WO2023031512A1 - Jet fuel composition - Google Patents

Jet fuel composition Download PDF

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Publication number
WO2023031512A1
WO2023031512A1 PCT/FI2022/050559 FI2022050559W WO2023031512A1 WO 2023031512 A1 WO2023031512 A1 WO 2023031512A1 FI 2022050559 W FI2022050559 W FI 2022050559W WO 2023031512 A1 WO2023031512 A1 WO 2023031512A1
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WIPO (PCT)
Prior art keywords
jet fuel
vol
renewable
fuel component
composition
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PCT/FI2022/050559
Other languages
French (fr)
Inventor
Kati SANDBERG
Jenni NORTIO
Ulla Kiiski
Original Assignee
Neste Oyj
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Publication date
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Publication of WO2023031512A1 publication Critical patent/WO2023031512A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/08—Jet fuel

Definitions

  • the present invention relates to a jet fuel composition in general and in particular to a jet fuel composition comprising a renewable jet fuel component and a petroleum based (fossil based) jet fuel component.
  • the invention especially relates to a jet fuel composition with enhanced storage properties.
  • jet fuel might be stored for longer periods of time and long-term stability of the jet fuel is therefore important.
  • Such situations include military and other strategic uses.
  • the composition hereby provided presents a solution to the long-time storage of jet fuel compositions.
  • Jet fuel or aviation fuel is a fuel intended for use in aircraft powered by gas-turbine engines.
  • the most commonly used jet fuels Jet A and Jet A-l are produced to a standardized international specification.
  • Jet fuel is a mixture of different hydrocarbons. Their sizes, molecular weights or carbon numbers are resulting from the physical properties required by the product specification, e.g. flash point, freezing point, boiling range.
  • Kerosene-type jet fuel typically has a carbon number distribution between about 8 and 16 carbon atoms per molecule.
  • Fossil fuels or petroleum-based fuels may be at least partly replaced by synthetic fuels or fuels from biological sources or other renewable sources.
  • the renewable jet fuel demand is growing in the future due to global initiatives to decrease the emissions of GHG, CO2, etc.
  • One possible solution is to increase the use of renewable fuels in jet fuels.
  • Fuels from biological sources may include renewable feedstocks such as fats and/or oils.
  • Several types of fuels may be obtained from these triacylglycerol-containing feedstocks.
  • a product that may be obtained from lipid feedstocks is a fuel which is produced from the fat or oil by a hydrodeoxygenation reaction at an elevated temperature and pressure in the presence of a catalyst.
  • the formed hydrocarbons from the hydrodeoxygenation reaction of the triacylglycerol-containing feedstocks typically need to be isomerised before the composition fulfils fuel specification.
  • the isomerisation forms branches (sidechains) to the hydrocarbon backbone, without change in the total carbon number. Branched or isomerised hydrocarbons/paraffins have lower melting point compared to unbranched hydrocarbons and isomerisation therefore improves the cold flow properties of a hydrocarbon composition.
  • Publication WO 2018/224730 describes a multipurpose fuel composition
  • a multipurpose fuel composition comprising petroleum based jet fuel component and renewable jet fuel component, wherein the fuel composition has a freezing point of -40°C or below.
  • the renewable jet fuel component comprises isomerised and normal paraffins (i- and n-paraffins), which originate from vegetable oils and/or animal fats.
  • a safe and reliable source of fuel is highly important, in certain occasions it must be possible to safely store jet fuel for a longer time (e.g. in military use). In such cases, it is important to ensure that the there are no changes in product quality and the product is thereby stable over a storage period.
  • An object of the present invention is to provide a jet fuel composition with improved storage stability.
  • the objects of the invention are achieved with a composition as characterized by what is stated in the independent claims.
  • the preferred embodiments of the invention are disclosed in the dependent claims.
  • An aspect of the invention is to provide a composition
  • a composition comprising a) a renewable jet fuel component, which comprises at least 94 wt.% isoparaffins and which fulfils the ASTM D7566 Annex A2 specification, and b) a petroleum based jet fuel component, wherein the amount of the renewable jet fuel component in the composition is from about 40 vol-% to about 65 vol-% and the amount of the petroleum based jet fuel component in the composition is from about 60 vol-% to about 35 vol-% and the composition has a higher PetroOxy value compared to the PetroOxy value of the petroleum based jet fuel component.
  • Another aspect of the invention is to provide a method to improve the storage stability of petroleum based jet fuel, wherein the method comprises blending a renewable jet fuel component, which fulfils the ASTM D7566, Annex A2 standard to the petroleum based jet fuel component, to a final jet fuel mixture containing from about 40 vol-% to about 65 vol-% of the renewable jet fuel component and from about 60 vol-% to about 35 vol-% of the petroleum based jet fuel component.
  • An advantage of the invention is that the long time storage stability of jet fuel can be improved. Storing the renewable jet fuel as a blend with the petroleum based jet fuel provides operational flexibility while the fuel is already a drop- in blend and ready for use.
  • Jet fuel or aviation fuel is fuel aimed for use in aircrafts powered by gasturbine engines. Jet fuel needs to fulfil certain physical properties in order to be classified as jet fuel.
  • the standards for definition of jet fuel include at least DEF STAN 91-091 2020], ASTM D1655-21a (JetA-1) and ASTM D7566-21.
  • the storage stability for any fuel is important, but for jet fuel, with strict quality requirements, it is even more important.
  • the storage of jet fuel is especially important in military uses or in places where the supply of jet fuel can be uncertain.
  • the storage stability of fuels can be improved using stability improving additives.
  • the stability of the petroleum based jet fuel when blending it with a renewable jet fuel component is not reduced during storage period of at least three years.
  • the storage stability of the petroleum based jet fuel is even improved when blended with a renewable jet fuel component.
  • the current invention thereby provides a jet fuel composition with improved storage stability.
  • the composition is a blend of a renewable jet fuel component, which comprises at least 94 wt.% isoparaffins and which fulfils the ASTM D7566 Annex A2 specification, and a petroleum based jet fuel component, where the blend contains from about 40 vol-% to about 65 vol-% of the renewable jet fuel component and from about 60 vol-% to about 35 vol-% of the petroleum based jet fuel component.
  • the here mentioned components of the final jet fuel mixture i.e. the renewable jet fuel component and the petroleum based jet fuel component are to be understood to represent the main components of the final jet fuel mixture and the composition or fuel can also contain other components or additives, which are allowed or required in jet fuel, such as antioxidants.
  • the renewable jet fuel component and/or the petroleum based jet fuel component also contains an antioxidant additive.
  • renewable jet fuel component which fulfils the ASTM D7566, Annex A2 standard
  • any synthetic hydrocarbon composition that fulfils the ASTM standard and is produced from any biological and/or renewable source with any suitable method.
  • biological or renewable source is meant to include feedstocks other than those obtained from petroleum crude oil (fossil-based oil or petroleum based oil).
  • the renewable source that can be used in the present invention includes, but is not limited to, bio oils and fats from plants and/or animals and/or fish and/or insects, and from processes utilizing microbes, such as algae, bacteria, yeasts and moulds, and suitable are also compounds derived from said fats and oils and mixtures thereof.
  • the species yielding the bio oils or fats may be natural or genetically engineered.
  • the bio oils and fats may be virgin oils and fats or recycled oils and fats.
  • Suitable bio oils containing fatty acids and/or fatty acid esters and/or fatty acid derivatives are wood-based and other plant-based and vegetable-based fats and oils such as rapeseed oil, colza oil, canola oil, tall oil, jatropha seed oil, sunflower oil, soybean oil, hempseed oil, olive oil, linseed oil, mustard oil, palm oil, peanut oil, castor oil, coconut oil, as well as fats contained in plants bred by means of gene manipulation, animal-based fats such as lard, tallow, train oil, and fats contained in milk, as well as recycled fats of the food industry and mixtures of the above, as well as fats and oils originating from processes utilizing microbes, such as algae, bacteria, yeasts and moulds.
  • microbes such as algae, bacteria, yeasts and moulds.
  • the renewable source also includes recyclable waste oils and fats or residues of recyclable waste oils and fats.
  • Bio oil and fat suitable as fresh feed may comprise C12-C24 fatty acids, derivatives thereof such as anhydrides or esters of fatty acids as well as monoglycerides, diglycerides and triglycerides of fatty acids or combinations of thereof.
  • Fatty acids or fatty acid derivatives, such as esters may be produced via hydrolysis of bio oils or by their fractionation or transesterification reactions of triglycerides or microbiological processes utilizing microbes.
  • the renewable jet fuel component according to the invention can be produced by any suitable method for converting a bio oil or fat into hydrocarbons, such as isomerised paraffins.
  • the paraffins are produced from renewable oil, such as vegetable oil or animal fat, which is subjected to a deoxygenation process for removal of heteroatoms, mainly oxygen from the renewable oil.
  • the deoxygenation treatment, to which the renewable raw material is subjected is hydrotreatment.
  • the renewable raw material is subjected to hydrodeoxygenation (HDO) which preferably uses an HDO catalyst.
  • HDO hydrodeoxygenation
  • Catalytic HDO is the most common way of removing oxygen and has been extensively studied and optimized.
  • the present invention is not limited thereto.
  • an HDO catalyst comprising hydrogenation metal supported on a carrier may be used. Examples include an HDO catalyst comprising a hydrogenation metal selected from a group consisting of Pd, Pt, Ni, Co, Mo, Ru, Rh, W or a combination of these.
  • Alumina or silica is suited as a carrier, among others.
  • the hydrodeoxygenation step may, for example, be conducted at a temperature of 100-500°C and at a pressure of 10-150 bar (absolute), corresponding to IMPa to 15 MPa.
  • the isomerised paraffins component is produced by a Fischer-Tropsch process starting from gasification of biomass.
  • This synthesis route is generally also called BTL, or biomass to liquid.
  • biomass such as lignocellulosic material
  • syngas gas mixture of hydrogen and carbon monoxide
  • the Fischer-Tropsch synthesis paraffins are produced from syngas.
  • the Fischer-Tropsch paraffins range from gaseous component to waxy paraffins and middle distillate boiling range paraffins can be obtained by distillation from the product.
  • the n-paraffins formed either by hydrotreating renewable oils or Fischer-Tropsch method need to be subjected to a further isomerisation treatment.
  • the isomerisation treatment causes branching of hydrocarbon chains, i.e. isomerisation, of the hydrotreated raw material. Branching of hydrocarbon chains improves cold properties, i.e. the isomeric composition formed by the isomerisation treatment has better cold properties compared to the hydrotreated raw material. Better cold properties refer to a lower temperature value of a freezing point.
  • the isomeric hydrocarbons, or isomerised paraffins, formed by the isomerisation treatment may have one or more side chains, or branches.
  • the isomerisation step may be carried out in the presence of an isomerisation catalyst, and in the presence of hydrogen added to the isomerisation process.
  • Suitable isomerisation catalysts contain a molecular sieve and/or a metal selected from Group VI 11 of the periodic table and optionally a carrier.
  • the isomerisation catalyst contains SAPO-11, or SAPO-41, or ZSM-22, or ZSM-23, or fernerite, and Pt, Pd, or Ni, and A12O3, or SiO2.
  • Typical isomerisation catalysts are, for example, Pt/SAPO-ll/AhOs, Pt/ZSM-22/Al 2 O 3 , Pt/ZSM-23/Al 2 O 3 , and Pt/SAPO-ll/SiO 2 .
  • the catalysts maybe used alone or in combination.
  • the presence of added hydrogen is particularly preferable to reduce catalyst deactivation.
  • the isomerisation catalyst is a noble metal bifunctional catalyst, such as Pt-SAPO and/or Pt-ZSM-catalyst, which is used in combination with hydrogen.
  • the isomerisation step may, for example, be conducted at a temperature of 200-500°C, preferably 280-400°C, and at a pressure of 5-150 bar (0.5 MPa - 15MPa), preferably 10-130 bar (lMPa-13MPa), more preferably 30-100 bar (3MPa - lOMPa) (absolute).
  • the isomerisation step may comprise further intermediate steps such as a purification step and a fractionation step.
  • the isomerisation may be performed e.g. at 300°C to 350°C.
  • Fractionation is not a compulsory step in this invention, but in an embodiment of the invention the isomerised paraffins formed in the isomerisation process can be fractionated in order to get a renewable jet fuel component that fulfils the ASTM D7566, Annex A2 standard.
  • the fractionation can be performed using any suitable method and is not limited to distillation. Distillation is the most commonly used method for separating various fractions from hydrocarbon compositions and is also suitable here.
  • jet fuel any component or fuel that fulfils any of the jet fuel standards, such as DEF STAN 91-091 (2020), ASTM D1655-21a (Jet A-l), and is produced from a petroleum or fossil based source.
  • composition according to the invention has an improved storage stability.
  • storage stability is here meant that the fuel can be stored for a certain time, at least three years, without significantly loosing fuel properties, i.e. the fuel should still be useful as a fuel even after storage and the fuel properties should not be significantly altered.
  • Storage stability can be measured with several well established methods.
  • Oxidation stability is a typical parameter to indicate stability of especially jet fuel.
  • Thermal oxidation stability of a fuel can be measured using ASTM D3241 standard test.
  • Another parameter to indicate stability is to measure the existence of reactive species in the fuel. This can be achieved with a gum method (1P540).
  • a method to measure the oxidation stability of a fuel is to measure the PetroOxy value of the fuel using EN 16091 (2011) standardised method. The oxidation stability is a good overall measure of the stability of the fuel.
  • the steps of PetroOxy EN16091 (2011) method are as follows:
  • a known volume of a sample is placed in a reaction vessel charged with oxygen to a pressure of 700 kPa ⁇ 5 kPa,
  • reaction vessel is heated to 140°C ⁇ 0.5°C
  • the pressure in the vessel drops as the oxygen is consumed during the oxidation of the sample.
  • the breakpoint is when pressure drops 10% from the maximum observed oxygen pressure.
  • the elapsed time from start to the breakpoint is the induction period at the test temperature of 140°C ⁇ 0.5°C. A longer time between start and breakpoint, i.e. a higher PetroOxy value in minutes, indicates that the fuel is less prone to oxidation.
  • the composition with improved storage stability comprises a blend of about 45 vol-% to about 55 vol-%, preferably from about 49 vol-% to about 50 vol-% of renewable jet fuel component and a petroleum based jet fuel component from about 55 vol-% to about 45 vol-%, preferably from about 51 vol-% to about 50 vol-%. It was observed that the concentration of renewable fuel must be at least 40 vol-% or above in order to improve the storage stability of the petroleum based jet fuel.
  • the current standard allows a maximum of 50 vol-% of renewable jet fuel in a final jet fuel.
  • the renewable jet fuel component comprises mainly a mixture of normal paraffins (n-paraffins) and isomerised paraffins (isoparaffins).
  • the paraffins of the renewable jet fuel component can be produced by any suitable method such as hydrodeoxygenation of a biological or renewable feed material comprising acylglycerols, followed by isomerisation of the hydrodeoxygenated material.
  • the isomerised hydrodeoxygenated material can further be subjected to a fractionation, such as distillation, to obtain a component that fulfils the ASTM D7566, Annex A2 standard.
  • the renewable jet fuel component of the composition has an amount of isoparaffins (i-paraffins) of at least 94 wt.% of the total paraffinic content.
  • the amount of isoparaffins is at least 95 wt.% and more preferably at least 97 wt-%.
  • the carbon chain length distribution of the renewable jet fuel component is as follows:
  • the carbon chain distribution is:
  • the improvement of the storage stability is measured as an increase of the PetroOxy value of the mixture compared to the petroleum based jet fuel.
  • the PetroOxy value should be regarded as a measurable property or parameter of the jet fuel.
  • the PetroOxy value depends on the physical and chemical properties of the composition and is to be considered as a parameter that describes the composition.
  • the increase in the PetroOxy value of the jet fuel composition is increased at least 3%, more preferably at least 5% as compared to the value of the petroleum based jet fuel.
  • the here mentioned components of the composition i.e. the renewable jet fuel component and the petroleum based jet fuel component are to be understood to represent the main components of the composition and the composition can also contain other components or additives such as antioxidants, which are allowed or required in jet fuel. Additives approved for use in jet fuel are listed in DEF STAN 91-091 specification. In one embodiment of the invention the composition also comprises one or more antioxidant additives.
  • the method comprises blending a renewable jet fuel component, which fulfils the ASTM D7566, Annex 2 standard to the petroleum based jet fuel component, to a final jet fuel mixture containing from about 40 vol- % to about 65 vol-% of the renewable jet fuel component and from about 60 vol-% to about 35 vol-% of the petroleum based jet fuel component.
  • the final jet fuel mixture contains the renewable jet fuel component from about 45 vol-% to about 55 vol-%, preferably from about 49 vol-% to about 50 vol-% and the petroleum based jet fuel component is from about 55 vol-% to about 45 vol-%, preferably from about 51 vol-% to about 50 vol-%.
  • the renewable jet fuel component is a mixture of paraffinic hydrocarbons.
  • the renewable jet fuel composition comprises at least 94 wt.% isoparaffins.
  • the renewable jet fuel component is produced by a process comprising hydrodeoxygenation of a renewable or biological feed material comprising acylglycerols, followed by isomerisation of the hydrodeoxygenated material.
  • the improvement of the storage stability is measured as an increase in the PetroOxy value.
  • the improvement of the storage stability can be measurable as an increase in the PetroOxy value of at least 3%, preferably of at least 5% of the final jet fuel mixture compared to the PetroOxy value of the petroleum based jet fuel.
  • the oxidation stability was tested for a petroleum based jet fuel (100%) before adding a renewable jet fuel component and after addition of the renewable component.
  • Two different Jet A-l fuels (PB1 and PB2) and two different blends with renewable jet fuel (RJF) were tested (compositions A and B in table 1).
  • the renewable jet fuel was produced by hydrodeoxygenation of acylglycerols followed by isomerisation, such that compositions A and B contained 94 wt.% isoparaffins.
  • the renewable jet fuel satisfies the ASTM D7566 Annex A2 requirements and the initial oxidation stability, (i.e. the oxidation stability measured immediately after blending) was tested using the EN 16091 (2011) (as described above) standardised method to provide a PetroOxy value as measured in minutes. The results of the initial oxidation stability are presented in table 1.
  • composition C As a comparison, a blend with 35 vol-% renewable jet fuel and 65 vol- % petroleum jet fuel was prepared, and the initial oxidation stability was measured and the results are also presented (composition C) in table 1.
  • Table 1 PetroOxy values for petroleum based (PB1 and PB2) Jet A-l fuel and blends with renewable jet fuel (RJF)
  • a blend of 50 vol-% renewable jet fuel component and 50 vol-% petroleum based jet fuel component was produced. Properties of the blend were tested at the making of the blend. The blend was stored for 3 years and the same properties were tested during the storage period. The measured properties at the beginning of the storage period and after three years storage varied as followed:

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Abstract

Disclosed is a jet fuel composition comprising a renewable jet fuel component, which comprises at least 94 wt.% isoparaffins and fulfils the ASTM D7566, Annex A2 standard, and a petroleum based jet fuel component, blended to a final jet fuel mixture containing from about 40 vol-% to about 65 vol-% of the renewable jet fuel component and from about 60 vol-% to about 35 vol-% of the petroleum based jet fuel component. Also disclosed is a method to improve the storage stability of petroleum based jet fuel.

Description

Jet Fuel Composition
FIELD OF THE INVENTION
The present invention relates to a jet fuel composition in general and in particular to a jet fuel composition comprising a renewable jet fuel component and a petroleum based (fossil based) jet fuel component. The invention especially relates to a jet fuel composition with enhanced storage properties.
There are situations and applications, where jet fuel might be stored for longer periods of time and long-term stability of the jet fuel is therefore important. Such situations include military and other strategic uses. The composition hereby provided presents a solution to the long-time storage of jet fuel compositions.
BACKGROUND OF THE INVENTION
Jet fuel or aviation fuel is a fuel intended for use in aircraft powered by gas-turbine engines. The most commonly used jet fuels Jet A and Jet A-l are produced to a standardized international specification. Jet fuel is a mixture of different hydrocarbons. Their sizes, molecular weights or carbon numbers are resulting from the physical properties required by the product specification, e.g. flash point, freezing point, boiling range. Kerosene-type jet fuel (including Jet A and Jet A-l) typically has a carbon number distribution between about 8 and 16 carbon atoms per molecule.
Fossil fuels or petroleum-based fuels may be at least partly replaced by synthetic fuels or fuels from biological sources or other renewable sources. The renewable jet fuel demand is growing in the future due to global initiatives to decrease the emissions of GHG, CO2, etc. One possible solution is to increase the use of renewable fuels in jet fuels. Fuels from biological sources may include renewable feedstocks such as fats and/or oils. Several types of fuels may be obtained from these triacylglycerol-containing feedstocks. One example of a product that may be obtained from lipid feedstocks, is a fuel which is produced from the fat or oil by a hydrodeoxygenation reaction at an elevated temperature and pressure in the presence of a catalyst.
The formed hydrocarbons from the hydrodeoxygenation reaction of the triacylglycerol-containing feedstocks typically need to be isomerised before the composition fulfils fuel specification. The isomerisation forms branches (sidechains) to the hydrocarbon backbone, without change in the total carbon number. Branched or isomerised hydrocarbons/paraffins have lower melting point compared to unbranched hydrocarbons and isomerisation therefore improves the cold flow properties of a hydrocarbon composition.
Publication WO 2018/224730 describes a multipurpose fuel composition comprising petroleum based jet fuel component and renewable jet fuel component, wherein the fuel composition has a freezing point of -40°C or below. The renewable jet fuel component comprises isomerised and normal paraffins (i- and n-paraffins), which originate from vegetable oils and/or animal fats.
A safe and reliable source of fuel is highly important, in certain occasions it must be possible to safely store jet fuel for a longer time (e.g. in military use). In such cases, it is important to ensure that the there are no changes in product quality and the product is thereby stable over a storage period.
Hereby is provided a jet fuel composition with improved storage stability.
BRIEF DESCRIPTION OF THE INVENTION
An object of the present invention is to provide a jet fuel composition with improved storage stability. The objects of the invention are achieved with a composition as characterized by what is stated in the independent claims. The preferred embodiments of the invention are disclosed in the dependent claims.
An aspect of the invention is to provide a composition comprising a) a renewable jet fuel component, which comprises at least 94 wt.% isoparaffins and which fulfils the ASTM D7566 Annex A2 specification, and b) a petroleum based jet fuel component, wherein the amount of the renewable jet fuel component in the composition is from about 40 vol-% to about 65 vol-% and the amount of the petroleum based jet fuel component in the composition is from about 60 vol-% to about 35 vol-% and the composition has a higher PetroOxy value compared to the PetroOxy value of the petroleum based jet fuel component.
Another aspect of the invention is to provide a method to improve the storage stability of petroleum based jet fuel, wherein the method comprises blending a renewable jet fuel component, which fulfils the ASTM D7566, Annex A2 standard to the petroleum based jet fuel component, to a final jet fuel mixture containing from about 40 vol-% to about 65 vol-% of the renewable jet fuel component and from about 60 vol-% to about 35 vol-% of the petroleum based jet fuel component. An advantage of the invention is that the long time storage stability of jet fuel can be improved. Storing the renewable jet fuel as a blend with the petroleum based jet fuel provides operational flexibility while the fuel is already a drop- in blend and ready for use.
DETAILED DESCRIPTION OF THE INVENTION
Jet fuel or aviation fuel is fuel aimed for use in aircrafts powered by gasturbine engines. Jet fuel needs to fulfil certain physical properties in order to be classified as jet fuel. The standards for definition of jet fuel include at least DEF STAN 91-091 2020], ASTM D1655-21a (JetA-1) and ASTM D7566-21.
The storage stability for any fuel is important, but for jet fuel, with strict quality requirements, it is even more important. The storage of jet fuel is especially important in military uses or in places where the supply of jet fuel can be uncertain. The storage stability of fuels can be improved using stability improving additives.
With this invention, the stability of the petroleum based jet fuel when blending it with a renewable jet fuel component is not reduced during storage period of at least three years. Surprisingly, the storage stability of the petroleum based jet fuel is even improved when blended with a renewable jet fuel component.
The current invention thereby provides a jet fuel composition with improved storage stability. The composition is a blend of a renewable jet fuel component, which comprises at least 94 wt.% isoparaffins and which fulfils the ASTM D7566 Annex A2 specification, and a petroleum based jet fuel component, where the blend contains from about 40 vol-% to about 65 vol-% of the renewable jet fuel component and from about 60 vol-% to about 35 vol-% of the petroleum based jet fuel component.
It should be noted that the here mentioned components of the final jet fuel mixture, i.e. the renewable jet fuel component and the petroleum based jet fuel component are to be understood to represent the main components of the final jet fuel mixture and the composition or fuel can also contain other components or additives, which are allowed or required in jet fuel, such as antioxidants.
In one embodiment of the invention the renewable jet fuel component and/or the petroleum based jet fuel component also contains an antioxidant additive.
With the term "renewable jet fuel component, which fulfils the ASTM D7566, Annex A2 standard" is hereby meant any synthetic hydrocarbon composition that fulfils the ASTM standard and is produced from any biological and/or renewable source with any suitable method. Here, the term biological or renewable source is meant to include feedstocks other than those obtained from petroleum crude oil (fossil-based oil or petroleum based oil).
The renewable source that can be used in the present invention includes, but is not limited to, bio oils and fats from plants and/or animals and/or fish and/or insects, and from processes utilizing microbes, such as algae, bacteria, yeasts and moulds, and suitable are also compounds derived from said fats and oils and mixtures thereof. The species yielding the bio oils or fats may be natural or genetically engineered. The bio oils and fats may be virgin oils and fats or recycled oils and fats.
Suitable bio oils containing fatty acids and/or fatty acid esters and/or fatty acid derivatives are wood-based and other plant-based and vegetable-based fats and oils such as rapeseed oil, colza oil, canola oil, tall oil, jatropha seed oil, sunflower oil, soybean oil, hempseed oil, olive oil, linseed oil, mustard oil, palm oil, peanut oil, castor oil, coconut oil, as well as fats contained in plants bred by means of gene manipulation, animal-based fats such as lard, tallow, train oil, and fats contained in milk, as well as recycled fats of the food industry and mixtures of the above, as well as fats and oils originating from processes utilizing microbes, such as algae, bacteria, yeasts and moulds.
The renewable source also includes recyclable waste oils and fats or residues of recyclable waste oils and fats.
Bio oil and fat suitable as fresh feed may comprise C12-C24 fatty acids, derivatives thereof such as anhydrides or esters of fatty acids as well as monoglycerides, diglycerides and triglycerides of fatty acids or combinations of thereof. Fatty acids or fatty acid derivatives, such as esters may be produced via hydrolysis of bio oils or by their fractionation or transesterification reactions of triglycerides or microbiological processes utilizing microbes.
The renewable jet fuel component according to the invention can be produced by any suitable method for converting a bio oil or fat into hydrocarbons, such as isomerised paraffins. In one embodiment the paraffins are produced from renewable oil, such as vegetable oil or animal fat, which is subjected to a deoxygenation process for removal of heteroatoms, mainly oxygen from the renewable oil.
In a preferred embodiment, the deoxygenation treatment, to which the renewable raw material is subjected, is hydrotreatment. Preferably, the renewable raw material is subjected to hydrodeoxygenation (HDO) which preferably uses an HDO catalyst. Catalytic HDO is the most common way of removing oxygen and has been extensively studied and optimized. However, the present invention is not limited thereto. As the HDO catalyst, an HDO catalyst comprising hydrogenation metal supported on a carrier may be used. Examples include an HDO catalyst comprising a hydrogenation metal selected from a group consisting of Pd, Pt, Ni, Co, Mo, Ru, Rh, W or a combination of these. Alumina or silica is suited as a carrier, among others. The hydrodeoxygenation step may, for example, be conducted at a temperature of 100-500°C and at a pressure of 10-150 bar (absolute), corresponding to IMPa to 15 MPa.
In an embodiment, the isomerised paraffins component is produced by a Fischer-Tropsch process starting from gasification of biomass. This synthesis route is generally also called BTL, or biomass to liquid. It is well established in the literature that biomass, such as lignocellulosic material, can be gasified using oxygen or air in high temperature to yield a gas mixture of hydrogen and carbon monoxide (syngas). After purification of the gas, it can be used as feedstock for a Fischer-Tropsch synthesis route. In the Fischer-Tropsch synthesis paraffins are produced from syngas. The Fischer-Tropsch paraffins range from gaseous component to waxy paraffins and middle distillate boiling range paraffins can be obtained by distillation from the product.
The n-paraffins formed either by hydrotreating renewable oils or Fischer-Tropsch method need to be subjected to a further isomerisation treatment. The isomerisation treatment causes branching of hydrocarbon chains, i.e. isomerisation, of the hydrotreated raw material. Branching of hydrocarbon chains improves cold properties, i.e. the isomeric composition formed by the isomerisation treatment has better cold properties compared to the hydrotreated raw material. Better cold properties refer to a lower temperature value of a freezing point. The isomeric hydrocarbons, or isomerised paraffins, formed by the isomerisation treatment may have one or more side chains, or branches.
The isomerisation step may be carried out in the presence of an isomerisation catalyst, and in the presence of hydrogen added to the isomerisation process. Suitable isomerisation catalysts contain a molecular sieve and/or a metal selected from Group VI 11 of the periodic table and optionally a carrier. Preferably, the isomerisation catalyst contains SAPO-11, or SAPO-41, or ZSM-22, or ZSM-23, or fernerite, and Pt, Pd, or Ni, and A12O3, or SiO2. Typical isomerisation catalysts are, for example, Pt/SAPO-ll/AhOs, Pt/ZSM-22/Al2O3, Pt/ZSM-23/Al2O3, and Pt/SAPO-ll/SiO2. The catalysts maybe used alone or in combination. The presence of added hydrogen is particularly preferable to reduce catalyst deactivation. In a preferred embodiment, the isomerisation catalyst is a noble metal bifunctional catalyst, such as Pt-SAPO and/or Pt-ZSM-catalyst, which is used in combination with hydrogen. The isomerisation step may, for example, be conducted at a temperature of 200-500°C, preferably 280-400°C, and at a pressure of 5-150 bar (0.5 MPa - 15MPa), preferably 10-130 bar (lMPa-13MPa), more preferably 30-100 bar (3MPa - lOMPa) (absolute). The isomerisation step may comprise further intermediate steps such as a purification step and a fractionation step. The isomerisation may be performed e.g. at 300°C to 350°C.
Fractionation is not a compulsory step in this invention, but in an embodiment of the invention the isomerised paraffins formed in the isomerisation process can be fractionated in order to get a renewable jet fuel component that fulfils the ASTM D7566, Annex A2 standard. The fractionation can be performed using any suitable method and is not limited to distillation. Distillation is the most commonly used method for separating various fractions from hydrocarbon compositions and is also suitable here.
With the term "petroleum based jet fuel" is meant any component or fuel that fulfils any of the jet fuel standards, such as DEF STAN 91-091 (2020), ASTM D1655-21a (Jet A-l), and is produced from a petroleum or fossil based source.
The composition according to the invention has an improved storage stability. With storage stability is here meant that the fuel can be stored for a certain time, at least three years, without significantly loosing fuel properties, i.e. the fuel should still be useful as a fuel even after storage and the fuel properties should not be significantly altered. Storage stability can be measured with several well established methods.
One way of measuring storage stability is simply to measure the fuel properties after storage and compare the properties of the fuel before storage. There are also several possible tests, which aim is to mimic and accelerate the detrimental effect of storage to a fuel. Various properties and parameters can be used to indicate the storage stability of a fuel. Oxidation stability is a typical parameter to indicate stability of especially jet fuel. Thermal oxidation stability of a fuel can be measured using ASTM D3241 standard test. Another parameter to indicate stability is to measure the existence of reactive species in the fuel. This can be achieved with a gum method (1P540). A method to measure the oxidation stability of a fuel is to measure the PetroOxy value of the fuel using EN 16091 (2011) standardised method. The oxidation stability is a good overall measure of the stability of the fuel. The steps of PetroOxy EN16091 (2011) method are as follows:
- at ambient temperature, a known volume of a sample is placed in a reaction vessel charged with oxygen to a pressure of 700 kPa ± 5 kPa,
- the reaction vessel is heated to 140°C ± 0.5°C,
- the pressure in the vessel is recorded at intervals of 1 second until the breakpoint is reached.
The pressure in the vessel drops as the oxygen is consumed during the oxidation of the sample. The breakpoint is when pressure drops 10% from the maximum observed oxygen pressure. The elapsed time from start to the breakpoint is the induction period at the test temperature of 140°C ± 0.5°C. A longer time between start and breakpoint, i.e. a higher PetroOxy value in minutes, indicates that the fuel is less prone to oxidation.
According to one aspect of the invention the composition with improved storage stability comprises a blend of about 45 vol-% to about 55 vol-%, preferably from about 49 vol-% to about 50 vol-% of renewable jet fuel component and a petroleum based jet fuel component from about 55 vol-% to about 45 vol-%, preferably from about 51 vol-% to about 50 vol-%. It was observed that the concentration of renewable fuel must be at least 40 vol-% or above in order to improve the storage stability of the petroleum based jet fuel.
The current standard allows a maximum of 50 vol-% of renewable jet fuel in a final jet fuel.
The renewable jet fuel component comprises mainly a mixture of normal paraffins (n-paraffins) and isomerised paraffins (isoparaffins). The paraffins of the renewable jet fuel component can be produced by any suitable method such as hydrodeoxygenation of a biological or renewable feed material comprising acylglycerols, followed by isomerisation of the hydrodeoxygenated material. The isomerised hydrodeoxygenated material can further be subjected to a fractionation, such as distillation, to obtain a component that fulfils the ASTM D7566, Annex A2 standard.
The renewable jet fuel component of the composition has an amount of isoparaffins (i-paraffins) of at least 94 wt.% of the total paraffinic content. Preferably the amount of isoparaffins is at least 95 wt.% and more preferably at least 97 wt-%. The carbon chain length distribution of the renewable jet fuel component is as follows:
- <C 15 is 32 to 39 wt.%,
- C15 - C18 is 60 to 69 wt.%, and
- >C18 is 0 to 3 wt.%.
Preferably the carbon chain distribution is:
- <C15 is 33 to 36 wt.%,
- C15 - C18 is 63 to 67 wt.%, and
- >C18 is 0 to 2 wt.%.
According to one aspect of the invention the improvement of the storage stability is measured as an increase of the PetroOxy value of the mixture compared to the petroleum based jet fuel. The PetroOxy value should be regarded as a measurable property or parameter of the jet fuel. The PetroOxy value depends on the physical and chemical properties of the composition and is to be considered as a parameter that describes the composition. Preferably the increase in the PetroOxy value of the jet fuel composition is increased at least 3%, more preferably at least 5% as compared to the value of the petroleum based jet fuel.
It should be noted that the here mentioned components of the composition, i.e. the renewable jet fuel component and the petroleum based jet fuel component are to be understood to represent the main components of the composition and the composition can also contain other components or additives such as antioxidants, which are allowed or required in jet fuel. Additives approved for use in jet fuel are listed in DEF STAN 91-091 specification. In one embodiment of the invention the composition also comprises one or more antioxidant additives.
Provided hereby is also a method to improve the storage stability of petroleum based jet fuel, wherein the method comprises blending a renewable jet fuel component, which fulfils the ASTM D7566, Annex 2 standard to the petroleum based jet fuel component, to a final jet fuel mixture containing from about 40 vol- % to about 65 vol-% of the renewable jet fuel component and from about 60 vol-% to about 35 vol-% of the petroleum based jet fuel component.
In one embodiment of the method the final jet fuel mixture contains the renewable jet fuel component from about 45 vol-% to about 55 vol-%, preferably from about 49 vol-% to about 50 vol-% and the petroleum based jet fuel component is from about 55 vol-% to about 45 vol-%, preferably from about 51 vol-% to about 50 vol-%. In one embodiment of the method the renewable jet fuel component is a mixture of paraffinic hydrocarbons. In one embodiment the renewable jet fuel composition comprises at least 94 wt.% isoparaffins.
In one embodiment of the method the renewable jet fuel component is produced by a process comprising hydrodeoxygenation of a renewable or biological feed material comprising acylglycerols, followed by isomerisation of the hydrodeoxygenated material.
In one embodiment of the method the improvement of the storage stability is measured as an increase in the PetroOxy value. The improvement of the storage stability can be measurable as an increase in the PetroOxy value of at least 3%, preferably of at least 5% of the final jet fuel mixture compared to the PetroOxy value of the petroleum based jet fuel.
Example 1
The oxidation stability was tested for a petroleum based jet fuel (100%) before adding a renewable jet fuel component and after addition of the renewable component. Two different Jet A-l fuels (PB1 and PB2) and two different blends with renewable jet fuel (RJF) were tested (compositions A and B in table 1). The renewable jet fuel was produced by hydrodeoxygenation of acylglycerols followed by isomerisation, such that compositions A and B contained 94 wt.% isoparaffins. The renewable jet fuel satisfies the ASTM D7566 Annex A2 requirements and the initial oxidation stability, (i.e. the oxidation stability measured immediately after blending) was tested using the EN 16091 (2011) (as described above) standardised method to provide a PetroOxy value as measured in minutes. The results of the initial oxidation stability are presented in table 1.
As a comparison, a blend with 35 vol-% renewable jet fuel and 65 vol- % petroleum jet fuel was prepared, and the initial oxidation stability was measured and the results are also presented (composition C) in table 1. Table 1. PetroOxy values for petroleum based (PB1 and PB2) Jet A-l fuel and blends with renewable jet fuel (RJF)
Figure imgf000011_0001
From the results presented in table 1, it can be seen that the PetroOxy value increased in two different Jet A-l quality petroleum based fuels, when a component of renewable jet fuel was added to the petroleum based Jet A-l fuels. From the results it can also be seen that the volume percentage of the renewable jet fuel component needs to be at least 40 vol-% for an increase in the initial oxidation stability as measured as a PetroOxy value. Increase in the PetroOxy value indicates that the blends have a better resistance against oxidation over time compared to the 100% petroleum based Jet A-l fuels and thereby an increased storage stability.
Example 2
A blend of 50 vol-% renewable jet fuel component and 50 vol-% petroleum based jet fuel component was produced. Properties of the blend were tested at the making of the blend. The blend was stored for 3 years and the same properties were tested during the storage period. The measured properties at the beginning of the storage period and after three years storage varied as followed:
• Existent gum: 2-5 mg/lOOml (method IP540-08),
• Acidity: 0.001 mgKOH/g (method ASTMD3242-11),
• Peroxides: 0.3-2.5 mg/kg (method ASTMD3703-13),
• PetroOxy: 1240-1380 min (method EN16091 (2011)).
From the results it is obvious that the fuel properties of the 50:50 volume based blend of a renewable and petroleum based jet fuel were sustained even after a three year storage period. It will be obvious to a person skilled in the art that, as the technology advances, the inventive concept can be implemented in various ways. The invention and its embodiments are not limited to the examples described above but may vary within the scope of the claims.

Claims

Claims
1. A composition comprising a) a renewable jet fuel component, which comprises at least 94 wt.% isoparaffins and which fulfils the ASTM D7566 Annex A2 specification, and b] a petroleum based jet fuel component, wherein the amount of the renewable jet fuel component in the composition is from about 40 vol-% to about 65 vol-% and the amount of the petroleum based jet fuel component in the composition is from about 60 vol-% to about 35 vol-% and the composition has a higher PetroOxy value compared to the PetroOxy value of the petroleum based jet fuel component.
2. The composition of claim 1, wherein the carbon chain distribution of the renewable jet fuel component as total paraffin is as follows:
- <C 15 is 32 to 39 wt.%,
- C15 - C18 is 60 to 69 wt.%, and
- >C18 is 0 to 3 wt.%.
3. The composition according to claim 1 or 2, wherein the amount of the renewable jet fuel component is from about 45 vol-% to about 55 vol-%, preferably from about 49 vol-% to about 50 vol-%, and the amount of the petroleum based jet fuel component is from about 55 vol-% to about 45 vol-%, preferably from about 51 vol-% to about 50 vol-%, in the composition.
4. The composition according to any of claims 1 to 3, wherein the renewable jet fuel component is produced by a process comprising hydrodeoxygenation of a renewable or biological feed material comprising acylglycerols, followed by isomerisation of the hydrodeoxygenated material.
5. The composition according to claim 4, wherein the process further comprises a fractionation step of the isomerised hydrodeoxygenated material.
6. The composition according to any of claims 1 to 5, wherein the composition further comprises at least one additive selected from jet fuel approved additives listed in DEF STAN 91-091 specification.
7. The composition according to any of claims 1 to 6, wherein the PetroOxy value increases with at least 3 %, preferably with at least 5%, as compared to the PetroOxy value of the petroleum based jet fuel component.
8. A method to improve the storage stability of petroleum based jet fuel, wherein the method comprises blending a renewable jet fuel component, which fulfils the ASTM D7566, Annex 2 standard to the petroleum based jet fuel component, to a final jet fuel mixture containing from about 40 vol-% to about 65 vol-% of the renewable jet fuel component and from about 60 vol-% to about 35 vol-% of the petroleum based jet fuel component.
9. The method according to claim 8, wherein the improvement of the storage stability is measurable as an increase in the PetroOxy value of at least 3%, preferably of at least 5% of the final jet fuel mixture compared to the PetroOxy value of the petroleum based jet fuel.
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