FI129568B

FI129568B - 2-butanone and ethanol as gasoline components

Info

Publication number: FI129568B
Application number: FI20215443A
Authority: FI
Inventors: Anna Karvo; Ulla Kiiski; Terhi Kolehmainen
Original assignee: Neste Oyj
Priority date: 2021-04-15
Filing date: 2021-04-15
Publication date: 2022-04-29
Also published as: WO2022219234A1; FI20215443A1

Abstract

Herein is provided a novel use of 2-butanone and ethanol as components to a gasoline composition for adjusting the distillation behaviour of the gasoline composition. The sum oxygenate content in the gasoline composition may be up to 34 vol-% and, the lower vapor pressure and predictable distillation curve provide advantages for planning and production of gasoline compositions by blending.

Description

2-BUTANONE AND ETHANOL AS GASOLINE COMPONENTS

TECHNICAL FIELD The present disclosure generally relates to gasoline compositions, for example gasoline fuels produced as blends. The disclosure relates particularly, though not exclusively, to use of specified components for improved oxygenate containing gasoline compositions. Further, the present disclosure relates to adjusting physical properties of gasoline compositions.

BACKGROUND Gasoline is a liquid product also known as petrol, primarily used as fuel. Gasoline has traditionally consisted mostly of hydrocarbons, obtained by fractional distillation of the naturally occurring petroleum and typically blended to meet desired quality. The demand for sustainable alternative fuels or components in gasoline is constantly growing. When used as a road transport fuel, the gasoline must fulfil the standards of automotive fuels, e.g. European standards and requirements in European standard EN228:2012 Amended 2017. Today, ethanol is the most frequently used bio-based component in gasoline blends, but alternative gasoline components are also identified and studied. However, an upper limit for the oxygen content in gasolines typically restricts the use of oxygen containing components in gasoline blends. The physical behaviour of a gasoline blend comprising an amount of ethanol is not always optimal when it comes to e.g. distillation behaviour, dry vapor pressure, flexibility of the gasoline blending, emission control of volatile hydrocarbons, and water tolerance. Distillation characteristics directly affect vehicle performance, such as starting, driveability, and fuel economy. Hence, balanced distillation characteristics in the gasoline ensure or improve driveability. It would be desirable if the ethanol used in gasoline blends could be S replaced fully or partly by other components of biological origin and, therefore, there is a S 25 constant need for research for alternative or supplementary bio-based components to o ethanol. = Attempts to complement or replace ethanol as a gasoline blend component typically focus a n at one of the physical properties at a time. Even though there is some interrelation, one I property cannot predict another and they can even be counterproductive. In the prior art, = 30 publication EP 1 252 268 discloses a method of reducing the vapor pressure of ethanol- N containing motor fuels for spark ignition combustion engines, wherein the fuel may contain other alkanols.

In the prior art, there are further publications reporting results regarding e.g. vapor pressure.

Different methods for determining vapor pressure of a fuel sample are available, such as dry vapor pressure equivalent (DVPE) or Reid vapor pressure (RVP). For example, patent application publication US 2006/0162243 relates to compositions of oxygenated gasolines further comprising a RVP-reducing compound that have reduced vapor pressure, and methods of reducing vapor pressure.

The gasoline blends reported therein comprise oxygen-containing components in blends comprising 2.5 vol% ethanol, 5 % ethanol, or 10 % ethanol.

However, these blends have an unpredictable nature, and some of them were reported to have negative blend RVP values.

It should further be noted that these results — contain uncertainty because of methods for determining vapor pressure of a fuel sample, DVPE is considered better suited for gasoline blends comprising ethanol than RVP.

Another publication of prior art, EP 1 589 091 A1, uses said dry vapour pressure equivalent (DVPE) to study fuel composition including a hydrocarbon liquid and ethanol by using an oxygen-containing additive.

The aim was to find a method for lowering DVPE.

It provides a broad experimental part covering basic lab tests, drivability tests, exhaust emissions and fuel consumption for a large number of different compositions containing oxygen-containing additives.

Regardless the extent of experimentation, no specific preference among composition varieties was highlighted.

The authors conclude that it is not always necessary to reduce the excess DVPE of the motor fuel induced by the presence of ethanol to the level of the DVPE of the source gasoline.

To overcome some problems of the prior art, the object of the present invention is to provide an improved use and composition of a base gasoline, ethanol and a further component for adjusting the distillation behaviour of gasoline compositions comprising ethanol.

In particular an aim is to provide use and composition, where the distillation curves are balanced and more predictable.

O Another object is to provide controlled distillation behaviour for a gasoline composition o comprising ethanol by substituting some or all of the ethanol with a further gasoline a component. o = Yet another object is to provide a gasoline composition that makes use of flexible gasoline N 30 compositions wherein the distillation behaviour is controlled by choosing specific 3 components for addition to the blend, thereby providing a beneficial E70 value in the N composition thereof and/or a beneficial vapor pressure. - In addition, an object is to provide the use of ethanol and a further gasoline component as blending components in a gasoline composition.

Finally, an object is to provide a new gasoline composition for the above use.

SUMMARY According to a first example aspect here is provided a use of 2-butanone and ethanol as components to a gasoline composition for adjusting the distillation behaviour of the gasoline composition. According to a second example aspect here is provided the use of 2-butanone and ethanol as gasoline components, wherein the gasoline composition comprises 2-butanone in an amount of from 3 vol-% to 30 vol-% of the total volume of the gasoline composition; ethanol in an amount of 1 vol-% to 15 vol-% of the total volume of the gasoline composition; wherein said gasoline composition further comprises a base gasoline, which base gasoline is a combination of hydrocarbons having a carbon number from C4 to C12, preferably from C4 to C9. — Said use has been shown to provide advantages for adjusting the distillation behaviour of the gasoline composition comprising ethanol. Advantageously the amount of the base gasoline is from 66 vol-% to 96 vol-%, preferably at least 80 vol-%, at least 82 vol-%, at least 85 vol-% or at least 87 vol-%, and/or preferably at most 94 vol-%, at most 90 vol-% or at most 88 vol-% of the gasoline composition. Said — base gasoline is a combination of hydrocarbons comprising paraffinic, aromatic and olefinic hydrocarbons having a carbon number from C4 to C12, preferably from C4 to C9. The present inventors have found the use according to the first aspect providing improved distillation behaviour of a gasoline composition comprising ethanol. More specifically, a local — deviation at 70 *C from the constant (upward) slope of the distillation curve typically O 25 observed for gasoline composition comprising ethanol, has been proven to be smoothened O by the present use and composition. In practice, this provides improved predictability for the o E70 value for the gasoline composition thus facilitating the preparation of gasoline r compositions especially by blending gasoline components. The lower vapor pressure and E predictable distillation curve provide advantages for planning and production by blending of si 30 gasoline compositions. 5 Typically, distillation curves for base gasolines consisting of hydrocarbons follow a roughly N linear shape with a steady, upward slope between 10 vol-% and 90 vol-% evaporated temperatures. However, corresponding distillation curves for gasoline compositions of ethanol and base gasoline have a shape that deviates from that by a sharp drop below and near to boiling point of ethanol. As said drop deviation is typically observed as a local decrease of the (upward) slope of the distillation curve generally coincides with a distillation temperature of 70 °C, smoothening or decreasing this deviation by inclusion of 2-butanone in the gasoline composition decreases the E70 value of the final gasoline composition compared to gasoline composition of ethanol and base gasoline. Gasoline standards often define a lower and an upper limit for acceptable E70 values. As an advantage of the present use, improved predictability of the E70 value thus facilitates optimization of preparation of gasoline compositions especially by blending of gasoline components.

Furthermore, the gasoline composition as disclosed herein has an advantageous oxygenate profile. Regarding the gasoline properties required by standards and regulatory bodies, the gasoline composition meets or exceeds requirements, such as European standard EN228:2017. Notably, the present gasoline composition and use thereof overrule some presumptions related to ethanol as a gasoline component. For example, the disadvantages — related to poor predictability vapor pressure and/or distillation behaviour of gasoline blends containing ethanol are alleviated by use of both 2-butanone and ethanol as blends components. Beneficial vapor pressure characteristics together with relatively high density of 2-butanone further enable the use of inexpensive and light blend components, such as butane in a gasoline product, which would not be an option if ethanol alone was used as the oxygenate.

Different non-binding example aspects and embodiments have been illustrated in the foregoing. The embodiments in the foregoing are used merely to explain selected aspects or steps that may be utilized in different implementations. Some embodiments may be presented only with reference to certain example aspects. It should be appreciated that corresponding embodiments apply both to the use and gasoline composition according to N the aspects of the present disclosure.

N

O BRIEF DESCRIPTION OF THE FIGURES S Some example embodiments will be described with reference to the accompanying figures, E in which: O 30 Fig. 1 shows distillation curves for gasoline compositions comprising various amounts of 2- > butanone as the only component blended to an essentially oxygen free base gasoline to 3 form a gasoline composition.

Fig. 2 shows reference distillation curves for gasoline compositions comprising ethanol as the only component blended to an essentially oxygen free base gasoline to form a gasoline blend.

Fig. 3 shows distillation curves for gasoline compositions comprising both ethanol and 2- 5 butanone in various vol-% amounts as the oxygen-containing blending components in gasoline compositions.

DETAILED DESCRIPTION In the following description, like reference signs denote like elements or steps. All standards referred to herein are the latest revisions available, unless otherwise mentioned.

As used herein, a gasoline composition refers to a blend of three or more gasoline components. Methods for preparing a gasoline composition typically comprise selecting components, optionally analysis thereof, addition by volume in an order, and mixing to obtain a gasoline composition. Optionally, premixes of two or more components can be prepared and further component(s) added thereto.

The gasoline composition is preferably suitable for intended use as a transportation fuel or road transport fuel, specifically an automotive gasoline. More preferably it meets all requirements set in a standard for automotive gasolines, such as European quality standard EN 228:2012, Amended 2017.

A base gasoline in the context of the present disclosure refers to a combination of hydrocarbons having a carbon number from C4 to C12, preferably from C4 to C9. Typically, the base gasoline refers to a combination of hydrocarbons having a carbon number from C4 to C12, preferably from C4 to C9, comprising paraffins, cycloparaffins, and aromatic and olefinic hydrocarbons. As used herein, the base gasoline is referred to as a component in — relation to the total gasoline composition, even though according to general understanding O 25 — in the field, the different hydrocarbons of the base gasoline may originate from various O sources and processes, such as from FCC, reformation, alkylation, distillation, o hydrodeoxygenation, isomerization or combinations thereof.

E Base gasoline can be considered as a blend stock for oxygenate blending. Hence, the base o gasoline in the context of the present disclosure is an essentially oxygen-free gasoline 3 30 component.

O Essentially oxygen free base gasoline is beneficial for the gasoline composition in that it does not increase or contribute to the oxygen content, which might be limited by regulations. For example, the vol-% amounts of ethanol and 2-butanone in the present invention may be selected so that the oxygen content of the gasoline composition is at most 8.6 wt-%, or preferably at most 3.7 wt-%, such as from 2.1 to 3.7 wt-% based on the total weight of the gasoline composition, and said oxygen content originates solely from said 2-butanone and ethanol.

A base gasoline may have a boiling point in the range from 30°C to 230°C, preferably from 30°C to 210°C, preferably as measured according to EN ISO 3405:2011. The base gasoline may for example be obtained as a distillation cut originating from crude oil or from hydrotreated renewable feed, or through blending of different cuts of essentially oxygen free gasoline components.

By way of example, when originating from crude oil distillation, the base gasoline may be an essentially oxygen free combination of hydrocarbons comprising paraffinic, aromatic and olefinic hydrocarbons having a carbon number from C4 to C12, preferably from C4 to C9. More specifically, said base gasoline may comprise olefinic hydrocarbons from about 8 vol- % to about 30 vol-%, e.g. from about 12 vol-% to about 25 vol-%, and aromatic hydrocarbons from about 25 vol-% to about 50 vol%, e.g. from about 30 vol-% to about 45 vol-%, the remainder of the base gasoline being paraffinic hydrocarbons, preferably each within said carbon number ranges.

Methods for characterising a hydrocarbon composition by hydrocarbon functional groups (paraffinic (alkanes), naphthenic (cyclo-alkanes), olefinic (alkenes) and aromatic) and carbon number are known in the field and may be performed for example according to EN ISO 22854 or by other gas chromatography-based detailed hydrocarbon analysis. Typically, a base gasoline is the predominant gasoline component in the present gasoline composition, in other words, it is the component of the largest volume. In the present gasoline composition, it may be present in an amount from 66 vol-% to 96 vol-%, preferably N 25 at least 80 vol-%, at least 82 vol-%, at least 85 vol-% or at least 87 vol-%, and/or preferably N at most 94 vol-%, at most 90 vol-% or at most 88 vol-% of the total volume of the gasoline 2 composition. Hence, the amount of the essentially oxygen free base gasoline in present © gasoline compositions may typically be from 66 vol-% to 88 vol-% when the rest of the E gasoline composition consists of oxygen containing components. Q 30 In specific embodiments, where at least a part of the base gasoline hydrocarbons is of 5 renewable origin, this renewable part typically consists mainly of paraffinic hydrocarbons, O preferably obtained by process comprising hydrodeoxygenation, isomerization and distillation, although renewable aromatic and olefinic cuts are available as well. Examples of a highly renewable gasoline compositions comprising 66 vol-% of paraffinic base gasolines have been assessed. When such renewable base gasoline in an amount from 36-56 vol-% of the total gasoline composition is blended with 2-butanone and ethanol, the renewable content depending on the origin of oxygenates may be from 40 vol-% to 70 vol- % or up to 90 vol-%. With relative low contents of e.g. non-renewable aromatic and/or olefinic base gasoline hydrocarbons are used, such highly renewable gasoline compositions can still meet all specifications set to transportation fuel or road transport fuel gasolines.

Vol-% refers in the context of this disclosure to vol-% based on the total volume of the gasoline composition.

As used herein, renewable in relation to a gasoline component or a precursor thereto refers to the origin of said component, hence being derived from a renewable source. This is used in the field of fuels as an opposite to components derived from fossil sources, also referred to as non-renewable components. Here, a component of renewable origin corresponds to a bio-component content of 100 %, which is typically given as m/m. In general, as used herein, “renewable” refers to objects of bio-origin or derived from wastes or residues. The bio-component content in a gasoline composition end product may be calculated based on the origin of the components therein. In some cases, a component may be partly renewable, for example the base gasoline may comprise both fossil and renewable hydrocarbons as a blend. The bio-component content of a gasoline composition is also of interest, especially for regulatory and commercial reasons.

Ethanol has been available as a renewable component for decades commercially. It may be produced e.g. by fermenting biomass material rich in carbohydrates, such as plants, plant parts or derivatives thereof, through acid hydrolysis of biomass, such as lignocellulosic biomass, and/or via gasification of biomass. Preferably the ethanol used in the present gasoline composition is of renewable origin.

— 25 2-butanone is commercially available mostly as a synthetic variety, produced using fossil O hydrocarbons as starting material, and hence as a non-renewable component. O Nevertheless, processes for production of 2-butanone from renewable raw materials are © under constant development and some methods for obtaining renewable 2-butanone are I indeed available. N 30 Processes starting from glucose fermentation and proceeding via 2,3-butanediol to yield 3 renewable 2-butanone have been published. Another route produces ketones by acid- N catalyzed hydrolysis of cellulosic and/or hemi-cellulosic feed stocks at elevated N temperatures to yield levulinic acid. The decarboxylation of levulinic acid over a catalyst, such as CuO, yields 2-butanone. Advanced purification methods, such as combination of extraction and distillation, enable cost efficient yield for renewable 2-butanone for a gasoline component.

According to a preferred embodiment, both the ethanol and 2-butanone used in the present gasoline composition are of renewable origin.

According to an example of such embodiment, the renewable ethanol and renewable 2-butanone contribute to the bio- content of the gasoline composition, whereby said bio-content may be as high as 34 wt-% or more, or 30 wt-% or more, of the gasoline composition.

This is achieved by the sum amount of renewable 2-butanone and renewable ethanol being from 4 to 34 vol-%, preferably from 10 to 30 vol-%, more preferably from 12 to 25 vol-%, of the gasoline composition.

Should the base gasoline, ethanol and 2-butanone all be of renewable origin, said bio- content may be as high as 100 wt-% of the gasoline composition.

As used herein, “fossil” or “derived from petroleum” refer to non-renewable components, and non-renewable energy in contrast to renewable counterparts.

Said renewable and fossil components are considered differing from one another based on their origin and impact on environmental issues.

Therefore, they are treated differently under legislation and regulatory framework.

Typically, renewable and fossil components are differentiated based on their origin and information thereof provided by the producer.

However, chemically the renewable or petroleum origin of any hydrocarbons can be determined e.g. by isotopic distribution involving '*C, '3C and/or 12C as described in ASTM D6866:2018. A renewable gasoline component or at least partly renewable gasoline composition is characterised by mandatorily having a higher content of '*C isotopes than similar components derived from fossil sources.

Said higher content of '*C isotopes is an inherent N 25 feature characterising the renewable gasoline component and distinguishing it from fossil N gasoline components. 2 © Thus, in gasoline compositions wherein the compositions are based on partly fossil based © material and partly renewable gasoline component(s), the renewable component can be E: determined by measuring the 1*C activity.

Analysis of '*C (also referred to as carbon dating Q 30 or radiocarbon analysis) is an established approach to determine the age of artefacts based 5 on the rate of decay of the isotope '*C, as compared to '2C.

This method may be used for O determining the physical percentage fraction of renewable materials in bio/fossil mixtures as renewable material is far less aged than fossil material and so the types of material contain very different ratios of '*C:'?C.

Thus, a particular ratio of said isotopes can be used as a “tag” to identify a renewable carbon compound and differentiate it from non-renewable carbon compounds.

While the renewable component reflects the modern atmospheric '*C activity, very little *C is present in fossil material (oil, coal). Therefore, the renewable fraction of a gasoline composition or gasoline component is proportional to its '*'C content.

Samples of gasoline compositions may be analysed to determine the amount of renewable- sourced carbon in the gasoline composition.

This approach would work equally for co- processed gasolines or gasolines produced from mixed feedstocks.

It is to be noted that there is not necessarily any need to test input materials or blending components when using this approach as renewable content of the gasoline composition may be directly measured.

The isotope ratio does not change in the course of chemical reactions.

Therefore, the isotope ratio can be used for identifying renewable organic compounds and renewable gasoline components, and distinguishing them from non-renewable, fossil materials.

Biological material has about 100 wt-% renewable (i.e. contemporary or biobased or biogenic) carbon, C, content which may be determined using radiocarbon analysis by the isotopic distribution involving 1*C, "*C and/or 1?2C as described for example in ASTM D6866 (2018). Other examples of a suitable method for analysing the content of carbon from biological or renewable origin are DIN 51637 (2014) or EN 16640 (2017). In the context of the present use, one or more of components selected from 2-butanone, ethanol and the base gasoline of the gasoline composition is at least partly renewable.

At least partly renewable means that all or a part of said component is of renewable origin and contributes to bio-content.

For example, should the base gasoline be partly renewable, it can contain a cut of fossil hydrocarbons having a carbon number from C4 to C12, preferably from C4 to C9, and another cut of renewable hydrocarbons having a carbon number from C4 to C12, preferably from C4 to C9. — 25 However, should the component consist of renewable it is herein referred to as renewable O component.

For example, as used herein, the renewable base gasoline base gasoline is a o combination of renewable hydrocarbons having a carbon number from C4 to C12, a preferably from C4 to C9 and could be differentiated from non-renewable base gasoline by 7 radiocarbon analysis.

Correspondingly, 2-butanone or ethanol may be renewable, or both & 30 2-butanone and ethanol are renewable. 3 The present invention relates to a use of 2-butanone and ethanol as components to a N gasoline composition for adjusting the distillation behaviour of a gasoline composition N comprising ethanol.

Preferably, per volume, said gasoline composition according to said use comprises 2-butanone in an amount of from 3 vol-% to 30 vol-% of the gasoline composition, ethanol in an amount of 1 vol-% to 15 vol-% of the gasoline composition, and a base gasoline, which base gasoline is a combination of hydrocarbons having a carbon number from C4 to C12, preferably from C4 to C9. Preferably the ethanol used is renewable ethanol.

According to preferred embodiment, the use of 2-butanone and ethanol as components to a gasoline composition as provided herein, comprises based on the total volume of the gasoline composition, 2-butanone from 3 vol-% to 30 vol-%, ethanol from 1 vol-% to 15 vol-%, and a base gasoline form 66 vol-% to 96 vol-%, preferably at least 70 vol-%, at least 80 vol-%, at least 85 vol-% or at least 87 vol-%, and/or preferably at most 92 vol-%, at most 90 vol-% or atmost 88 vol-%, which base gasoline is a combination of hydrocarbons having a carbon number from C4 to C12, preferably from C4 to C9. Said composition has shown good distillation behaviour.

Further benefits are obtained through lower vapor pressure of such gasoline composition.

According to a preferred embodiment, in the gasoline composition, the sum of the vol-% amounts of 2-butanone, ethanol and base gasoline is at least 95 vol-%, preferably at least 99 vol-%. According to a specific embodiment, said gasoline composition essentially consists of the 2-butanone, ethanol and the base gasoline.

Hence, 2-butanone, ethanol and the base gasoline are the three components of said gasoline composition, and no further components are present.

The present inventors found that it is essential to have 2-butanone in the present gasoline N composition to provide the advantageous distillation behaviour, especially as compared to 5 25 a gasoline composition comprising ethanol.

Further, the impact of ethanol on DVPE and N vehicle-related evaporative emissions have been recognized.

However, surprisingly some © © of the inferior physical properties of an ethanol - base gasoline blend, were mitigated when E the gasoline composition comprised base gasoline, ethanol in an amount of 1 vol-% to 15 @ vol-% and 2-butanone in an amount of from 3 vol-% to 30 vol-% of the gasoline composition. <r = 30 The general idea is to have a composition, wherein base gasoline is the predominant N component and the two oxygen containing components are present as minor components.

According to further embodiments, the sum amount of 2-butanone and ethanol is from 4 to

34 vol-%, preferably from 10 to 30 vol-%, more preferably from 12 to 25 vol-%, of the gasoline composition volume.

According to further embodiments, said gasoline composition comprises 2-butanone based on the total volume of the gasoline composition from 3 vol-% to 25 vol-%, preferably from 3 vol-% to 20 vol-%, more preferably from 5 vol-% to 17 vol%, more preferably from 5 vol-% to 13 vol-%, from 7 vol-% to 13 vol-%, such as from 11 vol-% to 13 vol-%. 2-butanone has been found to provide an advantageous oxygenate for gasoline compositions with lower relative oxygen content than for example ethanol.

According to yet further embodiments, said gasoline composition comprises ethanol in an amount of from 1 vol-% to 10 vol-%, preferably from 3 vol-% to 7 vol-%, more preferably from 5 vol-% to 7 vol-%, such as about 5 vol-%, of the gasoline composition.

Using ethanol in addition to 2-butanone provides advantages through better commercial availability, especially as to renewable ethanol, and wide regulatory acceptance of ethanol as a gasoline component.

It has been found in through the experiments conducted, that it is advantageous to provide a gasoline composition with ethanol and 2-butanone in such amounts that, in the gasoline composition, the vol-% amount of ethanol and the vol-% amount of 2-butanone are equal or the vol-% amount of 2-butanone is larger than the vol-% amount of ethanol, preferably in such amounts that the vol-% ratio of ethanol to 2-butanone in the gasoline composition is — within a range from 1:1 to 1:4, more preferably within a range from 1:2 to 1:3, such as 5:12. Through such ratios, the advantageous effect of 2-butanone prevails in the gasoline composition, while the advantages of ethanol as a component may be utilized.

For gasoline, vapor pressure is important for both performance and environmental reasons.

First, because gasoline engines (spark ignition) require the fuel to be vaporized in order to N 25 burn, gasoline must meet a minimum vapor pressure requirement to ensure that it is volatile N enough to vaporize under cold start conditions.

Engines also have a maximum limit for vapor 2 pressure set by concerns over vaporization in the fuel line that can result in vapor lock, or © a blocking of the fuel line.

However, the most critical limit to vapor pressure in most markets = now is environmental concern about evaporative emissions outside of the vehicle, which N 30 contribute to pollution.

Typically, it is this concern that sets the critical maximum vapor 3 pressure specification for most grades of gasoline.

O For a gasoline composition the E70 value defines the percentage (vol-%) evaporated at 70 °C at standard atmospheric pressure.

A standardised method for determining E70, as well as E100 and E150 values, for a gasoline composition is defined in EN ISO 3405:2011.

According to an embodiment the E70 value (preferably measured according to the EN ISO 3405:2011) of said gasoline composition is from 22 vol-% to 46 vol-%, preferably from 26 vol-% to 45 vol-%, more preferably from 32 vol-% to 42 vol-%, such as from 35 vol-% to 39 vol-%.

Another measure related to vapor pressure is DVPE. DVPE is a parameter which indicates the usability of a fuel under various temperature conditions. The higher the DVPE, the higher the volatilization tendency of fuel with the effect that fuel evaporation loss and environmental contamination at elevated temperature increase. DVPE is particularly relevant for light fuels, such as gasoline. Summer grade fuel and fuel designated for countries in which high temperatures predominate must have a lower DVPE than winter grade fuels. DVPE may be measured e.g. according to EN 13016-1:2007. According to an embodiment, the dry vapor pressure equivalent (DVPE) of the gasoline composition is more or equal to 60 kPa; and 70 kPa or less, 80 kPa or less, 90 kPa or less, such as from 60 to 70 kPa, from 60 to 80 kPa or from 60 to 90 kPa. According to a preferred embodiment, both the E70 value (measured according to the EN ISO 3405:2011) of said gasoline composition is from 22 vol-% to 46 vol-%, preferably from 26 vol-% to 45 vol-%, more preferably from 32 vol-% to 42 vol-%, such as from 35 vol-% to 39 vol-%, and the dry vapor pressure equivalent (DVPE) of said gasoline composition is more or equal to 60 kPa; and 70 kPa or less, 80 kPa or less, 90 kPa or less, are satisfied for a gasoline composition. Each of distillation behaviour, vapor pressure and vapor/liguid-ratio, are parameters describing the volatility of a gasoline blend, and they are given as separate limits in EN 228:2012. DVPE, is considered as the correct parameter to describe the vapor pressure of oxygenated blends. Even though it is linked to distillation, the change in E70 value cannot - 25 — be directly derived by the measured DVPE.

N N The gasoline compositions of the present disclosure and the use thereof allow for adjusting 2 the distillation behaviour of the gasoline composition comprising ethanol to a smooth and © steady upward slope between temperature points defining the 10 vol-% and 90 vol-% = evaporated shares. Examples of said smooth and steady upward slope between N 30 temperature points defining the 10 vol-% and 90 vol-% evaporated shares can be seen in 3 figures 1 and 3, wherein 2-butanone is present as a gasoline component. Figures 1-3 N provide a temperature (y-axis) as a function of share (vol-%) of the total volume evaporated N (x-axis).

The distillation curves shown in figure 1 for gasoline compositions comprising various amounts of 2-butanone (MEK, methyl ethyl ketone) as the only blending component to a base gasoline in the gasoline composition provide very smooth increase with practically constant gradient providing almost linear curve.

Figure 3 shows distillation curves for gasoline compositions comprising together with base gasoline, both 2-butanone and ethanol, in various amounts as the oxygen-containing blending components in gasoline compositions.

Conversely, the distillation curve for a blend of base gasoline (90 vol-%) and ethanol (10 vol-%) only, in figure 2, has several points exhibiting sharp turns, specifically at 50 vol-%, about 70 °C, where the turn to a steeper slope produces a notable angle to said distillation curve causing difficulties for both production and end use.

Hence, the technical effect underlying the present use and gasoline composition is distillation behaviour of gasoline composition, which is improved when the gasoline composition comprises both 2-butanone and ethanol as described herein.

Challenges met with gasoline blends comprising ethanol are discussed for example in: The World Wide Fuel Charter, 5" edition (2013), pages 37-39 explain the science around volatility: Vapor pressure, Destillation, Ethanol's Impact on Volatility (https://www.acea.be/uploads/publications/ WWFC 19 gasoline diesel. pdf) [retrieved 2021-04-14]. The vapor pressure must be tightly controlled at high temperatures to reduce the possibility of hot fuel handling problems, such as vapor lock or excessive evaporative emissions (page 35). Distillation of gasoline yields either a set of 'T points (T50 is the temperature at which 50% of the gasoline distils) or 'E' points (E100 is the percentage of a gasoline distilled at 100 degrees). Excessively high T50 (low E100) can lead to poor starting and warm-up - 25 performance at moderate ambient temperatures.

Control of the Distillation Index (DI), O derived from T10, T50, T90, and oxygen content, also can be used to assure good cold O start and warm-up performance (page 36). © As a pure compound, ethanol exhibits straightforward behaviour regarding vapor pressure = and distillation.

When added to a base gasoline, however, the behaviour of the mixture is N 30 anything but straightforward.

As a result, the vapor pressure and distillation of ethanol- 3 gasoline blends, at a minimum, must be carefully regulated to ensure proper vehicle N operation and emissions control. - To prevent excess evaporative emissions, the vapor pressure of the finished gasoline composition, not just the base gasoline, must be controlled (pages 38-39). Ethanol's impact on the distillation curve is just as complex, if not more so. The distillation measurement must be adjusted to account for the impact, and the blend’s distillation must be well-controlled (page 39). From this disclosure, the skilled person would appreciate that by no means a method of merely lowering the DVPE of a gasoline composition is interchangeable with, predicts, or even anticipates a method for adjusting the distillation behaviour of a gasoline composition. The distillation behaviour is much more complex than can be foreseen merely by the DVPE alone. As conclusion, distillation behaviour of ethanol containing gasoline blends which has been found challenging is now countered by use of three-component gasoline composition comprising both 2-butanone and ethanol together with essentially oxygen free base gasoline.

EXAMPLES A number of various gasoline compositions were prepared and tested according to the — following methods and examples. Example 1. Distillation behaviour The first set of examples illustrate the maximum oxygen content (based on EN228:2017) in the blends, and the E70 values, for blends according to the invention for which the vapor pressure is kept on a reasonable level. Distillation, vapor pressure and vapor/liquid-ratios are all parameters describing the volatility of a gasoline blend and set as separate limits. Therefore, they all were analysed in the present experiments. The results confirm that even though DVPE, is linked to distillation, one cannot directly deduce the change in E70, E100 or E150 values by the measured DVPE. N The blends were mixed and analyzed for distillation behaviour, including E70, E 100 and E

N S 25 150, and the distillation curves were constructed. Figures 1-3 provide a temperature (y-axis) a as a function of share (vol-%) of the total volume evaporated (x-axis). Oo = In all the experiments, the base gasoline was a 95-octane gasoline without oxygen (“BOB”) a n having the distillation properties given in table 1. + +

LO N O N

Table 1. Distillation properties of the base gasoline (BOB) used in the examples. Rss | - Further, a blend was prepared comprising ethanol (ETOH) as the only blending component to the base gasoline by mixing of the components. ETOH10 contained 10 vol-% of ethanol and the remainder (90 vol-%) of BOB. It represents the blends typical for the prior art, specifically oxygenate containing blends, of which ETOH10 is most commonly available commercially. Corresponding to the base gasoline, the distillation behaviour was measured for this blend, ETOH10. This ethanol blend serves as a reference example against which the physical properties of the gasoline compositions according to the present invention are compared. It also shows the problematic drop at a distillation temperature of about 70 °C.The oxygen content was calculated and given with distillation properties in table 2. Table 2. Distillation properties of a common prior art gasoline blend containing ethanol. The results of table 2 reveal the high vapor pressure burdening ethanol blends. The = distillation behaviour of the ETOH10 sample is given in figure 2. The ethanol blends tend to < follow unsteady curves with breaks (as shown in Table 2 and/or in figure 2) and have E70 O 15 — value of about 52 vol-%. Especially when plotted together with the relative smooth © distillation curve for the base gasoline (BOB) used in these examples, said figure underlines I the problematic distillation behaviour related to ethanol as blend component. a

Q 5 The difficulties related to distillation of a mixture of ethanol with base gasoline are at least O 20 — partly related to azeotrope formation. Ethanol forms azeotropes with the hydrocarbons typical for gasoline. An azeotrope is a mixture of two or more liguids in such a ratio that the composition of the mixture cannot be changed by simple distillation. This means that the azeotropes of ethanol and hydrocarbons distil at a nearly constant temperature. This phenomenon results in an essentially flat distillation curve in the standard ASTM distillation measurement until the azeotropes of ethanol and hydrocarbons have been eliminated from the liquid.

When the ethanol has distilled completely from the liquid, the distillation curve rapidly returns to that of the hydrocarbon-only gasoline. However, the phenomenon is not constant, but of varying magnitude. Therefore, when planning refinery gasoline blending, the prediction of certain distillation points, especially E70, is challenging when ethanol is a component.

Next, gasoline compositions comprising different amounts of 2-butanone (methyl ethyl ketone, MEK) as oxygen-containing blending component were prepared by mixing with the base gasoline. The proportions and references used for different gasoline compositions are given in table 3.

Table 3. Gasoline compositions comprising different amounts of 2-butanone tested. we | a ow es | sow we | wow Es | s + = The gasoline compositions MEK3, MEK5, MEK10 and MEK 15 were analysed the same way as the base gasoline and comparative ethanol blends earlier. The properties measured are compiled in table 4.

Table 4. Analysis results for gasoline compositions MEK3, MEK5, MEK10 and MEK 15. 3 s : s i 0 3 The distillation curves for the gasoline compositions comprising 2-butanone and base N 20 gasoline are shown in figure 1. It is clear that the distillation curves for these MEK-samples N follow a conventional, steady distillation curve without breaks, which provides the best control of the distillation. Furthermore, it appears from both the data in the table and the curves in figure 1 that the E70 (vol-% evaporated at 70 °C) is about 37 to 39 vol-% for these blends.

Also, the vapor pressure is substantially lower than the vapor pressure for the ethanol blends in the comparative examples in Table 2, and it is the same or lower than the vapor pressure of the oxygen free BOB. This property provides flexibility in blending and improved emission control for the volatile hydrocarbons.

Finally, three-component gasoline compositions comprising 2-butanone (MEK) and ethanol (ETOH) were prepared by mixing of the components. The proportions are given in table 5 and analysis results in table 6 Table 5. Three-component gasoline compositions analysed.

EGER | 8] >< = [vem | www) | MEKITETOHIS | m] TS] 8 Table 6. Analysis results for gasoline compositions MEK6-ETOH6, MEK12-ETOH3, MEK24-ETOH10 and MEK17-ETOH15.

MEK6- | MEK12- | MEK24- | MEK17- CHOWN) | aa] 30] 00] a] O The distillation curves for the gasoline compositions MEK6-ETOH6, MEK12-ETOH3, O MEK24-ETOH10 and MEK17-ETOH15 are shown in figure 3. It is clear that the distillation a 15 curves for gasoline compositions comprising various amounts of 2-butanone and ethanol 7 MEK6-ETOH6, MEK12-ETOH3, MEK24-ETOH10 and MEK17-ETOH15, follow essentially & conventional, steady distillation curve without breaks, which provides the best control of the si distillation. Furthermore, the E70 (vol-% evaporated at 70 °C) is from about 42 vol-% to 47 2 vol-%.

S N 20 When comparing ethanol and 2-butanone as oxygenated blending components for gasoline, they both boil at rather similar temperatures, 78.2*C and 79.6*C, respectively.

However, when 2-butanone was used as a further component in gasoline composition, this sharp distillation profile change typical for ethanol, was not observed, but the distillation curve resembled more that of an hydrocarbon gasoline. Surprisingly, 2-butanone does not increase the vapor pressure.

Example 2. High bio-content blends exemplified with variable highly paraffinic base gasolines. Three compositions were compiled to study whether renewable components could be used for the gasoline composition. Since paraffinic renewable base gasolines are available through processes comprising hydrodeoxygenation, isomerization and distillation, different paraffinic base gasoline compositions were studied. Nevertheless, renewable aromatic or renewable olefinic cuts may be applied accordingly.

In these examples, the total gasoline composition comprised 66 vol-% of the base gasoline, and 30 vol-% 2-butanone and 4 vol-% ethanol. However, the specific hydrocarbon composition of the base gasoline varied.

The first gasoline composition (gasoline composition 1) comprised 30 vol-% 2-butanone, 4 vol-% ethanol and 66 vol-% of paraffinic base gasoline having high isoparaffin content. The base gasoline was an isomerate, wherein the isoparaffin content was > 73 vol-% of the base gasoline volume.

The second gasoline composition (gasoline composition 2) comprised the same amounts of 2-butanone, 30 vol-%, and ethanol 4 vol-% and the rest was of base gasoline. Said base gasoline comprised alkylate and naphtha in ratio 1:2 correspondingly. Of said components of the base gasoline, the alkylate had an isoparaffin content > 98 vol-% of said alkylate volume. In said naphtha, the isoparaffin content was 55-60 vol-% of the naphtha volume.

= In the third gasoline composition (gasoline composition 3), the amounts of 2-butanone and a 25 ethanol were the same, 30 vol-% and 4 vol-% of the total composition volume respectively. 2 The base gasoline comprised isopentane 18.2 vol-%, isomerate 33.3 vol-% and iso-octane S 48.5 vol-% of the base gasoline composition. Said isopentane and iso-octane were = essentially isomeric.

a @ To summarize, in all gasoline composition studied here, the sum of 2-butanone and ethanol > 30 was 34 vol-% and the rest consisted of base gasoline. However, the differences in the base N gasoline compositions resulted in different gasoline properties as seen in table 7.

N

Table 7. Analysis results for gasoline compositions comprising paraffinic base gasoline.

TTT m-% aamen | ja | ja [77 [90 je | gasoline composition 2 |81 [70 [725 Jas [28 |71 [sO = gasoline composition 3 —|102 [94 |721 för [av [70 [80 | As seen from the results in table 7, the gasoline compositions according to the present invention containing highly paraffinic base gasoline are available. With regard to certain gasoline properties and limitations, a replacement of an amount of the base gasoline with e.g. aromatic hydrocarbons would contribute to the properties of the gasoline composition, helping it to meet gasoline standards. For example 90 % renewable content or 90 % bio- content may be derived from said results, by using 56 vol-% of renewable and 10 vol-% non-renewable base gasoline, where the non-renewable base gasoline could be for example a highly aromatic cut from mineral oil distillation or a highly olefinic cut from mineral oil distillation or a combination thereof. Correspondingly, bio-contents from 99 % to 45 % are conceivable. The corresponding base gasoline variations could apply to further ratios between the renewable and non-renewable component within the teaching given here, such as from 6:1 to 1:6 respectively. Various embodiments have been presented. It should be appreciated that in this document, — words comprise, include, and contain are each used as open-ended expressions with no intended exclusivity. The foregoing description has provided by way of non-limiting examples of particular implementations and embodiments a full and informative description of the best mode presently contemplated by the inventors for carrying out the invention. It is however clear to N 20 aperson skilled in the art that the invention is not restricted to details of the embodiments & presented in the foregoing, but that it can be implemented in other embodiments using 2 equivalent means or in different combinations of embodiments without deviating from the S characteristics of the invention. = Furthermore, some of the features of the afore-disclosed example embodiments may be S 25 used to advantage without the corresponding use of other features. As such, the foregoing 5 description shall be considered as merely illustrative of the principles of the present O invention, and not in limitation thereof. Hence, the scope of the invention is only restricted by the appended patent claims.

Claims

1. Use of 2-butanone and ethanol as components to a gasoline composition for adjusting the distillation behaviour of the gasoline composition, the gasoline composition comprising 2-butanone in an amount of from 3 vol-% to 30 vol-% of the gasoline composition, ethanol in an amount of 1 vol-% to 15 vol-% of the gasoline composition, and wherein said gasoline composition further comprises essentially oxygen free base gasoline, which base gasoline is a combination of hydrocarbons having a carbon number from C4 to C12, preferably from C4 to C9.

2. The use according to claim 1, wherein said gasoline composition essentially consists of the 2-butanone, ethanol and the base gasoline.

3. The use according to claim 1 or 2, wherein said gasoline composition comprises 2- butanone in an amount of from 3 vol-% to 25 vol-%, preferably from 3 vol-% to 20 vol-%, more preferably from 5 vol-% to 17 vol%, more preferably from 7 vol-% to 13 vol-%, such as from 11 vol-% to 13 vol-%, of the gasoline composition.

4. The use according to any of the preceding claims, wherein said gasoline composition comprises ethanol in an amount of from 1 vol-% to 10 vol-%, preferably from 3 vol-% to 7 vol-%, more preferably from 5 vol-% to 7 vol-%, such as about 5 vol-%, of the gasoline composition.

5. The use according to any of the preceding claims, wherein said gasoline composition comprises the base gasoline in an amount of from 66 vol-% to 96 vol-%, preferably at least 80 vol-%, at least 82 vol-%, at least 85 vol-% or at least 87 vol-%, and/or preferably at most 94 vol-%, at most 90 vol-% or at most 88 vol-% of the gasoline composition.

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6. The use according to any of the preceding claims, wherein said base gasoline is a N combination of hydrocarbons comprising paraffinic, aromatic and olefinic hydrocarbons - 25 having a carbon number from C4 to C12, preferably from C4 to C9.

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7. The use according to any of the preceding claims, wherein the sum of the vol-% i amounts of 2-butanone and ethanol is from 4 to 34 vol-%, preferably from 10 to 30 vol-%, Q more preferably from 12 to 25 vol-%, of the gasoline composition volume.

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8. The use according to any of the preceding claims, wherein the sum of the vol-%

O N 30 amounts of 2-butanone, ethanol and base gasoline is at least 95 vol-%, preferably at least

99 vol-%, more preferably the gasoline composition consists essentially of ethanol, 2- butanone, and base gasoline.

9. The use according to any of the preceding claims, wherein the vol-% ratio of ethanol to 2-butanone in the gasoline composition is within a range from 1:1 to 1:4, more preferably within a range from 1:2 to 1:3, such as 5:12.

10. The use according to any of the preceding claims, wherein the E70 value (measured according to the EN ISO 3405:2011) of said gasoline composition is from 22 vol-% to 46 vol-%, preferably from 26 vol-% to 45 vol-%, more preferably from 32 vol-% to 42 vol-%, such as from 35 vol-% to 39 vol-%.

11. The use according to any of the preceding claims, wherein the dry vapor pressure equivalent (DVPE) of said gasoline composition is more or equal to 60 kPa; and 90 kPa or less.

12. The use according to any of the preceding claims, wherein one or more of components selected from 2-butanone, ethanol and the base gasoline of the gasoline composition is at least partly renewable.

13. The use according to any of the preceding claims, wherein 2-butanone or ethanol is renewable, or both 2-butanone and ethanol are renewable.

14. The use according to claim 13, comprising renewable 2-butanone and renewable ethanol from 4 to 34 vol-%, preferably from 10 to 30 vol-%, more preferably from 12 to 25 — vol-%, of the gasoline composition volume.

15. The use according to claim 13, comprising renewable base gasoline in an amount from 36-56 vol-% of the total gasoline composition volume.

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