepared by polymerizing a monomer composition comprisingi) from 10 to 70 % by weight of monomers selected from alkyl maleate compound of Formula (I), maleimide compound of Formula (II) or a mixture thereof, based on the total weight of the alpha-olefin maleic anhydride copolymer,"wherein R in Formula (I) and Formula (II) is a linear or branched alkyl group having from 10 to 40 carbon atoms; andii) from 30 to 90 % by weight of one or more non-functionalized alpha-olefin of formula (III), based on the total weight of the alpha-olefin maleic anhydride copolymer,wherein R2 is a linear alkyl group having from 8 to 40 carbon atoms, preferably from 10 to 40 carbon atoms, more preferably from 15 to 35 carbon atoms.202400230 Foreign Filings 283. The emulsion formulation according to claim 1 or 2, wherein the alpha-olefin maleic anhydride copolymers is selected from the group consisting of a polymer prepared by polymerizing a monomer composition comprising C18-C22 alkyl maleate and C20-C32 non-functionalized alpha-olefin, a polymer prepared by polymerizing a monomer composition comprising C18-C22 alkyl maleate and C20-C24 nonfunctionalized alpha-olefin, a polymer prepared by polymerizing a monomer composition comprising C18-C22 alkyl maleate and C10-C18 non-functionalized alpha-olefin, or a mixture thereof.

4. The emulsion formulation according to any one of the previous claims, wherein the nonionic surfactant is an alcohol ethoxylate.

5. The emulsion formulation according to claim 4, wherein the nonionic alcohol ethoxylate is an alcohol ethoxylate with the Formula R(OC2H4)nOH, wherein R is a branched or linear aliphatic hydrocarbyl radical containing from 6 to 16 carbon atoms, preferably 8 to 14 carbon atoms, and wherein n ranges from 1 to 20, preferably from 7 to 15.

6. The emulsion formulation according to any one of the previous claims, wherein the biosurfactant is selected from the group consisting of rhamnolipids, sophorolipids, glucolipids, or a mixture thereof.

7. The formulation according to claim 6, wherein the biosurfactant is a sophorolipid.

8. The emulsion formulation according to claim 7, wherein in the sophorolipid the ratio by weight of lactone form to acid form is in the range of 20:80 to 80:20, preferably in the range of 30:70 to 40:60.

9. The emulsion formulation according to any one of the previous claims, wherein the carrier medium is a mixture of water, glycols or glycol ethers, and optionally an organic solvent.

10. The emulsion formulation according to any one of the previous claims, wherein the emulsion formulation further comprises a polyalkyl (meth)acrylate polymer d).

11. A method of preparing the emulsion formulation as defined in any one of claims 1 to 10 comprising mixing one or more alpha-olefin maleic anhydride copolymer, with one or more nonionic surfactant, one or more biosurfactant, the carrier medium and any other optional components.

12. A crude oil composition comprising the emulsion formulation as defined in any of claims 1 to 10 and a crude oil.

13. Use of the emulsion formulations according to any one of claims 1 to 10 as crude oil paraffin inhibitors and pour point depressants, wherein the emulsion formulation is added to crude oil.202400230 Foreign Filings 2914. Method of treating a crude oil with an emulsion formulation as defined in any one of claims 1 to 10 to enhance the cold flow properties of the crude oil, wherein the emulsion formulation is added to the crude oil.

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