Fuel composition

Abstract

A gasoline fuel composition for a spark-ignition internal combustion engine comprising (a) a gasoline blending component, (b) a renewable naphtha at a level of 10-30% v / v and (c) an oxygenated hydrocarbon at a level of 20% v / v or less, wherein the gasoline blending component comprises (a) 0-30% v / v alkylate, (b) 0-15% v / v isomerate; (c) 0-20% v / v catalytic cracking overhead naphtha; and (d) 20-40% v / v heavy reformate, wherein the total amount of alkylate, isomerate, catalytic cracking overhead naphtha and heavy reformate is at least 50% v / v based on the total fuel composition, and wherein the gasoline fuel composition meets EN228 specification. While the low octane number of renewable naphtha would normally severely limit its blendability in gasoline to low levels, it has now been discovered that renewable naphtha can be included in, for example, ethanol-containing gasoline fuel compositions at surprisingly and significantly high renewable naphtha to ethanol blending ratios.

Description

Technical Field

[0001] The present invention is in the field of fuel formulations, in particular gasoline-type fuel formulations for spark-ignition internal combustion engines. Background Art

[0002] Fuels are typically produced by refining crude oil (petroleum). This typically involves separating the various fractions of crude oil by distillation. One such fraction is naphtha, which is a volatile liquid fraction distilled between the light gaseous components of crude oil and the heavier kerosene fraction. Naphtha contains a mixture of hydrocarbons (straight chain alkanes, branched chain alkanes, cycloalkanes and aromatic hydrocarbons) with boiling points between about 30°C and about 200°C. The density of naphtha is typically 750-785 kg / m 3 Naphtha has many uses, one of which is as a motor fuel.

[0003] Although the longer chain molecules in gasoline have a high cetane number and can be blended into diesel, naphtha has historically not been used in gasoline, or has been used only in low quantities, due to its low octane number. This is despite naphtha having distillation properties comparable to gasoline.

[0004] Renewable fuels ("biofuels") derived from biomass are increasingly being used as more sustainable alternatives to fossil fuels. Due to the increase in the production of renewable naphtha in recent years, it is advantageous to be able to blend renewable naphtha into gasoline, particularly to blend it into gasoline with a high blending ratio. Renewable naphtha using a higher blending ratio has the advantage of being able to achieve higher CO2 emission reductions, and can contribute to meeting the prescribed emission reduction targets specified in the Paris Agreement (2016). At the same time, it is desirable to be able to formulate a gasoline fuel composition that meets existing gasoline fuel specifications, such as, but not limited to, EN228 and North American specifications, such as ASTM D4814-13b, U.S. Conventional, CaRFG Phase 3, Federal RFG Phase II, CAN / CGSB-3.5.

[0005] WO2017 / 093203 discloses a liquid fuel composition for a spark-ignition internal combustion engine, comprising (a) a gasoline blending component, (b) a Fischer-Tropsch derived naphtha at a level of up to 50% v / v and (c) an oxygenated hydrocarbon at a level of less than 50% v / v.

[0006] US2009 / 300971 discloses a naphtha composition produced from a renewable feedstock, wherein the naphtha has a boiling point range of about 70°F to about 400°F and a specific gravity of about 0.680 to about 0.740 at 20°C. In one embodiment, the renewable naphtha is used as an alternative gasoline fuel for an internal combustion engine when blended with ethanol at 1-85% by volume.

[0007] WO2018 / 234187 relates to a method for producing renewable base oils, diesel and naphtha from biologically derived feedstocks. However, no specific gasoline fuel formulation containing renewable naphtha produced in the method is disclosed in WO2018 / 234187.

[0008] WO2018 / 069137 relates to a method for preparing an alkylated gasoline composition comprising renewable naphtha and isooctane and isopentane. The examples of alkylated gasoline in Table 2 contain up to 5% by volume of renewable naphtha. The gasoline composition in this application does not contain oxygenates and focuses on small general-purpose gasoline engines for various portable gasoline-powered tools such as chain saws and lawn mowers.

[0009] US9885000B2 relates to a renewable hydrocarbon composition obtainable from renewable biological raw materials. The composition can be used as a fuel component.

[0010] WO2009 / 148909 relates to a process for producing a naphtha product from a renewable feedstock. The renewable naphtha product can be used as a fuel or a fuel blendstock.

[0011] Although the low octane number of renewable naphtha would normally severely limit its blendability in gasoline to low levels, the inventors have now discovered that renewable naphtha can be included in, for example, ethanol-containing gasoline fuel compositions at surprisingly and significantly high blending ratios of renewable naphtha (e.g., high blending ratios of renewable naphtha with ethanol) while still meeting gasoline fuel specifications such as, but not limited to, EN228 and North American specifications, e.g., ASTM D4814-13b, U.S. Conventional, CaRFG Phase 3, Federal RFG Phase II, CAN / CGSB-3.5. Summary of the invention

[0012] According to a first aspect of the present invention, there is provided a gasoline fuel composition for a spark-ignition internal combustion engine comprising (a) a gasoline blending component, (b) a renewable naphtha at a level of 10-30% v / v and (c) an oxygenated hydrocarbon at a level of 20% v / v or less,

[0013] wherein the gasoline blending components comprise (a) 0-30% v / v alkylate, (b) 0-15% v / v isomerate, (c) 0-20% v / v catalytic cracking tops (CCT) naphtha; and (d) 20-40% v / v heavy reformate, wherein the total amount of alkylate, isomerate, catalytic cracking tops (CCT) naphtha and heavy reformate is at least 50% v / v based on the gasoline fuel composition,

[0014] And wherein the gasoline fuel composition meets EN228 fuel specification.

[0015] According to another aspect of the present invention, there is provided a method for preparing a liquid fuel composition comprising blending (a) a gasoline blending component, (b) a renewable naphtha at a level of 10-30% v / v and (c) an oxygenated hydrocarbon at a level of 20% v / v or less,

[0016] wherein the gasoline blending components comprise (a) 0-30% v / v alkylate, (b) 0-15% v / v isomerate, (c) 0-20% v / v catalytic cracking tops (CCT) naphtha; and (d) 20-40% v / v heavy reformate, wherein the total amount of alkylate, isomerate, catalytic cracking tops (CCT) naphtha and heavy reformate is at least 50% v / v based on the gasoline fuel composition,

[0017] And wherein the gasoline fuel composition meets EN228 specifications.

[0018] The present invention enables the use of renewable naphtha at significantly higher blending ratios in gasoline, thereby providing a significant new outlet for renewable naphtha fuels.

[0019] The present inventors have surprisingly discovered that by blending gasoline blending components at specific concentrations and ratios, the limitations typically imposed by the low octane rating of renewable naphtha can be overcome.

[0020] Furthermore, the fuel composition of the present invention has the advantage of meeting the requirements of the EN228 fuel specification.

[0021] It has also been surprisingly found that the fuel compositions of the present invention have higher RON values ​​than expected.

[0022] The liquid fuel composition of the present invention also provides excellent fuel economy, emission and power benefits according to the requirements of EN228 specification. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 is a graphical representation of the results shown in Table 6.

[0024] Figure 2 is a graphical representation of the results shown in Table 7. DETAILED DESCRIPTION

[0025] The liquid fuel composition of the present invention comprises a gasoline blending component, such as a gasoline base fuel suitable for internal combustion engines, 10-30% v / v level of renewable naphtha and (c) 20% v / v or less level of oxygenated hydrocarbons. Thus, the liquid fuel composition of the present invention is a gasoline composition.

[0026] As used herein, the term "comprising" is intended to mean including at least the stated components, but may also include other components not specified.

[0027] Liquid fuel compositions herein include naphtha. Those skilled in the art will know the meaning of the term "naphtha". Typically, the term "naphtha" means a mixture of hydrocarbons typically having 5-12 carbon atoms and a boiling point in the range of 30°C to 200°C. Liquid fuel compositions herein include naphtha, which is renewable naphtha, also referred to as renewable naphtha distillate, or bio-renewable naphtha.

[0028] Renewable naphtha distillate can be produced as part of renewable diesel refining. Renewable diesel can be obtained from the processing of materials such as animal fats, algae and plant materials containing fatty acids. Plant materials may include vegetable-based materials, such as rapeseed oil and oils obtained from other plants, such as oils from trees, such as tall oil. Renewable diesel and renewable naphtha distillate can be obtained by hydrotreating of fatty acids and their derivatives such as triglycerides. Hydrotreating of fatty acids and their derivatives involves deoxygenation reactions, such as hydrodeoxygenation (HDO), and may also involve other hydrotreating reactions, such as isomerization (e.g., hydroisomerization) and cracking (e.g., hydrocracking). When refining renewable diesel, a renewable naphtha distillate is obtained. The distillate may have an initial boiling point (IBP) of about 30°C or about 35°C and a final boiling point (FBP) of about 200°C or about 205°C. The hydrocarbons present in this distillation generally range from hydrocarbons containing 4 or 5 carbon atoms to hydrocarbons containing about 10 or 11 or 12 carbon atoms.

[0029] Renewable fuels such as renewable naphtha distillate are collected from resources that replenish naturally on a human time scale, in contrast to fossil fuels such as petroleum gasoline derived from crude oil refining. Renewable naphtha distillate can be obtained by hydrotreating fatty acids and their derivatives present in fatty acid-containing materials such as animal fats and plant materials, the hydrotreating including hydrodeoxygenation and hydroisomerization, and the renewable naphtha distillate can include a fraction having an IBP of 30°C, such as an IBP of 30°C or higher, and a FBP of 200°C, such as a FBP of 200°C or lower. The term renewable naphtha as used herein 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 fraction can then be determined by a method involving 14C. 13 C and / or 12 The renewable content is determined by the isotopic distribution of C as described in ASTM D6866.

[0030] Because the paraffins of renewable naphtha are obtained from the processing of fatty acid-containing materials, such as animal fats and plant materials, the renewable naphtha distillate is paraffinic with little to no cycloparaffins and little to no aromatics or oxygenates.

[0031] Renewable naphtha distillate is mainly composed of paraffins (alkanes), which can be straight-chain normal paraffins or branched iso-paraffins. Renewable naphtha can have 90% by volume or more of C5-C 12 Paraffins, such as 95% by volume or more of C5-C 12 Paraffins, or 98% by volume or more of C5-C 12 Chain alkanes.

[0032] When the renewable naphtha distillate is produced as part of refining renewable diesel as described above, the renewable naphtha distillate may contain 30 vol% or more, such as 40 vol% or more, of C5-C6 paraffins.

[0033] In addition to containing mainly paraffins, the renewable naphtha distillate also has a low content of naphthenes (cycloalkane), which are alkanes having at least one non-aromatic ring structure, wherein the ring generally has 5 or 6 carbon atoms. The renewable naphtha distillate may have 5 volume % or less of cycloalkanes, such as 1 volume % or less of cycloalkanes, or 0.5 volume % or less of cycloalkanes.

[0034] In addition to containing mainly paraffins, the renewable naphtha distillate also has a very low content of aromatics. Aromatic compounds contain benzene rings or other aromatic ring structures. The renewable naphtha distillate may have 1 volume % or less aromatics, such as 0.5 volume % or less aromatics, or 0.1 volume % or less aromatics.

[0035] In addition to containing mainly paraffins, renewable naphtha distillates also have very low levels of oxygenates. Oxygenates are organic molecules that contain oxygen as part of their chemical structure and are commonly used as gasoline additives to reduce carbon oxides and smoke produced during fuel combustion. Common oxygenates include alcohols, ethers, and esters. Renewable naphtha distillates may have 1 volume % or less of oxygenates, such as 0.5 volume % or less of oxygenates, or 0.1 volume % or less of oxygenates, although it is preferably substantially free of oxygenates.

[0036] The renewable naphtha used herein has a low octane number, i.e., for example, has a RON and / or MON of 35 to 70, such as 35 to 60, or 35 to 50, or 35 to 45. It has been surprisingly found that, despite the low octane quality of the renewable naphtha, it can be included in the gasoline fuel composition of the present invention at relatively high levels, and the final gasoline fuel composition has a higher octane number (RON) than expected.

[0037] The renewable naphtha distillate may have a vapor pressure of less than 30 kPa, such as less than 25 kPa, such as less than 20 kPa. The vapor pressure of the renewable naphtha may also be 10 kPa or more, such as 15 kPa or more.

[0038] In a preferred embodiment, the renewable naphtha used herein comprises: 90% by volume or more of C5-C 12 Paraffins, 30 volume % or more of C5-C6 paraffins, 5 volume % or less of cycloparaffins, 1 volume % or less of aromatics, 1 volume % or less of oxygen-containing compounds.

[0039] The renewable naphtha distillate may have a boiling point range of 30°C to 200°C, such as 90°C to 200°C, or 40°C to 180°C.

[0040] The amount of renewable naphtha present in the gasoline fuel composition of the present invention is 10-30% by volume, preferably 15-25% by volume, even more preferably 18-22% by volume, and in particular 20% by volume, based on the total fuel composition. In order to increase the renewable part of the gasoline composition of the present invention, it is preferred to add as much renewable naphtha as possible.

[0041] The renewable naphtha may comprise an iso-paraffin / normal-paraffin ratio greater than 1, such as greater than 1.2, for example between 1 and 2.

[0042] The renewable naphtha component of the present invention can be prepared according to the methods provided in WO2018 / 069137, WO2018 / 234187, US9885000B2 and WO2009 / 148909, all of which are incorporated herein by reference in their entirety. These references also provide further details of the chemical and physical properties of the renewable naphtha component.

[0043] The renewable naphtha component is commercially available from Neste Oyj, Finland under the trade name Neste renewable naphtha (also known as NexNaphtha). The renewable naphtha component is also commercially available from UPM under the trade name BioVerno naphtha.

[0044] In the liquid fuel compositions herein, the renewable naphtha component of the present invention may include a mixture of two or more renewable naphthas, or a mixture of a renewable naphtha with a petroleum-derived naphtha and / or a Fischer-Tropsch derived naphtha.

[0045] By "Fischer-Tropsch derived" is meant that the naphtha is the product of or derived from the product of the Fischer-Tropsch synthesis process (or Fischer-Tropsch condensation process). Fischer-Tropsch derived naphtha may also be referred to as GTL (gas to liquid) naphtha. Further details of GTL naphtha may be found in WO2017 / 093203, which is incorporated herein by reference in its entirety.

[0046] It will be appreciated by those skilled in the art that the gasoline blending component may already contain some naphtha components. The above mentioned concentrations of naphtha refer to the concentration of naphtha added to the liquid fuel composition as a blend with the gasoline blending component and do not include the concentration of any naphtha component already present in the gasoline blending component.

[0047] In addition to renewable naphtha, the liquid fuel composition of the present invention also comprises oxygenated hydrocarbons at 20% by volume or less, preferably 5-15% by volume level, based on the liquid fuel composition. In one embodiment, the oxygenated hydrocarbons are present at a level of 7-12% by volume based on the liquid fuel composition. In another embodiment, the oxygenated hydrocarbons are present at a level of 10-15% by volume based on the liquid fuel composition.

[0048] It will be appreciated by those skilled in the art that the gasoline base fuel may already contain some oxygenated hydrocarbon components. The above oxygenated hydrocarbon concentrations refer to the concentration of oxygenated hydrocarbons added to the liquid fuel composition as a blend with the gasoline base fuel, and do not include the concentration of any oxygenated hydrocarbon components already present in the gasoline base fuel.

[0049] Examples of suitable oxygenated hydrocarbons that may be blended into gasoline include alcohols, ethers, esters, ketones, aldehydes, carboxylic acids and their derivatives, and oxygen-containing heterocyclic compounds and mixtures thereof. In one embodiment of the present invention, the oxygenated hydrocarbon is selected from alcohols, ethers and esters and mixtures thereof.

[0050] Suitable alcohols for use herein include methanol, ethanol, propanol, 2-propanol, butanol, tert-butyl alcohol, isobutyl alcohol, 2-butanol and mixtures thereof. Suitable ethers for use herein include ethers containing 5 or more carbon atoms per molecule, such as methyl tert-butyl ether and ethyl tert-butyl ether and mixtures thereof. A preferred ether for use herein is ethyl tert-butyl ether (ETBE). Suitable esters for use herein include esters containing 5 or more carbon atoms per molecule.

[0051] The oxygenated hydrocarbon is preferably selected from alcohols, ethers and mixtures thereof. In a preferred embodiment of the invention, the oxygenated hydrocarbon is selected from alcohols, preferably at a level of 0.1-10% v / v, more preferably at a level of 5-10% v / v, based on the total gasoline fuel composition. In another embodiment of the invention, the oxygenated hydrocarbon is selected from ethers, preferably at a level of 0.1-15% v / v, based on the total gasoline fuel composition. In another preferred embodiment of the invention, the oxygenated hydrocarbon is a mixture of an alcohol and an ether, such as a mixture of at least one alcohol and at least one ether, preferably comprising 5-10% v / v of an alcohol and 2-5% v / v of an ether, based on the gasoline fuel composition.

[0052] A particularly preferred oxygenated hydrocarbon for use herein is ethanol. Ethanol is preferably present in the fuel composition herein at a level of 0.1-10% v / v, more preferably 5-10% v / v based on the total gasoline fuel composition. In one embodiment of the invention, ethanol is present as the only oxygenated hydrocarbon.

[0053] A particularly preferred ether for use as the oxygenated hydrocarbon herein is ETBE. In one embodiment of the invention, ETBE is present in the fuel composition herein at 0.1-15% v / v based on the total gasoline fuel composition. In another embodiment of the invention, ETBE is present as the sole oxygenated hydrocarbon.

[0054] In a particularly preferred embodiment of the present invention, the oxygenated hydrocarbon herein is a mixture of ethanol and ETBE comprising 5-10% v / v ethanol and 2-5% v / v ETBE based on the total gasoline fuel composition.

[0055] When both the oxygenated hydrocarbon and naphtha are of renewable origin, the share of renewable content in the gasoline composition increases. For example, bioethanol can be used as the oxygenated hydrocarbon herein.

[0056] The liquid fuel composition of the present invention comprises a gasoline blending component. The gasoline blending component comprises (a) 0-30% v / v alkylate, (b) 0-15% v / v isomerate; (c) 0-20% v / v catalytic cracking overhead; and (d) 20-40% v / v heavy reformate, wherein the total amount of alkylate, isomerate, catalytic cracking overhead and heavy reformate is at least 50% v / v based on the total fuel composition.

[0057] In the liquid fuel composition of the present invention, the gasoline blending component may be a gasoline base fuel comprising the above-mentioned components (a), (b), (c) and (d).

[0058] Conventional gasoline blending components are present in a major amount in a gasoline or liquid fuel composition, such as greater than 50% v / v of the liquid fuel composition, and may be present in an amount of up to 90% v / v, or 95% v / v, or 99% v / v, or 99.9% v / v, or 99.99% v / v, or 99.999% v / v. Suitably, the liquid fuel composition contains or consists essentially of a combination of the gasoline blending component and 10-30% v / v of renewable naphtha and 20% v / v or less levels of oxygenated hydrocarbons and optionally one or more conventional gasoline fuel additives (as described below).

[0059] The gasoline blending component comprises 0-30% v / v, preferably 15-30% v / v, more preferably 15-25% v / v alkylate based on the total gasoline fuel composition.

[0060] Alkylate is a complex combination of hydrocarbons produced by distillation of the reaction products of isobutane and monoolefins generally ranging in carbon number from C3 to C5. Alkylate is a refinery stream and is composed primarily of hydrocarbons ranging in carbon number from C7 to C5. 12 The composition is branched chain saturated hydrocarbons having a temperature range of 0.1 to 0.25 °C and a boiling point range of about 90°C to 220°C (194°F to 428°F).

[0061] The gasoline blending component comprises 0-15% v / v, preferably 5-10% v / v of isomerate based on the total gasoline fuel composition.

[0062] Isomerate is a complex combination of hydrocarbons obtained by catalytic isomerization of linear paraffinic C4 to C6 hydrocarbons. Isomerate is a refinery stream and consists primarily of saturated hydrocarbons such as isobutane, isopentane, 2,2-dimethylbutane, 2-methylpentane, and 3-methylpentane, and has a boiling point in the range of approximately 35°C to 220°C (95°F to 428°F).

[0063] The gasoline blending component comprises 20-40% v / v heavy reformate based on the total gasoline fuel composition, provided that the total amount of alkylate, isomerate, catalytic cracking overheads and heavy reformate in the final fuel composition is at least 50% v / v based on the total gasoline fuel composition.

[0064] In one embodiment of the invention, the gasoline blending component comprises 30-35% v / v heavy reformate based on the total fuel composition. In another embodiment of the invention, the gasoline blending component comprises 20-25% v / v heavy reformate based on the total fuel composition.

[0065] Heavy reformate (or heavy catalytic reformed naphtha) is a complex combination of hydrocarbons produced by distillation of products from a catalytic reforming process. Heavy reformate is mainly composed of hydrocarbons with carbon numbers ranging mainly from C7 to C 12 Heavy reformate is a refinery stream rich in aromatics and high octane components (typically 98-102 RON) depending on requirements, unit type and naphtha feed and is used for motor gasoline blending or as a feedstock.

[0066] The gasoline blending component comprises 0-20% v / v, preferably 5-20% v / v of catalytic cracking overheads based on the total fuel composition, provided that the total amount of alkylate, isomerate, catalytic cracking overheads and heavy reformate in the final fuel composition is at least 50% v / v based on the total fuel composition.

[0067] CCT naphtha (or light catalytic cracking naphtha), also known as FCC naphtha (fluid catalytic cracking naphtha), is a complex combination of hydrocarbons produced by distilling products from a fluid catalytic cracking process. Fluid catalytic cracking (FCC) is widely used to convert high boiling point, high molecular weight hydrocarbon fractions of petroleum crude oil into more valuable gasoline, olefinic gases and other products. The FCC end products are cracked petroleum naphtha, fuel oil and waste gas. After further treatment to remove sulfur compounds, cracked naphtha becomes a high octane component of the blended gasoline in the refinery. CCT naphtha / FCC naphtha consists of hydrocarbons with carbon numbers mainly in the range of C4 to C11 and boiling points in the range of about -20°C to 190°C (-4°F to 374°F). CCT naphtha / FCC naphtha is a refinery stream and, depending on requirements, unit type and naphtha feed, contains a relatively large proportion of unsaturated hydrocarbons and is used for motor gasoline blending or as a feedstock. CCT naphtha / FCC naphtha has CAS number 64741-55-5.

[0068] The liquid fuel composition according to the invention has a research octane number (RON) in the range of 85 to 105, for example meeting Eurocode 95 or premium grade 98. The liquid fuel composition used in the invention has a motor octane number in the range of 75 to 90.

[0069] Although not critical to the present invention, the gasoline composition of the present invention can conveniently include one or more optional fuel additives. The concentration and properties of the optional fuel additives that can be included in the gasoline blending component of the present invention or the gasoline composition are not critical. Non-limiting examples of suitable types of fuel additives that can be included in the gasoline blending component of the present invention or the gasoline composition include antioxidants, corrosion inhibitors, detergents, defogging agents, antiknock additives, metal deactivators, valve seat shrinkage protective agent compounds, dyes, solvents, carrier fluids, diluents and markers. Examples of suitable such additives are generally described in U.S. Patent number 5,855,629.

[0070] Conveniently, the fuel additive may be blended with one or more solvents to form an additive concentrate, and the additive concentrate may then be mixed with the gasoline blending component or gasoline composition of the present invention.

[0071] The (active matter) concentration of any optional additive present in the gasoline blending component or gasoline composition of the invention is preferably up to 1% m / m, more preferably in the range 5-2000 mg / kg, advantageously in the range 300-1500 mg / kg, such as 300-1000 mg / kg.

[0072] As stated above, the gasoline composition may also contain synthetic or mineral carrier oils and / or solvents.

[0073] Examples of suitable mineral carrier oils are fractions obtained in crude oil processing, such as bright stock or base oils having a viscosity of, for example, SN 500-2000; and aromatics, paraffins and alkoxyalkanols. Also useful as mineral carrier oils are fractions obtained in mineral oil refining and known as "hydrocracked oils" (vacuum fractions, boiling in the range of about 360° C. to 500° C., obtainable from natural mineral oils catalytically hydrogenated under high pressure and isomerized and dewaxed).

[0074] Examples of suitable synthetic carrier oils are: polyolefins (poly-alpha-olefins or poly(internal olefins)), (poly)esters, (poly)alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-initiated polyethers, alkylphenol-initiated polyetheramines and carboxylic acid esters of long-chain alkanols.

[0075] Examples of suitable polyolefins are olefin polymers, in particular olefin polymers based on polybutene or polyisobutene (hydrogenated or non-hydrogenated).

[0076] Examples of suitable polyethers or polyetheramines are preferably compounds containing polyoxy-C2-C4-alkylene moieties, which can be obtained by 60 -Alkanol, C6-C 30 -alkanediol, mono- or di-C2-C 30 -alkylamine, C1-C 30-alkylcyclohexanol or C1-C 30 -alkylphenols are obtained by reacting 1 mol to 30 mol 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, monoamines or polyamines. Such products are described in particular in EP-A-310 875, EP-A-356 725, EP-A-700 985 and US-A-4,877,416. For example, the polyetheramines used can be poly-C2-C6-oxyalkyleneamines or functional derivatives thereof. Typical examples thereof are tridecanol butoxylates or isotridecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates, and the corresponding reaction products with ammonia.

[0077] Examples of carboxylic acid esters of long-chain alkanols are in particular esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, as described in particular in DE-A-38 38 918. The mono-, di- or tricarboxylic acids used may be aliphatic or aromatic acids; suitable ester alcohols or polyols are in particular long-chain representatives having, for example, 6 to 24 carbon atoms. Typical representatives of esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctyl, isononyl, isodecanol and isotridecanol, for example di(n-tridecyl or isotridecyl)phthalate.

[0078] Further suitable carrier oil systems are described, for example, in DE-A-38 26 608, DE-A-41 42 241, DE-A-43 09 074, EP-A-0 452 328 and EP-A-0 548 617, which are incorporated herein by reference.

[0079] Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers having about 5 to 35, for example about 5 to 30, C3-C6-alkylene oxide units, for example selected from propylene oxide, n-butylene oxide and isobutylene oxide units or mixtures thereof. Non-limiting examples of suitable starting alcohols are long-chain alkanols or phenols substituted with long-chain alkyl groups, wherein the long-chain alkyl groups are in particular straight-chain or branched C6-C6-alkylene oxides. 18 Preferred examples include tridecanol and nonylphenol.

[0080] Further suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A-10 102 913.6.

[0081] Mineral carrier oils, synthetic carrier oils, and mixtures of mineral and synthetic carrier oils may also be used.

[0082] Any solvent and optional co-solvent suitable for use in the fuel may be used. Examples of suitable solvents for the fuel include: non-polar hydrocarbon solvents such as kerosene, heavy aromatic solvents ("mineral spirit heavy", "Solvesso 150"), toluene, xylene, paraffin, petroleum, white spirits, those sold under the trade name "SHELLSOL" by Shell companies, etc. Examples of suitable co-solvents include: polar solvents such as esters, and in particular alcohols (e.g. tert-butyl alcohol, isobutyl alcohol, hexanol, 2-ethylhexanol, 2-propylheptanol, decanol, isotridecanol, butyl glycol and alcohol mixtures such as those sold under the trademark "LINEVOL" by Shell companies, in particular LINEVOL 79 alcohol, which is C 7-9 A mixture of primary alcohols, or C 12-14 alcohol mixture, which is commercially available).

[0083] Dehazers / emulsifiers suitable for use with liquid fuels are well known in the art. Non-limiting examples include glycol oxyalkylated polyol blends (such as those sold under the trade name TOLAD TM 9312 sold), alkoxylated phenol formaldehyde polymers, by using C 1-18 Epoxide and diepoxide oxyalkylated phenol / formaldehyde or C 1-18 Alkylphenol / formaldehyde resin oxyalkylates (such as those sold under the trade name TOLAD TM 9308), and C crosslinked with diepoxides, diacids, diesters, diols, diacrylates, dimethacrylates or diisocyanates. 1-4 Epoxide copolymers, and blends thereof. The glycol oxyalkylated polyol blend can be prepared using C 1-4 Epoxide oxyalkylated polyols. 18 Epoxide and diepoxide alkoxylated C 1-18 The alkylphenol / formaldehyde resin alkoxylate may be based on, for example, cresol, tert-butylphenol, dodecylphenol or dinonylphenol, or a mixture of phenols (such as a mixture of tert-butylphenol and nonylphenol). The amount of defogging agent used should be sufficient to suppress the fogging that may occur when gasoline without the defogging agent comes into contact with water, and this amount is referred to herein as the "fog suppression amount". Typically, this amount is about 0.1-20 mg / kg (e.g., about 0.1-10 mg / kg), more preferably 1-15 mg / kg, still more preferably 1-10 mg / kg, advantageously 1-5 mg / kg, based on the weight of the gasoline.

[0084] Other conventional additives used in gasoline are corrosion inhibitors, for example based on ammonium salts of organic carboxylic acids, which tend to form films, or based on ammonium salts of heterocyclic aromatic hydrocarbons for non-ferrous metal corrosion protection; antioxidants or stabilizers, for example based on amines such as phenylenediamines, for example p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, dicyclohexylamine or derivatives thereof, or based on phenols such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid; antistatic agents; metallocenes such as ferrocene; methyl-cyclo-pentadienyl manganese tricarbonyl; lubricating additives such as certain fatty acids, alkenyl succinates, bis(hydroxyalkyl) fatty amines, hydroxyacetamides or castor oil; and dyes (markers). If appropriate, amines may also be added, for example as described in WO03 / 076554. Optionally, anti-seat recession additives such as sodium or potassium salts of polymeric organic acids may be used.

[0085] The gasoline compositions herein may also comprise a detergent additive. Suitable detergent additives include those disclosed in WO2009 / 50287, which is incorporated herein by reference.

[0086] Preferred detergent additives for use in the gasoline compositions herein generally have at least one hydrophobic hydrocarbon group having a number average molecular weight (Mn) of from 85 to 20,000 and at least one polar moiety selected from:

[0087] (A1) a monoamino or polyamino group having up to 6 nitrogen atoms, at least one of which is basic;

[0088] (A6) polyoxy-C2- to -C4-alkylene groups which are terminated by hydroxyl, monoamino or polyamino groups, in which at least one nitrogen atom is basic, or by carbamate groups;

[0089] (A8) a moiety derived from succinic anhydride and having a hydroxyl group and / or an amino group and / or an amide group and / or an imide group; and / or

[0090] (A9) Moieties obtained by Mannich reaction of substituted phenols with aldehydes and monoamines or polyamines.

[0091] The hydrophobic hydrocarbon group in the above detergent additives that ensures sufficient solubility in the base fluid has a number average molecular weight (Mn) of 85 to 20,000, especially 113 to 10,000, and especially 300 to 5000. Typical hydrophobic hydrocarbon groups, especially those combined with polar moieties (A1), (A8) and (A9), include polyalkene / polyolefins, such as polypropylene, polybutene and polyisobutene, each of which has an Mn of 300 to 5000, preferably 500 to 2500, more preferably 700 to 2300, and especially 700 to 1000.

[0092] Non-limiting examples of the above detergent additive package include the following:

[0093] The additive comprising monoamino or polyamino groups (A1) is preferably a polyolefin monoamine or polyolefin polyamine based on polypropylene with an Mn of 300 to 5000 or conventional (i.e., predominantly internal double bonds) polybutene or polyisobutylene. When polybutene or polyisobutylene predominantly having internal double bonds (usually in the β and γ positions) is used as a starting material for the preparation of the additive, possible preparation routes are by chlorination and subsequent amination, or by oxidation of the double bonds with air or ozone to give carbonyl or carboxyl compounds and subsequent amination under reducing (hydrogenation) conditions. The amine used for the amination here can be, for example, ammonia, a monoamine or a polyamine, such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. Corresponding additives based on polypropylene are described in particular in WO-A-94 / 24231.

[0094] Further preferred additives comprising monoamino groups (A1) are the hydrogenation products of reaction products of polyisobutene having an average degree of polymerization of from 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A-97 / 03946.

[0095] Further preferred additives comprising monoamino groups (A1) are compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of amino alcohols, as described in particular in DE-A-196 20 262.

[0096] The additive comprising a polyoxy-C2-C4-alkylene moiety (A6) is preferably a polyether or a polyetheramine, which can be obtained by 60 -Alkanols, C6- to C 30 -alkanediol, mono- or di-C2-C 30 -alkylamine, C1-C 30 -alkylcyclohexanol or C1-C 30 -alkylphenols are obtained by reacting 1 mol to 30 mol 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, monoamines or polyamines. Such products are described in particular in EP-A-310 875, EP-A-356 725, EP-A-700 985 and US-A-4 877 416. In the case of polyethers, such products also have carrier oil properties. Typical examples of these products are tridecanol butoxylates, isotridecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates, and the corresponding reaction products with ammonia.

[0097] The additive comprising moieties (A8) derived from succinic anhydride and having hydroxyl and / or amino and / or amide and / or imide groups is preferably the corresponding derivative of polyisobutenyl succinic anhydride, which can be obtained by reacting conventional or highly reactive polyisobutenes having an Mn of 300 to 5000 with maleic anhydride by a thermal route or via chlorinated polyisobutene. Of particular interest are derivatives with aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. Such additives are described in particular in US-A-4 849 572.

[0098] The additive comprising a part (A9) obtained by the Mannich reaction of substituted phenols with aldehydes and mono- or polyamines is preferably a reaction product of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine. The polyisobutenyl-substituted phenols can be derived from conventional or highly reactive polyisobutenes having an Mn of from 300 to 5000. Such "polyisobutene-Mannich bases" are described in particular in EP-A-831 141.

[0099] 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 comprising: polyolefin monoamines, polyetheramines, polyolefin Mannich amines and polyolefin succinimides. Conveniently, the nitrogen-containing detergent may be a polyolefin monoamine.

[0100] In the above, the amounts of components (concentrations, % v / v, mg / kg (ppm), % m / m) are the amounts of active substance, ie excluding volatile solvent / diluent materials.

[0101] The liquid fuel composition of the present invention can be produced by mixing renewable naphtha and oxygenated hydrocarbons with a gasoline blending component. Since the blending component mixed with renewable naphtha and oxygenated hydrocarbons is a gasoline blending component, the liquid fuel composition produced is a gasoline composition.

[0102] The fuel composition of the invention is suitable for use in spark ignition internal combustion engines, such as those used in passenger cars. Thus, according to another aspect of the invention there is provided the use of a gasoline composition as described above for fuelling a spark ignition internal combustion engine in a passenger car.

[0103] The fuel composition of the present invention is also suitable for use in a spark-ignited internal combustion engine when used in the powertrain of a hybrid electric vehicle, in particular a plug-in hybrid electric vehicle (PHEV). Therefore, according to another aspect of the present invention, there is provided the use of a gasoline composition as described above for fueling a spark-ignited internal combustion engine when used in the powertrain of a hybrid electric vehicle, in particular a plug-in hybrid electric vehicle.

[0104] The fuel composition of the present invention has been found to be particularly useful in reducing particulate matter (PM) emissions. Thus, according to a further aspect of the present invention, there is provided the use of a gasoline composition as described above for reducing particulate matter emissions (PM emissions) in a spark ignition internal combustion engine such as in a passenger car.

[0105] The invention is further described by reference to the following non-limiting examples.

[0106] Example 1

[0107] Several fuel blends were prepared having the properties and compositions shown in Table 1 below.

[0108] Fuel A is a standard refinery E10 gasoline market fuel formulation (containing 10% v / v ethanol) meeting EN228 Class A specifications.

[0109] Fuel B is an E20 gasoline fuel formulation containing 20% ​​v / v ethanol and 20% v / v renewable naphtha (but does not meet the EN228 Class A specification due to not meeting the EN228 maximum oxygen specification of 3.7 wt %.

[0110] Fuel C is a gasoline fuel formulation meeting EN228 Class A specifications and containing 9% v / v ethanol and 20% v / v renewable naphtha.

[0111] Fuel D is a gasoline fuel formulation meeting EN228 Class A specifications and containing 8% v / v ethanol and 20% v / v renewable naphtha.

[0112] The renewable naphtha used in Fuels B, C and D was supplied by UPM under the trade name UPM BioVerno Naphtha.

[0113] The ethanol used in the examples is bioethanol modified with 2% toluene and supplied by Clariant under the trade name Sunliquid (RTM) bioethanol (99.8%).

[0114] The alkylate / isomerate / ETBE components used in the examples were supplied together as a mixture by Shell Global Solutions under the trade name ASF.

[0115] The CCT naphtha (also known as FCC naphtha) used had the CAS number 64741-55-5.

[0116] The heavy reformate used had CAS number 64741-68-0.

[0117] The fuel analysis results in Table 1 below demonstrate that renewable naphtha can be blended with gasoline blending components at specific concentrations / ratios to yield ethanol-containing fuels that comply with EN228.

[0118] Table 1

[0119]

[0120]

[0121] 1. Fuel A is a standard refinery market fuel and therefore fuel blending details are not available.

[0122] 2. Fuel B is an E20 blend and exceeds the current EN228 specification, which is designed for E10 fuel, for a mass fraction of 3.7% m / m.

[0123] 3. Supplied as a mixture containing alkylates, isomerates and ETBE

[0124] ND = Not Determined

[0125] N / A = Not Applicable

[0126] *Comparative Example

[0127] As can be seen from Table 1 above, the RON (measured) of Fuel C is 97, and the RON (measured) of Fuel D is 96. This is surprising given the high levels of renewable naphtha present in the formulation and is greater than would be expected from calculating the RON values ​​using the individual RON numbers of the components used in the composition (see Table 2 below). As can be seen from Table 2 below, the calculated RON value of Fuel C is 92, while the measured RON value is 97. It can also be seen that the calculated RON value of Fuel D is 91, while the measured RON value is 96.

[0128] Table 2

[0129]

[0130] Emissions and power performance testing

[0131] Fuel A (E10), Fuel B (E20) and Fuel C (according to the present invention) were tested in a gasoline single cylinder engine manufactured by AVL to see if Fuel C would give comparable fuel consumption, pre-catalyst emissions and power performance to standard E10 and E20 fuels. The engine specification details are listed in Table 3 below.

[0132] Table 3: Engine specification details

[0133]

[0134] All fuels were tested in two engine configurations representing current and future engine hardware. A wide range of engine conditions (full load and part load at steady state test conditions) was tested for each configuration.

[0135] Pre-catalyst emissions were measured with a Horiba Mexa 7100 system and fuel consumption was determined using an AVL 735 Coriolis meter. In-cylinder pressure measurements were made using an AVL piezoelectric GU22C sensor. Power output is related to indicated mean effective pressure (IMEP), which is derived from the in-cylinder pressure measurements. Tables 4 and 5 list the full-load operating conditions for the gasoline direct injection (GDI) configuration and the port fuel injection (PFI) configuration, respectively.

[0136] Table 4: Operating conditions for gasoline direct injection (GDI) configuration

[0137]

[0138]

[0139] Table 5: Operating conditions for port fuel injection (PFI) configuration

[0140]

[0141] result

[0142] Tables 6 and 7 list the IMEP results obtained over a certain speed range for both engine configurations under full-load engine operating conditions.

[0143] Table 6: IMEP results for gasoline direct injection (GDI) configuration

[0144]

[0145] Table 7: IMEP results for Port Fuel Injection (PFI) configuration

[0146]

[0147] The results listed in Tables 6 and 7 are shown in Figure 6 and 7. Figure 1 and Figure 2 middle.

[0148] Tables 8 and 9 below list the fuel consumption and pre-catalyst emissions results obtained for the two engine configurations at 1300 rpm.

[0149] Table 8: Fuel consumption and emissions results for gasoline direct injection (GDI) configuration

[0150]

[0151] 1 Particle number emission

[0152] 2 Particle emissions

[0153] Table 9: Fuel consumption and emissions results for the Port Fuel Injection (PFI) configuration

[0154]

[0155] 1 Particle number emission

[0156] 2 Particle emissions

[0157] discuss

[0158] The IMEP results at different engine speeds for both engine configurations (GDI and PFI) show that Fuel C (the fuel according to the present invention) performs similarly to conventional E10 (Fuel A) and E20 (Fuel B) fuel compositions.

[0159] For both engine configurations, Fuel C has similar fuel consumption performance as the conventional E10 (Fuel A) fuel composition. For E20 (Fuel B), its fuel consumption performance is lower compared to E10 (Fuel A) because the calorific value (lower heating value) is different and affects the fuel consumption values.

[0160] For both engine configurations, the pre-catalyst emissions (CO, NOx, THC) performance of Fuel C is similar to that of Reference Fuels A and B (E10 and E20).

[0161] Although PN emissions of all three fuels were at comparable levels, Fuel C showed beneficial results on PM emissions compared to regular E10 fuel (Fuel A).

Claims

1. A gasoline fuel composition for a spark-ignition internal combustion engine comprising (a) a gasoline blending component, (b) a renewable naphtha at a level of 10-30% v / v and (c) an oxygenated hydrocarbon at a level of 5-15% v / v, wherein the oxygenated hydrocarbon is a mixture of an alcohol and an ether, wherein the gasoline blending component comprises (a) 15-30% v / v alkylate, (b) 0-15% v / v isomerate, (c) 5-20% v / v catalytic cracking overhead naphtha; and (d) 20-40% v / v heavy reformate, wherein the total amount of alkylate, isomerate, catalytic cracking overhead naphtha and heavy reformate is at least 50% v / v based on the gasoline fuel composition, And wherein the gasoline fuel composition meets EN228 specifications.

2. The gasoline fuel composition of claim 1, wherein the gasoline blending component comprises 30-35% by volume of heavy reformate, based on the gasoline fuel composition.

3. The gasoline fuel composition of claim 1, wherein the gasoline blending component comprises 20-25% by volume of heavy reformate based on the gasoline fuel composition.

4. The gasoline fuel composition of claim 1, wherein the alcohol is selected from the group consisting of methanol, ethanol, propanol, 2-propanol, butanol, tert-butanol, isobutanol and 2-butanol and mixtures thereof.

5. The gasoline fuel composition of claim 4, wherein the alcohol is ethanol.

6. A gasoline fuel composition according to claim 5, wherein the ethanol is present at a level of 5-10% v / v based on the gasoline fuel composition.

7. The gasoline fuel composition of claim 1, wherein the ether is ETBE.

8. A method for preparing a gasoline fuel composition comprising blending (a) a gasoline blending component, (b) a renewable naphtha at a level of 10-30% v / v, and (c) an oxygenated hydrocarbon at a level of 5-15% v / v, wherein the oxygenated hydrocarbon is a mixture of an alcohol and an ether, wherein the gasoline blending component comprises (a) 15-30% v / v alkylate, (b) 0-15% v / v isomerate; (c) 5-20% v / v catalytic cracking overhead naphtha; and (d) 20-40% v / v heavy reformate, wherein the total amount of alkylate, isomerate, catalytic cracking overhead naphtha and heavy reformate is at least 50% v / v based on the gasoline fuel composition, and wherein the gasoline fuel composition meets EN228 specification.

9. Use of the gasoline fuel composition according to any one of claims 1 to 7 for providing fuel for a spark ignition internal combustion engine.

10. The use according to claim 9, wherein the spark-ignition internal combustion engine is a spark-ignition internal combustion engine in a passenger car.

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