CN115812096A

CN115812096A - Fuel composition

Info

Publication number: CN115812096A
Application number: CN202180049652.2A
Authority: CN
Inventors: J·施特龙克; Y·V·海姆伯格; F·J·巴尔塔萨
Original assignee: Shell Internationale Research Maatschappij BV
Current assignee: Shell Internationale Research Maatschappij BV
Priority date: 2020-07-20
Filing date: 2021-07-15
Publication date: 2023-03-17
Also published as: EP4182420A1; BR112023000164A2; CA3189342A1; WO2022017912A1; JP2023534510A; MX2023000822A; US20230227742A1

Abstract

A gasoline fuel composition for a spark-ignition internal combustion engine comprising (a) a gasoline blending component, (b) 10-30% v/v level of renewable naphtha and (c) 20% v/v or less level of oxygenated hydrocarbons, 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 rating of renewable naphthas will generally severely limit their blendability in gasoline to low levels, it has now been found that renewable naphthas can be included in, for example, ethanol-containing gasoline fuel compositions at surprisingly and significantly high renewable naphtha to ethanol blending ratios.

Description

Fuel composition

Technical Field

The present invention is in the field of fuel formulations, particularly gasoline type fuel formulations for spark-ignited internal combustion engines.

Background

Fuels are typically produced by refining crude oil (petroleum). This typically involves separating various fractions of the crude oil by distillation. One such fraction is naphtha, which is a volatile liquid fraction that distills between the light gaseous components of the crude oil and the heavier kerosene fraction. Naphtha contains a mixture of hydrocarbons (linear, branched, naphthenic, and aromatic) boiling between about 30 ℃ and about 200 ℃. The density of the naphtha is generally in the range from 750 to 785kg/m ³ . Naphtha has many uses, one of which is as an automotive fuel.

Naphtha has historically not been used in gasoline, or only in low amounts, due to the low octane number, although the longer chain molecules in gasoline have high cetane numbers and can be blended into diesel. This is true despite the fact that naphtha has comparable distillation properties to gasoline.

Renewable fuels derived from biomass ("biofuels") are increasingly being used as a more sustainable alternative to fossil fuels. Due to the recent increase in the production of renewable naphthas, it would be advantageous to be able to blend renewable naphthas into gasoline, particularly at high blending ratios. The use of renewable naphthas with higher blending ratios has the potential to achieve higher CO ₂ Emission reduction, and can help meet regulatory emission reduction targets as specified by the paris protocol (2016). At the same time, it is desirable to be able to formulate gasoline fuel compositions that meet existing gasoline fuel specifications, such as, but not limited to, EN228 and North American specifications, e.g., ASTM D4814-13b, american convention, caRFG No. 3, federal RFG No. II, CAN/CGSB-3.5.

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

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 at 20 ℃ of about 0.680 to about 0.740. In one embodiment, the renewable naphtha is used as an alternative gasoline fuel for internal combustion engines when blended with ethanol at 1 to 85 volume percent.

WO2018/234187 relates to a process for producing renewable base oils, diesel and naphtha from feedstocks of biological origin. However, no specific gasoline fuel formulation containing renewable naphtha produced in the process is disclosed in WO 2018/234187.

WO2018/069137 relates to a process for preparing an alkylated gasoline composition comprising renewable naphtha and isooctane and isopentane. The example of alkylated gasoline in table 2 contains up to 5 vol% renewable naphtha. The gasoline composition in this application is free of oxygenates and focuses on small general purpose gasoline engines for various portable gasoline powered tools such as chain saws and lawn mowers.

US9885000B2 relates to a renewable hydrocarbon composition obtainable from a renewable biological feedstock. The composition is useful as a fuel component.

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 fuel blend.

While the low octane number of renewable naphthas will generally severely limit their blendability in gasoline to low levels, the present inventors have now discovered that renewable naphthas CAN be included in, for example, ethanol-containing gasoline fuel compositions in surprisingly and significantly high blend ratios of renewable naphthas (e.g., high blend ratios of renewable naphthas with ethanol) while still meeting gasoline fuel specifications, such as, but not limited to, EN228 and north american specifications, e.g., ASTM D4814-13b, american convention, calfg 3, federal RFG II, CAN/CGSB-3.5.

Disclosure of Invention

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 to 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 to 30% v/v alkylate, (b) 0 to 15% v/v isomerate, (c) 0 to 20% v/v catalytic cracking overhead (CCT) naphtha; and (d) 20-40% v/v heavy reformate, wherein the total amount of alkylate, isomerate, catalytic cracking overhead (CCT) naphtha, and heavy reformate is at least 50% v/v based on the gasoline fuel composition,

and wherein the gasoline fuel composition meets EN228 fuel specification.

In accordance with 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) 10 to 30% vol/vol level of renewable naphtha and (c) 20% vol/vol or less level of oxygenated hydrocarbon,

and wherein the gasoline fuel composition meets EN228 specification.

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

The present inventors have surprisingly found that limitations typically encountered due to the low octane number of renewable naphthas can be overcome by blending gasoline blending components in specific concentrations and ratios.

In addition, the fuel composition of the present invention has the advantage of meeting EN228 fuel specification requirements.

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

The liquid fuel compositions of the present invention also provide excellent fuel economy, emissions and power benefits as required by the EN228 specification.

Drawings

FIG. 1 is a graphical representation of the results shown in Table 6.

Fig. 2 is a graphical representation of the results shown in table 7.

Detailed Description

The liquid fuel composition of the present invention comprises gasoline blending components such as a gasoline base fuel suitable for use in an internal combustion engine, a renewable naphtha at a level of 10 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.

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

The liquid fuel composition herein comprises 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 boiling points in the range of 30 ℃ to 200 ℃. The liquid fuel composition herein comprises naphtha, which is renewable naphtha, also referred to as renewable naphtha distillate, or bio-renewable naphtha.

The renewable naphtha distillate may be produced as part of a renewable diesel refinery. Renewable diesel may be obtained from the processing of fatty acid containing materials such as animal fats, algae, and plant materials. The plant material may include vegetable-based materials such as rape oil as well as oils obtained from other plants, such as oils from trees, e.g. tall oil. Renewable diesel and renewable naphtha distillates may be obtained from the 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 ℃ or about 35 ℃ and a Final Boiling Point (FBP) of about 200 ℃ or about 205 ℃. The hydrocarbons present in the distillation typically range from hydrocarbons containing 4 or 5 carbon atoms to hydrocarbons containing about 10 or 11 or 12 carbon atoms.

Renewable fuels such as renewable naphtha distillates are collected from resources that are naturally supplemented on a human time scale, as opposed to fossil fuels such as petroleum gasoline derived from crude oil refining. The renewable naphtha distillate may be obtained from hydrotreating of fatty acids and their derivatives present in fatty acid-containing materials (such as animal fats and plant materials), including hydrodeoxygenation and hydroisomerization, and may include fractions having an IBP of 30 ℃, such as an IBP of 30 ℃ or higher, and an FBP of 200 ℃, such as an FBP of 200 ℃ 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 gas samples using radioactive carbon Analysis (Liquid and gases Using Radiocarbon Analysis)" for determination of Biobased Content of Solid, liquid and gas samples. Then can be related to ¹⁴ C、 ¹³ C and/or ¹² Isotopic distribution of C to determine renewable content as described in ASTM D6866.

Because the paraffins of renewable naphtha are obtained from the processing of fatty acid containing materials, such as animal fats and plant materials, renewable naphtha distillates are paraffins with little naphthenes and little aromatics or oxygenates.

Renewable naphtha distillates are composed primarily of paraffins (alkanes), which may be linear normal paraffins or branched isoparaffins. The renewable naphtha can have 90 vol% or more C ₅ -C ₁₂ Alkanes, such as C95 vol% or more ₅ -C ₁₂ Paraffins, or 98 vol% or more of C ₅ -C ₁₂ An alkane.

Renewable naphtha distillate when produced as part of refining renewable diesel as described above, renewable naphthaThe distillate may comprise 30 vol% or more, such as 40 vol% or more of C ₅ -C ₆ An alkane.

In addition to containing primarily paraffins, renewable naphtha distillates have a low content of naphthenes (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 vol% or less naphthenes, such as 1 vol% or less naphthenes, or 0.5 vol% or less naphthenes.

In addition to containing primarily paraffins, renewable naphtha distillates have a very low content of aromatics. Aromatic compounds contain a benzene ring or other aromatic ring structure. The renewable naphtha distillate may have 1 vol% or less aromatics, such as 0.5 vol% or less aromatics, or 0.1 vol% or less aromatics.

In addition to containing primarily paraffins, renewable naphtha distillates have a very low content 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 soot produced during fuel combustion. Common oxygenates include alcohols, ethers and esters. The renewable naphtha distillate may have 1 vol% or less oxygenates, such as 0.5 vol% or less oxygenates, or 0.1 vol% or less oxygenates, although it is preferably substantially free of oxygenates.

The renewable naphtha used herein has a low octane number, i.e. for example has a RON and/or MON of from 35 to 70, such as from 35 to 60, or from 35 to 50, or from 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 compositions of the present invention at relatively high levels, and that the final gasoline fuel composition has a higher octane number (RON) than expected.

The renewable naphtha distillate may have a vapor pressure less than 30kPa, such as less than 25kPa, such as less than 20 kPa. The vapor pressure of the renewable naphtha can likewise be 10kPa or higher, such as 15kPa or higher.

In a preferred embodiment, the renewable naphtha as used herein comprises: 90% by volume or more of C ₅ -C ₁₂ Paraffin, 30 vol% or more C ₅ -C ₆ Paraffins, 5 volume% or less naphthenes, 1 volume% or less aromatics, 1 volume% or less oxygenates.

The renewable naphtha distillate may have a boiling point range of 30 ℃ to 200 ℃, such as 90 ℃ to 200 ℃, or 40 ℃ to 180 ℃.

The amount of renewable naphtha present in the gasoline fuel composition of the present invention is from 10 to 30 volume%, preferably from 15 to 25 volume%, even more preferably from 18 to 22 volume%, and especially 20 volume% based on the total fuel composition. To increase the renewable portion of the gasoline composition of the present invention, it is preferred to be able to add as much renewable naphtha as possible.

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

The renewable naphtha oil 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.

Renewable naphtha components are commercially available from the nano-meter company of Finland (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.

In the liquid fuel compositions herein, the renewable naphtha component of the invention can include a mixture of two or more renewable naphthas, or a mixture of renewable naphthas with petroleum-derived naphthas and/or fischer-tropsch-derived naphthas.

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

It will be understood by those skilled in the art that the gasoline blend component may already contain some naphtha component. The above-mentioned concentration of naphtha means the concentration of naphtha added to the liquid fuel composition as a blend with the gasoline blending component and excludes the concentration of any naphtha component already present in the gasoline blending component.

In addition to the renewable naphtha, the liquid fuel composition of the present invention also comprises oxygenated hydrocarbons at a level of 20 volume% or less, preferably at a level of 5 to 15% volume/volume based on the liquid fuel composition. In one embodiment, the oxygenated hydrocarbon is present at a level of 7 to 12% v/v based on the liquid fuel composition. In another embodiment, the oxygenated hydrocarbon is present at a level of 10 to 15% v/v based on the liquid fuel composition.

It will be appreciated by those skilled in the art that the gasoline base fuel may already contain some oxygenated hydrocarbon component. The above-mentioned concentration of oxygenated hydrocarbons means the concentration of oxygenated hydrocarbons added to the liquid fuel composition as a blend with the gasoline base fuel and does not include the concentration of any oxygenated hydrocarbon components already present in the gasoline base fuel.

Examples of suitable oxygenated hydrocarbons that may be incorporated into gasoline include alcohols, ethers, esters, ketones, aldehydes, carboxylic acids and their derivatives, as well as oxygenated heterocyclic compounds and mixtures thereof. In one embodiment of the invention, the oxygenated hydrocarbon is selected from the group consisting of alcohols, ethers, and esters, and mixtures thereof.

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. The 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.

The oxygenated hydrocarbon is preferably selected from the group consisting of alcohols, ethers and mixtures thereof. In a preferred embodiment of the invention, the oxygenated hydrocarbon is selected from alcohols, preferably at a level of from 0.1 to 10% v/v, more preferably at a level of from 5 to 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 from 0.1 to 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 to 10% v/v alcohol and 2 to 5% v/v ether based on the gasoline fuel composition.

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 to 10% v/v, more preferably from 5 to 10% v/v, based on the total gasoline fuel composition. In one embodiment of the invention, ethanol is present as the sole oxygenated hydrocarbon.

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 compositions herein at from 0.1 to 15% v/v based on the total gasoline fuel composition. In another embodiment of the invention, ETBE is present as the sole oxygenated hydrocarbon.

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

When both the oxygenated hydrocarbon and the naphtha are renewable sources, the share of renewable content in the gasoline composition increases. For example, bioethanol may be used as oxygenated hydrocarbon herein.

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 of a 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.

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

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

The gasoline blend component comprises 0 to 30% vol/vol, preferably 15 to 30% vol/vol, more preferably 15 to 25% vol/vol alkylate based on the total gasoline fuel composition.

The alkylate is obtained by reacting isobutane with a hydrocarbon generally having a carbon number in the range of C ₃ To C ₅ A complex combination of hydrocarbons resulting from the distillation of the reaction product of the monoolefin. Alkylate is a refinery stream and is predominantly composed of carbon numbers predominantly in C ₇ To C ₁₂ A branched saturated hydrocarbon composition in the range and boiling point in the range of about 90 ℃ to 220 ℃ (194 ° F to 428 ° F).

The gasoline blend component comprises 0 to 15% v/v, preferably 5 to 10% v/v, of the isomerate based on the total gasoline fuel composition.

The isomerate being derived from straight-chain paraffins C ₄ To C ₆ A complex combination of hydrocarbons obtained by catalytic isomerization of hydrocarbons. The isomerate is a refinery stream and consists primarily of saturated hydrocarbons such as isobutane, isopentane, 2,2-dimethylbutane, 2-methylpentane and 3-methylpentane, and boils in the range of about 35 ℃ to 220 ℃ (95 ° f to 428 ° f).

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 overhead, and heavy reformate in the final fuel composition is at least 50% v/v based on the total gasoline fuel composition.

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

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 mainly consists of carbon number mainly at C ₇ To C ₁₂ An aromatic hydrocarbon composition in the range and boiling point in the range of about 90 ℃ to 230 ℃ (194 ° F to 446 ° F). Heavy reformate is a refinery stream rich in aromatics and high octane components (typically 98-102 RON) depending on requirements, plant type and naphtha feed, and is used for automotive gasoline blending or as a feedstock.

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

CCT naphtha (or light cat cracked naphtha), also known as FCC naphtha (fluid catalytic cracked naphtha), is a complex combination of hydrocarbons produced by distillation of products from a fluid catalytic cracking process. Fluid Catalytic Cracking (FCC) is widely used to convert high boiling, 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 offgas. After further processing to remove sulfur compounds, the cracked naphtha becomes the high octane component of the refinery's blended gasoline. CCT naphtha/FCC naphtha consists of hydrocarbons with carbon numbers predominantly in the C4 to C11 range and boiling points in the range of about-20 ℃ to 190 ℃ (-4 ° f to 374 ° f). CCT naphtha/FCC naphtha is a refinery stream and contains a relatively large proportion of unsaturated hydrocarbons depending on requirements, type of plant and naphtha feed, and is used for mogas blending or as feedstock. CCT naphtha/FCC naphtha has a CAS number of 64741-55-5.

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

Although not critical to the present invention, the gasoline composition of the present invention may conveniently include one or more optional fuel additives. The concentration and nature of the optional fuel additives that may be included in the gasoline blend components or gasoline compositions of the present invention are not critical. Non-limiting examples of suitable types of fuel additives that can be included in the gasoline blend components or gasoline compositions of the present invention include antioxidants, corrosion inhibitors, detergents, dehazers, antiknock additives, metal deactivators, valve seat recession protector compounds, dyes, solvents, carrier fluids, diluents, and markers. Examples of suitable such additives are generally described in U.S. Pat. No. 5,855,629.

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

The (active matter) concentration of any optional additives present in the gasoline blend component or gasoline composition of the present invention is preferably at most 1%m/m, more preferably in the range of 5-2000mg/kg, advantageously in the range of 300-1500mg/kg, such as 300-1000mg/kg.

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

Examples of suitable mineral carrier oils are fractions obtained in crude oil processing, such as bright stock or base oils having, for example, a SN 500-2000 grade viscosity; and aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. Also useful as mineral carrier oils are the fractions obtained in mineral oil refining and are known as "hydrocracked oils" (vacuum fractions, boiling in the range of about 360 ℃ to 500 ℃, obtainable from natural mineral oils which are catalytically hydrogenated and isomerized and dewaxed at high pressure).

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 esters of long-chain alkanols.

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

Examples of suitable polyethers or polyether amines are preferably those containing polyoxy-C ₂ -C ₄ Compounds of alkylene moieties obtainable by reacting C ₂ -C ₆₀ Alkanol, C ₆ -C ₃₀ Alkanediols, mono-or di-C ₂ -C ₃₀ Alkyl amine, C ₁ -C ₃₀ Alkylcyclohexanols or C ₁ -C ₃₀ Alkylphenols are obtained by reaction with from 1 to 30mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group 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 U.S. Pat. No. 4,877,416. The polyetheramine used may be, for example, poly-C ₂ -C ₆ -an oxyalkylene amine or a functional derivative thereof. Typical examples thereof are tridecanol butoxylates or isotridecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates, and also the corresponding reaction products with ammonia.

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-38 918. 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, from 6 to 24 carbon atoms. Typical representatives of esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol, for example di (n-tridecyl or isotridecyl) phthalate.

Other suitable carrier oil systems are described, for example, in DE-A-38 608, 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.

Examples of particularly suitable synthetic carrier oils are those having about 5 to 35, such as about 5 to 30C ₃ -C ₆ Alcohol-initiated polyethers of oxyalkylene 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, in particular straight or branched C ₆ -C ₁₈ -an alkyl group. Preferred examples include tridecanol and nonylphenol.

Other suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A-10 102 913.6.

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

Any solvent and optional co-solvent suitable for use in fuels may be used. Examples of suitable solvents for fuels include: non-polar hydrocarbon solvents such as kerosene, heavy aromatic solvents ("miscella heavy", "Solvesso 150"), toluene, xylene, paraffin, petroleum, white spirits (white spirits), those sold under the trade name "SHELLSOL" by Shell companies, and the like. Examples of suitable co-solvents include: polar solvents, such as esters, and in particular alcohols (for example tert-butanol, isobutanol, hexanol, 2-ethylhexanol, 2-propylheptanol, decanol, isotridecyl alcohol, butylethylene glycol and alcohol mixtures, such as those sold by the Shell company under the trademark "LINEVOL", in particular LINEVOL 79 alcohol, which is C _7-9 Mixtures of primary alcohols, or C _12-14 Alcohol mixtures, which are commercially available).

Dehazing/demulsifying agents 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 tradename TOLAD) ^TM Sold as 9312), alkoxylated phenol-formaldehyde polymers,By using C _1-18 Modified phenol/formaldehyde or C by oxyalkylation of epoxide and diepoxide _1-18 Alkyl phenol/formaldehyde resin oxyalkylates (such as TOLAD under the trade name TOLAD) ^TM Sold 9308), and C crosslinked with diepoxides, diacids, diesters, diols, diacrylates, dimethacrylates or diisocyanates _1-4 Epoxide copolymers, and blends thereof. The diol oxyalkylation polyol blend may be with C _1-4 An epoxide oxyalkylated polyol. By using C ₁ - ₁₈ Epoxide and diepoxide alkoxylation modified C _1-18 The alkylphenol/formaldehyde resin alkoxylate may be based on, for example, cresol, tert-butylphenol, dodecylphenol or dinonylphenol, or mixtures of phenols (such as mixtures of tert-butylphenol and nonylphenol). The amount of dehazer used should be sufficient to suppress fogging which may occur when gasoline without the dehazer is contacted with water and this amount is referred to herein as the "dehazing amount". Typically, the amount is from about 0.1 to 20mg/kg (e.g., from about 0.1 to 10 mg/kg), more preferably from 1 to 15mg/kg, still more preferably from 1 to 10mg/kg, advantageously from 1 to 5mg/kg, based on the weight of the gasoline.

Other conventional additives used in gasoline are corrosion inhibitors, for example based on ammonium salts of organic carboxylic acids, which salts tend to form films, or based on ammonium salts of heterocyclic aromatics for corrosion protection of nonferrous metals; antioxidants or stabilizers, for example based on amines such as phenylenediamine, for example p-phenylenediamine, N' -di-sec-butyl-p-phenylenediamine, dicyclohexylamine or derivatives thereof, or on phenols such as 2,4-di-tert-butylphenol or 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid; an antistatic agent; metallocenes such as ferrocene; methyl-cyclopentadienyl manganese tricarbonyl; lubricity additives, such as certain fatty acids, alkenyl succinates, bis (hydroxyalkyl) fatty amines, hydroxyacetamides, or castor oil; and dyes (markers). If appropriate, it is also possible to add amines, as described, for example, in WO 03/076554. Optionally, an anti-valve seat recession additive, such as a sodium or potassium salt of a polymeric organic acid, may be used.

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

Preferred detergent additives for use in the gasoline compositions herein typically have at least one hydrophobic hydrocarbon group having a number average molecular weight (Mn) of from 85 to 20000 and at least one polar moiety selected from:

(A1) A mono-or polyamino group having up to 6 nitrogen atoms, wherein at least one nitrogen atom has basic properties;

(A6) Poly oxo-C ₂ -to-C ₄ -alkylene groups terminated by hydroxyl, mono-or polyamino groups, wherein at least one nitrogen atom has basic properties, or by carbamate groups;

(A8) A moiety derived from succinic anhydride and having a hydroxyl group and/or an amino group and/or an amido group and/or an imido group; and/or

(A9) A moiety obtained by Mannich reaction of a substituted phenol with an aldehyde and a monoamine or polyamine.

The hydrophobic hydrocarbon groups of the detergent additives which ensure sufficient solubility in the base fluid have a number average molecular weight (Mn) of from 85 to 20000, in particular from 113 to 10000, in particular from 300 to 5000. Typical hydrophobic hydrocarbon groups, particularly in combination with the polar moieties (A1), (A8) and (A9), include polyolefins (polyalkene/polyolefins), such as polypropenyl, polybutenyl and polyisobutenyl, each having an Mn of from 300 to 5000, preferably from 500 to 2500, more preferably from 700 to 2300, and particularly from 700 to 1000.

Non-limiting examples of the detergent additive package described above include the following:

the additives comprising mono-or polyamino groups (A1) are preferably polyolefin mono-or polyamines based on polypropylene having an Mn of 300 to 5000 or on conventional (i.e.predominantly having internal double bonds) polybutenes or polyisobutylenes. When polybutenes or polyisobutylenes having predominantly internal double bonds, usually in the beta and gamma positions, are used as starting materials for the preparation of the additives, 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 (hydrogenating) conditions. The amine used for the amination here may be, for example, ammonia, a mono-or polyamine, such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. Corresponding additives based on polypropylene are described in particular in WO-A-94/24231.

Other preferred additives comprising monoamino groups (A1) are the hydrogenation products of the reaction products of polyisobutenes 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.

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.

Comprising polyoxy-C ₂ -C ₄ The additive of the alkylene moiety (A6) is preferably a polyether or polyetheramine, which may be reacted by C ₂ -to C ₆₀ -alkanol, C ₆ -to C ₃₀ Alkanediols, mono-or di-C ₂ -C ₃₀ Alkyl amine, C ₁ -C ₃₀ Alkylcyclohexanols or C ₁ -C ₃₀ Alkylphenols are obtained by reaction with from 1 to 30mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group 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, 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 also the corresponding reaction products with ammonia.

The additive comprising the moiety (A8) derived from succinic anhydride and having hydroxyl and/or amino and/or amido and/or imido groups is preferably the corresponding derivative of polyisobutenyl succinic anhydride, which is obtainable by reacting a conventional or highly reactive polyisobutene having an Mn of from 300 to 5000 with maleic anhydride by thermal route or via a 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-se:Sup>A-4 849 572.

The additive comprising the moiety (A9) obtained by mannich reaction of a substituted phenol with an aldehyde and a mono-or polyamine is preferably the reaction product of a polyisobutene-substituted phenol with formaldehyde and a mono-or polyamine such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine. The polyisobutenyl-substituted phenol may be derived from a conventional or highly reactive polyisobutylene having an Mn of 300 to 5000. Such "polyisobutene-Mannich bases" are described in particular in EP-A-831 141.

Preferably, the detergent additive used in the gasoline composition of the present invention comprises at least one nitrogen-containing detergent, more preferably at least one nitrogen-containing detergent comprising 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.

In the above, the amount of the component (concentration,% volume/volume, mg/kg (ppm),% m/m) is the amount of active substance, i.e. excluding volatile solvent/diluent materials.

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

The fuel composition of the present invention is suitable for use in spark-ignition internal combustion engines, such as those used in passenger vehicles. Thus, according to another aspect of the present invention there is provided the use of a gasoline composition as hereinbefore described for fuelling a spark-ignition internal combustion engine in a passenger vehicle.

The fuel composition of the invention is also suitable for use in a spark-ignition internal combustion engine when used in the driveline of a hybrid electric vehicle, particularly 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 hereinbefore described 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.

The fuel compositions of the present invention have 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 vehicle.

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

Example 1

Several fuel blends were prepared having the properties and compositions shown in table 1 below.

Fuel a is a standard refinery E10 gasoline market fuel formulation (containing 10% v/v ethanol) meeting EN228 class a specifications.

Fuel B was an E20 gasoline fuel formulation containing 20% v/v ethanol and 20% v renewable naphtha (but not meeting EN228 class a specifications due to not meeting the maximum 3.7 wt% oxygen specification in EN 228).

Fuel C is a gasoline fuel formulation that meets EN228 class a specifications and contains 9% v/v ethanol and 20% v/v renewable naphtha.

Fuel D is a gasoline fuel formulation that meets EN228 class a specifications and contains 8% v/v ethanol and 20% v/v renewable naphtha.

Renewable naphthas used in fuels B, C and D are supplied by UPM under the trade name UPM BioVerno naphtha.

Ethanol used in the examples was not bioethanol modified with 2% toluene as supplied by Clariant corporation (Clariant) under the trade name Sunliquid (RTM) bioethanol (99.8%).

The alkylate/isomerate/ETBE components used in the examples are supplied together as a mixture under the trade name ASF by Shell Global Solutions, inc (Shell Global Solutions).

The CCT naphtha (also known as FCC naphtha) used has a CAS number of 64741-55-5.

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

The fuel analysis results in table 1 below show that renewable naphtha can be blended with gasoline blend components in specific concentrations/ratios to give ethanol-containing fuels in accordance with EN 228.

TABLE 1

1. Fuel a is a standard refinery market fuel and therefore no fuel blending details are available.

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

3. Provided in the form of a mixture containing alkylate, isomerate and ETBE

ND = not determined

N/A = not applicable

* Comparative example

As can be seen from table 1 above, the RON (measured value) of fuel C is 97, and the RON (measured value) of fuel D is 96. This is surprising in view of the high level 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 within the composition (see table 2 below). As can be seen in Table 2 below, the calculated RON value for fuel C is 92, while the measured RON value is 97. It can also be seen that the calculated RON value for fuel D is 91 and the measured RON value is 96.

TABLE 2

Emissions and power performance testing

Fuel a (E10), fuel B (E20) and fuel C (according to the 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 the standard E10 and E20 fuels. The engine specification details are listed in table 3 below.

Table 3: details of engine specifications

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

Pre-catalyst emissions were measured with the 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. The power output is related to an Indicated Mean Effective Pressure (IMEP) derived from 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.

Table 4: operating conditions for Gasoline Direct Injection (GDI) configuration

Table 5: operating conditions for a Port Fuel Injection (PFI) configuration

Results

Tables 6 and 7 list IMEP results obtained for a range of speeds for two engine configurations at full engine operating conditions.

Table 6: IMEP results for Gasoline Direct Injection (GDI) configuration

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

The results listed in table 6 and table 7 are illustrated in fig. 1 and fig. 2, respectively.

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

Table 8: fuel consumption and emissions results for Gasoline Direct Injection (GDI) configuration

¹ Particle number emissions

² Particulate matter emissions

Table 9: fuel consumption and emissions results for Port Fuel Injection (PFI) configurations

¹ Particle number emission

² Particulate matter emissions

Discussion of the related Art

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.

For both engine configurations, fuel C has fuel consumption properties similar to conventional E10 (fuel a) fuel compositions. For E20 (fuel B), the fuel consumption performance is lower compared to E10 (fuel a) because the calorific value (lower calorific value) is different and affects the fuel consumption value.

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).

Although PN emissions for all three fuels are at comparable levels, fuel C shows beneficial results for PM emissions compared to the conventional E10 fuel (fuel a).

Claims

1. A gasoline fuel composition for a spark-ignition internal combustion engine comprising (a) a gasoline blending component, (b) 10 to 30% vol/vol level of renewable naphtha and (c) 20% vol/vol or less level of oxygenated hydrocarbons,

wherein 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 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.

2. The gasoline fuel composition of claim 1 comprising 5-15% vol/vol oxygenated hydrocarbon based on the gasoline fuel composition.

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

4. The gasoline fuel composition of claim 1 or 2, wherein the gasoline blending component comprises 20-25 vol% heavy reformate based on the gasoline fuel composition.

5. The gasoline fuel composition of any one of claims 1-4, wherein the gasoline blending component comprises 5-20 vol% of a catalytically cracked overhead naphtha, based on the gasoline fuel composition.

6. The gasoline fuel composition of any of claims 1-5, wherein the gasoline blending component comprises 15-30 vol% alkylate, based on the gasoline fuel composition.

7. The gasoline fuel composition of any of claims 1-6, wherein the oxygenated hydrocarbon is selected from the group consisting of alcohols, ethers, and mixtures thereof.

8. The gasoline fuel composition of any of claims 1-7, wherein the oxygenated hydrocarbon is an alcohol.

9. The gasoline fuel composition of any one of claims 1-7, wherein the oxygenated hydrocarbon is an ether.

10. The gasoline fuel composition of any of claims 1-7, wherein the oxygenated hydrocarbon is a mixture of an alcohol and an ether.

11. The gasoline fuel composition of claim 8 or 10, 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.

12. The gasoline fuel composition of claim 11, wherein the alcohol is ethanol.

13. The gasoline fuel composition of claim 12, wherein the ethanol is present at a level of 5-10% v/v based on the total fuel composition.

14. The gasoline fuel composition of claim 9 or 10, wherein the ether is ETBE.

15. A process for preparing a gasoline fuel composition comprising blending (a) a gasoline blend component, (b) a renewable naphtha at a level of 10 to 30% v/v, and (c) an oxygenated hydrocarbon at a level of 20% v/v or less, wherein the gasoline blend component comprises (a) 0 to 30% v/v of an alkylate, (b) 0 to 15% v/v of an isomerate; (c) 0-20% v/v catalytically cracked overhead naphtha; 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 gasoline fuel composition, and wherein the gasoline fuel composition meets EN228 specification.

16. Use of a gasoline composition according to any one of claims 1-14 for fueling a spark-ignition internal combustion engine, such as in a passenger vehicle.