fuel composition

Abstract

A fuel composition comprising (i) 35% to 95% by volume of renewable alcohol components and (ii) 5% to 65% by volume of renewable naphtha components, wherein the renewable naphtha components have a total isoparaffin and n-paraffin content of at least 90% by mass, an isoparaffin content of at least 60% by mass, an n-paraffin content of less than 30% by mass, and an isoparaffin to n-paraffin ratio greater than 3:1. The fuel composition satisfies the requirements of flexible fuel specifications such as California CCR §2292.4, while reducing CO emissions and NO emissions. x It provides a reduction in emissions.

Description

[Technical Field]

[0001] The present invention relates to fuel formulations, particularly fuel formulations for flexible fuel vehicles (FFVs). [Background technology]

[0002] Flexible fuel vehicles, also known as flex-fuel vehicles or FFVs, are vehicles that include internal combustion engines, such as spark-ignition internal combustion engines, and can operate on gasoline or blends of gasoline with alcohols such as ethanol or methanol. While the use of ethanol in conventional gasoline vehicles is typically limited to 10-15% by volume due to the technical limitations of the engine, FFVs can operate on a wide range of ethanol-containing formulations from E0 (0% ethanol) to E85 in the United States or E100 in Brazil. E85 is a blend of gasoline and ethanol, typically containing 51-83% by volume ethanol, or 53-85% by volume denatured ethanol. Ethanol can be derived from biological sources, for example, by fermentation of sugar-containing feedstocks using yeast, by alcohol synthesis after biomass gasification, or by fermentation using anaerobic bacteria after gasification.

[0003] Gasoline used in high-ethanol-containing flex fuels such as E85 has traditionally been produced by refining crude oil (petroleum). This typically involves separating various fractions of crude oil by distillation. One such fraction is naphtha, a volatile liquid fraction distilled between the lighter gaseous components of crude oil and the heavier kerosene fraction. Naphtha contains a mixture of hydrocarbons (straight-chain alkanes, branched alkanes, cycloalkanes, and aromatic hydrocarbons) with boiling points ranging from approximately 30°C to approximately 200°C. The density of naphtha is typically 750–785 kg / m³. 3 Naphtha has many uses, one of which is as an automotive fuel or as a blending component of automotive fuels.

[0004] While the long-chain molecules in diesel fuel have a high cetane number and can be blended into diesel, naphtha has historically not been used in gasoline fuel, or only in small amounts, due to its low octane number. This was true despite the fact that naphtha has distillation properties comparable to those of gasoline.

[0005] In recent years, with the increasing production of renewable naphtha, biofuels derived from biomaterials are increasingly being used as a more sustainable alternative to fossil fuels. Therefore, it would be advantageous to use renewable naphtha as a substitute blending component for conventional gasoline in E85 type flex fuel compositions so that the final flex fuel composition can be a fully renewable or nearly fully renewable fuel suitable for use in flexible fuel vehicles.

[0006] Attempts have been made to produce fully renewable E85 fuels containing bioethanol and renewable naphtha. For example, U.S. Patent Application Publication 2013 / 0131360 relates to a method for producing naphtha products from renewable feedstock by converting naturally occurring triglycerides and fatty acids into a composition containing hydrocarbons within the naphtha boiling point range. U.S. Patent Application Publication 2013 / 0131360 also refers to the resulting bio-renewable naphtha product, thereby allowing naphtha to be used as a chemical feedstock, fuel, fuel blend stock, or solvent. Example 3 of U.S. Patent Application Publication 2013 / 0131360 discloses bio-renewable naphtha as a blend stock for 100% renewable E85 gasoline. Example 5 of U.S. Patent Application Publication 2013 / 0131360 provides the compositional properties of the bio-renewable naphtha produced in Example 2. From Table 4, it can be seen that the level of "isoparaffin" is 59.893% by weight, and the level of "paraffin" is 32.407% by weight.

[0007] No information is provided regarding the emission profile of the final E85 product.

[0008] U.S. Patent No. 10,414,992(B2) relates to a fuel composition comprising a) 70 to 86 volume percent of ethanol and b) 5 to 20 volume percent of a hydrocarbon component comprising hydrocarbons derived from feedstock including tall oil material, wherein the hydrocarbon component has 50 to 70 RON and comprises 25 to 60 mass percent of naphthene.

[0009] An article published in Biomass Magazine on October 23, 2019, by Pearson Fuels reports replacing petroleum with renewable naphtha in E85 flex fuel for the California market (https: / / biomassmagazine.com / articles / 16560 / pearson-fuels-blends-ethanol-renewable-naphtha-into-advanced-e85 (accessed May 24, 2023)). Furthermore, an article by Melissa Anderson published on the Advanced Biofuels USA website on July 22, 2022, also mentions Pearson. Advanced Biofuels reports that it is producing E85 almost entirely from bio-based inputs using ethanol and renewable naphtha, and that it is being sold in Southern California (https: / / advancedbiofuelsusa.info / in-pursuit-of-pure-the-quest-to-make-e85-a-totally-biobased-fuel / (accessed May 24, 2023)). Furthermore, an article titled "2021 California E85 Sales Schopper Previous Record; Momentum Continus in 2022," published on the Advanced Biofuels USA website on March 28, 2022, is by Pearson. Fuels reports that it blends renewable naphtha with E85, resulting in a nearly 100 percent renewable fuel (https: / / advancedbiofuelsusa.info / 2021-california-e85-sales-shatter-previous-record-momentum-continues-in-2022 / (accessed May 24, 2023)). These articles do not contain specific information about the properties of renewable naphtha.

[0010] Despite reports of the availability of renewable E85 flex fuels in certain regions, it is desirable to blend renewable flex fuels that provide an improved emissions profile, particularly by providing reductions in both CO and NOx emissions. Typically, there is a trade-off between CO and NOx emissions, and therefore, CO and NOx emissions. x Formulating a fuel mixture that reduces both emissions is a challenging task.

[0011] At the same time, it is desirable that the renewable flex fuel composition be formulated to comply with relevant flex fuel specifications, such as, but not limited to, U.S. Federal ASTM 5798, California CCR §2292.4, and EU EN 15293:2018. [Overview of the Initiative]

[0012] According to the present invention, (i) Alcohol content of 35% to 95% by volume, (ii) A fuel composition is provided comprising 5% to 65% by volume of renewable naphtha components, wherein the renewable naphtha components have a total paraffin content of at least 90% by mass, an isoparaffin content of at least 60% by mass, an n-paraffin content of less than 30% by mass, and an isoparaffin to n-paraffin ratio greater than 3:1.

[0013] According to the present invention, CO emissions and NO emissions are reduced. x Further applications of the fuel compositions defined above are provided for reducing emissions, and in particular, the fuel compositions are used to refuel flexible fuel vehicles.

[0014] Remarkably, by blending renewable naphtha components with specific physicochemical properties with renewable alcohol components at specific concentrations, CO emissions and NO emissions can be reduced. xWhile providing a reduction in emissions, the inventors have found that a renewable fuel composition is provided that meets the requirements of flexible fuel specifications such as ASTM 5798 in the United States Federal, CCR §2292.4 in the State of California in the United States, and EU EN 15293:2018.

[0015] Also, surprisingly, it has been found that the fuel composition of the present invention maintains a high octane (RON) value despite the low RON value of the renewable naphtha.

[0016] The liquid fuel composition of the present invention also provides a reduction in CO2 emissions from tank to wheel, a reduction in particulate emissions, and excellent fuel economy, acceleration, and power performance.

Brief Description of the Drawings

[0017] [Figure 1-1] Shows the physicochemical properties of the renewable naphtha and gasoline-based fuels used in the examples. [Figure 1-2] Shows the physicochemical properties of the renewable naphtha and gasoline-based fuels used in the examples. [Figure 1-3] Shows the physicochemical properties of the renewable naphtha and gasoline-based fuels used in the examples. [Figure 1-4] Shows the physicochemical properties of the renewable naphtha and gasoline-based fuels used in the examples. [Figure 1-5] Shows the physicochemical properties of the renewable naphtha and gasoline-based fuels used in the examples. [Figure 1-6] Shows the physicochemical properties of the renewable naphtha and gasoline-based fuels used in the examples. [Figure 2-1] Shows the RON numbers of the renewable naphtha and gasoline-based fuels used in the examples, as well as the RON numbers of the fully formulated fuel compositions tested in the examples. [Figure 2-2] Shows the RON numbers of the renewable naphtha and gasoline-based fuels used in the examples, as well as the RON numbers of the fully formulated fuel compositions tested in the examples. [Figure 3-1] The two-day test sequence used in the examples is shown below. [Figure 3-2] The two-day test sequence used in the examples is shown below. [Modes for carrying out the invention]

[0018] The first essential component of the fuel composition of the present invention is renewable naphtha. Based on the fuel composition, the renewable naphtha is present at a level in the range of 5% to 65% by volume, preferably 5% to 50% by volume, more preferably 10% to 40% by volume, even more preferably 10% to 30% by volume, and particularly 10% to 20% by volume.

[0019] In one embodiment of the present invention, renewable naphtha is present in a level ranging from 20% to 40% by volume, based on the fuel composition.

[0020] Those skilled in the art will know what the term “naphtha” means. Typically, the term “naphtha” refers to a mixture of hydrocarbons having 5 to 12 carbon atoms and a boiling point in the range of 30 to 200°C. The liquid fuel compositions herein contain naphtha, which is renewable naphtha, also known as renewable naphtha distillate or biorenewable naphtha.

[0021] Renewable naphtha can be obtained from a variety of processes and from a variety of feedstocks. Preferably, the renewable naphtha used herein is obtained as a byproduct of the production of hydrogenated vegetable oil (HVO) (also known as renewable diesel). This involves the hydrogenation of fatty acids and their derivatives, e.g., triglycerides present in fatty acid-containing materials such as animal fats and plant materials. Plant materials may include both plant-based materials such as vegetable oils, and oils obtained from other plants, such as wood oils, e.g., tall oil. Renewable diesel and renewable naphtha distillates can be obtained from the hydrogenation of fatty acids and their derivatives. The hydrogenation of fatty acids and their derivatives may involve deoxygenation reactions such as hydrodeoxygenation (HDO), and may also involve other hydrogenation reactions such as isomerization (e.g., hydroisomerization) and decomposition (e.g., hydrocracking). When renewable diesel is refined, renewable naphtha distillates are also obtained. Renewable naphtha distillates include fractions containing IBP at 30°C or higher and FBP at 200°C or lower. The hydrocarbons present within the distillation range typically range from those containing 4 or 5 carbon atoms to those containing approximately 10, 11, or 12 carbon atoms.

[0022] As an alternative process for producing renewable naphtha, (i) Shell IH 2 Examples include (RTM) processes, integrated processes of hydrothermal decomposition and hydrogenation at moderate pressures (250-500 psi) and temperatures in the range of 350-450°C, (ii) renewable gas-to-liquid (GTL) processes including water electrolysis, catalytic reverse water-gas shift reaction, Fischer-Tropsch synthesis and hydrogenation treatment for producing green hydrogen, and (iii) ethanol-to-gasoline (ETG) processes.

[0023] Renewable fuels, such as renewable naphtha distillates, are collected from resources that are naturally replenished on a human timescale, in contrast to fossil fuels such as petroleum gasoline derived from crude oil refining. Suitable feedstocks for producing renewable fuels include edible and non-edible vegetable oils, animal fats, agricultural waste products and residues, municipal solid waste algal oils, crops of interest, and woody biomass. As used herein, the term renewable naphtha means a naphtha fraction containing biobased carbon atoms as determined according to ASTM Method D6866-10, entitled "Standard Test Methods for Determining the Biobased Content of Solid, Liquid and Gaseous samples using Radiocarbon Analysis." The renewable contents are then determined as described in ASTM D6866. 14 C, 13 C and / or 12 This can be determined by the isotopic distribution including C.

[0024] When renewable naphtha paraffins are obtained from the processing of fatty acid-containing materials such as animal fats and plant materials, the renewable naphtha distillate is paraffinic, contains little naphthene, and is substantially free of aromatic compounds or oxygenated substances.

[0025] The renewable naphtha distillate is mainly composed of paraffins (alkanes) which can be linear n-paraffins or branched isoparaffins. The renewable naphtha used in the present invention has an all-paraffin content of at least 90% by mass, an isoparaffin content of at least 60% by mass, an n-paraffin content of at most 30% by mass, and an isoparaffin to n-paraffin ratio of 3:1 or more. Surprisingly, by selecting renewable naphthas having these amounts of all paraffins, n-paraffins and isoparaffins and including them in a fuel blend together with an alcohol, preferably an alcohol from a renewable source, when used in a spark ignition internal combustion engine, particularly a spark ignition internal combustion engine in a flexible fuel vehicle, it has been found that an improved fuel composition can be produced which shows both a reduction in CO emissions and a reduction in NOx emissions. This is particularly surprising because there is often a trade-off between CO emissions and NO x emissions.

[0026] The renewable naphtha has 90% by volume or more of C5-C 12 paraffins, for example, 95% by volume or more of C5-C 12 paraffins, or 98% by volume or more of C5-C 12 paraffins.

[0027] When the renewable naphtha distillate is produced as part of the purification of renewable diesel as described above, the renewable naphtha distillate may contain 30% by volume or more of C5-C6 paraffins, for example, 40% by volume or more of C5-C6 paraffins.

[0028] The renewable naphtha used in the present invention preferably has an average carbon number greater than 7.0, more preferably greater than 7.1, even more preferably greater than 7.3, particularly greater than 7.37. The relatively heavy average carbon number of the renewable naphtha used in the present invention has been found to provide a surprising reduction in FFV emissions such as PM and NO x compared to gasoline and light renewable naphtha.

[0029] In addition to primarily containing paraffin, renewable naphtha distillates also contain low-content naphthenes (cycloalkanes) having at least one non-aromatic ring structure, where the ring typically has 5 or 6 carbon atoms. The renewable naphtha used herein preferably contains 5% by mass or less of naphthenes, for example, 4% by mass or less of naphthenes, or 3.4% by mass or less of naphthenes.

[0030] In addition to primarily containing paraffin, renewable naphtha distillates also have very low concentrations of aromatic compounds. These aromatic compounds contain benzene rings or other aromatic ring structures. The renewable naphtha used herein preferably has an aromatic content of 0.5% by mass or less, more preferably 0.4% by mass or less (measured according to ASTM D6729).

[0031] In addition to primarily containing paraffin, renewable naphtha distillates also contain very low levels of oxygenates. Oxygenates are organic molecules that contain oxygen as part of their chemical structure and are typically used as gasoline additives to reduce carbon oxides and soot produced during fuel combustion. Common oxygenates include alcohols, ethers, and esters. Renewable naphtha distillates may contain less than 1% by volume of oxygenates, for example, less than 0.5% by volume of oxygenates, or less than 0.1% by volume of oxygenates, but are preferably essentially oxygenate-free.

[0032] The renewable naphtha used herein has a low octane number, i.e., RON and / or MON of 35-70, e.g., 35-60, or 35-50, or 35-45, or 38-42. Surprisingly, despite the low octane quality of renewable naphtha, it has been found that renewable naphtha can be included in the fuel compositions of the present invention at relatively high levels without adversely affecting the Research Octane Number (RON) of the final gasoline fuel composition. This is shown in Figure 2.

[0033] The renewable naphtha distillates used herein preferably have a Reed vapor pressure (measured according to ASTM D5191) in the range of 8 to 30 kPa, more preferably in the range of 10 to 28 kPa, and even more preferably in the range of 25 to 28 kPa. Compared to the 50 to 80 kPa of gasoline, the low Reed vapor pressure of the renewable naphtha distillates used in this invention is surprisingly low compared to CO and NO. x It was found that this reduces FFV emissions such as those mentioned above.

[0034] The renewable naphtha used herein preferably has a specific gravity at 15°C (measured according to ASTM D6729) in the range of 0.660 to 0.715, more preferably in the range of 0.675 to 0.715, even more preferably in the range of 0.680 to 0.705, and particularly in the range of 0.691 to 0.702.

[0035] The renewable naphthas used herein may have a boiling point range of 30 to 200°C, for example, 90 to 200°C, or 40 to 180°C.

[0036] The renewable naphtha component of the present invention is described in International Publication No. 2018 / 069137 and International Publication No. 2018 / 234187. They may be prepared in accordance with the methods provided in International Publication No. 2009 / 148909 and European Patent Application Publication No. 3397734(B1), all of which are incorporated herein by reference in their entirety.

[0037] In preferred embodiments, particularly in spark-ignition internal combustion engines, and especially in flexible fuel vehicles, CO emissions and NO emissions are particularly important. x From the perspective of reducing both emissions, renewable naphtha has the following characteristics: (i) a total paraffin content of at least 90% by mass, an isoparaffin content of at least 60% by mass, an n-paraffin content of up to 30% by mass, and an isoparaffin to n-paraffin ratio of 3:1 or higher; (ii) an aromatic content of 0.5% by mass or less; (iii) a Reed vapor pressure in the range of 8 to 30 kPa; and (iv) a specific gravity at 15°C in the range of 0.660 to 0.715.

[0038] The preferred renewable naphtha component for use in this specification is heavy naphtha, marketed under the trade name "AltAir Paramount Renewable Naphtha, Heavy grade," from the World Energy AltAir Paramount plant in California, USA, which utilizes beef tallow and small amounts of non-edible vegetable oil as feedstocks, and has the physicochemical properties shown in Figure 1.

[0039] In addition to renewable naphtha, the liquid fuel composition of the present invention preferably contains an alcohol component of renewable origin at a level of 35% to 95% by volume, preferably 50% to 95% by volume, more preferably 60% to 90% by volume, even more preferably 70% to 90% by volume, and particularly 80% to 90% by volume, based on the fuel composition. In one embodiment, the renewable alcohol component is present at a level of 51% to 85% by volume, based on the total fuel composition. In another embodiment, the renewable alcohol component is present at a level of 60% to 80% by volume, based on the total fuel composition.

[0040] Suitable alcohols for use herein include methanol, ethanol, propanol, 2-propanol, butanol, tert-butanol, isobutanol, 2-butanol, and mixtures thereof.

[0041] The specific alcohol used herein is ethanol, in particular bioethanol.

[0042] When both alcohol and naphtha are of renewable origin, the proportion of renewable content in the fuel composition increases. Preferably, the fuel composition contains at least 95% by volume of renewable components, more preferably at least 99% by volume of renewable components, and particularly 100% by volume of renewable components.

[0043] While the level of renewable components is preferably as high as possible, the fuel composition of the present invention may also contain one or more petroleum-derived gasoline blend components. If present, the petroleum-derived gasoline blend components may be in the form of a gasoline-based fuel. Preferably, the fuel composition contains up to 10% by volume, more preferably up to 5% by volume, and even more preferably up to 2% by volume of petroleum-derived gasoline blend components. In a particularly preferred embodiment, the fuel composition does not contain petroleum-derived gasoline blend components.

[0044] The fuel composition according to the present invention preferably has a research octane number (RON) in the range of 85 to 105. The fuel composition according to the present invention preferably has a motor octane number in the range of 75 to 90.

[0045] Although not essential to the present invention, the fuel composition of the present invention may conveniently contain one or more optional fuel additives. The concentration and properties of the optional fuel additives that may be included in the fuel composition are not important.

[0046] The concentration of any optional additive (active substance) present in the fuel composition of the present invention is preferably in the range of 1% m / m, more preferably in the range of 5 to 2000 mg / kg, and advantageously in the range of 300 to 1500 mg / kg, for example, 300 to 1000 mg / kg.

[0047] Suitable additives for use in the fuel compositions herein include, for example, ammonium salts of organic carboxylic acids, such as ammonium salts that tend to form a film, or corrosion inhibitors based on heterocyclic aromatic ammonium salts for non-ferrous metal corrosion protection; antioxidants or stabilizers, antistatic agents based on amines such as phenyldiamine, e.g., p-phenylenediamine, N,N'-di-sec-butyl-p-phenyldiamine, dicyclohexylamine, or derivatives thereof, or derivatives of phenols such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid; metallocenes such as ferrocene; methyl-cyclopentadienyltricarbonylmanganese; lubricating additives, e.g., certain fatty acids, alkenyl succinates, bis(hydroxyalkyl) fatty amines, hydroxyacetamide, or castor oil; and dyes (markers). Where appropriate, amines may be added, for example, as described in International Publication No. 03 / 076554. Optionally, anti-valve seat recession additives, such as sodium or potassium salts of polymeric organic acids, may be used.

[0048] The gasoline compositions described herein may also include detergent additives. Suitable detergent additives are those disclosed in International Publication No. 2009 / 50287, which is incorporated herein by reference.

[0049] Preferred detergent additives for use in the gasoline compositions herein typically include at least one hydrophobic hydrocarbon group having a number-average molecular weight (Mn) of 85 to 20,000, (A1) A mono or polyamino group having up to 6 nitrogen atoms, of which at least one nitrogen atom is basic. (A6) A hydroxyl group, a mono or polyamino group having at least one nitrogen atom with basic properties, or a polyoxy-C2-C4 alkylene group terminated by a carbamate group. (A8) A moiety derived from succinic anhydride having a hydroxyl group and / or an amino group and / or an amide group and / or an imide group, and / or (A9) It comprises a substituted phenol and at least one polar moiety selected from moieties obtained by a Mannich reaction with an aldehyde and a mono or polyamine.

[0050] To ensure proper solubility in the base fluid, the hydrophobic hydrocarbon groups in the above-mentioned cleaning additive have a number-average molecular weight (Mn) of 85 to 20,000, particularly 113 to 10,000, and especially 300 to 5,000. Typical hydrophobic hydrocarbon groups particularly related to the polar moieties (A1), (A8), and (A9) include polyalkenes (polyolefins), such as polypropenyl, polybutenyl, and polyisobutenyl groups, each having a Mn of 300 to 5,000, preferably 500 to 2,500, more preferably 700 to 2,300, and especially 700 to 1,000.

[0051] Non-limiting examples of the above-mentioned bases of cleaning additives include the following: Additives containing a mono or polyamino group (A1) are preferably polyalkene monoamines or polyalkene polyamines based on polypropene having 300 to 5000 Mn or conventional (i.e., mainly having internal double bonds) polybutene or polyisobutene. When polybutene or polyisobutene, mainly having internal double bonds (usually at the β and γ positions), is used as a starting material in the preparation of the additive, possible preparation routes are by chlorination and subsequent amination, or by oxidation of the double bonds in air or ozone to form a carbonyl or carboxyl compound and subsequent amination under reducing (hydrogenation) conditions. The amines used here for amination may be, for example, ammonia, monoamine, or polyamine, such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, or tetraethylenepentamine. Corresponding polypropene-based additives are described in particular in International Publication No. 94 / 24231(A).

[0052] More preferred additives containing a monoamino group (A1) are hydrogenation products of reaction products of a nitrogen oxide or a mixture of nitrogen oxide and oxygen of polyisobutene having an average degree of polymerization of 5 to 100, particularly as described in International Publication No. 97 / 03946(A).

[0053] A more preferred additive containing a monoamino group (A1) is a compound obtained from polyisobutene epoxide by reaction with an amine and subsequent dehydration and reduction of the amino alcohol, as described in particular in German Patent No. 196 20 262(A).

[0054] The additive containing the polyoxy-C2~C4-alkylene moiety (A6) is preferably C2-~C 60 - Alkanol, C6-~C 30 -Alkanediol, mono- or di-C2~C 30 -alkylamines, C1~C 30 -Alkylcyclohexanol, or C1-C 30 -Polyethers or polyetheramines are obtained by the reaction of alkylphenols with 1 to 30 moles of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl or amino group, and, in the case of polyetheramines, by subsequent reductive amination with ammonia, monoamine, or polyamine. Such products are described in particular in European Patent No. 310 875(A), European Patent No. 356 725(A), European Patent No. 700 985(A), and U.S. Patent No. 4 877 416(A). In the case of polyethers, such products also have carrier oil properties. Typical examples of these are tridecanol butoxylate, isotridecanol butoxylate, isononylphenol butoxylate, and polyisobutenol butoxylate, and polyisobutenol propoxylate, and the reaction products with the corresponding ammonia.

[0055] Additives (A8) derived from succinic anhydride and containing a moiety having a hydroxyl group and / or an amino group and / or an amide group and / or an imide group are preferably corresponding derivatives of polyisobutenyl succinic anhydride obtained by reacting conventional polyisobutene or highly reactive polyisobutene having 300 to 5000 Mn with maleic anhydride via a thermal route or via chlorinated polyisobutene. Of particular interest are derivatives having aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, or tetraethylenepentamine. Such additives are described in particular in U.S. Patent No. 4,849,572(A).

[0056] Additive (A9), which includes a portion obtained by a Mannich reaction between a substituted phenol and an aldehyde and a mono or polyamine, is preferably a reaction product of a polyisobutene-substituted phenol with formaldehyde and a mono or polyamine, such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, or dimethylaminopropylamine. The polyisobutenyl-substituted phenol may be derived from conventional polyisobutene or highly reactive polyisobutene having a Mn of 300 to 5000. Such "polyisobutene-Mannich bases" are described in particular in European Patent No. 831 141(A).

[0057] Preferably, the detergent additive used in the gasoline composition of the present invention contains at least one nitrogen-containing detergent, more preferably at least one nitrogen-containing detergent containing a hydrophobic hydrocarbon group having a number average molecular weight in the range of 300 to 5000. Preferably, the nitrogen-containing detergent is selected from the group consisting of polyalkene monoamines, polyetheramines, polyalkene mannichamines, and polyalkene succinimides. Conveniently, the nitrogen-containing detergent may be a polyalkene monoamine.

[0058] In the above, the amounts of components (concentration, %v / v, mg / kg (ppm), %m / m) refer to those of the active substance, i.e., excluding volatile solvents / diluent materials.

[0059] The fuel composition of the present invention can be produced by mixing renewable naphtha and alcohol components in appropriate amounts.

[0060] The fuel composition of the present invention is particularly suitable for use in internal combustion engines, such as those used in flexible fuel vehicles.

[0061] The fuel composition of the present invention, when used particularly in spark-ignition internal combustion engines and especially in flexible fuel vehicles, reduces CO emissions and NO emissions. x It has been found to be particularly useful in reducing emissions. Preferably, CO emissions and NO emissions. x The reduction in emissions is compared to an equivalent gasoline-based fuel composition (i.e., one containing conventional gasoline-based fuel instead of renewable naphtha) with the same ethanol content. CO emissions and NO emissions are also reduced. x Emissions can be measured by the bag discharge method in accordance with the vehicle testing procedure of Title 40, Part 1066 of the U.S. Environmental Protection Agency (EPA) Code of Federal Regulations. Accordingly, according to another aspect of the present invention, CO emissions and NO x The use of the above fuel compositions is provided to reduce emissions, and in particular, the fuel compositions are used to refuel an internal combustion engine in a flexible fuel vehicle. The internal combustion engine is preferably a spark-ignition internal combustion engine.

[0062] According to a further aspect of the present invention, CO emissions and NO emissions in a spark-ignition internal combustion engine in the powertrain of a flexible fuel vehicle. x A method is provided for reducing emissions, which involves burning a fuel composition in a spark-ignition internal combustion engine and the CO and NO emissions generated by the spark-ignition internal combustion engine. x This includes measuring the reduction in emissions.

[0063] The use and method of the present invention, which contains petroleum-derived gasoline-based fuel instead of renewable naphtha, preferably exhibits lower CO emissions and NO emissions compared to similar fuel compositions containing the same level and type of ethanol. x Reduce both emissions by at least 5%, more preferably CO emissions and NO emissions. x A reduction of at least 10% in both emissions, more preferably in CO emissions and NO emissions. x This can provide at least a 15% reduction in emissions for both.

[0064] The present invention will be further described with reference to the following non-limiting embodiments. [Examples]

[0065] Several fuel blends having the compositions detailed below were prepared. Each fuel blend contained the same amount of denatured ethanol as indicated. Furthermore, each fuel blend contained either naphtha components or ordinary unleaded gasoline. No additive packages were used in any of the fuel blends.

[0066] Standard fuel 1 (Ref-1) contained 20% by volume of regular unleaded gasoline and 80% by volume of denatured ethanol, having the physicochemical properties shown in Figure 1.

[0067] Standard fuel 2 (Ref-2) contained 40% by volume of regular unleaded gasoline and 60% by volume of denatured ethanol, the same fuel used in Ref-1.

[0068] Standard fuel 3 (Ref-3) contained 15% by volume of regular unleaded gasoline used in Ref-1 and 85% by volume of denatured alcohol.

[0069] Fuel A-E80 contained 20 vol% AltAir Paramount Renewable Naphtha Full Range Grade, a renewable naphtha supplied by AltAir Paramount Refinery of World Energy LLC. in California, USA, having the physicochemical properties shown in Figure 1, and 80% denatured ethanol.

[0070] Fuel A-E60 contained 40 vol% full-range grade AltAir naphtha (the same as used in A-E80) and 60 vol% denatured ethanol.

[0071] Fuel B-E80 contained 20 vol% Neste renewable naphtha / Eni bionaphtha blend and 80 vol% denatured ethanol, supplied from Shell Rotterdam Botlek Tank Terminal in the Netherlands, having the physicochemical properties shown in Figure 1.

[0072] Fuel C-E85 contained 15 vol% gas-liquid (GTL) naphtha supplied from the Shell Pearl plant, Qatar having the physicochemical properties shown in Figure 1, and 85 vol% denatured ethanol.

[0073] Fuel C-E80 contained 20% by volume of GTL naphtha (the same as used in C-E85) and 80% by volume of denatured ethanol.

[0074] Fuel C-E60 contained 40% by volume of GTL naphtha (the same as used in C-E85) and 60% by volume of denatured ethanol.

[0075] Fuel D-E80 contained 20 vol% Ekobenz ethanol-gasoline (ETG), a renewable automotive fuel produced by the ethanol-gasoline process supplied from Ekobenz, Poland, and 80 vol% denatured ethanol, having the physicochemical properties shown in Figure 1. The ETG process for producing such an ETG product is described in particular in European Patent Application Publication No. 2940103(A1).

[0076] Fuel-D-E60 contained 40% by volume of Ekobenz ETG automotive fuel (the same as used in D-E80) and 60% by volume of denatured ethanol.

[0077] Fuel E-E80 contained 20 vol% AltAir Paramount Renewable Naphtha Heavy Grade, a renewable naphtha supplied by the World Energy AltAir Paramount plant in California, USA, having the physicochemical properties shown in Figure 1, and 80 vol% denatured ethanol.

[0078] Fuel E-E60 contained 40% by volume of heavy AltAir naphtha (the same as used in E-E80) and 60% by volume of denatured ethanol.

[0079] Detailed hydrocarbon analyses (DHA) (according to ASTM D6729 and D6730 test methods) of various naphthas and gasolines used in fuel blends are shown in Figure 1. In Figure 1, graph (a) shows the normal paraffin and isoparaffin content, graph (b) shows the naphthene content, (c) shows the average carbon number, graph (d) shows the specific gravity, graph (e) shows the aromatic content, and graph (f) shows the RON of neat bionaphtha samples.

[0080] The RON values ​​of neat bionaphtha and gasoline were calculated from detailed hydrocarbon analysis, while the RON values ​​of all high-ethanol blends were measured using the ASTM D2699 test method. These RON values ​​can be seen in Figure 2. Given the low RON value of bionaphtha, the high RON values ​​of the final fuel compositions are surprising.

[0081] To test the performance of the above fuel, a 2021 Ford Transit Connect Flexible Fuel vehicle equipped with a 2.0-liter gasoline direct injection (GDI) i-4 engine with automatic start-stop technology and an 8-speed SelectShift (RTM) automatic transmission was used for vehicle testing, producing 162 hp at 6,500 rpm and 144 lb.ft. of torque at 4,500 rpm. Further details of the vehicle specifications are provided in Table 1 below.

[0082] [Table 1]

[0083] Each candidate fuel was tested against a standard fuel according to the two-day test sequence shown in Figure 3. The Worldwide Harmonized Light Duty Vehicles Test Procedure (WLTP) (industry standard test procedure) was selected, and emissions (CO, CO2, total hydrocarbons (THC), NO) were measured during each WLTP driving cycle. x Emissions and particulate matter (PM) and fuel economy were measured. The first step each day involved a cold start WLTP test where the emissions and fuel economy of the candidate fuel were measured. This was followed by a hot start WLTP ABABAB test sequence (A being the standard fuel and B being the candidate fuel). On the second day of the test sequence, three run performance tests were conducted, including acceleration, a steady-state power check, and a coast-down (for the final run only). Acceleration time was measured at 10–60 miles per hour (mph) with the throttle fully open. The steady-state power check involved measuring the peak power engine RPM, which was then converted to power in horsepower units. Coast-down time was measured at 70–30 mph, with dynamometer verification to ensure there was no drift.

[0084] Table 2 provides results for CO emissions, NOx emissions, cold-start and hot-start PM emissions, fuel economy, acceleration, and power output for fuel compositions containing AltAir heavy naphtha (E-E60 and E-E80) and standard gasoline-based flex fuels (E80 and E60). All metrics in Table 2 (and Table 3) were measured according to the U.S. Code of Federal Regulations, Title 40, Part 1066 - Vehicle Test Procedure. All results in Tables 2 and 3 are averaged over the number of test runs.

[0085] [Table 2]

[0086] The key findings from all experiments are summarized in Table 3 below, which shows a comparison between candidate fuels and standard fuels from the same two-day test sequence.

[0087] The key points of Table 3 are as follows: "Yes" means that the candidate fuel performs better than standard in both E60 and E80. "O" means that the candidate fuel is the same as the standard for both E60 and E80. "x" means that the candidate fuel is worse than standard for both E60 and E80.

[0088] [Table 3]

[0089] From Table 3, E80 and E60 (E-E80 and E-E60), which include AltAir heavy naphtha, are candidates that meet six of the nine parameters measured (i.e., CO emissions, NO emissions). xSince emissions, CO2 emissions, cold-start and warm-start particulate matter (PM) emissions, and fuel economy are better than standard, and the remaining three parameters (i.e., THC emissions, 10-60 mph acceleration, and steady-state power) are the same as standard, it can be understood that this provides the best overall result.

[0090] In contrast, E80 and E60 (A-E80 and A-E60), which contain AltAir full-range naphtha, performed better than the standard for only two of the nine parameters measured (i.e., CO emissions and cold-start PM). E80 (B-E80), which contains Neste / ENI naphtha, performed better than the standard for only two of the nine parameters measured (i.e., CO2 emissions and cold-start particulate matter). E80 and E60, which contain GTL naphtha, performed better than the standard for only four of the nine parameters measured (i.e., CO emissions, CO2 emissions, cold-start particulate matter, and hot-start particulate matter). E80 and E60 (D-E80 and D-E60), which contain Ekobenz ETG naphtha, performed better than the standard for only one of the nine parameters measured (i.e., CO emissions).

[0091] E80 and E60 (E-E80 and E-E60), which include AltAir heavy naphtha, are NO x It was the only fuel blend that performed better than the standard in terms of both emissions and CO emissions. x This is particularly surprising, as there is usually a trade-off between emissions and CO2 emissions.

Claims

1. A fuel composition, (i) 35% to 95% by volume of renewable alcohol components, (ii) A fuel composition comprising 5% to 65% by volume of renewable naphtha components, wherein the renewable naphtha components have a total isoparaffin and n-paraffin content of at least 90% by mass, an isoparaffin content of at least 60% by mass, an n-paraffin content of less than 30% by mass, and an isoparaffin to n-paraffin ratio greater than 3:

1.

2. The fuel composition according to claim 1, wherein the renewable naphtha component has a specific gravity in the range of 0.660 to 0.

715.

3. The fuel composition according to claim 1 or 2, wherein the renewable naphtha component has an aromatic content of 0.5% by mass or less.

4. The fuel composition according to any one of claims 1 to 3, wherein the renewable naphtha component has an average carbon number greater than 7.

37.

5. The fuel composition according to any one of claims 1 to 4, wherein the renewable naphtha component comprises less than 5% by mass of naphthene.

6. The fuel composition according to any one of claims 1 to 5, wherein the renewable naphtha component has an RVP in the range of 8 to 30 kPa.

7. The fuel composition according to any one of claims 1 to 6, wherein the fuel composition comprises 80% to 90% by volume of the renewable alcohol component.

8. The fuel composition according to any one of claims 1 to 7, wherein the fuel composition comprises 10% to 20% by volume of the renewable naphtha component.

9. The fuel composition according to any one of claims 1 to 8, wherein the renewable alcohol component is ethanol.

10. CO emissions and NO ｘ Use of the fuel composition according to any one of claims 1 to 9 for reducing emissions.

11. The use according to claim 10, wherein the fuel composition is used in a spark-ignition internal combustion engine of a flexible fuel vehicle.

12. CO emissions and NO emissions from spark-ignition internal combustion engines in the powertrains of flexible fuel vehicles. ｘ A method for reducing emissions, comprising burning a fuel composition in a spark-ignition internal combustion engine, and reducing CO emissions and NO emissions generated by the spark-ignition internal combustion engine. ｘ A method that includes measuring the reduction of emissions.

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