fuel composition

Abstract

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 20% v / v or less, the gasoline blending component comprises: (a) 0 to 30% v / v alkylate; (b) 0 to 15% v / v isomerate; (c) 0 to 20% v / v catalytic cracking top naphtha; and (d) 20% to 40% v / v heavy reformate, wherein the total amount of alkylate, isomerate, catalytic cracking top naphtha, and heavy reformate is at least 50% v / v based on the total fuel composition; A gasoline fuel composition, wherein the gasoline fuel composition meets the EN228 standard. Although the low octane number of renewable naphtha normally significantly limits 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 in surprising and significantly high blend ratios of renewable naphtha to ethanol.

Description

[Technical Field]

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

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

[0003] While the long-chain molecules in gas oil 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 small amounts, due to its low octane number. This was true despite the fact that naphtha has distillation properties comparable to those of gasoline.

[0004] Renewable fuels derived from biological materials ("biofuels") are increasingly being used as more sustainable alternatives to fossil fuels. Due to the recent increase in renewable naphtha production, it would be advantageous to be able to blend renewable naphtha into gasoline, especially at high blend ratios. The use of higher blend ratios of renewable naphtha has the advantage of enabling higher CO2 reductions and may help meet the regulatory reduction targets set forth in the Paris Agreement (2016). At the same time, it is desirable to be able to formulate gasoline fuel compositions that comply with existing gasoline fuel specifications, such as, but not limited to, EN228 and North American standards, such as ASTM D4814-13b, US Conventional, CaRFG Phase 3, Federal RFG Phase II, and CAN / CGSB-3.5.

[0005] WO 2017 / 093203 discloses a liquid fuel composition for spark-ignition internal combustion engines 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] U.S. Patent Application Publication No. 2009 / 300971 discloses a naphtha composition produced from renewable feedstocks, the naphtha having 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 combustion engines when blended with ethanol at 1% to 85% by volume.

[0007] WO 2018 / 234187 relates to a process for producing renewable base oils, diesel, and naphtha from biogenic feedstocks. However, WO 2018 / 234187 does not disclose specific gasoline fuel formulations containing the renewable naphtha produced by the process.

[0008] WO 2018 / 069137 relates to a process for preparing an alkylate gasoline composition containing renewable naphtha, isooctane, and isopentane. The alkylate gasoline examples in Table 2 contain up to 5% by volume of renewable naphtha. The gasoline compositions in this application do not contain oxygenates and are focused on small utility engines used in various portable gasoline-powered tools, such as chainsaws and lawn mowers.

[0009] US Patent No. 9,885,000 (B2) relates to renewable hydrocarbon compositions obtainable from renewable biological feedstocks, which can be used as fuel components.

[0010] WO 2009 / 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 as a fuel blendstock.

[0011] Although the low octane number of renewable naphtha normally significantly limits its blendability in gasoline to low levels, it has now been discovered by the inventors that renewable naphtha can be included in, for example, ethanol-containing gasoline fuel compositions at surprising and significantly high blend ratios of renewable naphtha to ethanol while still meeting gasoline fuel specifications such as, but not limited to, EN228 and North American standards such as ASTM D4814-13b, US Conventional, CaRFG Phase 3, Federal RFG Phase II, and 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) renewable naphtha at a level of 10-30% v / v; and (c) oxygenated hydrocarbons at a level of 20% v / v or less, the gasoline blending components comprise: (a) from 0% v / v to 30% v / v alkylate; (b) from 0% v / v to 15% v / v isomerate; (c) from 0% v / v to 20% v / v catalytic cracked tops (CCT) naphtha; and (d) from 20% v / v to 40% v / v heavy reformate, wherein the total amount of alkylate, isomerate, catalytic cracked tops (CCT) naphtha, and heavy reformate is at least 50% v / v, based on the gasoline fuel composition; A gasoline fuel composition is provided, wherein the gasoline fuel composition meets the EN228 fuel specification.

[0013] According to another aspect of the present invention, there is provided a process for preparing a liquid fuel composition comprising blending (a) a gasoline blending component, (b) renewable naphtha at a level of 10% v / v to 30% v / v, and (c) oxygenated hydrocarbons at a level of 20% v / v or less, the gasoline blending components comprise: (a) from 0% v / v to 30% v / v of alkylate; (b) from 0% v / v to 15% v / v of isomerate; (c) from 0% v / v to 20% v / v of catalytic cracking tops (CCT) naphtha; and (d) from 20% v / v to 40% v / v of 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; A process is provided in which the gasoline fuel composition meets the EN228 standard.

[0014] The present invention allows for significantly higher blend ratios of renewable naphtha in gasoline, thereby providing an important new outlet for renewable naphtha fuel.

[0015] Surprisingly, it has been discovered by the present inventors that by blending gasoline blending components in specific concentrations and ratios, the limitations normally experienced due to the low octane of renewable naphtha can be overcome.

[0016] Furthermore, the fuel compositions of the present invention have the advantage that they meet the requirements of the EN228 fuel specification.

[0017] Surprisingly, the fuel compositions of the present invention have also been found to have higher than expected RON values.

[0018] The liquid fuel compositions of the present invention also provide excellent fuel economy, emissions, and power benefits as required by the EN228 standard. [Brief explanation of the drawings]

[0019] [Figure 1] 1 is a graphical representation of the results shown in Table 6. [Figure 2] 10 is a graphical representation of the results shown in Table 7. DETAILED DESCRIPTION OF THE INVENTION

[0020] The liquid fuel composition of the present invention comprises a gasoline blending component, such as a gasoline base fuel, suitable for use in an internal combustion engine, renewable naphtha at a level of 10% v / v to 30% v / v, and (c) an oxygenated hydrocarbon at a level of 20% v / v or less. Thus, the liquid fuel composition of the present invention is a gasoline composition.

[0021] As used herein, the term "comprises" is intended to indicate that, at a minimum, the listed elements are included, but that other elements not specified may be included as well.

[0022] The liquid fuel compositions herein include naphtha. Those skilled in the art will know what is meant by the term "naphtha." Typically, the term "naphtha" refers to a mixture of hydrocarbons generally having 5 to 12 carbon atoms and having a boiling point in the range of 30 to 200°C. The liquid fuel compositions herein include naphtha, which is renewable naphtha, also known as renewable naphtha distillate or biorenewable naphtha.

[0023] Renewable naphtha distillates can be produced as part of the refinement of renewable diesel. Renewable diesel can be obtained from the processing of fatty acid-containing materials, such as animal fats, algae, and plant materials. Plant materials can include both plant-based materials, such as vegetable oils, and oils derived from other plants, such as oils from trees, e.g., tall oil. Renewable diesel and renewable naphtha distillates can be obtained from the hydroprocessing of fatty acids and their derivatives, e.g., triglycerides. Hydroprocessing of fatty acids and their derivatives involves deoxygenation reactions, such as hydrodeoxygenation (HDO), and may also involve other hydroprocessing reactions, such as isomerization (e.g., hydroisomerization) and cracking (e.g., hydrocracking). When refining renewable diesel, renewable naphtha distillates are obtained. Renewable naphtha distillates 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 within the distillation range typically range from those containing 4 or 5 carbon atoms to those containing about 10, 11, or 12 carbon atoms.

[0024] Renewable fuels, such as renewable naphtha distillates, are collected from resources that are naturally replenished on human timescales, in contrast to fossil fuels, such as petroleum gasoline, derived from the refining of crude oil. Renewable naphtha distillates can be obtained from hydroprocessing of fatty acids and their derivatives present in fatty acid-containing materials, such as animal fats and plant materials, where the hydroprocessing includes hydrodeoxygenation and hydroisomerization, and include fractions having an IBP of 30°C, e.g., IBP or 30°C or greater, and an FBP of 200°C, e.g., 200°C or less. As used herein, the term renewable naphtha refers to naphtha fractions containing biobased carbon atoms as determined in accordance with ASTM method D6866-10, entitled "Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gasous Samples Using Radiocarbon Analysis." The renewable content is then determined as described in ASTM D6866. 14 C. 13 C and / or 12 It can be determined by the isotope distribution, including C.

[0025] Because the paraffins in renewable naphtha are obtained from the processing of fatty acid-containing materials such as animal fats and vegetable materials, renewable naphtha distillates are paraffinic, contain little naphthenes, and are substantially free of aromatics or oxygenates.

[0026] Renewable naphtha distillate is composed primarily of paraffins (alkanes), which can be straight-chain n-paraffins or branched-chain isoparaffins. Renewable naphtha contains at least 90% by volume of C5-C 12 Paraffin, e.g., 95% by volume or more of C5-C 12 Paraffin or 98% or more by volume of C5-C 12 It may have paraffin.

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

[0028] In addition to containing primarily paraffins, renewable naphtha distillate also has a low content of naphthenes (cycloalkanes), which are alkanes having at least one non-aromatic ring structure, where the ring typically has 5 or 6 carbon atoms. The renewable naphtha distillate may have 5% or less by volume of naphthenes, e.g., 1% or less by volume of naphthenes, or 0.5% or less by volume of naphthenes.

[0029] In addition to containing primarily paraffins, renewable naphtha distillate also has a very low content of aromatic compounds. Aromatic compounds contain benzene rings or other ring structures that are aromatic. The renewable naphtha distillate may have 1% or less by volume of aromatic compounds, for example, 0.5% or less by volume of aromatic compounds, or 0.1% or less by volume of aromatic compounds.

[0030] In addition to containing primarily paraffins, renewable naphtha distillate also has a very low content 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 distillate may have 1% or less by volume of oxygenates, e.g., 0.5% or less by volume of oxygenates, or 0.1% or less by volume of oxygenates, but is preferably essentially free of oxygenates.

[0031] As used herein, renewable naphtha has a low octane number, i.e., a RON and / or MON of, for example, 35 to 70, such as 35 to 60, or 35 to 50, or 35 to 45. Surprisingly, it has been found that despite the low octane quality of renewable naphtha, renewable naphtha can be included at relatively high levels in the gasoline fuel composition of the present invention, with the final gasoline fuel composition having a higher than expected octane number (RON).

[0032] The renewable naphtha distillate may have a vapor pressure of less than 30 kPa, such as less than 25 kPa, for example, less than 20 kPa. The vapor pressure of the renewable naphtha may also be equal to or greater than 10 kPa, for example, equal to or greater than 15 kPa.

[0033] In a preferred embodiment, renewable naphtha as used herein is 90% by volume or more of C5-C 12 Paraffins, containing not less than 30% by volume of C5-C6 paraffins, not more than 5% by volume of naphthenes, not more than 1% by volume of aromatics, and not more than 1% by volume of oxygenates.

[0034] The renewable naphtha distillate may have a boiling range of 30 to 200°C, for example, 90 to 200°C, or 40 to 180°C.

[0035] The amount of renewable naphtha present in the gasoline fuel composition of the present invention is from 10% to 30% by volume, preferably from 15% to 25% by volume, even more preferably from 18% to 22% by volume, and especially 20% by volume, based on the total fuel composition. Preferably, as much renewable naphtha as possible can be added to increase the renewable portion of the gasoline composition of the present invention.

[0036] Renewable naphtha may contain an isoparaffin / n-paraffin ratio of greater than 1, such as greater than 1.2, for example, from 1 to 2.

[0037] The renewable naphtha component of the present invention is disclosed in WO 2018 / 069137, WO 2018 / 234187, It can be prepared according to the methods provided in U.S. Pat. No. 9,885,000 (B2) and WO 2009 / 148909, all of which are incorporated herein by reference in their entireties. These references also provide further details of the chemical and physical properties of renewable naphtha components.

[0038] Renewable naphtha components are commercially available from Neste Oyj, Finland, under the trade name Neste renewable naphtha, also known as NexNaphtha. Renewable naphtha components are also commercially available from UPM under the trade name BioVerno Naphtha.

[0039] In the liquid fuel compositions herein, the renewable naphtha component of the present invention may comprise a mixture of two or more renewable naphthas, or a mixture of renewable naphtha with petroleum-derived naphtha and / or Fischer-Tropsch-derived naphtha.

[0040] "Fischer-Tropsch derived" means that the naphtha is the product of or is derived from a Fischer-Tropsch synthesis process (or Fischer-Tropsch condensation process). Fischer-Tropsch derived naphtha is sometimes referred to as GTL (Gas-to-Liquid) naphtha. Further details of GTL naphtha can be found in WO 2017 / 093203, which is incorporated herein by reference in its entirety.

[0041] Those skilled in the art will appreciate that a gasoline blending component may already contain some naphtha components. The naphtha concentrations referred to above refer to the concentration of naphtha that is added to the liquid fuel composition in a blend with the gasoline blending component, and do not include the concentration of any naphtha components already present in the gasoline blending component.

[0042] In addition to renewable naphtha, the liquid fuel composition of the present invention comprises oxygenated hydrocarbons at a level of up to 20% by volume, preferably 5-15% v / v, based on the liquid fuel composition. In one embodiment, the oxygenated hydrocarbons are present at a level of 7-12% v / v, based on the liquid fuel composition. In another embodiment, the oxygenated hydrocarbons are present at a level of 10-15% v / v, based on the liquid fuel composition.

[0043] Those skilled in the art will appreciate that gasoline base fuels may already contain some oxygenated hydrocarbon components, and the concentrations of oxygenated hydrocarbons referred to above refer to the concentrations of oxygenated hydrocarbons that are added to the liquid fuel composition as a blend with the gasoline base fuel, and do not include the concentrations of any oxygenated hydrocarbon components already present in the gasoline base fuel.

[0044] Examples of suitable oxygenated hydrocarbons that may be incorporated into the 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.

[0045] Alcohols suitable for use herein include methanol, ethanol, propanol, 2-propanol, butanol, tert-butanol, isobutanol, 2-butanol, and mixtures thereof. Ethers suitable 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). Esters suitable for use herein include esters containing 5 or more carbon atoms per molecule.

[0046] The oxygenated hydrocarbon is preferably selected from alcohols, ethers, and mixtures thereof. In one preferred embodiment of the present invention, the oxygenated hydrocarbon is selected from alcohols, preferably at a level of 0.1% v / v to 10% v / v, more preferably at a level of 5% v / v to 10% v / v, based on the total gasoline fuel composition. In another embodiment of the present invention, the oxygenated hydrocarbon is selected from ethers, preferably at a level of 0.1% v / v to 15% v / v, based on the total gasoline fuel composition. In another preferred embodiment of the present invention, the oxygenated hydrocarbon is a mixture of alcohols and ethers, such as a mixture of at least one alcohol and at least one ether, preferably comprising 5% v / v to 10% v / v of alcohol and 2% v / v to 5% v / v of ether, based on the gasoline fuel composition.

[0047] A particularly preferred oxygenated hydrocarbon for use herein is ethanol. Ethanol is preferably present in the fuel compositions herein at a level of from 0.1% v / v to 10% v / v, more preferably from 5% v / v to 10% v / v, based on the total gasoline fuel composition. In one embodiment of the present invention, ethanol is present as the only oxygenated hydrocarbon.

[0048] A particularly preferred ether for use as the oxygenated hydrocarbon herein is ETBE. In one embodiment of the present invention, ETBE is present in the fuel compositions herein at a level of from 0.1% v / v to 15% v / v, based on the total gasoline fuel composition. In another embodiment of the present invention, ETBE is present as the only oxygenated hydrocarbon.

[0049] In a particularly preferred embodiment of the present invention, the oxygenated hydrocarbon herein is a mixture of ethanol and ETBE comprising from 5% v / v to 10% v / v of ethanol and from 2% v / v to 5% v / v of ETBE, based on the total gasoline fuel composition.

[0050] If both the oxygenated hydrocarbon and naphtha are of renewable origin, the proportion of renewable content in the gasoline composition increases. For example, bioethanol can be used as the oxygenated hydrocarbon herein.

[0051] The liquid fuel composition of the present invention comprises a gasoline blending component comprising (a) from 0% v / v to 30% v / v alkylate, (b) from 0% v / v to 15% v / v isomerate, (c) from 0% v / v to 20% v / v catalytic cracking tops, and (d) from 20% v / v to 40% v / v heavy reformate, wherein the total amount of alkylate, isomerate, catalytic cracking tops, and heavy reformate is at least 50% v / v, based on the total fuel composition.

[0052] In the liquid fuel composition of the present invention, the gasoline blending component may be a gasoline base fuel comprising components (a), (b), (c), and (d) above.

[0053] Conventionally, gasoline blending components are present in gasoline or liquid fuel compositions in major amounts, for example, greater than 50% v / v of the liquid fuel composition, and may be present in amounts 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 the gasoline blending component, together with 10% v / v to 30% v / v of renewable naphtha and oxygenated hydrocarbons at levels up to 20% v / v, and optionally one or more conventional gasoline fuel additives, such as those specified below.

[0054] The gasoline blending component comprises from 0% v / v to 30% v / v, preferably from 15 to 30% v / v, more preferably from 15 to 25% v / v alkylate, based on the total gasoline fuel composition.

[0055] Alkylate is a complex combination of hydrocarbons produced by the distillation of the reaction products of isobutane with monoolefinic hydrocarbons, the carbon numbers of which usually range from C3 to C5. Alkylate is a refinery stream, primarily consisting of C7 to C 12 It consists primarily of branched-chain saturated hydrocarbons with carbon numbers in the range of 194°F to 428°F (90°C to 220°C).

[0056] The gasoline blending component contains from 0% v / v to 15% v / v, preferably 5 to 10% by volume of the isomerate, based on the total gasoline fuel composition.

[0057] Isomerate is a complex combination of hydrocarbons obtained from the catalytic isomerization of normal paraffinic C4-C6 hydrocarbons. Isomerate is a refinery stream consisting primarily of saturated hydrocarbons such as isobutane, isopentane, 2,2-dimethylbutane, 2-methylpentane, and 3-methylpentane, boiling in the range of approximately 35°C to 220°C (95°F to 428°F).

[0058] The gasoline blending component comprises from 20% v / v to 40% v / v of heavy reformate, based on the total gasoline fuel composition, provided that the total amount of alkylate, isomerate, catalytic cracked tops, and heavy reformate in the final fuel composition is at least 50% v / v, based on the total gasoline fuel composition.

[0059] In one embodiment of the invention, the gasoline blending component comprises from 30% v / v to 35% v / v of heavy reformate based on the total fuel composition. In another embodiment of the invention, the gasoline blending component comprises from 20% v / v to 25% v / v of heavy reformate based on the total fuel composition.

[0060] Heavy reformate (or heavy catalytically reformed naphtha) is a complex combination of hydrocarbons produced from the distillation of the products from the catalytic reforming process. Heavy reformate is primarily composed of C7 to C8 hydrocarbons. 12 Heavy reformate is primarily composed of aromatic hydrocarbons with carbon numbers in the range of 194°F to 446°F (90°C to 230°C). Depending on the requirements, type of unit, and naphtha feedstock, a refinery stream rich in aromatics and high octane components (typically 98-102 RON), it can be used for mogas blending or as a feedstock.

[0061] The gasoline blending component comprises from 0% v / v to 20% v / v, preferably from 5% v / v to 20% v / v, of catalytic cracked tops, based on the total fuel composition, provided that the total amount of alkylate, isomerate, catalytic cracked tops, and heavy reformate in the final fuel composition is at least 50% v / v, based on the total fuel composition.

[0062] Fluid catalytic cracking (FCC) naphtha (or light catalytic cracking naphtha), also known as fluid catalytic cracking (FCC) naphtha, is a complex combination of hydrocarbons produced by distillation of the products from the fluid catalytic cracking process. Fluid catalytic cracking (FCC) is widely used to convert the high-boiling, high-molecular-weight hydrocarbon fractions of petroleum crude oil into more valuable gasoline, olefinic gases, and other products. The end products of FCC are cracked petroleum naphtha, fuel oil, and off-gas. After further processing to remove sulfur compounds, cracked naphtha becomes a high-octane component of refinery gasoline blends. CCT naphtha / FCC naphtha consists primarily of hydrocarbons with carbon numbers ranging from C4 to C11 and boiling between approximately -20°C and 190°C (-4°F and 374°F). CCT naphtha / FCC naphtha is a refinery stream that contains a relatively large proportion of unsaturated hydrocarbons and is used for mogas blending or as a feedstock, depending on the requirements, type of unit, and naphtha feedstock. CCT naphtha / FCC naphtha has the CAS number 64741-55-5.

[0063] The liquid fuel composition according to the present invention has a Research Octane Number (RON) in the range of 85 to 105, meeting, for example, the European specification of 95 or the premium product grade of 98. The liquid fuel composition used in the present invention has a motor octane number in the range of 75 to 90.

[0064] Although not critical to the present invention, the gasoline compositions of the present invention may advantageously contain one or more optional fuel additives. The concentration and nature of the optional fuel additives that may be included in the gasoline blending component or gasoline composition of the present invention are not critical. Non-limiting examples of suitable types of fuel additives that may be included in the gasoline blending component or gasoline composition of the present invention include antioxidants, corrosion inhibitors, detergents, defogging agents, anti-knock additives, metal deactivators, valve-seat recession protectant compounds, dyes, solvents, dispersants, diluents, and markers. Examples of suitable such additives are generally described in U.S. Pat. No. 5,855,629.

[0065] Conveniently, the fuel additive may be blended with one or more solvents to form an additive concentrate, which may then be combined with the gasoline blend component or gasoline composition of the present invention.

[0066] The (active substance) concentration of any optional additive present in the gasoline blending component or gasoline composition of the present invention is preferably at most 1% m / m, more preferably in the range 5 to 2000 mg / kg, advantageously in the range 300 to 1500 mg / kg, for example 300 to 1000 mg / kg.

[0067] As noted above, the gasoline composition may also contain synthetic or mineral carrier oils and / or solvents.

[0068] Examples of suitable mineral carrier oils are fractions obtained in crude oil processing, such as bright stock or base oils having viscosities in the SN500 to SN2000 range, as well as aromatic hydrocarbons, paraffinic hydrocarbons, and alkoxyalkanols. Fractions obtained in mineral oil refining and known as "hydrocracked oil" (vacuum distillation fractions having a boiling point range of about 360 to 500°C that can be obtained from natural mineral oils that have been catalytically hydrogenated under high pressure, isomerized, and further deparaffinized) are also useful as mineral carrier oils.

[0069] Examples of suitable synthetic carrier oils are polyolefins (poly-α-olefins or poly(internal olefins)), (poly)esters, (poly)alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-started polyethers, alkylphenol-started polyetheramines, and carboxylic acid esters of long-chain alkanols.

[0070] Examples of suitable polyolefins are in particular olefin polymers based on polybutene or polyisobutene (hydrogenated or not).

[0071] Examples of suitable polyethers or polyetheramines are preferably C2-C 60 -Alkanols, C6-C 30 -Alkanediols, mono- or di-C2-C 30 -Alkylamines, C1-C 30 -Alkylcyclohexanol, or C1-C 30These compounds contain polyoxy-C2-C4-alkylene moieties, which can be obtained by reacting 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, monoamines, or polyamines. Such products are described, inter alia, in EP 310875, EP 356725, EP 700985, and U.S. Pat. No. 4,877,416. For example, the polyetheramines used can be poly-C2-C6-alkylene oxide amines or their functional derivatives. Typical examples are tridecanol butoxylate or isotridecanol butoxylate, isononylphenol butoxylate, and polyisobutenol butoxylate and polyisobutenol propoxylate, and the corresponding reaction products with ammonia.

[0072] 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 German Patent No. 3838918. The mono-, di-, or tricarboxylic acids used can be aliphatic or aromatic acids, and suitable ester alcohols or polyols are particularly representative of long chains, for example, having 6 to 24 carbon atoms. Typical representatives of esters are the adipates, phthalates, isophthalates, terephthalates, and trimellitates of isooctanol, isononanol, isodecanol, and isotridecanol, such as di-(n- or isotridecyl)phthalate.

[0073] Further suitable carrier oil systems are described, for example, in DE 3826608, DE 4142241, DE 4309074, EP 0452328, and EP 0548617, which are incorporated herein by reference.

[0074] Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers having about 5 to 35, e.g., about 5 to 30, C3-C6-alkylene oxide units, e.g., selected from propylene oxide units, n-butylene oxide units, and isobutylene oxide units, or mixtures thereof. Non-limiting examples of suitable starting alcohols are long-chain alkanols or phenols substituted with long-chain alkyls, where the long-chain alkyl groups are, in particular, linear or branched C6-C 18 -alkyl groups. Preferred examples include tridecanol and nonylphenol.

[0075] Further suitable synthetic carrier oils are alkoxylated alkylphenols, as described in German Patent Application No. 10102913.6.

[0076] Mineral carrier oils, synthetic carrier oils, and mixtures of mineral and synthetic carrier oils may also be used.

[0077] Any solvent and optional co-solvent suitable for use in fuels can be used. Examples of solvents suitable for use in fuels include kerosene, heavy aromatic solvents ("Solvent Naphtha Heavy", "Solvesso 150"), toluene, xylene, paraffin, petroleum, white spirits, non-polar hydrocarbon solvents such as those sold by Shell Corporation under the trade name "SHELLSOL". Examples of suitable co-solvents include polar solvents such as esters and, in particular, alcohols (e.g., t-butanol, i-butanol, hexanol, 2-ethylhexanol, 2-propylheptanol, decanol, isotridecanol, butyl glycol, and alcohol mixtures such as those sold by Shell Corporation under the trademark "LINEVOL", in particular C 7-9 LINEVOL79 alcohol, a mixture of primary alcohols, or commercially available C 12-14 alcohol mixtures).

[0078] Dehazing / demulsifying agents suitable for use in liquid fuels are well known in the art, and non-limiting examples include glycoloxyalkylate polyol blends (such as those sold under the trade name TOLAD™ 9312), alkoxylated phenol formaldehyde polymers, phenol / formaldehyde or C1- 18 C modified by oxyalkylation with epoxides and diepoxides 1-18 Examples of suitable oxyalkylated polyols include alkylphenol / -formaldehyde resin oxyalkylates (e.g., those sold under the trade name TOLAD™ 9308) and C1-4 epoxide copolymers crosslinked with diepoxides, diacids, diesters, diols, diacrylates, dimethacrylates, or diisocyanates, as well as blends thereof. The glycoloxyalkylate polyol blend may be a polyol oxyalkylated with a C1-4 epoxide. 18 C1- modified by oxyalkylation with epoxides and diepoxides 18 The alkylphenol phenol / -formaldehyde resin oxyalkylates may be based, for example, on cresol, t-butylphenol, dodecylphenol, or dinonylphenol, or on a mixture of phenols (e.g., a mixture of t-butylphenol and nonylphenol). The dehazer should be used in an amount sufficient to suppress the haze that may result when dehazer-free gasoline comes into contact with water, this amount being referred to herein as a "haze-suppressing amount." Generally, this amount is from about 0.1 to about 20 mg / kg (e.g., from about 0.1 to about 10 mg / kg), more preferably from 1 to 15 mg / kg, even more preferably from 1 to 10 mg / kg, and advantageously from 1 to 5 mg / kg, based on the weight of the gasoline.

[0079] Further conventional additives for use in gasoline include, for example, corrosion inhibitors based on ammonium salts of organic carboxylic acids, which tend to form films, or ammonium salts of heteroaromatic compounds for non-ferrous metal corrosion protection; antioxidants or stabilizers based on amines such as phenyldiamines, for example, 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; antistatic agents; metallocenes such as ferrocene; methylcyclopentadienyltricarbonylmanganese; lubricity additives such as certain fatty acids, alkenyl succinic acid esters, bis(hydroxyalkyl) fatty amines, hydroxyacetamide, or castor oil; and dyes (markers). If appropriate, amines may also be added, for example, as described in WO 03 / 076554. Optionally, anti-valve seat recession additives such as sodium or potassium salts of polymeric organic acids may be used.

[0080] The gasoline compositions herein may also contain detergent additives. Suitable detergent additives include those disclosed in WO 2009 / 50287, which is incorporated herein by reference.

[0081] Preferred detergent additives for use in the gasoline compositions herein typically contain at least one hydrophobic hydrocarbon group having a number average molecular weight (Mn) of from 85 to 20,000; (A1) a mono- or polyamino group having up to six nitrogen atoms, at least one of which is basic; (A6) a polyoxy-C2- to C4-alkylene group terminated by a hydroxyl group, a mono- or polyamino group in which at least one nitrogen atom has basic properties, or a carbamate group; (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 (A9) It has a substituted phenol and at least one polar moiety selected from moieties obtained by the Mannich reaction of an aldehyde and a mono- or polyamine.

[0082] The hydrophobic hydrocarbon groups in the detergent additives, which ensure adequate solubility in the base fluid, have number average molecular weights (Mn) of 85 to 20 000, especially 113 to 10 000, and especially 300 to 5000. Typical hydrophobic hydrocarbon groups, especially those associated with polar moieties (A1), (A8), and (A9), include polyalkenes (polyolefins), such as polypropenyl, polybutenyl, and polyisobutenyl groups, each having an Mn of 300 to 5000, preferably 500 to 2500, more preferably 700 to 2300, and especially 700 to 1000.

[0083] Non-limiting examples of the above groups of detergent additives include the following:

[0084] Additives containing mono- or polyamino groups (A1) are preferably polyalkene monoamines or polyalkene polyamines based on polypropene having an Mn of 300 to 5000 or conventional (i.e., predominantly internal double bond) polybutene or polyisobutene. When polybutene or polyisobutene having predominantly internal double bonds (usually in β- and γ-positions) is used as the starting material for preparing the additive, possible preparation routes are chlorination and subsequent amination, or oxidation of the double bonds with air or ozone to form carbonyl or carboxyl compounds followed by amination under reducing (hydrogenation) conditions. The amines used here for amination can be, for example, ammonia, monoamines, or polyamines, such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, or tetraethylenepentamine. Corresponding additives based on polypropene are described, inter alia, in WO-A-94 / 24231.

[0085] Further preferred additives containing monoamino groups (A1) are the hydrogenated reaction products of polyisobutenes having an average degree of polymerization of 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A-97 / 03946.

[0086] Further preferred additives containing a monoamino group (A1) are compounds obtained from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in DE 19620262.

[0087] The additive containing the polyoxy-C2-C4-alkylene moiety (A6) is preferably a C2- to C4- 60 -Alkanols, C6-~C 30 -Alkanediols, mono- or di-C2-C 30 -Alkylamines, C1-C 30 -Alkylcyclohexanol, or C1-C 30Polyethers or polyetheramines obtained by reacting alkylphenols with 1 to 30 moles of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl or amino group, followed by reductive amination with ammonia, monoamines, or polyamines, in the case of polyetheramines. Such products are described, inter alia, in EP 310875, EP 356725, EP 700985, and U.S. Pat. No. 4,877,416. In the case of polyethers, such products also have carrier oil properties. Typical examples are tridecanol butoxylate, isotridecanol butoxylate, isononylphenol butoxylate, polyisobutenol butoxylate, and polyisobutenol propoxylate, and their corresponding reaction products with ammonia.

[0088] Additives (A8) derived from succinic anhydride and containing moieties containing hydroxyl and / or amino and / or amide and / or imide groups are preferably the corresponding derivatives of polyisobutenyl succinic anhydride, which are obtained by reacting conventional polyisobutenes or highly reactive polyisobutenes having an Mn of 300 to 5000 with maleic anhydride via a thermal route or via chlorinated polyisobutene. Of particular interest are derivatives containing aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, or tetraethylenepentamine. Such additives are described, inter alia, in U.S. Pat. No. 4,849,572.

[0089] The additive (A9) containing a moiety obtained by the Mannich reaction of a substituted phenol with an aldehyde and a mono- or polyamine is preferably a reaction product of a polyisobutenyl-substituted phenol with formaldehyde and a mono- or polyamine, such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, or dimethylaminopropylamine. The polyisobutenyl-substituted phenol can be derived from conventional polyisobutene or highly reactive polyisobutene having an Mn of 300 to 5000. Such "polyisobutene-Mannich bases" are described, inter alia, in EP 831141.

[0090] 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 polyalkene monoamines, polyetheramines, polyalkene Mannich amines, and polyalkene succinimides. Advantageously, the nitrogen-containing detergent may be a polyalkene monoamine.

[0091] In the above, the amounts of ingredients (concentrations, % v / v, mg / kg (ppm), % m / m) are of the active substance, i.e. excluding volatile solvent / diluent materials.

[0092] The liquid fuel composition of the present invention can be produced by blending renewable naphtha and oxygenated hydrocarbons with a gasoline blending component. The blending component into which the renewable naphtha and oxygenated hydrocarbons are blended is a gasoline blending component, and therefore the liquid fuel composition produced is a gasoline composition.

[0093] The fuel compositions of the present invention are suitable for use in spark-ignition internal combustion engines such as those used in passenger cars. Thus, according to another aspect of the present invention there is provided the use of a gasoline composition as described above for fuelling a spark-ignition internal combustion engine of a passenger car.

[0094] The fuel compositions of the present invention are also suitable for use in spark-ignition internal combustion engines when used in the powertrain of a hybrid electric vehicle, in particular a plug-in hybrid electric vehicle (PHEV). Thus, according to another aspect of the present invention, there is provided the use of a gasoline composition as described above for fuelling a spark-ignition internal combustion engine when used in the powertrain of a hybrid electric vehicle, in particular a plug-in hybrid electric vehicle.

[0095] The fuel compositions of the present invention have been found to be particularly useful for 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 a passenger car. [Example]

[0096] The present invention will now be further described with reference to the following non-limiting examples.

[0097] Example 1 Several fuel blends were prepared having the properties and compositions shown in Table 1 below.

[0098] Fuel A was a standard refinery E10 gasoline market fuel blend (containing 10% v / v ethanol) meeting EN228 Class A specifications.

[0099] Fuel B was an E20 gasoline fuel blend containing 20% ​​v / v ethanol and 20% by volume renewable naphtha (but does not meet the EN228 Class A specification because it fails the EN228 maximum oxygen specification of 3.7 wt%).

[0100] Fuel C was a gasoline fuel blend meeting EN228 Class A specifications and containing 9% v / v ethanol and 20% v / v renewable naphtha.

[0101] Fuel D was a gasoline fuel blend meeting EN228 Class A specifications and containing 8% v / v ethanol and 20% v / v renewable naphtha.

[0102] The renewable naphtha used in fuels B, C, and D was supplied by UPM under the trade name UPM BioVerno Naphtha.

[0103] The ethanol used in the examples was bioethanol supplied by Clariant under the trade name Sunliquid® bioethanol (99.8%) denatured with 2% toluene.

[0104] The alkylate / isomerate / ETBE components used in the examples were supplied together as a blend by Shell Global Solutions under the trade name ASF.

[0105] The CCT naphtha (also known as FCC naphtha) used had CAS number 64741-55-5.

[0106] The heavy reformate used had CAS number 64741-68-0.

[0107] The fuel analysis results in Table 1 below show that renewable naphtha can be blended with gasoline blending components at specific concentrations / ratios to provide EN228 compliant ethanol-containing fuels.

[0108] [Table 1]

[0109] As can be seen from Table 1 above, Fuel C has a measured RON of 97 and Fuel D has a measured RON of 96. This is surprising considering the high levels of renewable naphtha present in the formulation, and is greater than would be expected from calculating the RON value using the individual RON numbers of the components used in the composition (see Table 2 below). From Table 2 below, it can be seen that Fuel C has a calculated RON value of 92, while the measured RON value is 97. It can also be seen that Fuel D has a calculated RON value of 91, while the measured RON value is 96.

[0110] [Table 2]

[0111] Emissions test and power performance test To understand whether Fuel C exhibits fuel consumption, pre-catalyst emissions, and power performance comparable to standard E10 and E20 fuels, 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. The engine specifications are detailed in Table 3 below.

[0112] [Table 3]

[0113] 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 under steady state test conditions) were tested for each configuration.

[0114] Pre-catalyst emissions were measured with a Horiba Mexa7100 system, and fuel consumption was determined using an AVL735 Coriolis meter. In-cylinder pressure measurements were made using an AVL piezoelectric GU22C sensor. Power output is related to the indicated mean effective pressure (IMEP) derived from the in-cylinder pressure measurements. Tables 4 and 5 show the full-load operating conditions for gasoline direct injection (GDI) and port fuel injection (PFI) configurations, respectively.

[0115] [Table 4]

[0116] [Table 5]

[0117] result Tables 6 and 7 show the IMEP results obtained for the two engine configurations over a range of speeds at full load engine operating conditions.

[0118] [Table 6]

[0119] [Table 7]

[0120] The results shown in Tables 6 and 7 are graphically depicted in Figures 1 and 2, respectively.

[0121] Tables 8 and 9 below show the fuel consumption and pre-catalyst emissions results obtained for the two engine configurations at 1300 rpm.

[0122] [Table 8]

[0123] [Table 9]

[0124] Consideration The IMEP results for both engine configurations (GDI and PFI) at different engine speeds show that Fuel C (a fuel according to the invention) performs similarly to conventional E10 (Fuel A) and E20 (Fuel B) fuel compositions.

[0125] For both engine configurations, Fuel C has similar fuel consumption performance to the conventional E10 (Fuel A) fuel composition. For E20 (Fuel B), the calorific value (lower heating value) is lower compared to E10 (Fuel A), due to the different and impacting fuel consumption values.

[0126] For both engine configurations, the pre-catalyst emissions (CO, NOx, THC) performance of Fuel C is similar to the reference Fuels A and B (E10 and E20).

[0127] While PN emissions are comparable for all three fuels, Fuel C appears to show beneficial results in terms of PM emissions compared to the conventional E10 fuel (Fuel A). The following describes an embodiment. Aspect 1 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 20% v / v or less, the gasoline blending component comprises: (a) 0 to 30% v / v alkylate; (b) 0 to 15% v / v isomerate; (c) 0 to 20% v / v catalytic cracking top naphtha; and (d) 20% to 40% v / v heavy reformate, wherein the total amount of alkylate, isomerate, catalytic cracking top naphtha, and heavy reformate is at least 50% v / v based on the total fuel composition; A gasoline fuel composition, wherein the gasoline fuel composition meets the EN228 standard. Aspect 2 2. The gasoline fuel composition according to aspect 1, comprising 5 to 15% v / v of oxygenated hydrocarbons, based on the gasoline fuel composition. Aspect 3 Aspect 3. The gasoline fuel composition of aspect 1 or 2, wherein the gasoline blending component comprises 30 to 35 volume % of heavy reformate, based on the gasoline fuel composition. Aspect 4 Aspect 3. The gasoline fuel composition of aspect 1 or 2, wherein the gasoline blending component comprises 20 to 25 volume % of heavy reformate, based on the gasoline fuel composition. Aspect 5 Aspect 5. The gasoline fuel composition of any one of aspects 1 to 4, wherein the gasoline blending component comprises 5 to 20 volume % of catalytic cracking top naphtha, based on the gasoline fuel composition. Aspect 6 Aspect 6. The gasoline fuel composition of any one of aspects 1 to 5, wherein the gasoline blending component comprises 15 to 30 volume % alkylate, based on the gasoline fuel composition. Aspect 7 Aspect 7. The gasoline fuel composition according to any one of aspects 1 to 6, wherein the oxygenated hydrocarbon is selected from alcohols, ethers, and mixtures thereof. Aspect 8 Aspect 8. The gasoline fuel composition according to any one of aspects 1 to 7, wherein the oxygenated hydrocarbon is an alcohol. Aspect 9 Aspect 8. The gasoline fuel composition according to any one of aspects 1 to 7, wherein the oxygenated hydrocarbon is an ether. Aspect 10 Aspect 8. The gasoline fuel composition according to any one of aspects 1 to 7, wherein the oxygenated hydrocarbon is a mixture of an alcohol and an ether. Aspect 11 Aspect 11. The gasoline fuel composition according to aspect 8 or 10, wherein the alcohol is selected from methanol, ethanol, propanol, 2-propanol, butanol, tert-butanol, isobutanol, and 2-butanol, and mixtures thereof. Aspect 12 12. The gasoline fuel composition according to aspect 11, wherein the alcohol is ethanol. Aspect 13 Aspect 13. A gasoline fuel composition according to aspect 12, wherein the ethanol is present at a level of from 5% v / v to 10% v / v, based on the total fuel composition. Aspect 14 11. The gasoline fuel composition according to aspect 9 or 10, wherein the ether is ETBE. Aspect 15 1. A process 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 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 top naphtha, and (d) 20-40% v / v heavy reformate, wherein the total amount of alkylate, isomerate, catalytic cracking top, and heavy reformate is at least 50% v / v, based on the gasoline fuel composition, and the gasoline fuel composition meets the EN228 standard. Aspect 16 15. Use of a gasoline composition according to any one of aspects 1 to 14 for fuelling a spark-ignition internal combustion engine, such as a passenger car.

Claims

1. 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 5-20% v / v; the gasoline blending component comprises, based on the total fuel composition, (a) 15 to 30% v / v alkylate; (b) 5 to 15% v / v isomerate; (c) 5 to 20% v / v catalytic cracking top naphtha; and (d) 20% to 40% v / v heavy reformate, wherein the total amount of alkylate, isomerate, catalytic cracking top naphtha, and heavy reformate is at least 50% v / v; the oxygenated hydrocarbon is a mixture of an alcohol and an ether; A gasoline fuel composition, wherein the gasoline fuel composition meets the EN228 standard.

2. 2. The gasoline fuel composition of claim 1, comprising 5 to 15% v / v of oxygenated hydrocarbons, based on the gasoline fuel composition.

3. 3. The gasoline fuel composition of claim 1 or 2, wherein the gasoline blending component comprises 30 to 35 volume percent of heavy reformate, based on the gasoline fuel composition.

4. 3. The gasoline fuel composition of claim 1 or 2, wherein the gasoline blending component comprises 20 to 25 volume percent of heavy reformate, based on the gasoline fuel composition.

5. 5. A gasoline fuel composition according to any one of claims 1 to 4, wherein the alcohol is selected from methanol, ethanol, propanol, 2-propanol, butanol, tert-butanol, isobutanol and 2-butanol, and mixtures thereof.

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

7. 7. The gasoline fuel composition of claim 6, wherein the ethanol is present at a level of from 5% v / v to 10% v / v, based on the total fuel composition.

8. A gasoline fuel composition according to any one of claims 1 to 7, wherein the ether is ETBE.

9. 1. A process for preparing a gasoline fuel composition comprising blending (a) a gasoline blending component, (b) renewable naphtha at a level of 10-30% v / v, and (c) oxygenated hydrocarbons at a level of 5-20% v / v, the gasoline blending component comprises, based on the gasoline fuel composition, (a) 15 to 30% v / v alkylate; (b) 5 to 15% v / v isomerate; (c) 5 to 20% v / v catalytic cracking top naphtha; and (d) 20 to 40% v / v heavy reformate, wherein the total amount of alkylate, isomerate, catalytic cracking top, and heavy reformate is at least 50% v / v; the oxygenated hydrocarbon is a mixture of an alcohol and an ether; The process wherein the gasoline fuel composition meets the EN 228 standard.

10. 9. Use of a gasoline composition according to any one of claims 1 to 8 for fuelling a spark ignition internal combustion engine such as a passenger car.

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