WO2023061971A1

WO2023061971A1 - A new fuel composition comprising a symmetric branched c12-c18 ether, or 3-(((2-ethylhexyl)oxy)methyl)heptane

Info

Publication number: WO2023061971A1
Application number: PCT/EP2022/078173
Authority: WO
Inventors: Samson AFEWERKI; Armando Cordova; Ismail IBRAHEM
Original assignee: Organofuel Sweden AB
Current assignee: Organofuel Sweden AB
Priority date: 2021-10-11
Filing date: 2022-10-11
Publication date: 2023-04-20
Anticipated expiration: 2024-04-11

Abstract

The present invention relates to a fuel composition comprising at least 80 or 90 wt% of a symmetric branched C₁₂-C₁₈ ether, or 3-(((2-ethylhexyl)oxy)methyl)heptane, and up to 100 wt% of one or more additives/lubricants. The invention relates to use of the composition as well as processes for the preparation of 3-(((2-ethylhexyl)oxy)methyl)heptane.

Description

Title: A new fuel composition comprising a symmetric branched Cu-Cis ether, or 3-(((2- ethylhexyl)oxy)methyl)heptane.

Technical field

The present invention relates to a new fuel composition comprising a symmetric branched C12-C18 ether, or 3-(((2-ethylhexyl)oxy)methyl)heptane, and up to 100 wt% of one or more additives/lubricants. The invention relates to a use of the composition as well as processes for the preparation of 3-(((2-ethylhexyl)oxy)methyl)heptane.

Background

Climate changes are partly due to the emission of hazardous gases from the combustion of fossil fuels. There is an increasing need to minimize the emissions, especially carbon dioxide emissions. An area that has attracted a lot of attention is biofuel, such as alcohols produced from biomass or biowaste for reducing environmentally hazardous emissions.

Biodiesel may be obtained from vegetable oil or animal fats (biolipids) which are mainly fatty acid methyl esters (FAME), and transesterified with methanol. It can be produced from many types of oils, the most common being rapeseed oil (rapeseed methyl ester, RME) in Europe and soybean oil (soy methyl ester, SME) in the US. Methanol can also be replaced with ethanol for the transesterification process, which results in the production of ethyl esters. The transesterification processes use catalysts, such as sodium or potassium hydroxide, to convert vegetable oil and methanol into biodiesel and the undesirable byproducts glycerin and water, which will need to be removed from the fuel along with methanol traces. Biodiesel can be used pure (B100) in engines where the manufacturer approves such use, but it is more often used as a mix with diesel, BXX where XX is the biodiesel content in percent. FAME used as fuel is specified in DIN EN 14214 (2019) and ASTM D6751 (2020) standards.

Fuel equipment manufacturers (FIE) have raised several concerns regarding biodiesel, identifying FAME as being the cause of the following problems: corrosion of fuel injection components, low-pressure fuel system blockage, increased dilution and polymerization of engine sump oil, pump seizures due to high fuel viscosity at low temperature, increased injection pressure, elastomeric seal failures and fuel injector spray blockage. Pure biodiesel has an energy content about 5-10% lower than petroleum diesel. The loss in power when using pure biodiesel is 5-7%. Unsaturated fatty acids are the source for the lower oxidation stability; they react with oxygen and form peroxides and result in degradation byproducts, which can cause sludge and lacquer in the fuel system.

Hydrotreated Vegetable Oil (HVO) and Hydroprocessed Esters and Fatty Acids (HEFA) are renewable fuels or biofuels made by hydrocracking or hydrogenation of vegetable oils. Hydrocracking breaks big molecules into smaller ones using hydrogen while hydrogenation adds hydrogen to molecules. HVO is free or substantially free of acids. These methods can be used to create substitutes for diesel, jet fuel, gasoline, propane, kerosene and other chemical feedstock. For environmental reasons and to minimize carbon dioxide emissions, the aim is to increase the use of HVO. The vegetable oils used to make HVO are lower value oils such as palm oil, soy oil, corn oil, used cooking oil, tallow etc.. The amount of HVO and HEFA that can be produced is among others dependent on the amount of raw material (oils) available. The availability of the starting material varies per geographical area and season. As the global production capacity of HVO and HEFA have increased sharply in recent years, and is foreseen to continue to increase in coming years, there already is and will continue to be a shortage of starting material. This shortage has increased the price for suitable oils for HVO and HEFA processes, which has led to an increase in the price of HVO and HEFA, where prices more than doubled from late year 2020 to mid-2022.

Moore C. et al., Green Chemistry, 2017, 19, p 169, describes the problem of corrosion associated with use of ethanol as renewable fuel. Moore discloses an alternative process to Guerbet reaction using an acetaldehyde dehydrogenated from an ethanol derived biobuilding block.

Diesel is composed of about 75% saturated hydrocarbons (primarily alkanes including n-, iso- , and cycloalkanes), and 25% aromatic hydrocarbons (including naphthalenes and alkylbenzenes). The average chemical formula for common diesel fuel is C12H23, ranging from approx. C10H20 to C15H28. The standard for diesel fuel is EN 590 (2017). The principal measure of diesel fuel quality is its cetane number. A cetane number is a measure of the delay of ignition of a diesel fuel. A higher cetane number indicates that the fuel ignites more readily when sprayed into hot compressed air. European road diesel has a minimum cetane number of 51 (EN 590 standard (2017)).

WO2018/115575 discloses novel diesel fuel compositions comprising a combination of renewable paraffinic diesel component, a fossil diesel component and an oxygenate component, as well as methods for manufacture and use of the combination for reducing NOx emissions. Unfortunately, fossil diesel (at least 75vol. %) is still the major component in this composition.

Ethers have attracted attention for use in diesel oil as additives. Jadhav D., et al., ChemSusChem, 2017, 10, pp 2527-2533, disclose production and use of asymmetric ethers as lubricants. JP 2020059677 discloses production and use of ethers as oil in hydraulic fluid.

Rorrer J., ChemSusChem, 2018, 11, p 3104-3111, discloses a method for production of symmetric and asymmetric Cg-C -ethers using a tungstated zirconia catalyst. For diesel fuel applications, a mixture of ethers is produced to create a distribution of ethers that contain a desired molecular weight distribution. This method is not suitable for large scale production. Mixtures of ethers are difficult to reproduce at large scale.

JP2021024806 discloses a method for producing a saturated homoether via a carbonyl compound dimerized from a carbonyl compound, butanal or propanal using a Pd/AbOg or Ni catalyst. W02018034609 discloses a method for conversion of a starting alcohol comprising an oxidation step, a condensation step followed by a reduction step to obtain a product having a longer chain than the chain of the starting alcohol.

Summary of the invention

It is an aim of the present invention to at least partly overcome the above-mentioned problems, and to provide an improved renewable fuel/bio-diesel.

This aim is achieved by a composition as defined in claim 1.

The invention relates to a fuel composition comprising or consisting of at least 60 or 70 or 80 or 90 or 95 wt%, or 60 to 95 wt% of a symmetric branched C12-C18 ether, or 3-(((2-ethylhexyl)oxy)methyl)heptane, and up to 100 wt% of one or more suitable additives/lubricants.

The invention relates to a fuel composition comprising or consisting of at least 60 or 70 or 80 or 90 or 95 wt% 3-(((2-ethylhexyl)oxy)methyl)heptane, and up to 100 wt% of one or more suitable additives/lubricants.

The invention relates to a fuel composition comprising or consisting of at least 80 or 90 or 95 wt% 3-(((2-ethylhexyl)oxy)methyl)heptane, and up to 100 wt% of one or more suitable additives/lubricants.

The invention relates to a fuel composition comprising or consisting of at least 60 or 70 or 80 or 90 or 95 wt%, or 60 to 95 wt% of a symmetric branched C12-C18 ether, or 3-(((2-ethylhexyl)oxy)methyl)heptane, and

0.1 to 20 wt%, or 0.1 to 10 wt%, or 0.1 to 5 wt% of one or more suitable additives/lubricants.

In some aspects, 0.1 to 20 wt%, or 0.1 to 10 wt%, or 0.1 to 2 wt% residues, such as additives/lubricants may be present in the fuel composition. Examples of residues may be lubricants, such as PC 32™, Hydradd L1000™, LX 5100™, HFA 7025™, Improver L 315™, ADD 5- 6110™, HITEC 4140A™, OLI 9970™ and conductivity additives, such as Stadis 450™ and Plutostat™. In some aspects, the additives/lubricants are selected from the group comprising or consisting of Examples of residues may be lubricants, such as PC 32™, Hydradd L1000™, LX 5100™, HFA 7025™, Improver L 315™, ADD 5-6110™, HITEC 4140A™, and conductivity additives, such as Stadis 450™ and Plutostat™.

In some aspects, the fuel is renewable biofuel. In some aspects, the fuel is non-fossil fuel or non-fossil biofuel.

In some aspects, the fuel composition is characterized in having a lubricity ISO 12156 (2018) of 460 pm or less, a conductivity at 20°C ASTM D 2624 (2021) of 50 pS/m or more, a sulphur content, Q EN ISO 20846 (2019) of 10.0 mg/kg or less, a density at 15°C, EN ISO 12185 (1996), of 845 or 820 kg/m³ or less, a cetane Number, EN ISO 5165 (2020), of 51 or 70 or more, an oxidation stability, ISO 12205 (1995), 25 g/ m³ or less, and/or a flash point of at least 56 or 80 or 100°C.

It has surprisingly been found that the composition of the invention can be used as bio-diesel. No fossil diesel needs to be added to use this renewable fuel in motorized vehicles. The composition is neither corrosive. The renewable fuel of the invention is believed to reduce emission of environmentally hazardous gases, such as NO_X, CO, CO2, etc. The renewable fuel can be produced at large scale. The renewable fuel of the invention has improved viscosity at low temperature. The renewable fuel is expected to increase the injection pressure. The renewable fuel has improved oxidative stability and does not cause sludge and lacquer. The renewable fuel minimizes formation of degradation products. The renewable fuel has a high cetane number of over 70. The fuel of the invention is not dependent on oils as starting material as is the case for FAME, HVO or HEFA. Compared to HVO, production of the fuel of the invention can be constantly maintained independent of geographical area or seasons.

In some aspects, the fuel composition further comprises or consists of

5 to 15 wt%, or 9 to 10 wt% Cs alcohol and/or

1 to 15 wt%, or 7 to 8 wt% C12 alcohol, which Cs or C12 alcohol may be linear or branched.

In some aspects, this fuel composition is characterized in having a lubricity at 60°C ISO 12156-1 (2018) of 450 or 300 pm or less, a sulphur content, Q EN ISO 20846 (2019) of 20.0 or 10.0 or 5.0 or 3.0 or 1.0 mg/kg or less, and/or a flash point of at least 56 or 80°C.

In some aspects, the fuel composition comprises or consists of at least 70 or 80 or 90 or 95 or 99 wt% of a symmetric branched C12-C18 ether, or 3-(((2- ethylhexyl)oxy)methyl)heptane,

5 to 15 wt%, or 9 to 10 wt% Cs alcohol and/or

1 to 15 wt%, or 7 to 8 wt% C12 alcohol, which Cs or C12 alcohol may be linear or branched, and up to 100 wt% of one or more suitable additives/lubricants.

This composition of the invention can be used as bio-diesel. No fossil diesel needs to be added to use this bio-diesel in motorized vehicles. The composition is neither corrosive. The renewable fuel of the invention is believed to reduce emission of environmentally hazardous gases, such as NO_X, CO, CO2, etc. The renewable fuel can be produced at large scale. The addition of the lower alcohols to the renewable fuel of the invention improves viscosity at low temperature, increases the injection pressure and further improves oxidative stability, without causing sludge and lacquer. This renewable fuel minimizes formation of degradation products further. The addition is also believed to further improve fuel efficiency.

In some aspects, the one or more additives/lubricant is selected from the group comprising or consisting of engine oil, gear oil, transmission fluid or ionic liquids, including but not limited to hydroxyamic acid, succinic acid and derivatives, mono-, di-, or triglyceride, hydroxy polycarboxylic acid or derivative thereof, petroleum lubricant oil including but not limited to naphthenic base, paraffin base, and mixed based, synthetic oils including but not limited to alkylene polymers, alkylene oxide polymers, ester of organic and inorganic acids, acryl hydrocarbons and ethers, organic silicone compounds, or combinations thereof, ionic liquids including but not limited to imidazolium-, ammonium-, pyridinium-, and phosphonium-based ionic liquids, synthetic lubricants including but not limited to organic esters such as phosphate esters, polalkylene glycols, vegetable oil-based lubricants, polyalphaolefins, alkylated aromatics, polybutenes, polyesters, dibasic acid esters, polyol esters.

Further one or more additives may be selected from the group comprising or consisting of acetone, ether, nitrous oxide, nitromethane, butyl rubber, ferox, oxyhydrogen, ferrous picrate, silicone, tetranitromethane, ether and alcohol oxygenates including but not limited to methanol, ethanol, isopropyl alcohol, n-butanol, t-butanol, methyl tert-butyl ether, tertiary amyl methyl ether, tertiary hexyl methyl ether, ethyl tertiary butyl ether, tertiary amyl ethyl ether, and diisopropyl ether.

Lubricants can be used to improve the viscosity and/or density of the fuel.

The invention also relates to a use of the fuel composition as defined herein as bio-diesel fuel. The renewable fuel may be use in motorized vehicles, such as cars, airplanes, boats, industrial machines, generators and the like. The renewable fuel may be use as substitutes for gasoline, diesel, propane, kerosene and other chemical feedstock.

The renewable fuel composition as defined herein may also be used as lubricant/additive/transmission fluid in fossil fuel or other bio-fuel/renewable fuels, or in cosmetic and pharmaceutical products, or in hydraulic fluids.

Advantages of use of the composition as defined herein as lubricant/additive/transmission fluid are among others, lubrication, decreasing the wear and tear of engine components, especially the fuel pump, avoiding failure of the engine, increasing fuel efficiency, decreasing emissions by reducing the number of dangerous emissions coming from the engines, preventing corroding or even crystallization of fuel, improving conductivity, improving low- temperature conductivity retention, improving stability of the fuel, increasing lifespan of the engine, improving low-temperature handling, decreasing fuel consumption and reducing CO2 emissions, improving cooling engine, improving thermal and oxidative stability, enhancing flash point and autoignition temperatures.

Renewable additive/lubricants/transmission fluid according to the invention having a biomass origin have the further advantage of improved biodegradability, improved cost-effective, renewability and reduced negative environmental effects.

In some aspects, the invention relates to a further composition comprising or consists of

0.1 to 99 wt% of the fuel composition comprises or consists of

62 to 93.9 wt%, or 70 to 91.9 wt%, 80 to 99.9 wt%, or 85 to 99.9 wt% of a symmetric branched C12-C18 ether, or 3-(((2-ethylhexyl)oxy)methyl)heptane, optionally, 8 to 10 wt% Cs alcohol and/or

6 to 8 wt% C12 alcohol, which Cs or C12 alcohol may be linear or branched, and

0.1 to 20 wt%, or 0.1 to 10 wt%, or 0.1 to 5 wt% of one or more suitable additives/lubricants,

1 to 99.9 wt%, or up to 100 wt% of fossil fuel or other renewable fuels or bio-fuels.

In an aspect, the fossil fuel or other renewable fuels or bio-fuels is selected from the group comprising or consisting of diesel, jet fuel, gasoline, propane, kerosene, FAME, HVO, HEFA, RME and SME, or any mixture thereof. In an aspect, the fossil fuel or other renewable fuels or bio-fuels is diesel or gasoline. In an aspect, the fossil fuel or other renewable fuels or bio-fuels is selected from the group comprising or consisting of jet fuel, propane and kerosene, or any mixture thereof. In an aspect, the fossil fuel or other renewable fuels or bio-fuels is selected from the group comprising or consisting of jet fuel and kerosene, or any mixture thereof. In an aspect, the fossil fuel or other renewable fuels or bio-fuels is selected from the group comprising or consisting of FAME, HVO, HEFA, RME and SME, or any mixture thereof. In an aspect, the fossil fuel or other renewable fuels or bio-fuels is selected from the group comprising or consisting of FAME, HVO and HEFA, or any mixture thereof.

In some aspects, the further composition comprises or consists of

26 to 99 wt% of the composition as defined anywhere above, up to 100 wt% of fossil fuel, such as diesel or gasoline.

In some aspects, a fuel for motorize vehicles comprises or consists of at least 26 wt% of the composition as defined anywhere above.

The invention further relates to a process for preparation of 3-(((2- ethylhexyl)oxy)methyl)heptane comprising or consisting of the steps of a) converting acetaldehyde 1 and/or crotonaldehyde 2 into Cs aldehyde 4 and 5 using an N i (0)-AI or Pd(0)-AI or Pd(0)-C catalyst, at a hydrogen pressure of 0.6 to 0.12 MPa at a temperature of 50 to 150°C in an organic solvent

organic solvent, T 50-150°C H₂ (0.5-12 MPa)

b) converting Cs aldehyde 4 and 5 into Cs branched alcohol 6 using an N i (0) based catalyst or a copper based catalyst,

c) converting Cs branched alcohol 6 into 3-(((2-ethylhexyl)oxy)methyl)heptane 7 using an acid catalyst H2SO2 at a temperature of 160°C or more,

wherein the acid catalyst in step c) is selected from the group comprising or consisting of sulfuric acid, sulfonic acid, solid acids, montmorillonite clays solid acid catalysts, solid acid catalyst and immobilized sulfuric acid (SiCh-I^SC ) or sulfonic acid on silica (SiCh-SOsH).

An advantage of use of the acid catalyst in step c) is the improved yield and selectivity of the reaction towards compound 7 (C16). The boiling point of 2-ethyl hexanol is 184.7°C, at the temperature during the reaction, this compound is only boiling if there is not any catalyst. During our reaction, even the bath temperature could be 200°C, the real boiling temperature is lower than 184.7°C due to the azeotropic mixture of alcohol and water. Without any catalyst, this alcohol might be partly pyrolyzed to alkene mixtures.

In some aspects, the solvent in step c) is a mixture of alcohol and water or an azeotropic mixture of alcohol and water.

In some aspects, the acid catalyst in step c) is selected from the group comprising or consisting of sulfuric acid, sulfonic acid, solid acids such as Nation™ (sulfonated tetrafluoroethylene-based fluoropolymer-copolymer), Nation NR50™, montmorillonite clays solid acid catalysts, such as montmorillonite K10™montmorillonite KSF/O (mont-KSF/O) ™, solid acid catalyst, such as y-alumina, q-Alumina, Amberlyst A35™, Amberlyst 70™, Amberlyst 36™, Amberlyst 15™, Amberlyst 16™, Amberlyst 39™, Amberlyst 31™, Amberlyst 121™, CT 244™, Dowex 50Wx4- 50™, Dowex 50Wx2™, H-Beta™, Ar-SBA-15™, H3PW12O40 (HPW) ™, HPW/SiO2™, Zr-SBA-15™, ZSM-5™, CT-224™, DL-H/03™, DL-l/03™, Zeolite H-BEA-25™, Zeolite BEA™ SiO2:AI2O3, WOx/ZrO2™, and immobilized sulfonic acid on silica (SiCh-SOsH), and immobilized sulfuric acid on silica (SiCh-EhSC ).

In some aspects, the acid catalyst in step c) is sulfuric acid or sulfuric acid immobilized on silica. Sulfuric acid, immobilized or not, improves the yield in step c).

In some aspects, the acid catalyst in step c) is sulfuric acid. In some aspects, sulfuric acid is used as a liquid in step c). In some aspects, sulfuric acid is used heterogenous supported on silica. In some aspects, the concentration of sulfuric acid is from 2 to 5wt%, or about 4wt%. In some aspects, the temperature in step c) is at least 160°C, or about 180°C. In some aspects, the pressure in step c) is from 0.101325 to 10 MPa.

In some aspects, the organic solvents in step a) are selected from the group comprising or consisting of toluene, cyclohexane, ethyl acetate, methyl acetate, n-propyl acetate, i-propyl acetate p-Xylene, o-Xylene, m-Xylene, benzene, dichloromethane, chloroform, acetonitrile, acetic acid, acetone, methylethyl ketone, 2-butanone, 1,2-dichloromethane, diethylene glycol, diethyl ether, THF, 2-MeTHF, CPME, DMF, DMSO, NMP, ethylene glycol, heptane, 1,4- dioxane, pentane, hexane, ethylene, glycols, n-methyl and n-butyl acetate. In some aspects, the organic solvents in step a) is toluene.

In some aspects, the metal catalyst in step a) is Ni(0)-AI or Pd(0)-AI catalyst. In some aspects, the hydrogen pressure in step a) is from 0.9 to 1.1 or 1.0 MPa when Ni(0)-AI is used as a catalyst or from 0.8 to 1 MPa when Pd(0)-AI is used as a catalyst. In some aspects, the temperature is at least 100°C. In some aspects, the temperature in step a) is at least 60°C, when Ni(0)-AI is used as a catalyst.

In some aspects, a further purification step is performed to improve the purity and quality of the end product.

In some aspects, the process is performed in one-pot.

In some aspects, the alcohol 6 is prepared starting from ethanol,

In some aspects, 3-(((2-ethylhexyl)oxy)methyl)heptane is prepared starting from ethanol as outlined below.

The one or more catalyst may be selected from the group comprising or consisting of heterogeneous supported metal catalyst, a homogeneous organometallic complex, a metal- free catalyst, an enzyme or bacteria.

The one or more oxidants may be selected from the group comprising or consisting of: oxygen, air, hydrogen peroxide, or sodium hypochlorite.

In some aspects, the alcohol 16 is converted to an aldehyde (or a ketone) in the presence of: i. an oxidant selected from H2O2, O2, air and NaOCI, and ii. a catalyst system which is selected from:

- a heterogeneous supported metal catalyst, preferably selected from Pd(0)- na nocatalysts,

- an organometallic complex, preferably derived from Pd, Cu, Pt, Fe and Ir, more preferably selected from DABCO-CuCI-TEMPO method and CuCI-bipyridyl-TEMPO method,

- a metal-free catalyst (mediator), preferably selected from TEMPO ((2, 2,6,6- Tetramethylpiperidin-l-yl)oxyl) or derivative thereof, and

- an oxidizing enzyme, preferably oxidizing enzyme EC 1:10:3:2.

The one or more catalysts or metal catalysts may be nickel-based catalyst, a copper-based catalyst and/or palladium-based catalyst.

The reaction may be performed either neat (solvent free) or in organic or inorganic solvent. The temperature may be room temperature (16-26°C) or up to 500°C.

In some aspects, the process is performed in one-pot.

In some aspects, the acid catalyst in step c) is sulfuric acid. In some aspects, sulfuric acid is used as a liquid in step c). In some aspects, sulfuric acid is used heterogenous supported on silica. In some aspects, the concentration of sulfuric acid is from 2 to 5wt%, or about 4wt%. In some aspects, the temperature in step c) is at least 160°C, or about 180°C. In some aspects, the pressure in step c) is from 0.101325 to 10 MPa. In some aspects, a further purification step is performed to improve the purity and quality of the end product.

Brief description of the drawings

The invention will now be explained more closely by the description of different aspects of the invention and with reference to the appended figures.

Fig. 1-2 shows tables of results obtained with 3-(((2-ethylhexyl)oxy)methyl)heptane.

Fig. 3 shows a table with results obtained from 3-(((2-ethylhexyl)oxy)methyl)heptane mixed with 9 to 10 wt% Cs alcohol.

Fig. 4 shows results obtained with 3-(((2-ethylhexyl)oxy)methyl)heptane combined with various additives such as lubricity and conductivity improver.

The versions (year) of the test methods mentioned in the tables can be found below.

Detailed description

Aspects of the present disclosure will be described more fully hereinafter. The composition can, however, be realized in many different forms and should not be construed as being limited to the aspects set forth herein.

The terminology used herein is for the purpose of describing particular aspects of the disclosure only and is not intended to limit the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

As used herein "wt%" means weight percentage wt% or w/w%, i.e. a percentage of the sum of the weight of all ingredients, unless otherwise stated.

As used herein "renewable fuel" means bio-fuel, non-fossil fuel, bio-diesel, bio-oil, FAME, HVO or HEFA, RME, SME, renewable bio-fuel, renewable bio-diesel and the like. Especially, as used herein "renewable fuel" and "fuel" means non-fossil fuel. "Bio-diesel" as used herein means renewable fuel.

Unless otherwise defined, all terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.

The invention relates to a fuel composition comprising or consisting of

60 to 95 wt%, or at least 60 or 70 or 80 wt% of a symmetric branched C12-C18 ether, or 3-(((2- ethylhexyl)oxy)methyl)heptane, and

0.1 to 20 wt%, or 0.1 to 10 wt%, or 0.1 to 5 wt% or up to 100 wt% of one or more suitable additives/lubricants.

The fuel composition comprises or consists of

85 to 95 wt% of a symmetric branched C12-C18 ether, or 3-(((2-ethylhexyl)oxy)methyl)heptane, 8 to 10 wt% Cs alcohol and/or

6-8 wt% C12 alcohol, which Cs or C12 alcohol may be linear or branched, and

0.1 to 5 wt%, or 0.1 to 2 wt%, or 0.1 to 1 wt% or up to 100 wt% of one or more suitable additives/lubricants.

The fuel composition comprises or consists of

85 to 95 wt%, or 62 to 93.9 wt%, or 70 to 85.9 wt%, or 72 to 85.9 wt% of a symmetric branched C12-C18 ether, or 3-(((2-ethylhexyl)oxy)methyl)heptane,

8 to 10 wt% Cs alcohol and/or

6-8 wt% C12 alcohol, which Cs or C12 alcohol may be linear or branched, and

The fuel composition comprises or consists of

70 to 91.9 wt%, or 80 to 91.1 wt%, or 85 to 91.1 wt% of a symmetric branched C12-C18 ether, or 3-(((2-ethylhexyl)oxy)methyl)heptane,

8 to 10 wt% Cs alcohol, which Cs alcohol may be linear or branched, and

The fuel composition comprises or consists of

0.1 to 99 wt% or 1 to 50 wt% or 1 to 74 wt% of the fuel composition comprises or consists of

6 to 8 wt% C12 alcohol, which Cs or C12 alcohol may be linear or branched, and

1 to 99.9 wt%, or 50 to 99 wt%, or 26 to 99 wt%, or up to 100 wt% of fossil fuel, such as diesel, jet fuel, gasoline, propane or kerosene, or any mixture thereof , or other renewable fuels or bio-fuels/bio-diesels, such as FAME, HVO, HEFA, SME or RME, or any mixture thereof.

The renewable fuel composition comprises or consists of

1 to 90 wt% of the composition as defined anywhere above, up to 100 wt% of fossil fuel, such as diesel or gasoline.

The renewable fuel composition comprises or consists of

26 to 99 wt% of the composition as defined anywhere above, up to 100 wt% of fossil fuel, such as diesel, jet fuel, gasoline, propane or kerosene, or any mixture thereof , or other renewable fuels or bio-fuels/bio-diesels, such as FAME, HVO, HEFA, SME or RME, or any mixture thereof.

The additives/lubricants may be selected from the group comprising or consisting of lubricants, such as PC 32™, Hydradd L1000™, LX 5100™, HFA 7025™, Improver L 315™, ADD 5- 6110™, HITEC 4140A™, OLI 9970™ and conductivity additives, such as Stadis 450™ and Plutostat™. In some aspects, the additives/lubricants are selected from the group comprising or consisting of Examples of residues may be lubricants, such as PC 32™, Hydradd L1000™, LX 5100™, HFA 7025™, Improver L 315™, ADD 5-6110™, HITEC 4140A™, and conductivity additives, such as Stadis 450™ and Plutostat™.

Process Description for the Production of Cie ether:

The di(2-ethylhexyl) ether, alternative name: Bis(2-ethylhexyl) ether: IUPAC: 3-(((2- ethylhexyl)oxy)methyl)heptane, CAS: 10143-60-9, was synthesized by the acid catalyzed etherification of the branched alcohol 6.

The branched alcohol 6, was prepared by integrated catalytic system from simple C2 acetaldehyde. Acetaldehyde was catalytically transformed into branched saturated aldehyde 5 and subsequently, reduced into branched alcohol 6. The finale step is acid catalyzed etherification of Cs alcohol into desired final product Ci6 ether (Scheme 1).

Supported acid Catalytic amount

IUPAC: 3-(((2-ethylhexyI)oxy)methyl)heptane

CAS: 10143-60-9

Scheme 1. Integrated catalysis pathway for the conversion of simple aldehyde to higher value liquid fuel.

The Methods

The key intermediate in the process is the formation of the branched Cs aldehyde 5.

It was envisioned that a one-pot conversion of acetaldehyde 1 or crotonaldehyde 2, into a branched valuable Cs aldehyde 4 and 5, can be accomplished by a hydrogenation- condensation-hydrogenation in domino sequential reactions fashion (Scheme 2) via the in situ formation of intermediate butanal 3, followed by additional cascade hydrogenation to form the branched Cs alcohol 6. OH

Scheme 2. Cascade reaction

Several catalytic systems were investigated to achieve a new proposed approach.

1.1 Synthesis of the Cs branched aldehyde 5 and branched alcohol 6

1.1.1 Cascade organocatalysis-metal catalysis

A mild and eco-friendly integrated catalytic system was applied to convert simple aldehyde to linear or branched enals. An orga nocatalyst and a secondary amine pyrrolidine as catalyst was used for the aldol condensation to give the corresponding enals. The enals are subsequently and selectively hydrogenated using a recyclable heterogeneous metal catalyst (Scheme 3).

Scheme 3. Integrated catalysis for the conversion of simple aldehyde to higher value branched aldehyde.

At laboratory scale, both toluene (b.p. 110°C) and ethyl-acetate (EtOAc) (b.p. 77.0°C) were investigated as solvents. EtOAc is a better alternative solvent since it's non-toxic and available from biomass and have lower boiling point (b.p.) that facilitates the recycling of the solvent in the system, this is consistent with the renewable fuel project (Table 1).

Table 1. Organocatalytic condensation of acetaldehyde

Yield of Yield of

Entry Solvent Conversion (%) ^fb1 Crotonaldehyde (%)^[cl Hexadienal (%)^[b]

1 Toluene 94.0 68 2.0

2 EtOAc 96.0 63 9.0 [a] 5 mmol of CH3CHO (2.0 mmol/mL in organic solvent, 2.5 mL), 4 mol% of catalyst (0.1 mmol/mL in water, 2 mL), 60°C, 20 h. [b] Calculated based on NMR integration ratios and GC- MS yield of crotonaldehyde, [c] GC-MS yield, calibrated with dodecane internal standard.

However, scaling up the reaction to 100 L scale showed that the most efficient solvent is toluene, the EtOAc gave more oligomers.

, ₂ ,

65.0 % GC-MS yield 15.0 % GC-MS yield 8.4 % GC yield

Scheme 4. Acetaldehyde in toluene (concentration = 4 mol/L), 4 mol% of the catalyst (Pyrrolidine / Acetic acid, in water concentration 0.3 mol/L) at 60°C for 10 hours.

Next, the decantated/ separated organic phase continues to the next reactor for heterogenous metal catalyzed hydrogenation/ reduction with H2 gas, the catalytic active amount of Pd(O) are supported on alumina or on carbon (Scheme 5).

Toluene, C = 4 M 98% Conversion

(GC-MS analysis)

Scheme 5. The metal catalyzed reduction of linear enals.

Next step, in our continues process, is the condensation of the reactive intermediates aldehydes 3 and 9, catalyzed by the metal free secondary amine pyrrolidine and the presence of catalytic amount of acetic acid (Scheme 6).

4 mol% Pyrrolidine

10 enals

( C10 & C₁₂)

98% Conversion Based on GC-MS

Scheme 6. The metal-free catalyzed condensation reaction of linear aldehyde into branched enals. 1.1.2 One-pot Lewis base-Lewis acid metal system

In additional approach, we investigated a one-pot dual catalytic system, a base (potassium carbonate) in combination with supported Pd (0) on carbon to convert the acetaldehyde 1 into saturated branched aldehyde 4 (Table 2).

Table 2. One-pot conversion of acetaldehyde into longer branched aldehyde

Yield (%)^[bI

Entry Pd(0) mol% K₂CO₃ mol% Solvent¹³¹ Time (h) Conversion (%) ^[b] 1c 3 6 7

1 0.3 3.0 H₂O 12 98 6.0 9.0 72 12

2 0.3 5.0 H₂0/Toluene 18 99 31 1.0 56 13

[a] The concentration, C= 4M. [b] based on H-NMR analysis

As indicated in table 1, the formation of branched Ce aldehyde 13, was the predominant product. However, the product 13, can be further reduced and transformed into branched Ce alcohol 14, that can be further utilized in the synthesis of C12 ether 15 (Scheme 7).

Supported Supported acid Catalytic amount

Scheme 7. Catalytic metal catalyzed reduction of Ce aldehyde to branched Ce alcohol, followed by etherification

1.1.3 Heterogenous metal-based system

It was observed that one of the major challenges in this process is controlling the outcome products of the condensation reaction of acetaldehyde 1. Thus, it was decided to start from crotonaldehyde as feedstock in the one-pot heterogenous metal catalyzed synthesis of branched Cs aldehyde 5 and branched alcohols 6.

Transition metals such as Pd, Ni and Cu supported on aluminum and silica as heterogenous catalysts were investigated for the catalytic conversion of acetaldehyde 1 and crotonaldehyde 2 into Cs branched alcohols 6 (Catalyst from HALDOR TOPSOE & Johnson Matthey). In initial experiments, an autoclave batch reactor was used as reaction vessel to conduct this transformation and toluene was chosen as solvent for the one-pot experiments at different temperatures (Scheme 8).

,

No conversion

100% conv. of crotonaldehyde based on GC-MS analysis

Scheme 8. [a] Reaction condition: 750 mmol/ 61 mL of crotonaldehyde in 180 mL of solvent, C= 4M. Under indicated H2 gas pressure and indicated temperature and time, [b] Yields based on GC-MS analysis

Furthermore, utilizing the Pd(O) metal as catalyst instead of the Ni(0) afford the branched aldehyde 5 as major product in one pot starting from the crotonaldehyde 2, as feedstock (Scheme 9).

Scheme 9. [a] Reaction condition: 750 mmol/ 61 mL of crotonaldehyde in 180 mL of solvent, C= 4M. Under indicated H2 gas pressure and indicated temperature and time, [b] Yields based on GC-MS analysis

Scheme 10. [a] Reaction condition: 750 mmol/ 61 mL of crotonaldehyde in 180 mL of solvent, C= 4M. Under indicated H2 gas pressure and indicated temperature and time, [b] Yields based on GC-MS analysis To reduce the Cs, branched aldehyde 5, to branched alcohol 6, a Ni(0) based catalyst (From HALDOR TOPSOE) or a copper-based catalyst (from Johnson Matthey) can be applied.

1.2 Synthesis of the Cie branched ether 7

Finally, the target Ci6 ether 7, was synthesized by acid catalyzed etherification reaction. In our process sulfuric acid both as liquid and as heterogenous supported on silica were applied successfully, utilizing a dean-stark equipment to remove the formed water as by product (Scheme 11).

99% total conversion

99% total conversion

Scheme 11. [a] Reaction condition: Neat condition, [b] Yields based on GC-MS analysis

Di(2-ethylhexyl) ether as a Diesel Renewable fuel

In order to be useful as diesel fuel, the composition of the invention preferably fulfill the requirements of diesel fuel, such as the standard for diesel fuel is EN 590 (2017). Table 3. EN590 (2017)

For the "temperate" climatic zones the standard defines six classes from A to F. Table 4. Temperate climatic zones

For the "arctic" climatic zones the standard defines five classes from 0 to 4.

Table 5. Arctic climatic zones

The composition of the invention fulfills at least the one or more following requirements and can be used as renewable fuel: a lubricity ISO 12156 (2018) of 480, or 460 pm or less, a conductivity at 20°C ASTM D 2624 (2021) of 50 pS/m or more, a sulphur content, Q EN ISO 20846 (2019) of 10.0 mg/kg or less, a density at 15°C, EN ISO 12185 (1996), of 860, or 845 or 820 kg/m³ or less, and/or a cetane Number, EN ISO 5165 (2020), of 51 or 70 or more. The renewable fuel also meets one or more of the following requirements an oxidation stability, ISO 12205 (1995), 25 g/ m³ or less, a flash point of at least 56 or 80 or 100°C, kinematic viscosity at 40°C, EN 16896 (2016), between 1.400 and 4.500, 2.000 and 3.600 mm²/s, cloud point, EN 23015 (1994) obs. 16/0°C or less, cold filter plugging point (CFPP), Q EN 116 (2018), of -50°C or more, cetane index, Q ISO 4264 (2018), of 46 or more, an ash content, EN ISO 6245 (2001) of 0.010 mass% or less, and/or carbon residue micro (10%bot.), ISO 10370 (2014)/3405 (2019) of 0.30, or 0.10 mass% or less.

When 5 to 15 wt%, or 9 to 10wt% C8 alcohol and 1 to 15 wt%, or 7-8 wt% C12 alcohol, which C8 or C12 alcohol may be linear or branched, are added to the renewablefuel, at least the following requirement are met; a lubricity at 60°C ISO 12156-1 (2018) of 450 or 300 urn or less, and a sulphur content, Q EN ISO 20846 (2019) of 20.0 or 10.0 or 5.0 or 3.0 or 1.0 mg/kg or less. This mixed renewable fuel also meets one or more of the following requirements carbon residue micro (10%bot.), ISO 10370 (2014)/3405 (2019) of 0.30 mass% or less, kinematic viscosity at 40°C, EN 16896 (2016), between 2.000 and 4.500 mm²/s, a cetane Number, EN ISO 5165 (2020), of 51 or 70 or more, and/or cetane index, Q ISO 4264 (2018), of 50 or more, cold filter plugging point (CFPP), Q EN 116 (2018), of -50°C or more, a flash point of at least 56 or 80°C.

The present invention is not limited to the embodiments disclosed but may be varied and modified within the scope of the following claims.

Claims

1. A renewable fuel composition comprising at least 60 or 70 or 80 or 90 wt% of a symmetric branched C12-C18 ether, or 3-(((2- ethylhexyl)oxy)methyl)heptane, and up to 100 wt% of one or more additives/lubricants.

2. The renewable fuel composition according to claim 1, wherein the fuel composition is characterized in having a lubricity ISO 12156 (2018) of 480 pm or less, a conductivity at 20°C ASTM D 2624 (2021) of 50 pS/m or more, a sulphur content, Q EN ISO 20846 (2019) of 10.0 mg/kg or less, a density at 15°C, EN ISO 12185 (1996), of 860, or 845 or 820 kg/m³ or less, a cetane Number, EN ISO 5165 (2020), of 51 or 70 or more, an oxidation stability, ISO 12205 (1995), 25 g/m³ or less, and/or a flash point of at least 56 or 80 or 100°C.

3. The renewable fuel composition according to claim 1, wherein the fuel composition further comprises

5 to 15 wt%, or 9 to 10 wt% Cs alcohol and/or

1 to 15 wt%, or 7 to 8 wt% C12 alcohol, which Cs or C12 alcohols may be linear or branched.

4. The renewable fuel composition according to claim 3, wherein the fuel composition is characterized in having a lubricity at 60°C ISO 12156-1 (2018) of 450 or 300 pm or less, a sulphur content, Q EN ISO 20846 (2019) of 20.0 or 10.0 or 5.0 or 3.0 or 1.0 mg/kg or less, and/or a flash point of at least 56 or 80°C.

5. The renewable fuel composition according to claim 1 to 4, wherein the fuel composition comprises at least 70 to 99 wt% of a symmetric branched C12-C18 ether, or 3-(((2- ethylhexyl)oxy)methyl)heptane,

5 to 15 wt%, or 9 to 10 wt% Cs alcohol and/or

6. The renewable fuel composition according to claim 1 to 4, wherein the fuel composition comprises

8 to 10 wt% Cs alcohol, which Cs alcohol may be linear or branched, and

7. The renewable fuel composition according to claim 1 to 6, wherein the fuel composition comprises

6 to 8 wt% C12 alcohol, which Cs or C12 alcohol may be linear or branched, and

1 to 99.9 wt%, or 50 to 99 wt%, or 26 to 99 wt%, or up to 100 wt% of fossil fuel or other renewable fuels or bio-fuels/bio-diesels, or any mixture thereof.

8. The renewable fuel composition according to claim 7, wherein the fossil fuel is selected from the group comprising diesel, jet fuel, gasoline, propane and kerosene, or any mixture thereof.

9. The renewable fuel composition according to claim 7, wherein the fossil fuel is selected from the group comprising diesel and gasoline, or any mixture thereof.

10. The renewable fuel composition according to claim 7, wherein the renewable fuels or bio- fuels/bio-diesels is selected from the group comprising fatty acid methyl esters (FAME), Hydrotreated Vegetable Oil (HVO), Hydroprocessed Esters and Fatty Acids (HEFA), soy methyl ester (SME) and rapeseed methyl ester (RME), or any mixture thereof.

11. The renewable fuel composition according to any one of the preceding claims, wherein the one or more additive/lubricant is selected from the group comprising engine oil, gear oil, transmission fluid, including but not limited to hydroxyamic acid, succinic acid and derivatives thereof, mono-, di-, or triglyceride, hydroxy polycarboxylic acid or derivative thereof, or petroleum lubricant oil including but not limited to naphthenic base, paraffin base, and mixed based, or synthetic oils including but not limited to alkylene polymers, alkylene oxide polymers, ester of organic and inorganic acids, acryl hydrocarbons and ethers, organic silicone compounds, or combinations thereof, or ionic liquids including but not limited to imidazolium-, ammonium-, pyridinium-, and phosphonium-based ionic liquids, or synthetic lubricants including but not limited to organic esters such as phosphate esters, polalkylene glycols, or vegetable oil-based lubricants, or polyalphaolefins, alkylated aromatics, polybutenes, polyesters, dibasic acid esters, polyol esters, or acetone, ether, nitrous oxide, nitromethane, butyl rubber, ferox, oxyhydrogen, ferrous picrate, silicone, tetranitromethane, or ether and alcohol oxygenates including but not limited to methanol, ethanol, isopropyl alcohol, n-butanol, t-butanol, methyl tert-butyl ether, tertiary amyl methyl ether, tertiary hexyl methyl ether, ethyl tertiary butyl ether, tertiary amyl ethyl ether, and diisopropyl ether.

12. The renewable fuel composition according to any one of the preceding claims, wherein the one or more lubricant is selected from the group comprising PC 32™, Hydradd L1000™, LX 5100™, HFA 7025™, Improver L 315™, ADD 5-6110™, HITEC 4140A™, OLI 9970™.

13. The renewable fuel composition according to any one of the preceding claims, wherein the one or more additive is selected from the group comprising Stadis 450™ and Plutostat™.

14. Use of the renewable fuel composition according to any one of the preceding claims, as bio-diesel fuel.

15. Use of the renewable fuel composition according to any one of the preceding claims, in motorized vehicles, such as cars, airplanes, boats, industrial machines, generators and as substitutes for gasoline, diesel, propane and kerosene.

16. Use of the renewable fuel composition according to any one of claims 1 to 13, as lubricant/additive in fossil fuel or other renewable fuels, or in cosmetic and pharmaceutical products, or in hydraulic fluids.

17. A process for preparation of 3-(((2-ethylhexyl)oxy)methyl)heptane comprising the steps of a) converting acetaldehyde 1 and/or crotonaldehyde 2 into Cs aldehyde 4 and 5 using an Ni(0)-AI or Pd(0)-AI or Pd(0)-C catalyst, at a hydrogen pressure of 0.6 to 12 MPa at a temperature of 50 to 150°C in an organic solvent

organic solvent, T 50-150°C H₂ (0.5-12 MPa

b) converting Cs aldehyde 4 and 5 into Cs branched alcohols 6 using an Ni(0) based catalyst or a copper based catalyst,

a. c) converting Cs branched alcohols 6 into 3-(((2-ethylhexyl)oxy)methyl)heptane 7 using an acid catalyst at a temperature of 160°C or more,

wherein the acid catalyst in step c) is selected from the group comprising sulfuric acid, sulfonic acid, solid acids, montmorillonite clays solid acid catalysts, solid acid catalyst and immobilized sulfuric acid (SiCh-HzSC ) or sulfonic acid on silica (SiCh-SOsH).

18. A process for preparation of 3-(((2-ethylhexyl)oxy)methyl)heptane comprising the steps of

wherein the one or more catalyst may be selected from the group comprising heterogeneous supported metal catalyst, a homogeneous organometallic complex, a metal-free catalyst, an enzyme or bacteria, and wherein the acid catalyst in step c) is selected from the group comprising sulfuric acid, sulfonic acid, solid acids, montmorillonite clays solid acid catalysts, solid acid catalyst and immobilized sulfuric acid (SiCh-HzSC ) or sulfonic acid on silica (SiCh-SOsH).

19. The process according to claim 17 or 18, wherein the process is performed in one-pot.