Method of producing middle distillate blend

Abstract

The current invention relates to a method of producing a middle distillate blend. Especially the invention relates to a method of producing a middle distillate blend, by producing paraffinic hydrocarbons by hydrotreating a biobased feedstock, producing a hydrocarbon blending component by hydroprocessing a feedstock comprising a mixture a gas oil stream and at least one of liquefied waste plastic (LWP) and end-life-tires pyrolysis oil (ELTPO), and blending the produced paraffinic hydrocarbons and the hydrocarbon blending component to obtain the middle distillate blend.

Description

[0001] METHOD OF PRODUCING MIDDLE DISTILLATE BLEND

[0002] FIELD OF THE INVENTION

[0003] The current invention relates to a method of producing a middle distillate blend, especially the method comprises blending two components obtained in separate production processes. In particular, the invention relates to a method of producing a middle distillate blend by blending paraffinic hydrocarbons with a hydrocarbon blending component obtained from a feedstock comprising liquefied waste plastic (LWP) to obtain a blend with increased concentration of sustainable components.

[0004] BACKGROUND OF THE INVENTION

[0005] Environmental and climate concerns lead to a need for more sustainable and environmentally friendly solutions regarding industrial processes. There is a constant need and development for using renewable and recycled materials as raw material for obtaining hydrocarbon-based products, such as in middle distillate fuels and other applications such as feeds to further upgrading processes. Hydrocarbon products are used in various applications, such as solvents, fuels, lubricants and other petrochemical products as well as usage as petrochemical feeds including hydrocracking.

[0006] Biobased paraffinic hydrocarbons have been used as such or as renewable blending components in various applications, including middle distillate fuels. However, even if the production of biobased paraffinic hydrocarbons is one possible method of decreasing the dependency on fossil oil as a hydrocarbon source, there is a need for other sources and possibilities to lower dependency on virgin fossil oil. Although biobased paraffinic hydrocarbons have excellent properties and are highly useful e.g. as renewable components in middle distillate fuels and in other applications, there can be limitations to the amount of biobased paraffinic hydrocarbons, which can be used in various applications. These limitations can be due to some properties of the biobased paraffinic hydrocarbons but also due to limitations in certain standards. In addition, there is a need to develop alternative ways to lower dependency of virgin fossil oil as a source for hydrocarbons.

[0007] In addition to finding renewable raw material as an alternative for fossil oil, there is also a need to recycle waste. Waste plastic is a growing environmental concern, since many of the polymers constituting the plastics are very stable and do not degrade in nature. Disposal of waste plastic by direct incineration increases greenhouse gases and also leads to other environmental concerns in the form of air and land pollution. Disposal of waste plastic by direct incineration is largely considered a waste of valuable raw material and a contributor to carbon dioxide emissions, even if the energy in form of heat or electricity would be collected.

[0008] There is a growing interest in making use of waste plastic for producing various hydrocarbon components, which can be utilized in the production of new plastics, chemicals or other materials. Plastics or polymers mainly constitute carbon and hydrogen. However, waste plastics also contain many heteroatom impurities, such as oxygen, nitrogen, metal and / or chlorine impurities, which can cause problems in upgrading processes and challenges to product quality, if impurities are not properly managed by the processing.

[0009] BRIEF DESCRIPTION OF THE INVENTION

[0010] An object of the present invention is to provide a method of producing a middle distillate blend so as to solve the above problems relating to use of renewable and recycled raw material. The objects of the invention are achieved by a method as characterized by what is stated in the independent claim. Specific embodiments of the invention are disclosed in the dependent claims.

[0011] An object of the current invention is therefore to provide a method of producing a middle distillate blend, the method comprising: a] producing paraffinic hydrocarbons by hydrotreating a biobased feedstock, b] producing a hydrocarbon blending component by hydroprocessing a feedstock comprising a mixture of a gas oil stream and at least one of liquefied waste plastic [LWP] and end-life-tires pyrolysis oil [ELTPO], and c] blending the produced paraffinic hydrocarbons and the hydrocarbon blending component to obtain the middle distillate blend.

[0012] An advantage of the current invention is therefore to obtain a middle distillate blend, which is more sustainable and includes less virgin fossil oil components and an increased amount of renewable and recycled components.

[0013] Another advantage of the current invention is to blend components with different properties to obtain a final product of middle distillate blend having properties required for middle distillate fuels, such as diesel and aviation fuel. In addition, the obtained middle distillate blend can be used as raw material in subsequent upgrading processes. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] In the following the invention will be described in greater detail by means of preferred embodiments with reference to the attached figures, in which

[0015] Figure 1 illustrates a process scheme according to the invention, and Figure 2 illustrates an alternative process including fractionations.

[0016] DETAILED DESCRIPTION OF THE INVENTION

[0017] General method

[0018] The current invention relates to a method of producing a middle distillate blend, where the method comprises blending two components obtained in separate processes. The blend is obtained from paraffinic hydrocarbons produced by hydrotreating a biobased feedstock and from a hydrocarbon blending component produced by hydroprocessing a feedstock comprising a mixture of a gas oil stream and at least one of liquefied waste plastic (LWP) and end-life-tires pyrolysis oil (ELTPO)ln one embodiment the hydrocarbon blending component is produced by hydroprocessing a feedstock comprising a mixture of a gas oil stream and liquefied waste plastic (LWP). The paraffinic hydrocarbon is obtained from a biobased feedstock and is thereby a renewable component, which does not contain any fossil oil components. The hydrocarbon blending component is obtained from a process where liquefied waste plastic (LWP), end-life-tires pyrolysis oil or a blend thereof is co-processed together with a gas oil stream. The LWP and ELTPO are recycled components of fossil origin. The final blend therefore comprises an increased amount of renewable and recycled components and can therefore be considered a more sustainable and environmentally friendly product. Even though the final product contains renewable and recycled components the properties of the product are not compromised.

[0019] The middle distillate blend is suitable for use as a fuel, such as diesel fuel or aviation fuel. In certain applications, the middle distillate blend could also be used as raw material in other industrial processes such as petrochemical processes including but not limited to cracking processes.

[0020] The invention is based on the realisation that the two blending components have complementary properties for example relating to density, cetane number, cold properties and variety of components relating to for example carbon number. In addition, with the two blending components it is possible to obtain a final middle distillate blend product with improved viscosity properties, density, suitable amounts of aromatics, and / or synergistic effects relating to distillation range and freezing point.

[0021] Definitions

[0022] Herein the term "hydrotreating" is meant to include any process of treating a feedstock such as a biobased feedstock with hydrogen in the presence of a catalyst. Hydrotreating a feedstock is mainly aimed at but not limited to removal of heteroatoms from the feedstock. Thereby, the term "hydrotreating" includes typically at least hydrodeoxygenation (HDO) where oxygen is removed, hydrodesulfurization (HDS) where sulfur is removed and hydrodenitrification (HDN) where nitrogen is removed. Hydrotreatment can also remove other heteroatoms such as chloride and metals.

[0023] Herein with the term "paraffinic hydrocarbons" is meant any composition comprising mainly n- and i-paraffins and only minor amounts of other hydrocarbons can be present.

[0024] With the term "hydroprocessing" is here meant any industrial process in which a feed is treated with hydrogen in the presence of a catalyst. The feed in a hydroprocessing process can typically be gas oil or similar feeds. The term "hydroprocessing" is here construed as a broad term and also encompasses the term "hydrotreating", and therefore hydroprocessing can also include HDO, HDS and HDN.

[0025] The terms "hydrotreating" and "hydroprocessing" encompasses processes which can be similar or different to each other. The process conditions, including the catalysts, can be the same or different for "hydrotreating" and "hydroprocessing", and there can be overlapping process conditions. A person skilled in the art is familiar with hydrotreating and hydroprocessing, and is able to modify the process conditions, including selection of catalysts, for specific feeds. Properties of the obtained product from hydrotreating and hydroprocessing is also routinely monitored in any industrial process.

[0026] With the term "isomerisation" or "hydroisomerisation" is here meant any process where e.g. hydrocarbons are subjected to a process where the structure of the hydrocarbon is altered without altering the carbon number of the hydrocarbons. Typically, isomerisation is performed under a hydrogen pressure in the presence of a catalyst, and aims at forming methyl, ethyl etc. side-chains to the hydrocarbons.

[0027] With the term "biobased feedstock" is hereby meant any biological or renewable material, which can be converted into paraffinic hydrocarbons in a hydrotreating process.

[0028] With the term "liquefied waste plastic", or LWP for short, is hereby meant a product of depolymerisation of waste plastic and is typically produced by hydrothermal liquefaction (HTL) or pyrolysis of waste plastic.

[0029] Herein with the terms "fractionation" and "distillation" are meant any typical refinery process which can separate components in a mixture or composition based on their boiling points.

[0030] Boiling point ranges are indicated as T(ICT), meaning that 10% of the components has a lower boiling point than this temperature and as T(90), meaning that 90 % of the components boil at this temperature. Boiling points are expressed as T(10) and T(90) respectively, if not otherwise indicated. Alternatively, boiling points can be indicated as IBP and FBP, where IBP is the initial boiling point and FBP is the final boiling point.

[0031] All standards are according to the latest standard in force at the time of submitting of this application, if not otherwise indicated.

[0032] Paraffinic Hydrocarbons

[0033] The current invention relates to producing paraffinic hydrocarbons by hydrotreating a biobased feedstock. The paraffinic hydrocarbons are produced by hydrotreating a biobased feedstock. In one embodiment of the current invention the biobased feedstock comprises vegetable oil, animal fat, fish fat, fish oil, algae oil, microbial oil, wood and / or other plant-based oil, fats contained in plants bred by means of gene manipulation, recycled fats from food industry, waste and residue fats or oils and any combination thereof.

[0034] In one embodiment of the current invention the hydrotreating step comprises hydrodeoxygenation to obtain paraffins and subsequent isomerisation of at least some of the obtained paraffins. Hydrodeoxygenation is a hydrotreatment process where oxygen is removed from the biobased feedstock to obtain mainly hydrocarbons. Typically, the biobased feedstock comprises oils and fats, which are mainly glycerides and / or fatty acids. Hydrodeoxygenation of glycerides and fatty acids uses hydrogen to remove oxygen in the form of water and to form straight chain paraffins from the fatty acids. At the same time or as a separate step, the double bonds of the fatty acids can be saturated forming saturated straight chain paraffins.

[0035] Straight chain paraffins are also called n-paraffins (or normal paraffins). The cold properties of n-paraffins are not optimal, and therefore typically the n- paraffins need to undergo an isomerisation reaction to form isomerised paraffins (or i-paraffins). In the isomerisation reaction straight chain paraffins are converted to mainly methyl substituted paraffins. In certain cases, in addition to mono-methyl paraffins, also di- and tri-methyl paraffins are obtained. Branched paraffins (i-par- affins) have improved cold properties compared to n-paraffins.

[0036] In one embodiment of the invention the biobased paraffins have also been subjected to a hydrocracking step. The hydrocracking step can be instead of or in addition to the isomerisation step. In the hydrocracking step the formed hydrocarbons are cracked (hydrocarbon chain is split into shorter hydrocarbon chains) in the presence of hydrogen.

[0037] Additionally or alternatively, hydrotreating biobased feedstock may remove sulfur from organic sulfur compounds as hydrogen sulfide (H2S), i.e. by hydrodesulfurization, (HDS), it may further remove nitrogen from organic nitrogen compounds as ammonia (NH3), i.e. by hydrodenitrification (HDN), and / or it may remove halogens for example chlorine from organic chloride compounds as hydrochloric acid (HC1) i.e. by hydrodechlorination (HDC1). It may further remove aromatic compounds by hydrodearomatization (HAD).

[0038] In addition or alternatively, the hydrotreating of biobased feedstock can also include gas-to-liquid (GTL) processes to obtain paraffinic hydrocarbons from biobased feedstock. Especially pyrolysis of lignocellulosic material such as woodbased material can be pyrolyzed to obtain pyrolysis oil. The pyrolysis oil can then further be hydrotreated to obtain the biobased paraffinic hydrocarbons.

[0039] In one embodiment the paraffinic hydrocarbons have a carbon number from C5 to C24, such as from C7 to C22, from C8 to C20, from C7 to C18 or such as from CIO to C18.

[0040] Reaction conditions and catalysts typically used in hydrotreating a biobased feedstock and in the isomerisation process are well known techniques to a skilled person in the art, examples of hydrodeoxygenation and isomerisation are described in more detail, e.g., in EP1741768. Hydrotreatment such as hydrodeoxygenation and subsequent isomerisation can be performed in the same or different reaction vessel(s), using one or more catalyst beds.

[0041] Hydrodeoxygenation of the biobased material is typically achieved under continuous hydrogen flow. It should be noted that under the HDO conditions also other heteroatoms such as sulfur and nitrogen are typically removed, if present. For achieving optimal results, the continuous hydrogen flow in hydrotreatment or hydrodeoxygenation preferably has H2 / feed ratio from 500 to 2000 n-L / L, more preferably from 800 to 1400 n-L / L.

[0042] The hydrotreatment or hydrodeoxygenation is advantageously performed at a temperature from 200 °C to 400 °C, preferably from 250 °C to 350 °C, more preferably from 280 °C to 340 °C. Typically the pressure in hydrotreatment or hydrodeoxygenation is from 2 MPa to 15 MPa.

[0043] The hydrotreatment or hydrodeoxygenation catalyst preferably comprises at least one component selected from 1UPAC group 6, 8 or 10 of the Periodic Table. Preferably the hydrodeoxygenation catalyst is a supported Pd, Pt, Ni, NiW, NiMo or CoMo catalysts and the support is zeolite, zeolite-alumina, alumina and / or silica, preferably the hydrodeoxygenation catalyst is NiMo / AhOs or C0M0 / AI2O3. In particular the hydrodeoxygenation catalyst is a sulfided NiW, NiMO or CoMo catalyst.

[0044] The isomerisation process may be carried out in the presence of an isomerisation catalyst, and preferably in the presence of hydrogen added to the isomerisation process. Suitable isomerisation catalysts contain a molecular sieve and / or a metal selected from Group VIII 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 ferrierite, and Pt, Pd, or Ni, and AI2O3, or Si02. Typical isomerisation catalysts are, for example, Pt / SAPO-ll / AhCh, Pt / ZSM-22 / AhO3, Pt / ZSM- 23 / AI2O3, and Pt / SAPO-ll / SiO2. The isomerisation catalysts may be used alone or in combination. 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.

[0045] The isomerisation process can be conducted at a temperature of 200- 500 °C, such as 280-400 °C, such as 280-370 °C and at a pressure of 1 MPa to 15 MPa (absolute), such as 2 MPa to 10 MPa (absolute).

[0046] A person skilled in the art is familiar with the hydrotreating, such as hydrodeoxygenation, and isomerisation processes.

[0047] In one embodiment of the current invention the middle distillate blend is a diesel range fuel, wherein the hydrotreating is aimed at obtaining specifically paraffinic hydrocarbons in diesel range with suitable diesel fuel properties.

[0048] In another embodiment of the current invention the middle distillate blend is an aviation fuel, wherein the hydrotreating is aimed at obtaining specifically paraffinic hydrocarbons in aviation fuel range with suitable aviation fuel properties. In another embodiment of the current invention the middle distillate blend is used as raw material in further upgrading processes, such as cracking and / or other petrochemical processes.

[0049] In one embodiment the hydrotreating of biobased feedstock is followed by a fractionation to obtain the biobased paraffinic hydrocarbons. Fractionation can especially be suitable for obtaining paraffinic hydrocarbons in aviation fuel range or alternatively to obtain paraffinic hydrocarbons in diesel range fuel.

[0050] In one embodiment of the invention fractionation of the hydrotreated product is performed such that the biobased paraffinic hydrocarbons have a boiling point range from about 160 °C (IBP) to about 380 °C (FBP) (diesel range fuel), such as from about 160 °C (IBP) to about 320 °C (FBP). In another embodiment the fractionation is performed such that the biobased paraffinic hydrocarbons have a boiling point range from about 120 °C (IBP) to about 290 °C (FBP) (aviation fuel).

[0051] Hydrocarbon blending component

[0052] The method of the current invention also includes producing a hydrocarbon blending component by hydroprocessing a feedstock comprising a mixture of liquefied waste plastic (LWP) and a gas oil stream.

[0053] Liquefaction processes are typically non-oxidative thermolysis or thermal decomposition processes. T echnologies include but are not limited to pyrolysis or hydrothermal liquefaction. The LWP is a mixture of hydrocarbonaceous organic components with a wide range of carbon chain lengths. Provided the large variations of carbon chain lengths and chemical structures and the properties of the LWP vary depending on the types of plastics (polymers) used in the production of LWP, the type of liquefaction process and conditions of the liquefaction process.

[0054] In one embodiment of the invention the LWP comprises olefins and paraffins in an amount of at least 50 wt.%, such as at least 60 wt.%, at least 65 wt.% or at least 70 wt.%. The olefins and paraffins in LWP can be both straight-chained (normal) or branched (isomerised). In addition to olefins and paraffins the LWP can also comprise naphthenes and aromatics.

[0055] Typical waste plastic feedstock used in the liquefaction method includes mainly polyethylene, polypropylene and / or polystyrene with varying amounts of other components such as polyamides, polyethylene terephthalate and polyvinyl chloride.

[0056] Liquefied waste plastic can be obtained by thermally decomposing waste plastic and subsequently collecting at least one liquid fraction from the process. In a typical pyrolysis process, the solid waste plastic is heated to a temperature of 400-600 °C under non-oxidative conditions. The polymers thermally decompose and consequently release vapours and gases that exit the reactor in the gas phase. This vapour / gas stream is subsequently cooled down to condense LWP product and to separate the gases. The LWP typically has a boiling range of about 40 °C - 550 °C, which corresponds approximately to carbon chain lengths of C5 to C55. Depending on the conversion technology, the final boiling point of the LWP can go up to 750 °C.

[0057] LWP is a thermal cracking product of various polymers and is a complex mixture of mainly paraffins, olefins, naphthenes and aromatic hydrocarbons. The total amount of olefins is typically high, from 40 wt.% to 60 wt.%, whereas the amount of aromatic hydrocarbons is typically lower than 20 wt.%. LWP also contains heteroatoms, including oxygen, nitrogen and chlorine, in the form of organic compounds with heteroatom substituents. The amounts of heteroatoms vary depending on the polymers used in production of LWP. Water is usually removed from the LWP product, but some dissolved water may still be present in the LWP.

[0058] Liquefied waste plastic can have undergone pretreatment processes. LWP pretreatment processes include but are not limited to reactive extraction, solvent extraction, adsorption, filtration, centrifugation, oxidation, reduction or any combination thereof.

[0059] The hydrocarbon blending component is produced by hydroprocessing a feedstock comprising in addition to LWP, ELTPO or any blend thereof also a gas oil stream. A gas oil (GO) stream can be any suitable oil stream from which a middle distillate product typically is formed in oil refinery processes, such as vacuum gas oil (VGO). Thereby in one embodiment the gas oil stream is a VGO stream having any boiling point range between 180 °C to 565 °C. VGO is typically defined as light VGO and heavy VGO.

[0060] Light vacuum gas oil can be defined as a product having a boiling point range from 360 °C to 420 °C.

[0061] Heavy vacuum gas oil can be defined as a product having a boiling point range from 420 °C to 565 °C.

[0062] Liquefied waste plastic (LWP) is a product produced from waste material and is generally considered a low-quality product, especially in oil refinery applications. The chemical composition of LWP can vary and LWP contains various impurities. Generally adding LWP to an existing oil refinery process, such as hydroprocessing a gas oil stream, is considered uncertain and not to improve the obtained hydroprocessed product. Despite these uncertainties concerning using LWP in the feed for hydoprocessing a gas oil stream, the results hereby presented, show that using LWP in the hydroprocessing feed surprisingly improved the properties of the hydroprocessed product and its usability as a hydrocarbon blending component especially together with paraffinic hydrocarbons.

[0063] In one embodiment the hydroprocessing is performed as a co-pro- cessing of a feed comprising end-life-tires pyrolysis oil (ELTPO). ELTPO is a pyrolysis oil obtained from used tyres, in a process where the tyres are decomposed in high temperature, such as from 300 °C to 550 °C, in an oxygen depleted atmosphere, to obtain pyrolysis oil (ELTPO), char and gases.

[0064] In one embodiment the hydroprocessing is performed as a co-pro- cessing of a feed further comprising biobased and / or renewable component(s), in addition to a gas oil stream and at least one of LWP and ELTPO.

[0065] In one embodiment of the current invention the hydroprocessing in step b) is performed on a mixture of liquefied waste plastic (LWP) and a gas oil stream, where the mixture contains LWP from about 5 wt.% to about 40 wt.%, preferably from about 10 wt.% to about 35 wt.%, such as from about 15 wt.% to about 25 wt.% and the balance being the gas oil stream. LWP is a recycled material, so including LWP in the mixture which is hydroprocessed to obtain the hydrocarbon blending component increases the content of recycled components in the middle distillate blend. It is estimated that the content of components originating from LWP is higher than the concentration of LWP in the feedstock subjected to hydroprocessing to obtain the hydrocarbon blending component. This means that when LWP is mixed with a gas oil stream, components originating from LWP are concentrated to the hydrocarbon blending component, thereby the concentration of sustainable components is generally higher than the concentration of LWP in the mixture to be hydroprocessed.

[0066] In one embodiment of the current invention the hydroprocessing of a feedstock comprising a mixture of a gas oil stream and at least one of liquefied waste plastic (LWP) and end-life-tires pyrolysis oil (ELTPO)comprises one or more hydroprocessing steps performed in the following conditions:

[0067] - a continuous hydrogen flow of H2 to feed ratio of 150 - 400 Nm3 / stdm3, preferably 180 - 250 Nm3 / stdm3,

[0068] - LHSV of 0.5 - 2.0 h-1, preferably 1.0 - 1.5 h-1,

[0069] - a temperature from 300 °C - 400 °C, preferably 350 - 390 °C, - a pressure from 4000 kPa - 8000 kPa, preferably from 4800 kPa - 6000 kPa, or from 4500 kPa to 5500 kPa, and

[0070] - in presence of a supported or unsupported catalyst comprising at least one component selected from 1UPAC group 6, 8 or 10 of Periodic Table, preferably the catalyst is a supported catalyst with active sites of Ni, Mo and / or Co and the support is AI2O3.

[0071] In one embodiment the hydroprocessing step is followed by a distillation step to obtain a distillation product boiling between about 150 °C (IBP) and about 370 °C (FBP) such as between 150 °C and 300 °C and / or between 300 °C and 370 °C, (IBP and FBP respectively), which distillation product forms the hydrocarbon blending component. Alternatively, the distillation is performed such that the hydroprocessed product boils from about 120 °C (IBP) to 220 °C (FBP).

[0072] It has been discovered that when LWP is hydroprocessed especially in a co-process with gas oil stream, components falling in the middle distillate range, such as from 150 °C to 300 °C, are predominantly formed. Thereby, components from LWP are enriched in the middle distillate range providing a higher concentration of recycled components. Thereby, a more sustainable and environmentally friendly middle distillate blend can be obtained, even if relatively low amounts of LWP is used in the co-processing process. It was estimated that the amounts of components originating from LWP was up to at least 40 wt.%, when hydroprocessing was run with an LWP content of 20 wt.% in the feed. Thereby, the components from LWP are concentrated in the middle distillate fuel range.

[0073] Blending the components to obtain the middle distillate blend

[0074] The current invention comprises blending the produced paraffinic hydrocarbons and the hydrocarbon blending component to obtain the middle distillate blend. It has surprisingly been found that producing a hydrocarbon blending component by hydroprocessing a feedstock comprising a mixture of LWP and a gas oil stream, provides a hydrocarbon blending component which blends well with a paraffinic hydrocarbon component. The properties of the two components complement each other and provide a middle distillate blend with suitable properties. A paraffinic hydrocarbon component, such as hydrogenated vegetable oil (HVO) typically has very good cold properties (especially when isomerised) and also a good cetane number. It has now been discovered that blending LWP with a gas oil stream, which is hydroprocessed, provides a blending component with suitable density and other fuel properties which complement the properties of the paraffinic hydrocarbons. The hydrocarbon blending component obtained from coprocessing LWP also provides a wider range of hydrocarbons, with various carbon numbers. A broad range of carbon numbers is important especially in middle distillate fuel. Thereby, the blend obtained resembles fossil products to which the engines have been originally designed, and thereby making the fuel more suitable for use in traditional fleets.

[0075] In one embodiment of the current invention the blending of the two components is performed such that the middle distillate blend comprises from about 15 vol.% to about 55 vol.%, such as about 25 vol.% to about 45 vol.%, of paraffinic hydrocarbons produced by hydrotreating a biobased feedstock and about 45 vol.% to about 85 vol.%, such as from about 55 vol.% to about 75 vol.%, of hydrocarbon blending component produced by hydroprocessing a feedstock comprising a mixture of LWP and a gas oil stream.

[0076] In another embodiment of the current invention the blending of the two components is performed such that the middle distillate blend comprises from about 15 vol.% to about 50 vol.%, such as from about25 vol.% to about 45 vol.%, of paraffinic hydrocarbons produced by hydrotreating a biobased feedstock and from about 50 vol.% to about 85 vol.%, such as from about 55 vol.% to about 75 vol.% of hydrocarbon blending component produced by hydroprocessing a feedstock comprising a mixture of LWP and a gas oil stream.

[0077] In one embodiment of the current invention the produced middle distillate blend is a diesel fuel, in another embodiment the produced middle distillate blend is an aviation fuel (which can also be called sustainable aviation fuel or SAF).

[0078] The method according to the invention can be performed to obtain or produce a middle distillate blend, which is suitable as diesel fuel or alternatively, the method is performed to obtain or produce an aviation fuel. Fractionation of a hydrocarbon mixture to obtain a middle distillate blend with specific properties is well known for a person skilled in the art. Fractionation can be performed using any suitable fractionation method such as distillation. With fractionation a final product with optimal properties is obtained. Depending on the final product and intended use, different properties can be desired.

[0079] In one embodiment the method according to the invention comprises at least one fractionation step or distillation step of the paraffinic hydrocarbons and / or the hydrocarbon blending component to obtain a middle distillate blend having a boiling point from about 120 °C (IBP) to about 300 °C (FBP) (aviation fuel), or a boiling point from about 150 °C (IBP) to about 370 °C (FBP) (diesel fuel). LWP is a unique mixture of components, with which the concentration of recycled components in a middle distillate blend can be increased. Hydroprocessing LWP especially in a co-process with gas oil, also produces unique hydrocarbons, which mixes with paraffinic hydrocarbons providing wanted properties of a middle distillate blend. For example, hydroprocessing LWP can provide naphthenes and aromatic components, which are not obtained by hydrotreating a biobased feedstock. Hydroprocessing LWP also provides a wider distillation range for the hydrocarbon blending components, which is beneficial for cold flow improving additives, when can be used in the blend, and viscosity of the obtained blend.

[0080] In one embodiment the blending to obtain the middle distillate blend is performed such that the middle distillate (diesel fuel) blend has:

[0081] - a density of at least 800 kg / m3as measured at 15 °C,

[0082] - a cetane number of at least 51,

[0083] - a total n-paraffinic content of at least 15 wt.%, and

[0084] - an aromatic content of equal to or below 30 wt.%, such as from 10 wt.% to 25 wt.%.

[0085] In another embodiment the blending to obtain the middle distillate blend is performed such that the middle distillate (diesel fuel) blend has a composition comprising:

[0086] - i-paraffins from 25 wt.% to 65 wt.%, such as from 28 wt.% to 57 wt.%,

[0087] - n-paraffins from 10 wt.% to 35 wt.%, such as from 15 wt.% to 30 wt.%,

[0088] - naphthenes 10 wt.% to 25 wt.%, such as from 12 wt.% to 22 wt.%, and

[0089] - aromatics 3 wt.% to 30 wt.%, such as 4 wt.% to 28 wt.% or such as 10 wt.% to 23 wt.%.

[0090] In one embodiment the blending to obtain the middle distillate blend is performed such that the middle distillate blend (aviation fuel) has:

[0091] - a density of at least 775 kg / m3as measured at 15 °C,

[0092] - a viscosity at -20 °C of up to 6 mm2 / s,

[0093] - a total n-paraffinic content of at least 15 wt.%, and

[0094] - a total aromatics content of equal to or lower than 21 wt.%, such as from 11 wt.% to 21 wt.%.

[0095] In another embodiment the blending to obtain the middle distillate blend is performed such that the middle distillate (aviation fuel) blend has:

[0096] - a density of at least 775 kg / m3as measured at 15 °C,

[0097] - a viscosity at -20 °C of up to 6 mm2 / s, - a freezing point of at least -47 °C and

[0098] - aromatic concentration of from about 10 vol.% to about 15 vol.%.

[0099] In another embodiment the blending to obtain the middle distillate blend is performed such that the middle distillate (aviation fuel) blend has a composition comprising:

[0100] - i-paraffins from 50 wt.% to 60 wt.%,

[0101] - n-paraffins from 15 wt.% to 25 wt.%,

[0102] - naphthenes from 10 wt.% to 15 wt.%, and

[0103] - total aromatics from 10 wt.% to 15 wt.%.

[0104] Especially, when the middle distillate blend is an aviation fuel, the properties of the aviation fuel are improved for the current blend according to the invention. For example, the cold viscosity decreases with use of LWP co-processing blending component, which enables higher use of paraffinic hydrocarbons (SAF) in the final blend. The cold viscosity of the blend is not linear. The LWP co-processed component (hydrocarbon blending component) has a better net heat of combustion value compared to its 100% fossil reference (with no LWP in feed). The net heat of combustion value is even further improved by blending with SAF.

[0105] Figure 1 illustrates an exemplary illustration of the method according to the invention. In figure 1 a biobased feedstock (10) is subjected to a hydrotreatment step (40) to obtain paraffinic hydrocarbons (60). A feed containing LWP (20) and gas oil (30) is co-processed in a hydroprocessing step (50) to obtain a hydrocarbon blending component (70). The paraffinic hydrocarbons (60) and hydrocarbon blending component (70) is introduced to a blending step (80) to obtain the middle distillate blend (90).

[0106] Figure 2 illustrates an embodiment of the invention in which a biobased feedstock (10) is subjected to a hydrotreatment step (40) to obtain paraffinic hydrocarbons (60). A feed containing LWP (20) and gas oil (30) is co-processed in a hydroprocessing step (50) to obtain a hydrocarbon blending component (70). The paraffinic hydrocarbons (60) are introduced to fractionation (62) to obtain fractions of which one fraction is obtained as paraffinic hydrocarbons (67), which corresponds to the paraffinic hydrocarbons (60) if no fractionation is needed (see Figure 1). The hydrocarbon blending component (70) is introduced to a distillation or fractionation (72) to obtain a fraction or distillation product containing hydrocarbon blending component (77), which corresponds to the hydrocarbon blending component (70), when no distillation is needed. The paraffinic hydrocarbons (67) and hydrocarbon blending component (77) are blended in a blending step (85) to obtain the middle distillate blend (95), according to the invention.

[0107] EXAMPLES

[0108] Example 1

[0109] A mixture containing liquefied waste plastic (LWP) and conventional heavy gas oil fraction (HGO) was subjected to a hydroprocessing process in a hydroprocessing unit. The amount of LWP in the feed was 5, 10 and 20 wt.%. The process of the hydroprocessing was as follows, a pressure of about 4500 kPa and a range of temperature from 350 °C to 380 °C, a WHSV of about 1 h1. Usual sulfur concentration of the feed is 1.7 wt.% and typical product obtained has about 500 ppm sulfur. The catalyst used in the hydroprocessing unit was mainly CoMo.

[0110] The product obtained from the hydroprocessing unit was distilled to typical fractions namely <150 °C, 150 - 300 °C, 300 - 370 °C and >370 °C. A series of runs were performed using the LWP co-feed to evaluate the products obtained and catalyst deactivation. All obtained products had good properties, but the product obtained using 20 wt.% LWP co-feed was chosen for further experiments. No catalyst deactivation could be found.

[0111] It was estimated based on simulated distillations that the middle distillate fraction boiling from 150 °C to 300 °C contained 13 wt.% LWP content at 5 wt.% LWP co-feed; 23 wt.% LWP content at 10 wt.% LWP co-feed; and 41 wt.% LWP content at 20 wt.% LWP co-feed. Thereby, the middle distillate fraction was estimated to contain up to 41 wt.% of components originating from LWP, when the hydroprocessing unit was run with a feed containing 20 wt.% LWP.

[0112] Example 2

[0113] Hydrocarbon blending components were produced using a 20 wt.% LWP co-feed and collecting the middle distillate fraction according to Example 1 was obtained. The components were obtained from two different LWP feeds and were called LWP1 and LWP2. Properties of the LWP1 and LWP2 co-processed components were measured and compared to a similar middle distillate fraction from the hydroprocessing unit (Ref.) without LWP co-feed and to the EN 590:2022 diesel specification. From the results of Table 1 it can be seen that the diesel properties are mainly maintained when adding LWP to the feed, and especially the cetane number was increased. Therefore, the fraction boiling between 150 °C and 300 °C is an excellent blending component especially for paraffinic hydrocarbons, such as HVO.

[0114] The properties of LWP1 and LWP2 are presented below in Table 1. All standards are according to the latest version of the standard at time of filing this application, unless otherwise indicated.

[0115] Table 1; Diesel properties of Reference (Ref) with no LWP addition and two different fractions with addition of 20 wt.% LWP in the feed (LWP1 & LWP2).

[0116] Example 3

[0117] Two different middle distillate blends with components produced according to Example 2 (LWP1) and paraffinic hydrocarbons (HVO diesel component) were prepared. The paraffinic hydrocarbons were produced in a method according to the current invention. The amount of LWP1 component was 84 vol.% (with 16 vol.% HVO) and 49 vol.% (with 51 vol.% HVO) respectively in the blends, named Blend 1 and Blend 2 respectively.

[0118] The diesel properties of the two blends are presented in Table 2 below.

[0119] The results of Table 2 show it is possible to obtain a blend of a hydrocarbon blending component (co-processed with LWP) and paraffinic hydrocarbons (HVO) with improved diesel properties. The density of the HVO component can be increased to be within the EN590:2022 standard (at least 800 kg / m3), while cetane value and cold properties of the blend are at a good level. Cetane value for diesel should be at least 51 according to EN 590 standard.

[0120] Table 2; Diesel properties of blends with LWP1 and HVO and 100 % HVO. Blends 1 and 2 are in vol%for the HVO and LWP1 components.

[0121] Example 4

[0122] The chemical composition of the components (LWP1 obtained as coprocessing according to the invention and HVO corresponding to paraffinic hydrocarbons according to the invention) as well as the blends of these components were analysed using GCxGC-MS. The analyses were run as generally disclosed in UOP 990-2011 and by Nousiainen M. in the experimental section of his Master's Thesis Comprehensive two-dimensional gas chromatography with mass spectrometric and flame ionization detectors in petroleum chemistry, University of Helsinki, August 2017. Some modifications to the analysis was done and the GCxGC was run in reverse mode, using a semipolar column (Rxil7Sil) first and a non-polar column (Rxi5Sil) thereafter, followed by FID detector, using run parameters: carrier gas helium 31.7 cm / sec; split ratio 1:350; injector 280 °C; Column T program 40 °C (Omin) - 5 °C / min - 250 °C (0 min) - 10 °C / min - 300 °C (5 min), run time 52 min; modulation period 10 sec; detector 300 °C with H240 ml / min and air 400 ml / min; makeup flow helium 30 ml / min; sampling rate 250 Hz and injection volume 0.2 microliters. Individual compounds were identified using GCxGC-MS, with MS-pa- rameters: ion source 280 °C; interface 300 °C; scan range 25 - 500 amu. Commercial tools (Shimadzu's LabSolutions, Zoex's GC Image) were used for data processing including identification of the detected compounds or hydrocarbon groups.

[0123] As can be seen from Table 3, the paraffinic hydrocarbon component (HVO) contains mainly iso-paraffins, while the hydrocarbon blending component (LWP1) obtained by co-processing LWP with gas oil, contains various hydrocarbons components. The blends of HVO and LWP1 components have a favourable mixture of hydrocarbons and excellent diesel properties.

[0124] Table 3; Chemical compositions in wt.% of the components (LWP1 and HVO) and of

[0125] Blends 1 and 2.

[0126] Example 5

[0127] A number of middle distillate blends in the aviation fuel range were prepared. The hydrocarbon blending component (LWP) was prepared from a mixture of LWP 30 wt.% and gas oil 70 wt.% in a hydroprocessing process according to Example 2. The hydrocarbon blending component (SAF) was fractionated after the hydroprocessing to obtain a product with an initial boiling point of about 150 °C and a final boiling point of about 220 °C. The paraffinic hydrocarbon component was a 100 % HVO component, which could be used as a sustainable aviation fuel (SAF) component. The SAF component had an initial boiling point of about 125 °C and a final boiling point of about 290 °C.

[0128] The blends were prepared with various amounts of the hydrocarbon blending component (LWP) and HVO component (SAF). Blends were prepared, with 10 wt.%, 20 wt.%, 30 wt.% and 50 wt.% SAF component and the balance being the LWP component.

[0129] Fuel properties especially relevant for aviation fuel were measured for the individual components (LWP and SAF components) as well as for the blends. The results can be seen in Table 4 below. The results are also compared to a 100% fossil component (Fossil), which did not contain any LWP in the hydroprocessing process. Results show that it is possible to obtain aviation fuel from the two components according to the invention. The density of the co-processed hydrocarbon blending component decreased with higher concentration of LWP in the feed, and was already 814.9 kg / m3for 15 wt.% LWP in the feed (results not shown), compared to a density of 841.3 kg / m3with 0 wt.% LWP in the feed.

[0130] Thereby, using LWP in the mixture to be hydroprocessed lowered the density to a suitable level. Also, other properties improved. For example, the cold viscosity was decreased with use of LWP co-processing blending component, which enables higher use of paraffinic hydrocarbons (SAF) in the final blend. The decrease in viscosity, when blending with SAF, was not linear. Also, the nitrogen and sulfur as well as aromatics content decreased when using LWP in the co-pro- cessing. When 15 w.% LWP was used in the co-processing with gas oil, the nitrogen content was 10 mg / g (ASTM D4629), sulfur content 2.4 mg / kg (ASTM D7039) and aromatic content 30.9 vol.% (ASTM D6379). When 30 wt.% LWP was used in the co-processing with gas oil, the nitrogen content was 2.4 mg / g (ASTM D4629), sulfur content 0.53 mg / kg (ASTM D7039) and aromatic content 22.3 vol.% (ASTM D6379). For the 100 % fossil reference (with not LWP in the feed), the nitrogen content was 15 mg / g (ASTM D4629), sulfur content 5.8 mg / kg (ASTM D7039) and aromatic content higher than 31 vol.% (ASTM D6379).

[0131] The LWP co-processed component (hydrocarbon blending component) has a better net heat of combustion value compared to its 100% fossil reference (with no LWP in feed). The net heat of combustion value is even further improved by blending with SAF. The density also further decreased with the blends. It should be noted that the LWP component is more dominant for the flash point driving the flash point of the blends higher than a linear calculation would be assumed. Also, the freezing point clearly did not show a linear dependency between the two components. The blends had significantly improved freezing point compared to the individual components.

[0132]

[0133] Table 4; Aviation fuel properties ofLWP component and SAF component, as well as blends of these two components The chemical composition of the LWP and SAF component as well as the

[0134] 50 / 50 blend of these components were analysed using GCxGC-MS with the same method as in Example 4. The results are summarised in Table 5 below.

[0135] Table 5; Chemical composition of the LWP and SAF components as well as a 50 / 50 blend of these components The requirement for ASTM D7566 is shown below in table 6.

[0136] Table 6. ASTM D 7566 requirements 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

CLAIMS1. A method of producing a middle distillate blend, the method comprising: a] producing paraffinic hydrocarbons by hydrotreating a biobased feedstock, b] producing a hydrocarbon blending component by hydroprocessing a feedstock comprising a mixture of a gas oil stream and at least one of liquefied waste plastic (LWP) and end-life-tires pyrolysis oil (ELTPO), and c] blending the produced paraffinic hydrocarbons and the hydrocarbon blending component to obtain the middle distillate blend.

2. The method according to claim 1, wherein the hydrotreating in step a) comprises hydrodeoxygenation to obtain paraffins, and subsequent isomerisation of at least some of the obtained paraffins.

3. The method according to claim 1 or 2, wherein the hydrotreating or the hydrodeoxygenation is performed using following conditions:- a continuous hydrogen flow with H2 / feed ratio of from 500 to 2000 n- L / L, preferably from 800 to 1400 n-L / L,- a temperature from 200 °C to 400 °C, preferably from 250 °C to 350 °C,- a pressure from 2 MPa to 15 MPa, and- in presence of a hydrodeoxygenation catalyst selected from 1UPAC group 6, 8 or 10 of Periodic Table, preferably the hydrodeoxygenation catalyst is selected from supported Pd, Pt, Ni, NiW, NiMo, CoMo and any combination thereof, wherein the support is zeolite, zeolite-alumina, alumina and / or silica.

4. The method according to claim 2 or 3, wherein the isomerisation is performed using following conditions:- a temperature from 200 °C to 500 °C, preferably from 280 °C to 400 °C,- a pressure of 1 MPa to 15 MPa, preferably from 2 MPa to 10 MPa, and- in presence of an isomerisation catalyst containing a molecular sieve and / or a metal selected from Group VIII of Periodic Table and optionally a carrier, preferably the isomerisation catalyst contains SAPO-11, SAPO-41, ZSM-22, ZSM-23 and / or ferrierite; and Pt, Pd and / or Ni; and AI2O3 and / or SiC .

5. The method according to any one of claim 1 - 4, wherein the biobased feedstock of step a) comprises vegetable oil, animal fat, fish fat, fish oil, algae oil, microbial oil, wood and / or other plant-based oil, fats contained in plants bred by means of gene manipulation, recycled fats from food industry, waste and residue fats or oils and any combination thereof.

6. The method according to any one of claim 1 - 5, wherein the hydrotreatment of step a) is followed by fractionation to obtain the paraffinic hydrocarbons.

7. The method according to any one of claim 1 - 6, wherein the gas oil in step b), is light vacuum gas oil and / or heavy vacuum gas oil.

8. The method according to any one of claim 1 - 7, wherein the hydroprocessing of step b) is performed as a co-processing of a feed further comprising biobased and / or renewable component's).

9. The method according to any one of claim 1 - 8, wherein the hydroprocessing of step b) is performed with a mixture of a gas oil stream and liquefied waste plastic (LWP) and the amount of LWP in the mixture is from about 5 wt.% to about 40 wt.%, preferably from about 10 wt.% to about 35 wt.%, such as from about 15 wt.% to about 25 wt.% and the balance being the gas oil stream.

10. The method according to any one of claim 1 - 9, wherein the hydroprocessing of step b) comprises one or more hydroprocessing steps performed in the following conditions:- a continuous hydrogen flow of H2 to feed ratio of 150 - 400 Nm3 / stdm3, preferably 180 - 250 Nm3 / stdm3,- LHSV of 0.5 - 2.0 h1, preferably 1.0 - 1.5 h1,- a temperature from 300 °C - 400 °C, preferably 350 - 390 °C,- a pressure from 4000 kPa - 6000 kPa, preferably from 4800 kPa - 5500 kPa, and- in presence of a supported or unsupported catalyst comprising at least one component selected from 1UPAC group 6, 8 or 10 of Periodic Table, preferably the catalyst is a supported catalyst with active sites of Ni, Mo and / or Co and the support is AI2O3.

11. The method according to any one of claim 1 - 10, wherein the hydroprocessing of step b) is followed by a distillation step to obtain a distillation product boiling between about 150 °C and about 370 °C, such as between about 150 °C and about 300 °C or between about 300 °C and about 370 °C, which distillation product forms the hydrocarbon blending component of step b).

12. The method according to any one of claim 1 - 11, wherein the blending of step c) is performed such that the middle distillate blend comprises from about 15 vol.% to about 55 vol.% of paraffinic hydrocarbons produced in step a) and about 45 vol.% to about 85 vol.% of hydrocarbon blending component produced in step b).

13. The method according to any one of claim 1 - 12, wherein the middle distillate blend is a diesel fuel or an aviation fuel.

14. The method according to any one of claim 1 - 13, wherein the blending of step c] is performed such that the middle distillate blend has: - a density of at least 800 kg / m3as measured at 15 °C,- a cetane number of at least 51,- a total n-paraffinic content of at least 15 wt.%, and- an aromatic content of equal to or lower than 30 wt.%.

15. The method according to any one of claim 1 - 13, wherein the blend- ing of step c] is performed such that the middle distillate blend has:- a density of at least 775 kg / m3as measured at 15 °C,- a viscosity at -20 °C of up to 6 mm2 / s,- a total n-paraffinic content of at least 15 wt.%, and- a total aromatics content of equal to or lower than 21 wt.%.

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