FI20225558A1 - A gasoline fuel - Google Patents

Abstract

The present invention relates to a gasoline fuel comprising essentially oxygen free base gasoline and 1-15 vol-% of tetrahydro-α,5-dimethyl-2-furanmethanol and to a method for manufacturing tetrahydro-α,5-dimethyl-2-furanmethanol.

Description

A GASOLINE FUEL

FIELD

The present invention relates to a gasoline fuel comprising a renewable component, a method for making said component as well as use of the component. The invention also relates to a method of preparing the gasoline fuel.

BACKGROUND AND OBJECTS

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, also in gasoline is however 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 in 2017.

Today, ethanol is the most frequently used bio-based component in gasoline blends, but alternative gasoline components are also studied. However, an upper limit for the oxygen content in gasoline fuels typically restricts the use of oxygen containing components in gasoline blends.

On the other hand, furfural is one promising platform chemical that is readily produced from biomass in industrial scale. Still, there is no economically feasible route to fuel

N 20 — components from furfural.

O

> It is an aim to provide a further alternative bio-based, i.e. renewable component for

T gasoline. It is another aim to provide a renewable component for gasoline that is based on > furfural obtained from biomass. It is in particular an aim to provide a renewable i component, which does not affect the properties of the gasoline fuel in a negative way.

O 25 Preferably, such a component would be usable as a dry vapour pressure equivalent a adjusting component of gasoline. It is another aim to provide methods for manufacturing such component, as well as uses for the component.

SUMMARY OF THE INVENTION

The invention is defined by the features of the independent claim. Some specific embodiments are defined in the dependent claims.

According to an aspect, there is provided a gasoline fuel comprising essentially oxygen free base gasoline and 1-15 vol-% of tetrahydro-a,5-dimethyl-2-furanmethanol.

According to another aspect, there is provided a method for hydrodeoxygenating 2-acetyl- 5-methylfuran to tetrahydro-a,5-dimethyl-2-furanmethanol by contacting 2-acetyl-5- methylfuran with hydrogen at a temperature of 100-300 °C, pressure of 6-10 MPa, a hydrogen flow of 200 to 2000 NI H9/l feed, using a catalyst comprising at least one of

RuZrOjp, RhZrO5 and NiZrO>.

According to a still further aspect, there is provided a method for manufacturing a bio- based tetrahydro-a,5-dimethyl-2-furanmethanol by - hydrating bio-based furfural into furfuryl alcohol; - hydrolysing the obtained furfuryl alcohol to 2-methylfuran; —- acetylating the obtained 2-methylfuran to 2-acetyl-5-methylfuran, using acetic acid anhydride; - hydrodeoxygenating the obtained 2-acetyl-5-methylfuran to tetrahydro-a,5-dimethyl-2- furanmethanol as described above.

This description also relates to use of tetrahydro-a,5-dimethyl-2-furanmethanol as a — gasoline component and/or as a dry vapour pressure equivalent adjusting component in

N gasoline fuels.

S

& Yet another aspect relates to a method for manufacturing a gasoline fuel, comprising ? mixing an oxygen free base gasoline with 1-15 vol-% of tetrahydro-a,5-dimethyl-2- - furanmethanol.

T a a 25 BRIEF DESCRIPTION OF DRAWING

LO

LO

N Figure 1 illustrates distillation curves for various gasoline blends.

N

DETAILED DESCRIPTION

In the present description, weight percentages (wt-%) are calculated on the total weight of the material in question (such as the gasoline fuel). Volume percentages (vol-%) are also calculated on the total volume of the material. Any amounts defined as ppm (parts per million), are based on weight. Further, in this description, “at least one” means that there is one or more of the items mentioned.

The term “renewable” in the context of a renewable gasoline component refers to one or more organic compounds derived from any renewable source (i.e., not from any fossil- based source). Thus, the renewable gasoline component is based on renewable sources and consequently does not originate from or is derived from any fossil-based material. Such a component is characterised by mandatorily having a higher content of 14C isotopes than similar components derived from fossil sources. Said higher content of 14C isotopes is an inherent feature characterising the renewable gasoline component and distinguishing it from fossil gasoline fuels. Thus, in gasoline blends, wherein a portion of the blends is — based on partly fossil based material and partly renewable gasoline component, the renewable component can be determined by measuring the 14C activity. Analysis of 14C (also referred to as carbon dating or radiocarbon analysis) is an established approach to determine the age of artefacts based on the rate of decay of the isotope 14C, as compared to 12C. This method may be used to determine 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 14C:12C. Thus, a

N particular ratio of said isotopes can be used as a “tag” to identify a renewable carbon

O compound and differentiate it from non-renewable carbon compounds. While the

O renewable component reflects the modern atmospheric 14C activity, very little 14C is n 25 present in fossil gasoline fuels (oil, coal). Therefore, the renewable fraction of any material

E of interest is proportional to its 14C content. Samples of gasoline blends may be analysed @ post-reaction to determine the amount of renewable sourced carbon in the gasoline fuel.

LO This approach would work egually for co-processed gasoline fuels or gasoline fuels

O produced from mixed feedstocks. It is to be noted that there is not necessarily any need to — test input materials when using this approach as renewability of the gasoline blend may be directly measured. The isotope ratio does not change during chemical reactions. Therefore,

the isotope ratio can be used for identifying renewable isomeric paraffin compositions, renewable hydrocarbons, renewable monomers, renewable polymers, and materials and products derived from said polymers, and distinguishing them from non-renewable materials. Feedstock of raw material of biological origin means material having only — renewable (i.e., contemporary or bio-based or biogenic) carbon, 14C, content which may be determined using radiocarbon analysis by the isotopic distribution involving 14C, 13C and/or 12C as described in ASTM D6866 (2018). Other examples of a suitable method for analysing the content of carbon from biological or renewable sources are DIN 51637 (2014) or EN 16640 (2017).

For the purpose of the present invention, a carbon-containing material, such as a feedstock or product is considered to be of biological i.e., renewable origin if it contains 90 % or more modern carbon (pMC), such as 100 % modern carbon, as measured using ASTM

D6866.

According to an aspect of the present invention, there is provided a gasoline fuel comprising essentially oxygen free base gasoline and 1-15 vol-% of tetrahydro-a,5- dimethyl-2-furanmethanol.

The present gasoline fuel thus provides a composition which contains a certain amount of tetrahydro-a, 5-dimethyl-2-furanmethanol, which is a component that can be derived from a renewable feedstock, for example from lignocellulosic feedstock. The amount of 1-15 vol- % has been calculated based on the estimated highest oxygen content (namely 8.9 wt-%) and the oxygen contents of the various components.

N A further advantage of the present gasoline fuel is that it provides an alternative > composition comprising oxygenates. Oxygenates, typically ethanol, in gasoline fuels ? decrease tail pipe emissions, which is a desirable effect, and brings renewable content to - 25 — the fuel While ethanol can also be of renewable origin, it can be challenging in gasoline

E fuels. Indeed, volatility of gasoline is important to the operation of spark ignition engines

O and their performance. Volatility can be characterised by dry vapour pressure eguivalent, a DVPE, which is controlled seasonally in order to satisfy the volatility needs of vehicles at

N different ambient temperatures. Therefore, both minimum and maximum vapour pressures — are usually specified. While ethanol as neat has very low DVPE i.e. 16 kPa at 37.8 °C, in gasoline blends it tends to increase the DVPE, sometimes resulting in the need for re-

blending to adjust DVPE. The DVPE effect is the strongest when using low ethanol concentrations and diminishes with increasing ethanol content. In gasoline production this means that lighter and cheaper (high DVPE) components like n-butane can be used in only smaller amounts, and a specific BOB (=blendstock for oxygenate blending) gasoline has to 5 be produced if ethanol is added afterwards.

The inventors have now surprisingly found that the tetrahydro-a,5-dimethyl-2- furanmethanol, a component having both an alcohol and an ether functionality, has no

DVPE raising effect and can thus be used as an DVPE adjusting component also in ethanol containing gasoline, helping in meeting DVPE requirements. One of the main benefits is — thus that higher volumes of lighter and cheaper components e.g. n-butane can be used in gasoline blending. Additionally, net heat of combustion decreases less when using tetrahydro-a,5-dimethyl-2-furanmethanol, compared to corresponding ethanol fuel blend.

These results are shown in more detail below in the Experimental part.

The gasoline fuel comprises an essentially oxygen free base gasoline, which is used in an amount sufficient to achieve the total of 100 vol-% of the final composition. It may be fossil-based, or it may be based on renewable feedstock, or a mixture of both. By “essentially oxygen free” it is meant that the base gasoline contains at most 0.1 wt-% of oxygen.

As used herein, a gasoline fuel thus refers to a blend of two or more gasoline components.

Methods for preparing a gasoline fuel typically comprise selecting the components, optionally analysis thereof, addition by volume, and mixing to obtain a gasoline fuel.

Optionally, premixes of two or more components can be prepared and further

N component(s) added thereto.

N

S The gasoline fuel is preferably suitable for intended use as a transportation fuel or road

N 25 transport fuel, specifically an automotive gasoline. More preferably it meets all

E reguirements set in a standard for automotive gasoline fuels, such as European guality @ standard EN 228:2012, amended in 2017.

IO a A base gasoline in the context of the present disclosure refers to a combination of

N 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 fuel, even though according to general understanding in the field, the different hydrocarbons of the base gasoline may originate from various sources and processes, such as from FCC, reformation, alkylation, distillation, hydrodeoxygenation, isomerization or combinations thereof.

Base gasoline can be considered as a blend stock for oxygenate blending. Hence, the base gasoline in the context of the present disclosure is an essentially oxygen-free gasoline component. Essentially oxygen free base gasoline is beneficial for the gasoline fuel 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 in the present invention may be selected so that the oxygen content of the gasoline fuel is at most 8.9 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 fuel.

A base gasoline may have a boiling point in the range from 30 °C to 230 °C, preferably from 30 °C to 210 °C, 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 having a carbon number from C4 to C12, preferably from C4 to C9. The hydrocarbons may be paraffinic, aromatic and/or

N olefinic, most typically the base gasoline comprises all of these. More specifically, said

N base gasoline may comprise olefinic hydrocarbons from about 8 vol-% to about 30 vol-%,

S e.g. from about 12 vol-% to about 25 vol-%, and aromatic hydrocarbons from about 25

N 25 — vol-% to about 50 vol%, e.g. from about 30 vol-% to about 45 vol-%, the remainder of the

E base gasoline being paraffinic hydrocarbons, preferably each within said carbon number 3 ranges.

N In specific embodiments, where at least a part of the base gasoline hydrocarbons is of

N renewable origin, this renewable part typically consists mainly of paraffinic hydrocarbons, preferably obtained by process comprising hydrodeoxygenation, isomerisation and distillation, although renewable aromatic and olefinic cuts are available as well. Examples of highly renewable gasoline fuels comprising 66 vol-% of paraffinic base gasoline fuels have been assessed. When such renewable base gasoline in an amount from 36-56 vol-% of the total gasoline fuel is blended with other components, the renewable content depending on the origin of oxygenates may be from 40 vol-% to 70 vol-% or up to 90 vol- % With relatively low contents of e.g. non-renewable aromatic and/or olefinic base gasoline hydrocarbons are used, such highly renewable gasoline fuels can still meet all specifications set to transportation fuel or road transport gasoline fuels.

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 22854:2016 or by other gas chromatography-based detailed hydrocarbon analysis.

Typically, a base gasoline is the predominant gasoline component in the present gasoline fuel, in other words, it is the component of the largest volume. According to an embodiment, the amount of the base gasoline is from 73 vol-% to 99 vol-%, preferably 75- — 85 vol-% of the gasoline fuel.

According to an embodiment, the gasoline fuel further comprises at least one octane adjusting component selected from a group consisting of ethanol, iso-propanol, methyl tert-butyl ether, ethyl tert-butyl ether, and mixtures thereof. The methyl tert-butyl ether,

MTPBE, is also known as tert-butyl methyl ether. The ethyl tert-butyl ether, ETBE, is 2- — ethoxy-2-methylpropane. The octane adjusting component increases the octane number of the gasoline fuel, the research octane number (RON) being determined as indicated in ISO 5164:2014. The maximum amount of oxygen allowed in gasoline fuels, according to EN

N 228:2012, amended in 2017, is 3.7 wt-%. Therefore, the oxygen content of the gasoline > fuel is preferably at most 3.7 wt-%, measured according to EN 1601:2017.

O

N 25 — According to another embodiment, the octane adjusting component is ethanol, in an

E amount of 1-12 vol-%. Such gasoline fuel thus comprises 1-12 vol-% of ethanol and 1-15 @ vol-% of tetrahydro-a,5-dimethyl-2-furanmethanol. Again, the amount of 1-12 vol-% has

LO been calculated based on the estimated highest oxygen content (namely 8.9 wt-%) and the

O oxygen contents of the various components, including the tetrahydro-a,5-dimethyl-2- — furanmethanol. The gasoline fuels typically also comprise minor amounts, such as less than 0.1 vol-% of additives. The aims of such additives are for example prevention of corrosion and deposit formation in the engine. Some examples of additives are performance additive(s), corrosion inhibitor(s) and antioxidant(s). One exemplary composition is 7 vol- % of tetrahydro-a,5-dimethyl-2-furanmethanol, 5 vol-% of ethanol, the rest being base gasoline.

The vol-% amounts of ethanol and other oxygenate components in the present composition may be selected so that the oxygen content of the gasoline fuel is at most 8.9 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 fuel. The upper limit of 3.7 wt-% is also mentioned in EN 228:2012.

According to an embodiment, the net heat of combustion of the gasoline fuel is 30-33 MJ/, — measured according to ASTM D240-17 (2017). The present renewable component has, despite having also an alcohol functionality, a different effect on the heat of combustion than ethanol. Indeed, it was analysed that an addition of 10 vol-% of tetrahydro-a,5- dimethyl-2-furanmethanol has the same effect of lowering the heat of combustion than 5 vol-% of ethanol. Tetrahydro-a,5-dimethyl-2-furanmethanol thus gives more options for blending, as it has a higher heat of combustion than ethanol for example (which is based on comparison of heats of combustion of blends comprising same amounts of tetrahahydro- a,5-dimethyl-2-furanmethanol or ethanol).

According to another embodiment, the dry vapour pressure equivalent of the composition is the same as the dry vapour pressure equivalent of the essentially oxygen free base — gasoline of the composition, measured according to EN 13016-1:2007. By “same” is here meant that the dry vapour pressure equivalent (DVPE) of the composition is at most 5 % different from the DVPE of the base gasoline fuel.

N

N The present description relates also to a method for hydrodeoxygenating 2-acetyl-5-

S methylfuran to tetrahydro-a,5-dimethyl-2-furanmethanol by contacting 2-acetyl-5-

N 25 — methylfuran with hydrogen at a temperature of 100-300 °C, pressure of 6-10 MPa, a

E hydrogen flow of 200 to 2000 NI H»/l feed, using a catalyst comprising at least one of 3 RuZrOy, RhZrO> and NiZrO>. &

ON The reaction that takes place in the hydrodeoxygenation is the following, i.e. the 2-acetyl- - 5-methylfuran reacts with hydrogen to yield tetrahydro-a,5-dimethyl-2-furanmethanol.

/ N CH, Ha CHa

H3e 0 — > HC,

O H

For the hydrodeoxygenation process, the 2-acetyl-5-methylfuran is preferably obtained from a renewable origin. The renewable origin may be for example a lignocellulosic feedstock. Details for the manufacturing of 2-acetyl-5-methylfuran are explained in more — detail below.

An advantage of the above method is that it allows deoxygenation of the raw material, 2- acetyl-5-methylfuran at lower temperature than conventional hydrodeoxygenation, leading to less harmful side reactions.

The hydrodeoxygenation is carried out in the presence of a catalyst and hydrogen. The — reaction temperature is 100-300 °C. According to an embodiment, the temperature of the hydrodeoxygenation is 150-250 °C, preferably 150-200 °C. The reaction pressure is 6-10

MPa, preferably 7-9 MPa.

In the hydrodeoxygenation process, the hydrogen flow may be 200 to 2000 NI H9/l feed, preferably 200-1000 NI H9/l feed. NI H9/l feed means normal litres of hydrogen per litre — of the feed into the reactor. According to another embodiment, the weight hourly space velocity, WHSV, is 0.3 — 0.7 h”! during the hydrodeoxygenation.

The catalyst used in hydrodeoxygenation comprises at least one of RuZrO5, RhZrO> and

NiZrO». Preferably, the catalyst comprises RhZrO>. The catalyst can be on a carrier, such

N as zirconia (ZrO). According to an embodiment, the metal content is over 0.1 wt-% of the

O

O 20 — total weight of the catalyst. According to another embodiment, the acidity of zirconia is

N below 120 umol NH3/g catalyst. According to yet another embodiment, the zirconia is

I a calcined at a temperature of at least at 500 *C before addition of the metal on the zirconia. e

LO In the hydrodeoxygenation process, the 2-acetyl-5-methylfuran is obtained from a

S renewable origin. The renewable origin may be for example a lignocellulosic feedstock.

N

— The present description also relates to a method for manufacturing a bio-based tetrahydro- a, 5-dimethyl-2-furanmethanol by

- converting bio-based furfural into 2-methylfuran; - acetylating the obtained 2-methylfuran to 2-acetyl-5-methylfuran, using acetic acid anhydride; - hydrodeoxygenating the obtained 2-acetyl-5-methylfuran to tetrahydro-a,5-dimethyl-2- furanmethanol as described above.

The 2-acetyl-5-methylfuran can thus be produced from furfural by a two or three step process. In the two step process furfural is directly hydrolysed into 2-methylfuran, followed by acetylation as described above. In the three step process, furfural is first hydrated into furfuryl alcohol. Thereafter, the furfuryl alcohol is hydrolysed into 2- methylfuran, followed by acetylation with acetic acid anhydride of the 2-methylfuran, producing the 2-acetyl-5-methylfuran.

The method steps of furfural hydrolysis into 2-methylfuran and furfural hydration into furfuryl alcohol followed by hydrolysis of the furfuryl alcohol into 2-methylfuran, are described for example in Biomass, Biofuels, Biochemicals. Recent Advances in

Development of Platform Chemicals 2020, Pages 283-297 Chapter 10 - Furfural as a platform chemical: From production to applications. Mario Kabbour and Rafael Luque.

The acetylation step is described for example in Frouri, et al, Inorganic hydroxide fluorides as solid catalysts for acylation of 2-methylfuran by acetic anhydride. Applied

Catalysis B: Environmental, Elsevier, 2015, 168-169, pp.515-523. Further information can — be found in the Diploma work of Kaisa Lamminpää, “Manufacturing of furfural and its derivatives from a biomass”, University of Oulu, 31.1.2008, pages 14, 15 and 18 For example, the reaction from furfural to furfuryl alcohol may be carried out in the presence of a catalyst comprising copper or nickel and chromium. The reaction may be carried out

S in vapour or liguid phase, and the reaction temperature is typically 120-150 *C. The

O 25 — reaction from furfural to 2-methylfuran may be carried out in gas phase in the presence of a n copper catalyst, at a temperature around 250 °C. x a The embodiments and variants described above apply mutatis mutandis to this method. e

LO The present description also relates to use of tetrahydro-a,5-dimethyl-2-furanmethanol as a

O gasoline component, as well as to its use as a dry vapour pressure eguivalent adjusting component in gasoline fuels. As has been described above and is further demonstrated below, the tetrahydro-a,5-dimethyl-2-furanmethanol can be used as a gasoline component,

having advantageous properties as a gasoline component. It also has no effect on the

DVPE, i.e. it does not raise it as ethanol does, and therefore it allows the use of other components that do increase the DVPE of the gasoline fuel. The embodiments and variants described above apply mutatis mutandis to these uses.

The present description yet further relates to a method for manufacturing a gasoline composition, comprising mixing an oxygen free base gasoline with 1-15 vol-% of tetrahydro-a,5-dimethyl-2-furanmethanol. The base gasoline may be of fossil origin, or it may be of renewable origin. It may also be a mixture of both fossil and renewable origin.

The embodiments and variants described above apply mutatis mutandis to this method.

It is to be understood that the embodiments of the invention disclosed are not limited to the particular structures, process steps, or materials disclosed herein, but are extended to equivalents thereof as would be recognized by those ordinarily skilled in the relevant arts.

It should also be understood that terminology employed herein is used for the purpose of describing particular embodiments only and is not intended to be limiting.

Furthermore, the described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. In the description, numerous specific details are provided, to provide a thorough understanding of embodiments of the invention.

The verbs “to comprise” and “to include” are used in this document as open limitations that neither exclude nor require the existence of also un-recited features. The features recited in dependent claims are mutually freely combinable unless otherwise explicitly stated. Furthermore, it is to be understood that the use of "a" or "an", i.e. a singular form,

N throughout this document does not exclude a plurality. & © EXPERIMENTAL PART

N Four different metal catalysts (RuZrO), RhZrO>, NiZrO, and as comparative catalyst i 25 PtZrO3) were prepared by using zirconia support. The metals were added on the zirconia

O in the form of their soluble salts (RuCl3*xH>O 0.85 wt-%; Rh(NO3)3 0.86 wt-%; 3 Ni(NO3)9*6H>O 13.5 wt-% and Pt(NH3)4(NO3)) 1.1 wt-%) Before the addition of

N ruthenium or rhodium, zirconia was calcined at 600 °C, while before adding platinum or nickel zirconia was calcined at 500 °C. After the addition of the metal, the product was calcined at 450 °C in the case of ruthenium or rhodium, and at 350 °C in the case of nickel or platinum. The catalysts were reduced in situ in the reactor at 400 °C under hydrogen flow before the feed was fed into the reactor.

The catalysts were used for hydrodeoxygenating 2-acetyl-5-methylfuran to tetrahydro-a,5- dimethyl-2-furanmethanol. The HDO-reaction took place either at 150 °C or at 200 °C, at a — pressure of 8 MPa and in the presence of hydrogen (2000 NI H»/l). It was observed that all of RuZrO>, RhZrO>, NiZrO> on zirconia gave better yields than PtZrO2, while RhZrO> at 150 *C gave the best yield.

Some gasoline fuels were prepared with tetrahydro-a,5-dimethyl-2-furanmethanol (gasoline A10) and ethanol (gasoline E9.25 and gasoline ES, comparative compositions) as components with an essentially oxygen free base gasoline (gasoline EO), as indicated in

Table 1.

Gasoline A10 Gasoline E9.25 | Gasoline ES Gasoline EO

Component tetrahydro-a,5- ethanol ethanol none dimethyl-2- furanmethanol wt% [126 [98 ~~ |47 0 |- vol Jo ~~ 1925 00000150 [-

Table 1

Properties of the compositions were tested, and the results are given in Table 2. The compositions were also distilled, and the results are given in Table 3 below, as well as shown in Figure 1. The test methods were as follows.

Dry vapour pressure equivalent DVPE, in kPa, was measured as defined in EN 13016- aN 1:2007.

O

N Density, in kg/m3, was measured as defined in EN ISO 12185:1996. ©

O Research octane number RON was measured as defined in ISO 5164:2014.

N 20 — Oxygen content, in wt-%, was measured as defined in EN 1601:2017.

E Net heat of combustion, in MJ/l, was measured as defined in ASTM D240-17 (2017). 00

O The given RONc (corrected RON) is equal to RON -0.2.

N

O

N

Composition DVPE, kPa | Density, | RONc | Oxygen Net heat of kg/m3 content, wt- | combustion, % MJ/1

Gasoline EO 7419 [951 fo [321

Gasoline ES 749.9

Gasoline E9.25 746.6

Gasoline A10 764.7

Table 2

Table 2 clearly shows that addition of 10 vol-% of tetrahydro-a,5-dimethyl-2- furanmethanol (A10) into the base gasoline EO did not affect the composition’s DVPE, while addition of ethanol increased it. The density of the composition increased, while its octane number was lower than for the base gasoline and compositions with ethanol.

Concerning the oxygen content, the maximum amount of oxygen allowed in gasoline fuels, according to EN228:2012, amended in 2017, is 3.7 wt-%. As the use of tetrahydro-a,5- dimethyl-2-furanmethanol in higher amounts (in vol-%) than ethanol leads to a lower — oxygen content (E9.25 compared to A10), this indicates that oxygen content can still be increased in the composition. Similarly, the net heat of combustion decreases less although the volume of added tetrahydro-a,S-dimethyl-2-furanmethanol is larger than the volume of added ethanol.

Fuel E70, E100, | E150, Initial boiling Final boiling vol-% | vol-% | vol-% point, °C point, °C

Gasoline EO 37.6 1555 | [288 0 [183

Gasoline ES 42 [59 [89 [303 [188]

Gasoline E925 [48 [e62 [90 [299 ~~ [1868 3 Gasoline ATG

N Table 3 g - 15 Table 3 as well as Figure 1 show the results of distillation. As can be seen the distillation

N r behaviour of A10 is different from that of EO. It is known that a low E100 may lead to poor a > starting and warm-up performance of a motor at moderate ambient temperatures. With the 00 2 present gasoline, both E70 and E100 are lower than for ethanol containing gasoline, while

LO

N being within the requirements of EN 228:2012. The distillation curve of A10 thus shows

O

N 20 that also DVPE is lower, which is expected as both E100 and DVPE relate to volatility.

Furthermore, it is known that some gasoline fuels reguire that their vapour pressure is tightly controlled at high temperatures to reduce the possibility of hot fuel operability problems, such as vapour lock or excessive evaporative emissions due to carbon canister overloading, especially at higher temperatures. The present gasoline fuel is therefore suitable also to very warm environments as it will not cause vapour lock or canister problems.

N

N

O

N

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Claims (17)

1. A gasoline fuel comprising essentially oxygen free base gasoline and 1-15 vol-% of tetrahydro-a,5-dimethyl-2-furanmethanol.

2. The gasoline fuel according to claim 1, wherein the gasoline fuel further comprises at least one octane adjusting component selected from a group consisting of ethanol, iso- propanol, methyl tert-butyl ether, ethyl tert-butyl ether, and mixtures thereof.

3. The gasoline fuel according to claim 1 or 2, wherein the net heat of combustion is 30-33 MJ/l, measured according to ASTM D240-17 (2017).

4. The gasoline fuel according to any of the preceding claims, wherein the dry vapour — pressure equivalent of the composition is the same as the dry vapour pressure equivalent of the essentially oxygen free base gasoline of the composition, measured according to EN 13016-1:2007.

5. The gasoline fuel according to any of the claims 2-4, wherein the octane adjusting component is ethanol, in an amount of 1-12 vol-%.

6. The gasoline fuel according to any of the preceding claims, wherein the oxygen content of the composition is at most 3.7 vol-%, measured according to EN 1601:2017.

7. A method for hydrodeoxygenating 2-acetyl-5-methylfuran to tetrahydro-a,5-dimethyl-2- furanmethanol by contacting 2-acetyl-5-methylfuran with hydrogen at a temperature of 100-300 °C, pressure of 6-10 MPa, a hydrogen flow of 200 to 2000 NI H»/I feed, using a N 20 catalyst comprising at least one of RuZrOy, RhZrO> and NiZrO». S

O

8. The method according to claim 7, wherein the temperature is 150-250 °C, preferably O - 150-200 °C. N I

= 9. The method according to claim 7 or 8, wherein the pressure is 7-

9 MPa. e O

10. The method according to any of the claims 7-9, wherein the hydrogen flow is 200 to N N 25 — 1000 NI H9/l feed. N

11. The method according to any of the claims 7-10, wherein the catalyst is on a carrier, and the metal content of the catalyst is over 0.1 wt-% of the total weight of the catalyst.

12. The method according to claim 11, wherein the carrier is zirconia and the acidity of zirconia is below 120 umol NH3/g catalyst.

13. The method according to any of the claims 7-12, wherein the catalyst comprises RhZrO2.

14. A method for manufacturing a bio-based tetrahydro-a,5-dimethyl-2-furanmethanol by - converting bio-based furfural into 2-methylfuran; - acetylating the obtained 2-methylfuran to 2-acetyl-5-methylfuran, using acetic acid anhydride; - hydrodeoxygenating the obtained 2-acetyl-5-methylfuran to tetrahydro-a,5-dimethyl-2- — furanmethanol according to any of the claims 7-13.

15. Use of tetrahydro-a,5-dimethyl-2-furanmethanol as a gasoline component.

16. Use of tetrahydro-a,5-dimethyl-2-furanmethanol as a dry vapour pressure equivalent adjusting component in gasoline fuels.

17. A method for manufacturing a gasoline fuel, comprising mixing an oxygen free base — gasoline with 1-15 vol-% of tetrahydro-a,5-dimethyl-2-furanmethanol. N N O N © <Q N I a a co LO LO LO N N O N