阅读说明：本技术 含烃燃料的低硫燃料混合物和生产这种混合物的方法 (Low sulfur fuel blends containing hydrocarbon fuels and process for producing such blends ) 是由 S·B·艾弗森 J·K·R·格雷罗 于 2020-05-15 设计创作，主要内容包括：本发明涉及一种低硫燃料混合物,其是含有可再生烃组分的第一燃料混合物组分和含有烃的第二燃料混合物组分的混合物,以形成最终的低硫燃料混合物的至少一部分具有小于0.5重量％的硫含量,其中,所述第一燃料混合物组分的特征在于具有特性(δ-(d1),δ-(p1),δ-(h1))＝(17-20,6-10,6-10)；其中,所述第一燃料混合物组分包含燃料物质,所述燃料物质包含70重量％的沸点高于220℃的化合物,并且所述燃料物质的特征还在于具有(δ-(d),δ-(p),δ-(h))＝(17-20,6-15,6-12)和包含一种或多种含硫溶剂的连接物质,所述连接物质的特征在于具有(δ-(d3),δ-(p3),δ-(h3))＝(17-20,3-6,4-6)；其中所述燃料物质以90重量％至99.5重量％的相对量存在于所述第一燃料混合物组分中,并且所述连接物质以0.5重量％至10重量％的相对量存在于所述第一燃料混合物组分中；其中所述第二燃料混合物组分的特征在于具有特性(δ-(d2),δ-(p2),δ-(h2))＝(17-20,3-5,4-7)并且选自超低硫燃料油(ULSFO)如RMG 180、低硫燃料油、船用瓦斯油、船用柴油、减压瓦斯油及其组合,其中所述第一燃料混合物组分以至多80重量％的相对量存在于所述最终的低硫燃料混合物中。(The invention relates to a low-sulfur fuel mixture that is a mixture of a first fuel mixture component containing a renewable hydrocarbon component and a second fuel mixture component containing a hydrocarbon to form a final low-sulfur fuel mixture, at least a portion of which has a sulfur content of less than 0.5 wt.%, wherein the first fuel mixture component is characterized by having a property (δ:) d1 ,δ p1 ,δ h1 ) (17-20,6-10, 6-10); wherein the first fuel mixture component comprises a fuel material comprising 70 wt% boiling pointA compound point greater than 220 ℃ and the fuel substance is further characterized as having (delta) d ,δ p ,δ h ) (17-20,6-15,6-12) and a linking species comprising one or more sulfur-containing solvents, said linking species characterized as having (δ) d3 ,δ p3 ,δ h3 ) (17-20,3-6, 4-6); wherein the fuel substance is present in the first fuel mixture component in a relative amount of 90 to 99.5 wt% and the connecting substance is present in the first fuel mixture component in a relative amount of 0.5 to 10 wt%; wherein the second fuel blend component is characterized by a property (δ) d2 ,δ p2 ,δ h2 ) (17-20,3-5,4-7) and is selected from Ultra Low Sulfur Fuel Oils (ULSFO) such as RMG 180, low sulfur fuel oils, marine gas oils, marine diesel, vacuum gas oils, and combinations thereof, wherein the first fuel blend component is present in the final low sulfur fuel blend in a relative amount of up to 80 wt.%.)

1. A low sulfur fuel blend that is a blend of a first fuel blend component containing a renewable hydrocarbon component and a second fuel blend component containing a hydrocarbon to form at least a portion of a final low sulfur fuel blend having a sulfur content of less than 0.5 wt.%, wherein the first fuel blend component is characterized as having a characteristic (δ) of_d1,δ_p1,δ_h1) (17-20,6-10, 6-10); wherein the first fuel mixture component comprises a fuel material comprising 70 wt% of a high boiling point material and a connecting materialA compound at 220 ℃ and said fuel substance being further characterized by having a property (delta)_d,δ_p,δ_h) (17-20,6-15,6-12), said linking species comprising one or more sulfur-containing solvents, said linking species characterized as having a property (δ)_d3,δ_p3,δ_h3) (17-20,3-6, 4-6); wherein the fuel substance is present in the first fuel mixture component in a relative amount of 90 to 99.5 wt% and the connecting substance is present in the first fuel mixture component in a relative amount of 0.5 to 10 wt%; wherein the second fuel blend component is characterized by a property (δ)_d2,δ_p2,δ_h2) (17-20,3-5,4-7) and is selected from Ultra Low Sulfur Fuel Oils (ULSFO) such as RMG 180, low sulfur fuel oils, marine gas oils, marine diesel, vacuum gas oils, and combinations thereof, wherein the first fuel blend component is present in the final low sulfur fuel blend in a relative amount of up to 80 wt.%.

2. A low sulphur fuel mixture according to claim 2, wherein the linking substance is a fuel oil having a sulphur content of at least 1 wt%, such as a fuel oil having a sulphur content of at least 1.5 wt%, preferably a fuel oil having a sulphur content of at least 2.0 wt%.

3. The low sulfur fuel mixture of any of claims 1-2, wherein the connection substance comprises a high sulfur fuel oil such as RMG380, vacuum gas oil, heavy vacuum gas oil, or a combination thereof.

4. A low sulphur fuel blend according to any preceding claim, wherein the first fuel blend component is present in the final low sulphur fuel blend in a relative amount of up to 10 to 75 wt%, and wherein the second fuel blend component is present in the final low sulphur fuel blend in a relative amount of 25 to 90 wt%.

5. A low sulphur fuel mixture according to any preceding claim, wherein the first fuel mixture component containing renewable hydrocarbon components comprises the fuel substance comprising at least 70 wt% boiling above 300 ℃, such as at least 70 wt% boiling above 350 ℃; preferably, the fuel substance of the first fuel mixture component comprises at least 70 wt.% of boiling point above 370 ℃, e.g. the fuel substance of the first fuel mixture component comprises at least 70 wt.% of boiling point above 400 ℃.

6. A low sulphur fuel mixture according to any preceding claim, wherein the fuel substance of the first fuel mixture component containing renewable hydrocarbon components comprises at least 50 wt% boiling points above 300 ℃, such as at least 50 wt% boiling points above 350 ℃; preferably, the fuel substance of the first fuel mixture component comprises at least 50 wt.% boiling above 370 ℃, e.g. the first fuel mixture component comprises at least 50 wt.% boiling above 400 ℃.

7. A low sulphur fuel blend as claimed in any preceding claim, wherein the fuel substance of the first fuel blend component containing renewable hydrocarbon components comprises at least 10 wt% boiling above 400 ℃, such as at least 10 wt% boiling above 450 ℃; preferably, the fuel substance of the first fuel mixture component comprises at least 10 wt.% of boiling points above 475 ℃, for example at least 10 wt.% of the boiling points of the first fuel mixture component is above 500 ℃.

8. A low sulphur fuel blend according to any preceding claim, wherein the sulphur content of the final low sulphur fuel blend is less than 0.1 wt%.

9. A low sulphur fuel mixture according to any preceding claim, wherein the sulphur content of the second fuel mixture components is at most 1 wt%, such as at most 0.5 wt%.

10. A low sulphur fuel blend according to any preceding claim, wherein the first fuel blend component is present in the final low sulphur fuel blend in a relative amount of from 50 wt% to 75 wt%, wherein the second fuel blend component is present in the final low sulphur fuel blend in a relative amount of from 25 wt% to 50 wt%, and wherein further the linking substance is present in the final low sulphur fuel blend in a relative amount of from 0.5 wt% to 5 wt%.

11. A low sulfur fuel blend as in any of the preceding claims, wherein the first fuel blend component is characterized by a property (δ)_d1,δ_p1,δ_h1)＝(17-20,7-9,8.5-10)。

12. A low sulphur fuel blend as claimed in any preceding claim, wherein the fuel substance of the first fuel blend component comprising a renewable hydrocarbon component has a water content of less than 1 wt%, for example a water content of less than 0.5 wt%; preferably, the water content of the first fuel mixture component comprising the renewable hydrocarbon component is less than 0.25 wt%, for example the water content is less than 0.1 wt%.

13. The low sulfur fuel mixture of any of claims 2-12, wherein the fuel substance is characterized by a property (δ)_d,δ_p,δ_h) (18.0-19.5, 6-12,7-10), and wherein the linking species is characterized by having a characteristic range (δ)_d3,δ_p3,δ_h3)＝(17-20,3-4.5,4-6.5)。

14. The low sulfur fuel mixture of any one of claims 2-13, wherein the linking substance further comprises a component from the group of ketones, alcohols, toluene, xylene, and/or creosols, or combinations thereof.

15. The low sulfur fuel mixture of claim 14, wherein the linking substance further comprises a mixture comprising: 25 to 90% by weight of a ketone, 0.1 to 40% by weight of an alkane, 1 to 40% by weight of an alcohol and 0.1 to 20% by weight of toluene and/or xylene and/or creosol.

16. The low-sulfur fuel mixture of any of the preceding claims, wherein the viscosity of the low-sulfur fuel mixture at 50 ℃ is in the range of 160cSt to 180cSt, the flash point of the low-sulfur fuel mixture is above 60 ℃, the pour point of the low-sulfur fuel mixture is below 30 ℃, and the total acid number is less than 2.5mg KOH/g.

17. A low sulfur fuel mixture as in any of the preceding claims, wherein the first fuel mixture component and/or the fuel substance is further characterized by:

a flash point in the range of 60 ℃ to 150 ℃,

-a pour point of less than 30 ℃,

-an ash content of less than 0.1 wt%,

-a Conradson carbon residue number of less than 18,

-an acid number of less than 2.5mg KOH/g.

18. A low sulfur fuel blend as in any of the preceding claims, wherein the fuel species of the first fuel blend component are further characterized as having an oxygen content of less than 15 wt.%, such as less than 12 wt.%; preferably, the first fuel mixture component is further characterized as having an oxygen content of less than 10 wt.%, such as less than 8 wt.%.

19. The low sulfur fuel mixture of claim 18, wherein the fuel substance of the first fuel mixture component is further characterized by a viscosity at 50 ℃ in the range of 1000 to 10000cSt, such as a viscosity at 50 ℃ in the range of 100 to 1000 cSt.

20. The low sulfur fuel mixture of any of the preceding claims, wherein the fuel substance of the first fuel mixture component is produced from biomass and/or waste material.

21. A low sulphur fuel mixture according to claim 20, wherein the production of the fuel substance of the first fuel mixture component is carried out by a hydrothermal liquefaction process.

22. A low sulphur fuel blend as claimed in claim 21, wherein the fuel substances of the first fuel blend component are produced by:

a. providing one or more biomass and/or waste materials contained in one or more feedstocks;

b. providing a feed mixture by slurrying the biomass and/or waste material in one or more fluids, wherein at least one of the fluids comprises water;

c. pressurizing the feed mixture to a pressure in the range of 100 bar to 400 bar;

d. heating the pressurized feed to a temperature in the range of 300 ℃ to 450 ℃;

e. maintaining the pressurized and heated feed mixture in the reaction zone for a conversion time of 3 minutes to 30 minutes;

f. cooling the converted feed mixture to a temperature in the range of from 25 ℃ to 200 ℃;

g. expanding the converted feed mixture to a pressure of from 1 bar to 120 bar;

h. separating the converted feed mixture into a crude oil, a gas phase and an aqueous phase, the aqueous phase comprising water-soluble organics and dissolved salts;

i. optionally, further upgrading the crude oil in one or more steps by reacting the crude oil with hydrogen in the presence of one or more heterogeneous catalysts at a pressure in the range of from 60 bar to 200 bar and a temperature of from 260 ℃ to 400 ℃; the upgraded crude oil is separated into a fraction comprising low boiling compounds and a first fuel component comprising high boiling compounds.

23. A low sulphur mixture according to any preceding claim for use as a marine fuel.

24. An intermediate blend component for forming a low sulfur fuel blend as in any of the preceding claims, said intermediate blend component comprising a hydrocarbon containing fuel species and a linking species to form at least a portion of said intermediate blend component, wherein said fuel species is characterized as having a property (δ) of_d,δ_p,δ_h) (17-20,6-12,7-10) and wherein said linking agent is characterized by having a property (δ)_d3,δ_p3,δ_h3) (17-20,3-6, 3-6); wherein the fuel substance is present in the intermediate mixture component in a relative amount of 90 to 99.5 wt.%, and wherein further the connecting substance is present in the intermediate mixture component in a relative amount of 0.5 to 10 wt.%.

25. The intermediate mixture component according to claim 24, wherein the fuel substance is present in the intermediate mixture component in a relative amount of at most 95 to 99.5 wt.%, and wherein further the connecting substance is present in the intermediate mixture component in a relative amount of at most 0.5 to 5 wt.%.

26. A process for producing a low sulfur fuel mixture containing renewable hydrocarbon components of any of the preceding claims having a sulfur content of less than 0.5 wt%, wherein the process comprises the steps of:

-providing a first fuel mixture component comprising a renewable component, said first fuel mixture component being characterized by having a property (δ)_d1,δ_p1,δ_h1) (17-20, 6-10) in the final contentUp to 80 wt% of the low sulfur fuel mixture of (a);

-providing a second fuel mixture component characterized by having a characteristic (δ)_d2,δ_p2,δ_h2)＝(17-20,3-6,3-6)；

-adding the first fuel mixture component to the second fuel mixture component to form the low sulfur fuel mixture.

27. The method of producing a fuel mixture of claim 26, wherein the method further comprises the steps of:

providing a connecting substance having a property (δ)_d3,δ_p3,δ_h3) (17-20,3-6,4-6) in a relative amount of 0.5 to 10 wt% of the final low sulfur fuel mixture;

-adding the connecting substance to the first fuel component or the second fuel component to form an intermediate mixture component;

-adding the second fuel mixture component or the first fuel mixture component to the intermediate mixture component to form the low sulfur fuel mixture.

28. The method according to any one of the preceding claims, wherein the first fuel mixture component and/or the second fuel mixture component and/or the intermediate mixture component is heated to a temperature in the range of 70 ℃ to 150 ℃ prior to forming the low sulfur fuel mixture.

29. The method according to any one of the preceding claims, wherein the intermediate mixture component comprising the first fuel mixture component or the second fuel mixture component and the connecting substance is subjected to an operation of forming a homogeneous mixture prior to the addition of the second fuel mixture component and/or the first fuel mixture component to form the low-sulfur fuel mixture.

30. The method of claim 29, wherein said forming a homogeneous mixture is performed by stirring said mixture or by pumping said mixture.

31. A method for preparing the production of a low sulfur fuel mixture according to any of the preceding claims, comprising measuring a property (δ) of a first fuel mixture component comprising a renewable hydrocarbon component_d1,δ_p1,δ_h1) Measuring a property (delta) of a component of the second fuel mixture_d2,δ_p2,δ_h2) Determining the compatibility of the first fuel component and the second fuel component based on the measurement of the characteristic.

32. The method of claim 31, wherein the compatibility is determined to be present based on the measured characteristic and the first fuel component and the second fuel component are accepted for direct blending.

33. The method of claim 32, wherein the first fuel component and the second fuel component are determined to be incompatible based on the measured characteristic, wherein a fuel having a characteristic ((δ) is selected_d3,δ_p3,δ_h3) And wherein the connecting substance is added to the first fuel component or the second fuel component to achieve compatibility.

Technical Field

The present invention relates to the field of low sulfur fuel blends containing hydrocarbons of renewable content, and to a process for producing such fuel blends.

Background

Climate change forces international society to set ambitious goals to reduce the total emission of greenhouse gases, with a maximum temperature rise of 2 ℃ until 2050. About 25% of the total greenhouse gas emissions come from transportation, which, despite the improved fuel efficiency, is the only area where emissions are still above the 1990 level (i.e. heavy trucks, sea and air) and the only area where carbon dioxide emissions continue to rise compared to the 1990 level. While light vehicles and buses can reduce emissions by improving fuel efficiency, electrification, hybrid vehicles, bioethanol, these options do not exist for heavy trucks, marine and aviation, and emissions in these areas are rising and are expected to continue to increase. Therefore, new solutions are needed for such transportation applications.

Hydrothermal liquefaction (HTL) is a very efficient thermochemical process to convert biogenic materials (e.g., biomass and waste streams) into renewable crude oil in high pressure water near the critical point of water (218 bar, 374 ℃), e.g., in high pressure water at pressures ranging from 150 bar to 400 bar, temperatures ranging from 300 ℃ to 450 ℃. Under these conditions, water acquires special properties that make it an ideal medium for many chemical reactions, such as the conversion of bio-organic materials to renewable crude oil. Since all organic carbon materials (including recalcitrant biopolymers such as lignin) are directly converted into renewable bio-crude oil, hydrothermal liquefaction has high resource efficiency due to its high conversion and carbon efficiency. It has a very high energy efficiency due to low parasitic losses and, unlike other thermochemical processes, it can handle wet materials without the need for drying or phase change without potential heat addition. Furthermore, the hydrothermal liquefaction process allows for a wide range of heat recovery processes. Renewable crude oil produced has many similarities to its petroleum counterparts and is typically much higher in quality than, for example, bio-oil produced by pyrolysis, which typically contains significant amounts of heteroatoms, such as oxygen (e.g., 40 wt.%), and high water content (e.g., 30 wt.% to 50 wt.%), which makes such bio-oil chemically unstable and immiscible with petroleum, and presents serious challenges for their upgrading and/or synergistic processing into finished products (e.g., transportation fuels). Catalytic hydrodeoxygenation employed from petroleum hydroprocessing has been demonstrated to at least partially convert pyrolysis-produced bio-oils into hydrocarbons or more stable bio-oils, but has limitations associated with very high hydrogen consumption due to high oxygen content, catalyst stability and reactor fouling, see published studies such as Xing (2019), Pinheiro (2019), Mohan (2006), Elliott (2007).

The quantity and quality of the renewable crude oil produced by hydrothermal liquefaction depends on the specific operating conditions and the hydrothermal liquefaction process employed, such as the feedstock, dry matter content, pressure and temperature during heating and conversion, catalyst, presence of liquid organic compounds, heating and cooling rates, separation system, etc. parameters.

For traditional petrochemical crude oil, renewable crude oil produced from hydrothermal liquefaction processes requires upgrading/refining (e.g., by catalytic hydrotreating and fractionation) before it can be used in end applications, such as directly in existing infrastructure as a drop in fuel. However, while renewable crude oils produced by aqueous liquid liquefaction are similar in many respects to their petroleum counterparts, they also have their unique properties, including:

higher boiling point and viscosity due to higher oxygen content than conventional petroleum derived oils

The boiling points of the oxygen and oxygen free differ greatly

Higher oxygen content than petroleum results in higher exotherms due to higher oxygen content in the upgrading process (e.g., by catalytic hydrogenation)

Renewable crude oil is not fully miscible/compatible with its petroleum counterpart or partially upgraded oil or fully upgraded oil (e.g. catalytically treated with hydrogen).

These different properties need to be taken into account in the hydrothermal production process, the direct use of the renewable crude oil or fractions thereof, and during the operation of the upgrading process, whether by upgrading the renewable crude oil alone or by co-processing it with other oils (e.g., regular or other oils) at the refinery.

For use of renewable oils or fractions thereof in finished fuel mixtures, such as low sulfur fuel mixtures of hydrocarbons containing renewable components, it is critical that all components be completely compatible or miscible, e.g., not separate during use, storage, and/or dilution with other fuel mixtures used in the same application, e.g., marine fuel mixtures containing renewable components conforming to ISO8217 RMG 180 specifications for low sulfur RMG 180 marine fuels, hydrocarbon mixtures for stationary engines and/or as hot fuel in heating applications.

Furthermore, for process and resource efficiency reasons as well as economic reasons, it is further desirable to convert as much renewable crude oil as possible into a product that can be used directly or further processed to be useful and valuable, and that produces minimal low value residue or waste products.

While such compatibility is desirable, it is generally not achieved without producing significant amounts of residue, without adding significant amounts of other additives, particularly for higher boiling fractions, for oils containing renewable components.

Object of the Invention

It is therefore an object of the present invention to provide a low sulphur fuel mixture comprising renewable components for e.g. marine, stationary engine and/or hot fuel applications without the above compatibility problems.

Disclosure of Invention

According to one aspect of the invention, the object is achieved by a low sulfur fuel blend of a first fuel blend component containing a renewable hydrocarbon component and a second fuel blend component containing a hydrocarbon to form a final low sulfur fuel blend, at least a portion of which has a sulfur content of less than 0.5 wt%, wherein the first fuel blend component is characterized by a property (δ:)_d1,δ_p1,δ_h1) (17-20,6-10, 6-10); wherein the first fuel mixture component comprises a fuel substance and a connecting substance, the fuel substance comprising 70 wt% of a compound having a boiling point above 220 ℃, and the fuel substance further characterized by having a property (δ)_d,δ_p,δ_h) (17-20,6-15,6-12), said linking species comprising one or more sulfur-containing solvents, said linking species characterized as having a property (δ)_d3,δ_p3,δ_h3) (17-20,3-6, 4-6); wherein the fuel substance is present in the first fuel mixture component in a relative amount of 90 to 99.5 wt% and the connecting substance is present in the first fuel mixture component in a relative amount of 0.5 to 10 wt%; wherein the second fuel blend component is characterized by a property (δ)_d2,δ_p2,δ_h2)＝(17-20,3-5,4-7) and is selected from Ultra Low Sulfur Fuel Oils (ULSFO) such as RMG 180, low sulfur fuel oils, marine gas oils, marine diesel, vacuum gas oils and combinations thereof, wherein the first fuel mixture component is present in the final low sulfur fuel mixture in a relative amount of up to 80 wt.%.

The low sulfur fuel blend specification according to the present invention not only allows for the production of more compatible and stable low sulfur blends containing renewable hydrocarbon components, but also allows for more of the first fuel species containing renewable components to be introduced into useful and valuable applications without generating substantial low value residue or waste products, e.g., the low sulfur fuel blends according to the present invention allow for the use of all or more of the high boiling fraction of the first fuel species in the low sulfur fuel blend while maintaining the desired properties of the final low sulfur fuel blend, e.g., for marine or hot fuel applications. Overall process efficiency and process economics are improved by maximizing the amount that can be used for such low sulfur fuel blends, thereby minimizing the amount of residue or low value products. Furthermore, since the basic idea of using renewable molecules is to reduce greenhouse gas emissions, higher utilization efficiency of renewable molecules (as achieved by the present invention) can lead to overall higher decarbonisation using existing infrastructure.

As will be further explained in the description of the preferred embodiments of the present invention, it has been found that a linking substance comprising one or more sulfur-containing solvents constitutes an advantageous linking substance that achieves the advantages described above. The use of such sulfur-containing connecting materials is surprising because the overall goal is to produce a low sulfur fuel mixture having a sulfur content of less than 0.5 wt.%. In some advantageous embodiments of the invention, the sulphur content of the low sulphur fuel blend is less than 0.1 wt%.

According to the present disclosure, the linking substance may be present in the first fuel component at a concentration in the range of 0.5 wt.% to 10 wt.% (e.g., 1.0 wt.% to 5.0 wt.%).

In many aspects of the invention, the concentration of the linking species in the final low sulfur fuel mixture may be in the range of 0.5 wt.% to 5.0 wt.%, such as in the range of 1.0 wt.% to 4.0 wt.%.

Preferred sulfur-containing connecting substances according to the invention include fuel oils having a sulfur content of at least 1 wt.%, for example fuel oils having a sulfur content of at least 1.5 wt.%, preferably fuel oils having a sulfur content of at least 2.0 wt.%. Non-limiting examples of preferred connecting substances according to the present invention are high sulfur fuel oils such as RMG380, vacuum gas oil, heavy vacuum gas oil, or combinations thereof. The use of this common higher sulfur-containing fuel oil as a tie material also has the advantage of being available at a relatively low cost. Other sulfur-containing solvents that may be used as a linking species according to the present invention include dimethyl disulfide and butyl mercaptan.

Typically, the first fuel blend component may be present in the final low sulfur fuel blend in a relative amount of up to 80%. In many embodiments of the invention, the first fuel blend component is present in the final low sulfur fuel blend in a relative amount of up to 10 to 75 wt.%, wherein the second fuel blend component is present in the final low sulfur fuel blend in a relative amount of 25 to 90 wt.%.

In a further advantageous embodiment of the invention, the first fuel mixture component is present in the final low sulfur fuel mixture in a relative amount of 50 to 75 wt.%, wherein the second fuel mixture component is present in the final low sulfur fuel mixture in a relative amount of 25 to 50 wt.%, and wherein the connecting substance is present in the final low sulfur fuel mixture in a relative amount of 0.5 to 5 wt.%.

The low sulphur fuel mixture according to the invention typically comprises higher amounts of higher boiling compounds than the prior art. In a preferred embodiment, the fuel first fuel mixture component comprising the renewable hydrocarbon component comprises a fuel material comprising at least 70 wt.% having a boiling point above 220 ℃. Preferably, the first fuel component comprises a fuel substance comprising at least 70 wt.% of fuel substances having a boiling point above 300 ℃, for example at least 70 wt.% of fuel substances having a boiling point above 350 ℃; typically, the first fuel mixture component comprises fuel species having a boiling point above 370 ℃ in an amount of at least 70 wt%, for example the first fuel mixture component comprises fuel species having a boiling point above 400 ℃ in an amount of at least 70 wt%.

In many embodiments according to the invention, the first fuel mixture component containing a renewable hydrocarbon component comprises the fuel substance comprising at least 50 wt.% of boiling points above 300 ℃, such as at least 70 wt.% of boiling points above 350 ℃; preferably, the fuel substance of the first fuel mixture component comprises at least 50 wt.% boiling above 370 ℃, e.g. the fuel substance of the first fuel mixture component comprises at least 50 wt.% boiling above 400 ℃.

In a further preferred embodiment, the first fuel mixture component containing a renewable hydrocarbon component comprises the fuel substance comprising at least 10 wt.% of boiling points above 400 ℃, such as at least 10 wt.% of boiling points above 450 ℃; preferably, the fuel substance of the first fuel mixture component comprises at least 10 wt% of the fuel substance having a boiling point above 475 ℃, for example at least 10 wt% of the fuel substance of the first fuel mixture component has a boiling point above 500 ℃.

According to a preferred embodiment of the present invention, the first fuel mixture component containing a renewable hydrocarbon component has a water content of less than 1 wt%, such as less than 0.5 wt%; preferably, the first fuel mixture component comprising a renewable hydrocarbon component has a water content of less than 0.25 wt.%, for example less than 0.1 wt.%.

In a preferred embodiment according to the invention, the first fuel mixture component comprises a fuel substance having an oxygen content of less than 15% by weight, for example a fuel substance having an oxygen content of less than 12% by weight; preferably, the fuel species of the first fuel blend component has an oxygen content of less than 10 wt%, for example less than 8 wt%.

In a preferred embodiment of the invention, the second fuel mixture component according to the invention has a sulphur content of at most 1 wt.%, for example at most 0.5 wt.%.

Hansen solubility parameters, which will be further explained and illustrated in the detailed description of preferred embodiments and examples of the invention, are used in the present invention to accurately characterize the different mixed components of a low sulfur fuel mixture to ensure complete compatibility and miscibility of the components for the full concentration range of the fuel mixture according to the present invention, e.g., the final low sulfur fuel mixture can be diluted with, for example, more secondary fuel components, as long as the resulting fuel mixture remains within the specified properties and concentration range without the resulting fuel mixture losing its compatibility/miscibility, and separation in the fuel tank, such as settling, can be avoided if the fuel tank should be filled and diluted with another fuel having the properties specified for the second fuel mixture component (e.g., if a low sulfur fuel mixture according to the present invention is not available).

According to the present invention, a first fuel mixture component comprising a renewable fuel component comprises a fuel substance and a connecting substance. The first fuel mixture component according to the invention is generally composed of a characteristic range of (δ)_d1,δ_p1,δ_h1) Hansen solubility parameters of (17-20,6-10, 6-10). A preferred embodiment is one wherein the first fuel mixture component is characterized by having a characteristic of (δ)_d1,δ_p1,δ_h1) Hansen solubility parameter of (17-20,7-9, 8.5-10);

according to the invention, the fuel substance contained in the first fuel mixture component is characterized by a property (δ)_d,δ_p,δ_h) The Hansen solubility parameter of ═ (18.0-19.5, 6-12,7-10) and the linker substances according to the invention are characterized by a characteristic range of (delta)_d3,δ_p3,δ_h3) Hansen solubility parameter of (17-20,3-4.5, 4-6.5). Thereby meeting the hansen solubility criteria for the first fuel mixture component described above.

The second fuel mixture according to the invention is generally characterized by having the characteristic (δ)_d2,δ_p2,δ_h2) (17-20,3-5,4-7) and is selected from Ultra Low Sulfur Fuel Oils (ULSFO), such as RMG 180, low sulfur fuel oils, marine gas oils, marine diesel, vacuum gas oils, and combinations thereof.

In some embodiments of the invention, the linking substance further comprises a component from the group of ketones, alcohols, toluene, xylene, and/or creosol (creosol), or combinations thereof.

In a preferred embodiment of the invention, the connecting means comprise a further component mixture comprising from 25% to 90% by weight of ketones, from 0.1% to 40% by weight of alkanes, from 1% to 40% by weight of alcohols and from 0.1% to 20% by weight of toluene and/or xylene and/or creosols.

A preferred embodiment of the invention is one wherein the low sulfur fuel mixture has a viscosity at 50 ℃ in the range of 160cSt to 180cSt, a flash point above 60 ℃, a pour point below 30 ℃, and a total acid number of less than 2.5mg KOH/g.

Advantageously, the first fuel component containing a renewable component is further characterized by:

a flash point in the range of 60 ℃ to 150 ℃,

-a pour point of less than 30 ℃,

-an ash content of less than 0.1 wt%,

-a Conradson carbon residue number of less than 18, and

-an acid number of less than 2.5mg KOH/g.

In a preferred embodiment, the oxygen content of the first fuel component containing renewable components is less than 5 weight percent.

The first fuel component containing a renewable component is further characterized by a viscosity at 50 ℃ in the range of 1000 to 10000cSt, for example a viscosity at 50 ℃ in the range of 100 to 1000 cSt.

According to a preferred embodiment of the invention, the fuel substance of the first fuel component containing renewable components is produced from biomass and/or waste material.

According to a particularly preferred embodiment of the invention, the production of the fuel substance of the first fuel mixture component is carried out by a hydrothermal liquefaction process.

In a preferred embodiment, the fuel substance of the first fuel component containing renewable components is produced by the following hydrothermal liquefaction process:

a. providing one or more biomass and/or waste materials contained in one or more feedstocks;

b. providing a feed mixture by slurrying the biomass and/or waste material in one or more fluids, wherein at least one of the fluids comprises water;

c. pressurizing the feed mixture to a pressure in the range of 100 bar to 400 bar;

d. heating the pressurized feed to a temperature in the range of 300 ℃ to 450 ℃;

e. the pressurized and heated feed mixture is maintained in the reaction zone for a conversion time of 3 minutes to 30 minutes.

f. Cooling the converted feed mixture to a temperature in the range of from 25 ℃ to 200 ℃;

g. expanding the converted feed mixture to a pressure of from 1 bar to 120 bar;

h. separating the converted feed mixture into a crude oil, a gas phase and an aqueous phase, the aqueous phase comprising water-soluble organics and dissolved salts;

i. optionally, further upgrading (upgrade) the crude oil by reacting the crude oil with hydrogen in the presence of one or more heterogeneous catalysts in one or more steps at a pressure in the range of from 60 bar to 200 bar and a temperature of from 260 ℃ to 400 ℃; the upgraded crude oil is separated into a fraction comprising low boiling compounds and a first fuel component comprising high boiling compounds.

The carbon footprint of low sulfur fuel blends comprising renewable components according to the present invention is generally lower than their fossil counterparts. Typically, the carbon footprint of the mixture is at least 25% less than its fossil counterpart, e.g., at least 35% less than its fossil counterpart; preferably, the low sulfur mixture has a carbon footprint that is at least 50% less than its fossil counterpart, such as at least 65% less than its fossil counterpart.

The object of the invention is further achieved by providing an intermediate mixture component for forming a low-sulfur fuel mixture according to any of the preceding claims, said intermediate mixture component comprising a hydrocarbon-containing fuelA substance and a connecting substance to form at least a portion of the intermediate mixture component, wherein the fuel substance is characterized by having a characteristic (δ)_d,δ_p,δ_h) (17-20,6-12,7-10) and wherein said linking agent is characterized by having a property (δ)_d3,δ_p3,δ_h3) (17-20,3-6, 3-6); wherein the fuel substance is present in the intermediate mixture component in a relative amount of 90 to 99.5 wt% and wherein the connecting substance is present in the intermediate mixture component in a relative amount of 0.5 to 10 wt%.

Preferably, the fuel substance is present in the intermediate mixture component in a relative amount of at most 95 to 99.5 wt% and wherein the connecting substance is present in the intermediate mixture component in a relative amount of at most 0.5 to 5 wt%.

The object is also achieved by a method for producing a fuel mixture containing renewable hydrocarbon components and having a sulphur content of less than 0.5 wt.%, wherein the method comprises the steps of:

-providing a first fuel mixture component comprising a renewable component, said first fuel mixture component being characterized by having a property (δ)_d1,δ_p1,δ_h1) (17-20, 6-10) in an amount of up to 80% by weight of the final low sulfur fuel mixture;

-providing a second fuel mixture component characterized by having a characteristic (δ)_d2,δ_p2,δ_h2)＝(17-20,3-6,3-6)；

-adding the first fuel mixture component to the second fuel mixture component to form the low sulfur fuel mixture.

In a preferred embodiment, the method further comprises the steps of:

providing a connecting substance having a property (δ)_d3,δ_p3,δ_h3) (17-20,3-6,4-6) in a relative amount of 0.5 to 10 wt% of the final low sulfur fuel mixture;

-adding the connecting substance to the first fuel component or the second fuel component to form an intermediate mixture component;

-adding the second fuel mixture component or the first fuel mixture component to the intermediate mixture component to form the low sulfur fuel mixture.

According to a preferred embodiment, the first fuel mixture component and/or the second fuel mixture component may be heated to a temperature in the range of 70 ℃ to 150 ℃ prior to forming the low sulfur fuel mixture.

Forming a homogeneous blend of intermediate blend components comprising the first fuel component or the second fuel component and a linking substance prior to adding the second fuel component and/or the first fuel component to a first blend thereby forming the low sulfur fuel blend. The operation of forming a homogeneous mixture may be performed by stirring the mixture or by pumping the mixture.

In another aspect of the invention, the object is achieved by a method for preparing the production of a low sulphur fuel mixture according to the invention, comprising measuring a property (δ) of a first fuel mixture component comprising a renewable hydrocarbon component_d1,δ_p1,δ_h1) Measuring a property (delta) of a component of the second fuel mixture_d2,δ_p2,δ_h2) The compatibility of the first fuel component and the second fuel component is determined based on the measurement of the characteristic.

In one embodiment, compatibility is determined to be present based on the measured characteristic and the first fuel component and the second fuel component are accepted for direct blending.

In another embodiment, the first fuel component and the second fuel component are determined to be incompatible based on the measured property, where the property ((δ) is selected to have_d3,δ_p3,δ_h3) And wherein the linking substance is added to the first fuel component or the second fuel component to achieve compatibility.

Drawings

The invention will be described below with reference to embodiments shown in the drawings, in which:

FIG. 1 shows a schematic of a continuous high pressure process for converting carbonaceous material to renewable hydrocarbons;

FIG. 2 is a process flow diagram of the apparatus for producing oil of example 1;

FIG. 3 shows a schematic of the catalytic upgrading process for producing partially upgraded renewable oil of example 2;

FIG. 4 is a schematic flow diagram of a unit for upgrading renewable crude oil in examples 2 and 3;

FIG. 5 is a photograph of solvent grades used in the solubility test;

fig. 6 shows a photograph of the field test used to evaluate solubility: (1) indicating that both solvents are completely soluble, (2) indicating that both solvents are partially soluble.

Fig. 7 shows a 3D plot of hansen solubility parameters for renewable crude oil (oil a) produced in example 1.

Fig. 8a and 8b summarize solvents and solvent mixtures to determine hansen solubility parameters for estimating hansen solubility parameters for renewable crude oil produced in example 1.

Figure 9 summarizes the characteristics of the renewable liquids produced by the hydrothermal liquefaction and upgrading process.

Fig. 10 shows a 3D plot of hansen solubility parameters for renewable crude oils (oil a, oil B, and oil C produced in example 1).

Fig. 11 shows a 3D plot of hansen solubility parameters for renewable crude oil-oil a (example 1), partially upgraded renewable oil (example 2), and upgraded renewable oil (example 3).

Fig. 12a, 12b, and 12c show 3D plots of hansen solubility parameters for petroleum crude, VGO, and bitumen compared to renewable crude, partially upgraded oil, and upgraded oil, respectively.

Fig. 13 summarizes hansen solubility parameters for different renewable liquids, petroleum, VGO, and asphalt.

Fig. 14a and 14b show 3D plots of hansen solubility parameters for ultra low sulfur fuel oil and high sulfur fuel oil compared to partial upgraded oil, partial upgraded heavy fraction, and upgraded heavy fraction.

FIG. 15 shows an example of a low sulfur fuel blend containing renewable components in accordance with a preferred embodiment of the present invention.

Figure 16 shows field testing and microscope images of the mixture between the partially upgraded heavy fraction (hfpou) and the Marine Gas Oil (MGO) described in example 14.

Figure 17 shows field tests and microscope images of the mixture between a portion of the upgraded heavy fraction (hfpou) and High Sulfur Fuel Oil (HSFO) described in example 15.

PREFERRED EMBODIMENTS FOR CARRYING OUT THE INVENTION

Fig. 1 illustrates an embodiment of a continuous high pressure production process for converting carbonaceous material (e.g., biomass and/or waste) into renewable oil.

As shown in fig. 1, carbonaceous material in the form of biomass and/or waste material is first subjected to a feed mixture preparation step (1). The feed mixture preparation step converts the carbonaceous material into a pumpable feed mixture and typically includes mechanical means for reducing the size of the carbonaceous material and slurrying the carbonaceous material with other components of the feed mixture, such as water, catalyst and other additives such as organics. In a preferred embodiment of the present invention, the feed mixture may be preheated in a pretreatment step. Typically, the feed mixture is preheated to a temperature in the range of from about 100 ℃ to about 250 ℃ in the pretreatment step.

Non-limiting examples of biomass and waste materials according to the present invention include biomass and waste materials, such as woody biomass and residues (e.g., wood chips, sawdust, forestry thinning, road cutting, bark, branches, garden and park waste and weeds); energy crops such as dwarf, willow, miscanthus, and reed; agricultural products and by-products, such as grasses, straw, stalks, stover, rice hulls, corn cobs, and husks (e.g., from wheat, rye, corn kernels (corn rice), sunflower); empty fruit bunches produced in palm oil production, palm oil manufacturing enterprise waste water (POME), residues from sugar production (e.g., bagasse, distillers grains, molasses), greenhouse waste; energy crops, for example, miscanthus, switchgrass, sorghum, jatropha; aquatic biomass, e.g., macroalgae, microalgae, cyanobacteria; animal bedding and fertilisers, such as fibre fractions from animal production; municipal and industrial waste streams such as black liquor (black liquor), paper sludge, pulp and off-grade fibers in paper production; residues and by-products of food production, such as juice, vegetable oil or wine production residues, spent coffee residues; municipal solid waste, such as the biological fraction of municipal solid waste, classified household waste, restaurant waste, slaughterhouse waste, sewage sludge (e.g., primary sludge, secondary sludge from wastewater treatment), biogas residue and biogas slurry produced by anaerobic digestion, and combinations thereof.

Many carbonaceous materials according to the present invention relate to lignocellulosic materials, such as woody biomass and agricultural residues. Such carbonaceous materials typically comprise lignin, cellulose and hemicellulose.

One embodiment of the invention comprises carbonaceous material having a lignin content in the range of 1.0 wt% to 60 wt%, for example having a lignin content in the range of 10 wt% to 55 wt%. Preferably, the lignin content in the carbonaceous material is in the range of 15 to 40 wt%, for example 20 to 40 wt%.

The cellulose content in the carbonaceous material is preferably in the range of 10 to 60 wt%, for example in the range of 15 to 45 wt%. Preferably, the cellulose content in the carbonaceous material is in the range of 20 to 40 wt%, such as 30 to 40 wt%.

Preferably, the hemicellulose content in the carbonaceous material is in the range of 10 to 60 wt%, for example the cellulose content is 15 to 45 wt%. Preferably, the cellulose content in the carbonaceous material is in the range of 20 to 40 wt%, such as 30 to 40 wt%.

The second step is a pressurization step (2) in which the feed mixture is pressurized by pumping means to a pressure of at least 150 bar and at most about 450 bar.

Subsequently, the pressurized feed mixture is heated to a reaction temperature of about 300 ℃ to at most about 450 ℃.

The feed mixture is typically maintained under these conditions for a sufficient time (e.g., 2 to 30 minutes to convert the carbonaceous material) and then cooled and reduced in pressure.

Subsequently, the product mixture comprising liquid hydrocarbon product, water containing water soluble organic compounds and dissolved salts, gas comprising carbon dioxide, hydrogen and methane, and suspended particles from the converted carbonaceous material is cooled in one or more steps to a temperature in the range of from 50 ℃ to 250 ℃.

The cooled or partially cooled product mixture then enters a pressure reduction device, in which the pressure is reduced from the conversion pressure to a pressure of less than 200 bar, for example a pressure of less than 120 bar.

Suitable pressure reduction devices include pressure reduction devices having a plurality of tubular members arranged in series and/or parallel, the length and internal cross-section of which is adapted to reduce the pressure to a desired level, and pressure reduction means including pressure reduction pump means.

The converted feed mixture is further separated into at least a gas phase (which contains carbon dioxide, hydrogen, carbon monoxide, methane and other short hydrocarbons (C)₂-C₄) Alcohols and ketones), a crude oil phase, an aqueous phase (which has water soluble organic compounds and dissolved salts), and finally suspended particles, e.g., inorganics and/or char and/or unconverted carbonaceous material, depending on the particular carbonaceous material being processed and the particular processing conditions.

The aqueous phase from the first separator typically contains dissolved salts (e.g., homogeneous catalysts such as potassium and sodium) and water-soluble organic compounds. Many embodiments of continuous high pressure processing of carbonaceous materials into hydrocarbons according to the present invention include: a recovery step for recovering the homogeneous catalyst and/or the water-soluble organics from said separated aqueous phase and recycling these at least partially to the feed mixture preparation step. Thereby increasing the overall oil yield and energy efficiency of the process. A preferred embodiment according to the invention is where the recovery system comprises an evaporation and/or distillation step, wherein the heat for evaporation and/or distillation is provided at least partly by transferring heat from a high pressure water cooler via a heat transfer medium, such as hot oil or steam, thereby improving the overall heat recovery and/or energy efficiency.

The renewable crude oil may be further subjected to an upgrading process (not shown) wherein it is pressurized in one or more steps to a pressure in the range of about 20 bar to about 200 bar, for example in the range of 50 to 120 bar, then heated in one or more steps to a temperature in the range of 300 ℃ to 400 ℃ and contacted with hydrogen and a heterogeneous catalyst contained in one or more reaction zones and finally fractionated into fractions of different boiling points.

Example 1: there is provided a first fuel component containing a renewable component in accordance with a preferred embodiment of the present invention

Three different renewable crude oils (oil a, oil B, and oil C) were produced from birch and pine using the experimental procedure in fig. 1. The analysis of the received chips is shown in table 1 below.

Table 1: a component for drying the ashless carbonaceous material.

Preparation of the feedstock

Wood chips are comminuted to wood flour in a hammer mill system and mixed with circulating water (including dissolved salts and water soluble organics), circulating oil, catalyst to produce a homogeneous and pumpable feed mixture. Potassium carbonate was used as catalyst and sodium hydroxide was used to adjust the pH. Attempts were made to keep the potassium concentration constant during the run, i.e. to measure the potassium concentration in the aqueous phase and based thereon determine the catalyst concentration that needs to be replenished. The amount of sodium hydroxide added is sufficient to maintain the outlet pH of the separated aqueous phase in the range of 8.0 to 8.5. CMC (carboxymethyl cellulose, M) was further added at a concentration of 0.8 wt%_w30000) was added to the feed slurry as a texturing agent to avoid settling in the feedwell and improve pumpability.

Since there was neither an aqueous phase nor an oil phase in the first cycle (batch), crude tall oil (tall oil) was used as the start-up oil and 5.0 wt% ethanol and pure water (reverse osmosis water, RO water) were used to simulate the aqueous phase in the first cycle. Multiple cycles (batches) are required before the process can be considered as steady state and produce representative oil and water phases. Approximately 6 cycles are required to produce an oil having a start up oil (start up oil) concentration of less than 10%. Thus, 6 cycles were performed, in which the oil and water phases produced in the previous cycle were added to the feed mixture of the subsequent cycle. The feed composition for the 6 th cycle run is shown in table 2 below:

table 2: composition of feed mixture for the 6 th cycle run.

The feed mixtures in table 2 were all processed at a pressure of about 320 bar and a temperature of about 400 ℃. From the start of each test, the degassed product was collected as a separate mass balance sample (MB) in a bucket and numbered MB1, MB2, MB3, etc. The collected product was weighed and the oil and water phases were separated by weight and weighed. The data for each batch was recorded electronically and manually.

Total mass balance

Total Mass Balance (MB)_Tot) Is the ratio of the total mass leaving the unit to the total mass entering the unit over a certain time. The total mass balance may also be considered as a quality parameter of the generated data. The average value was 100.8%, and the standard deviation was

Oil yield from biomass (OY)

The Oil Yield (OY) from biomass represents the proportion of input dry biomass that is converted to dry ash-free oil. It is defined as the mass of dry ash-free oil produced from dry biomass at a particular time divided by the mass of dry biomass entering the unit at the same time. The recycled oil is not included in the equilibrium and when calculating the oil yield from the biomass it is subtracted from the total amount of oil recovered. The average Oil Yield (OY) was found to be 45.3 wt%, with a standard deviation of 4.1 wt%, i.e. 45.3% of the dry biomass (wood + CMC) mass in the feed was converted to dry ash-free oil.

Detailed oil analysis

The data measured for the oil are shown in table 3.

Table 3: oil data on cycle 6

Energy recovery in produced hydro distillate Oil

Energy recovery (ER oil) indicates how much chemical energy is recovered in the oil in the feed wood. It does not take into account the energy required for heating, nor the electrical energy supplied to the unit. For calculation of recovery, the High Heating Value (HHV) of the oil was 38.6MJ/kg, used with the HHV of the wood mixture given in Table 1. The final energy recovery of the oil from cycle 6 was 85.6% with a standard deviation of 7.7, i.e. 85.6% of the (chemical) energy in the wood supplied to the process was recovered in the produced oil.

Gas production and gas analysis

The gas is produced during the process of converting biomass to oil. The yield of gas produced from dry wood in the feed was 41.2 wt%. The gas is mainly composed of CO₂、CH₄And other short hydrocarbons (C)₂-C₄)、H₂And some lower alcohols. The gas was sampled and analyzed by Sveriges Tekniska Forskning institute (SP) in Sweden. Table 4 shows the gas analysis of the 6 th cycle and the estimated gas heating value from the gas composition. Since the HTL process operates under reducing conditions, it is assumed that the gas does not contain oxygen (O)₂) And the detected oxygen in the gas is from air leaking into the sample bag when filled with the gas sample. Correcting for oxygen (and nitrogen) in the gas composition. The calculated elemental composition of the gas is shown in table 4.

Table 4: gas composition of gas produced in process

Assuming oxygen (O) in the received gas (a.r)₂) From air contamination of the gas when filling the sample bag. The resulting gas composition is assumed to be free of air (oxygen).

Table 5: elemental gas composition

Element(s)	By weight%
		C	32.0
H	3.8
		N	0.0
O	64.1
		Total of	100

Based on MEK free (MEK free bases)

Example 2: providing a first fuel component comprising a renewable component by upgrading a renewable crude oil

Renewable crude oils (oil a, oil B, and oil C) were produced from pine wood as described in example 1, partially upgraded by hydrotreating, as shown in fig. 3.

The process was carried out in a continuous experimental process unit using a downflow tubular reactor. Three separate heating zones are used to ensure isothermal distribution in the catalyst bed. Thus, the reactor is divided into three sections comprising a preheating zone, a catalyst bed (isothermal zone) and an outlet zone. The reactor is filled with 25% to 50% of a degradation catalyst with a silicon carbide inert material. A commercially available NiMo-S catalyst was used.

First, the catalyst bed was dried in a nitrogen atmosphere at a temperature ranging from 100 ℃ to 130 ℃ and then activated by a presulfiding process using a sulfurized diesel containing 2.5 wt% of dimethyl disulfide (Sulphur-spiked diesel) at 45 bar, a hydrogen flow rate of 24L/hour, a temperature ranging from 25 ℃ to 320 ℃ (35/h rate) for about 40 hours or until the sulfur saturation level dropped, i.e., until the overactivity of the catalyst disappeared. This is monitored by changes in sulfur product saturation or liquid gravity; once the specific gravity of the product is stabilized, the renewable crude oil is introduced into the system at the desired flow rate.

At constant hydrogen flow (900scc H)₂In cc oil), an operating pressure of 90 bar and an operating temperature in the isothermal zone comprising the heterogeneous catalyst of 320 ℃ at a Weight Hourly Space Velocity (WHSV) of 0.2h^-1To 0.5h^-1The range of (1).

The quality of the resulting partially upgraded oil had the following characteristics (table 6).

Table 6: physicochemical Properties of renewable crude oil and partially upgraded oil

The results shown in table 6 indicate that decreasing space velocity, water increases, but viscosity, oxygen content, and TAN decrease. This effect is associated with a higher decarboxylation/methanation and hydrodeoxygenation/dehydration reaction ratio.

Example 3: providing a first fuel component comprising renewable components by further upgrading a portion of the upgraded oil

As shown in fig. 3, a portion of the upgraded oil product as described in example 2 is subjected to further hydrotreating stages.

The process was carried out in a continuous experimental procedure unit using a downflow tubular reactor. Three separate heating zones are used to ensure isothermal distribution in the catalyst bed. Thus, the reactor is divided into three sections comprising a preheating zone, a catalyst bed (isothermal zone) and an outlet zone. The reactor was filled with 50% degradation catalyst with inert material of silicon carbide. A commercially available NiMo-S catalyst was used.

The catalyst bed was first dried in a nitrogen atmosphere at a temperature ranging from 100 ℃ to 130 ℃ and then activated by a presulfiding process using a sulphurized diesel containing 2.5% by weight of dimethyl disulphide, at 45 bar, at a hydrogen flow rate of 24L/h, at a temperature ranging from 25 ℃ to 320 ℃ (35/h rate) for about 40 hours or until the sulphur saturation level dropped, i.e. until the excessive activity of the catalyst had disappeared. This is monitored by changes in sulfur product saturation or liquid gravity; once the specific gravity of the product is stabilized, the renewable crude oil is introduced into the system at the desired flow rate.

At constant hydrogen flow (1300scc H)₂In a/cc oil), an operating pressure of 120 bar and an operating temperature in the isothermal zone containing the heterogeneous catalyst of 370 ℃, a Weight Hourly Space Velocity (WHSV) of 0.3. After hydrotreating a portion of the upgraded oil, the boiling point and residuals were significantly reduced as shown in table 7. That is, the fraction from the Initial Boiling Point (IBP) to 350 ℃ is more than doubled by the upgrading process, the residue (BP)>550 ℃) from 16.3% to 7.9%.

Table 7: physicochemical Properties of renewable crude oil and partially upgraded oil

	Partially upgraded oil I	Upgrading oil
			Reaction WHSV [ h-1]	-	0.3
TAN [ mg KOH/g oil]	14.7	<0.1
			Density @15.6 ℃ [ kg/m ]3]	926	903
H/C	1.64	1.73
			Oxygen [ wt.%]	0.6	0.0
HHV[MJ/kg]	43.9	44.3
			Yield of water [ wt.%]	9.7	0.1
IBP-350 ℃ distillate [% ]]	64	67
			Residue of the reaction>550℃	16.3	7.9

Example 4: hansen solubility parameter

Hansen Solubility Parameter (HSP) is a method to describe the solubility, miscibility and stability of various solvents and substances, widely used in, for example, the polymer and coating industries. This method is well described in c.m. Hansen, "Hansen Solubility Parameters-a Users Handbook", second edition, CRC Press, Taylor & Francis Group, LLC (2007), hereby incorporated by reference.

The method takes into account three types of molecular interactions: delta E_dIndicating dispersion (related to van der waals forces); delta E_pRepresenting polarity (associated with dipole moment) and Δ E_hRepresenting hydrogen bonding (equation 1). The total solubility parameter (δ T) is obtained by dividing equation 1 by the molar volume yield (equation 2).

ΔE＝ΔE_d+ΔE_p+ΔE_h(formula 1)

These three parameters can be illustrated in 3D plots as fixed points of pure solvent and solubility spheres of complex mixture samples, as described by hansen. The center of the solubility sphere corresponds to its Hansen solubility parameter, its radius (R)_O) Or so-called interaction radius, determines the boundary of a suitable solvent that is normally contained within the sphere, with the insoluble solvent being located on the outside of the sphere. The hansen solubility parameter is based on the "similar solubility" principle, where the distance of the hansen solubility parameter measures the similarity, which means that solvents with similar δ D, δ P and δ H parameter values may be compatible.

When determining the solubility curve of a complex mixture, two parameters should be included in the study, the distance between materials in the sphere plot (Ra) and the relative distance of a solvent or a mixture of two or more solvents from the center of the sphere (RED number).

Ra can beTo be determined by the sum of the volume or weight of the respective parameters (formula 3), and the RED number corresponds to Ra and the radius of the sphere (R)_O) The ratio of (equation 4).

Ra²＝4(δ_d1-δ_d2)²+(δ_p1-δ_p2)²+(δ_h1-δ_h2)²(formula 3)

When the solvent and the sample to be detected have the same hansen solubility parameters, the relative distance RED is equal to 0; the RED value of a compatible solvent or mixture thereof will be less than 1 and will gradually increase as the solubility between the solvent and solute decreases.

Determination of hansen solubility parameters

The hansen solubility parameters for the renewable crude oils produced in example 1 (oil a, oil B, oil C) and the upgraded renewable oils from examples 2 and 3, as well as the different fossil crude oils and boiling point fractions, were determined using the following solvents and procedures.

Material

For comparison purposes, the solubility curve of fossil crude oil was determined. For the solubility test, the following solvents obtained from commercial chemical suppliers were used: 1-propanol (not less than 99.5%), 1-butanol (99.8%), 2-butanone (not less than 99.0%), 2-heptanone (not less than 98%), acetaldehyde (not less than 99%), acetyl chloride (not less than 99.9%), acetone (not less than 99.9%), acetonitrile (not less than 99.9%), acetylacetone (not less than 99%), 1-butylmercaptan (99%), cyclohexane (not less than 99.5%), cyclopentanone (not less than 99%), diethyl ether (not less than 99.0%), ethyl acetate (99.8%), furfural (not less than 98%), hexanal (not less than 97%), hexane (not less than 97.0%), isopropyl acetate (98%), lactic acid solution (85%), m-cresol (99%), methanol (not less than 99.9%), pentane (not less than 99%), liquid phenol (not less than 89.0%), tetrahydrofuran (not less than 99.9%), toluene (99.8%): Sigma-Aldrich. Tetrahydrofurfuryl alcohol (99%), 1-methylimidazole (99%), 2, 6-dimethylphenol (99%), dimethyl disulfide (not less than 99.0%), glycidyl methacrylate (not less than 97.0%), and trihydroxymethyl phosphate (90%): aldrich. 2-methoxyphenol (more than or equal to 98 percent), anisole (99 percent), dichloromethane (more than or equal to 99.5 percent) and propylene oxide (more than or equal to 99 percent): alfa Aesar. Glycerol and ethylene glycol (general use): BDH. Hydrogen peroxide (USP-10 vol): atoma.

Step of estimating Hansen solubility parameters

Hansen Solubility Parameters for the oils studied were determined by a set of Solubility tests and HSP models described in c.m. Hansen, "Hansen Solubility Parameters-a Users Handbook", second edition, CRC Press, Taylor & Francis Group, LLC. (2007), and HSPiP software written by Abbott S.

Initially, 20 organic solvents were mixed with the oil in question at ambient temperature and classified as "good" (i.e. soluble), "partially soluble" or "poor" (i.e. insoluble) solvents according to observed and measured solubility.

The solvent set used for the first screening had a broad hansen solubility parameter, since the solubility parameter of the oil under study was unknown. After the initial solubility test is completed and the first approximation of HSP's is obtained, a solvent with parameters closer to those of the oil under study is selected to improve the accuracy of the Hansen solubility parametric model. pseudo-3-D representations (spheres) of hansen solubility parameters were constructed from the initial results using HSPiP software, as shown in figure 8.

In this representation, the "good" solvent is placed on the interior or surface of the sphere, while the partially soluble or insoluble solvent is placed on the exterior of the sphere. Once the initial Hansen solubility parameters are determined for the oil under study, the software estimates the relative distance (RED) by equation 5. RED is the corrected difference between the solubility parameters of the two substances (Ra, i.e. sample and solvent under investigation) and the maximum solubility parameter difference R that still allows the sample to dissolve in the solvent_MThe ratio of (a) to (b).

Thus, when the solvent and the sample under study have the same hansen solubility parameter, the relative distance RED is equal to 0 (RED-0). When HSP of the solvent is placed on the surface of the sphere, RED is equal to 1(RED ═ 1), when the sample is insoluble in the solvent, or the solvent is a poor solvent, RED is greater than 1(RED > 1).

Once the approximate hansen solubility parameters and RED values of the relevant oils are estimated, the accuracy of the model can be improved.

This is achieved by performing solubility tests using a new set of solvents or solvent mixtures selected according to the RED values predicted by HSPiP software. The hansen solubility parameters of the test solvents and mixtures should be placed on the surface and near the center of the 3D sphere model. After model refinement, HSPiP software can be used as a prediction tool to select the appropriate solvent according to the desired function (i.e., solubility bridge, demulsifier, precipitation of insoluble materials on certain chemicals). The list of solvents and solvent mixtures used is shown in FIGS. 8a/8 b.

Solubility testing was performed by placing approximately 0.5g of one sample and 5ml of solvent or mixture in a set of capped conical glass tubes. Solubility tests were performed in triplicate. The tube was kept under sonication for 5 hours and allowed to stand overnight at room temperature. Subsequently, the contents of each tube were visually inspected and classified into 5 categories: soluble (1): when there was no observable phase separation or solid precipitation in the glass tube; partially soluble (2-4): the presence of large solids or oil lumps indicates that the sample is not completely dissolved in the solvent or mixture; and, insoluble (0): mixtures of phases with well-defined boundaries. The partially soluble range is from 2 to 4, with 2 indicating the highest relative solubility. Fig. 5 shows an example of each solubility class.

Samples were marked as "indeterminate" because it was difficult to visually distinguish between soluble (1) and partially soluble (2) due to the darker color of the samples. To evaluate the solubility of these "uncertain" samples, the "spot test" method was used as a more accurate indicator of mixture stability/compatibility. This method is widely used to assess the compatibility of marine fuel blends and has been used, for example, by Redelius [ p.redelius, "building solvent model using hansen solvent parameter," Energy and Fuels, vol.18, No.4, pp.1087-1092,2004 ] for hansen solubility parameter analysis. The spot test was performed by: a drop of each "indeterminate" solution was placed on the filter paper and the evaluation Test was performed according to the standard of the drop Test method given in p.products, and r.s.sheet, "clean lines and Compatibility of basic Fuels by Spot Test," vol.4, no.reactive 2014, pp.2014-2016,2016: if a uniform stain is formed as shown in fig. 6a, the mixture is considered to be completely soluble (i.e., category 1), while if two separate concentric spots are formed as shown in fig. 6b, the solvent is considered to be partially soluble (i.e., category 2).

Example 5: hansen solubility parameters for renewable crude oils.

Hansen solubility parameters and solubility curves for the renewable crude oils (oil a, oil B, and oil C) produced by hydrothermal liquefaction in example 1 were determined using a total of 36 solvents and 23 solvent mixtures. The results are summarized in FIGS. 8a/8 b. The 3D representation of HSP for oil a (fig. 7) has a good degree of fit of 0.965, 24 solvents inside the sphere and 33 outside the sphere. The score and RED values for each solvent are shown in FIGS. 8a/8 b. The solvent with the RED value equal to 1 is positioned on the surface of the sphere, the solvent with the RED value less than 1 is positioned inside the sphere, and the solvent with the RED value more than 1 is positioned outside the sphere. Thus, the closer the RED value is to 0, the closer the solvent or mixture is to the center of the sphere. To estimate the correlation between hansen solubility parameters for renewable crude oils, parameters for oil B and oil C were also determined. In this case, 11 solvents were sufficient for HSP determination, as shown in fig. 8a/8 b.

Three renewable crude oils, oil A (delta)_D:19.19，δ_P:14.52，δ_H:11.61，R₀9.3), oil B (delta)_D:18.36，δ_P:10.43，δ_H:10.06，R₀6.7) and oil C (. delta.)_D:18.13，δ_P:9.59，δ_H:9.25，R₀6.8) have similar solubility curves, as can be seen in FIG. 10. However, oil a has a higher polarity and stronger hydrogen bonding interactions than oil B and oil C. Comparing the parameters of three biological crude oilsIt can be seen that they are similar, with the only exception that oil C is partially soluble in 1-methylimidazole, while oil a and oil B are soluble, as shown in figure 8 a. The difference in hansen solubility parameters of the renewable crude oils studied can be related to the biomass feedstock used to produce each oil, i.e. Birch (Birch) in oil a; pine ew (pine ew) in oil B and oil C, and the processing conditions described in example 1.

Example 6: hansen solubility parameter for partially upgraded and upgraded oils

Fig. 8a/8b and 9 summarize hansen solubility parameter scores and RED values for partially upgraded renewable oils of example 2.

As shown in FIG. 8 a/FIG. 8b, a total of 18 solvents were used to determine the partially upgraded renewable oil II (δ) from example 2_D：17.95，δ_P：10.96，δ_H: 9.96) of the Hansen solubility parameter. A 3D representation of hansen solubility spheres from a portion of the upgraded oil from example 2 is shown in fig. 11. The degree of fit of hansen solubility spheres was 0.883, excluding 1 outlier solvent. The hansen solubility curve of the upgraded renewable oil was determined according to the method described in example 3 using 15 solvents. Hansen solubility spheres for upgraded oil are shown in fig. 10, with a fitness of 1.000, hansen solubility parameters: delta_D：17.36，δ_P：8.01，δ_H：7.59。

As can be seen in fig. 11, the hansen solubility parameters and the radius of solubility of the biocrude, partially upgraded oil and upgraded oil are different, indicating the effect of the upgrading process on the solubility characteristics. Renewable crude oil (oil a) has strong polarity, high dispersion interactions and strong hydrogen bonding interactions. Renewable crude oil is subjected to a step of upgrading (partial upgrading) including hydrogenation, total deoxygenation, mild cracking, so-called partially upgraded oils show significant reduction in polarity, hydrogen bonding interactions and solvent radii. This can be attributed to the fact that the presence of oxygen, heteroatoms and metals contributes greatly to the polarity parameter. In fact, the higher the crude oil is upgraded, the lower the values of the three hansen solubility parameters, which can be clearly seen when comparing the solubility curves of renewable crude oil and partially upgraded oil with fully upgraded oil. The latter exhibit lower dispersibility, polarity and hydrogen bonding interactions and lower dissolution radii.

The RED value of the partially upgraded oil in the bio-crude solubility sphere range is quite low (0.524) indicating complete dissolution. However, the RED value of upgraded oil (0.934) is close to the solubility limit of RED ≧ 1, indicating its poor solubility in biocrude. Thus, the solubility between biocrude and upgraded oil is inversely proportional to its degree of upgrading.

Example 7: compatibility of upgraded renewable oils with petroleum crude

The compatibility of renewable oils with petroleum is important for many practical applications of renewable oils (e.g., for co-processing and pipeline transportation in petroleum refineries).

Hansen solubility parameter analysis is used for the purpose of testing the compatibility of upgraded renewable oils with Vacuum Gas Oil (VGO), bitumen and petroleum crude. The results are shown in fig. 13 and visualized in fig. 12a, 12b and 12 c. It can be seen from the figure that there are differences in the polarity and hydrogen bonding parameters for petroleum crude, VGO and bitumen compared to upgraded renewable oil. However, the solubility curves also indicate that there are regions of overlap between their hansen solubility parameter spheres. Furthermore, the center of the petroleum crude oil is located at the solubility boundary of the upgraded oil, i.e., RED of 0.981, which not only increases the solubility ratio of upgraded biocrude to petroleum crude oil, but also indicates that after deep hydroprocessing, the solubility curve of upgraded biocrude becomes very close to that of petroleum crude oil, which means that after renewable crude oil is upgraded by hydroprocessing, the upgraded oil has similar properties to fossil crude oil.

Example 8: co-processing of biocrude and/or partially upgraded renewable oil with petroleum crude

To evaluate the synergistic treatment of renewable crude oil and/or partially upgraded renewable oil with petroleum crude oil and petroleum crude oil heavy fractions such as Vacuum Gas Oil (VGO), the solubility curve of petroleum crude oil was determined. Determination of fossil crude oil (. delta.) Using 21 solvents in total_D：18.47，δ_P：6.67，δ_H: 3.58) andVGO(δ_D：19.1-19.4，δ_P：3.4-4.2，δ_H: 4.2-4.4) of the Hansen solubility parameter. Its 3D representation had a good fit of 1.000 with a solubility radius of 5.6 and 5.8, respectively. FIG. 12a, FIG. 12b and FIG. 12c show the renewable crude oil, partially upgraded crude oil, fossil crude oil, VGO and bitumen (. delta.) obtained_D：18.4，δ_P：4.0，δ_H：0.6；R₀: 5.76) of the solubility profile of the polymer. The asphalt Hansen Solubility parameter is determined by Redelius, "Bitumen Solubility Model using Hansen Solubility Parameters, Energy and Fuels, vol.18, No.4, pp.1087-1092,2005.

Although the dispersion interaction parameters of bio-crude, fossil crude, VGO and bitumen are similar, there are considerable differences in the polar and hydrogen bonding interaction parameters. The RED values of the fossil oil, VGO and bitumen in the solubility spheres of the biocrude are 1.248, 1.415 and 1.506, respectively. These RED values are above the solubility limit for RED ≧ 1, indicating only partial dissolution in the biocrude (FIG. 11 a). This was confirmed by laboratory tests of blending bio-crude in a proportion of 5 to 50 wt% in petroleum crude. The same behavior was observed when comparing hansen solubility parameters of partially upgraded oil with petroleum crude, VGO and bitumen, where the polar and hydrogen bond interaction parameters differed greatly. The RED values of mineral oil, VGO and bitumen within the solubility sphere of the partially upgraded oil are above the solubility limit for RED ≧ 1 (1.282, 1.534 and 1.611, respectively), indicating the partial solubility of the partially upgraded oil at room temperature. The solubility of the mixture of partially upgraded biocrude and petroleum crude, bitumen or vacuum residuum is improved by increasing the temperature. Experimental testing has shown that mixtures of partially upgraded biocrude and petroleum or derived heavy fractions in a ratio of 9:1 become soluble and compatible when heated to temperatures of 70 ℃ to 130 ℃, as determined by spot test analysis. Thus, in one advantageous embodiment of the invention, the first fuel mixture component and the second fuel mixture component comprising renewable hydrocarbons and linking materials are heated to 70 ℃ to 150 ℃ (e.g., 80 ℃ to 120 ℃) prior to operating them to form a homogeneous mixture. For the selection of ligation materials that meet all of the above solubility and availability criteria, various ligation materials (e.g., solvent combinations) were screened on the HSPiP software to determine a suitable mixture that does not exceed the solubility limit (i.e., RED ≦ 1). By testing various solvents and mixtures; mixing tests confirmed that the addition of 2 wt.% toluene or mixed MEK/m-cresol (70: 30) increased the solubility of the bio-crude and bitumen. Although the mixture is not completely compatible at room temperature, when the mixture is heated to 150 ℃, it becomes compatible and analyzed by spot test.

Example 9: hansen solubility parameters for fractions of renewable crude oil and upgraded renewable oil

The compatibility of biocrude feedstock, partially upgraded oil, and fractions of upgraded oil with their fossil counterparts is important for evaluating these mixtures in processes such as recycling in renewable oil hydroprocessing and co-processing with petroleum fractions and/or other bio-oils. Thus, the hansen solubility parameters of the fractions listed below were determined by the method described in example 5. The upgraded fraction is obtained by distilling a portion of the upgraded oil, and the upgraded oil is produced as described in examples 2 and 3. Fig. 14a and 14b show a 3D representation of hansen solubility curves for the upgraded heavy fraction.

Table 8: hansen solubility parameters for biocrude feedstock, partially upgraded oil, and upgraded oil

PUO: partially upgraded oil

UO: upgrading oil

As can be seen from fig. 14a and 14b, the hansen solubility parameter and the solubility radius become similar to fossil fuels, i.e., Ultra Low Sulfur Fuel Oil (ULSFO) and High Sulfur Fuel Oil (HSFO).

Example 10: compatible diluents, viscosity reducers and storage stability enhancers for renewable crude oils

Fully compatible synthetic diluents or viscosity and/or density reducers for renewable crude oils are desirable for many practical applications, including diluents for improving the flowability of renewable crude oils, increasing separation efficiency during production, e.g., by solvent/diluent assisted separation of renewable crude oils or increasing the storage stability of crude oils.

Using the solubility curve of the bio-crude, a series of solvents located within the sphere of the solubility curve of the hansen solubility parameter of "oil a" were selected. These solvents are selected to be suitable for making up the desired "synthetic light" mixture.

The following criteria were used to further narrow the solvent list: a) low toxicity, b) easy separation from renewable crude oil, e.g., in terms of boiling point, c) non-complex geometry, d) solvent that does not increase the oxygen content of the biocrude, e) solvent that is free of other heteroatoms (i.e., nitrogen, sulfur, chlorides, etc.) or metals that contribute to the degradation of biocrude quality, f) local availability of solvent, and g) cost.

The light fraction boiling at 130 ℃ was cut off from the renewable crude oil a produced in example 1 from the rotary evaporator. Gas chromatography analysis based on renewable light crude oil establishes a family of compounds representing the major volume percentage of the renewable light crude oil fraction, i.e., substituted benzene: 15% by volume, C₄-C₆Ketone: 50% by volume, alkane: 24 vol%, and alcohol: 11% by volume.

Based on this approach, it was determined that mixtures containing methyl ethyl ketone, alkanes (e.g., octane, nonane), p-xylene and/or toluene, and 1-butanol and/or propanol are suitable for simulating the light fraction of renewable crude oil as "synthetic lights".

Table 9: hydrofacial action^TMCrude oil light fraction determination and mixture examples

^aPara-xylene may be substituted by tolueneOr by a 50%/50% toluene/xylene solvent mixture

Table 10: HS parameters for pure solvent and mixture examples

The volume percent of each solvent in the selected mixture is shown in table 9. The initial RED fraction (1.53) of the hansen solubility parameter for a similar mixture (table 9) was obtained using the light volume concentration obtained by GC-MS.

Table 9 further shows some volume concentrations of solvent mixtures with similar RED values, which means that all mixtures that are suitable are close enough to the properties of a true light mixture from renewable crude oil.

The hansen solubility parameters of the solvent and the linking substance are shown in table 10.

Example 11: synergistic treatment of biocrude and/or partially upgraded renewable and petroleum crude oils using a linking substance

For the selection of solvents that meet all of the above solubility and availability criteria, various linking substances (e.g., solvent combinations) were screened on the HSPiP software to determine a suitable mixture that does not exceed the solubility limit (i.e., RED ≦ 1).

By testing various solvents and mixtures; it was confirmed that 1) 2 wt% of toluene or mixed MEK/m-cresol (70: 30) the solubility of the biological crude oil and the asphalt is increased. Although the mixture was not completely compatible at room temperature, it became compatible when heated to 150 ℃ and analyzed by spot test. 2) The bio-crude and Vacuum Gas Oil (VGO) mixture was approximately delta by the addition of 2 wt% HSP_D：15.6，δ_P：8.3，δ_H: 9.4 (e.g., 60 wt.% acetone +30 wt.% propanol +10 wt.% pentane). 3) The partial upgradant and VGO mixtures are compatible without the use of tie materials and up to 25% proportions of partial upgradant.

Example 12: connecting substance for mixing renewable oil with bunker fuel for producing low-sulphur bunker mixtures

Mixing tests were conducted using renewable liquids at concentrations ranging from 2 wt% to 50 wt% to test the solubility of the sweet marine fuel blend stock with renewable liquids (crude oil, partially upgraded renewable oil, and 350+ ° c boiling fraction from the same oil). Tests have shown that at any mixing ratio tested, renewable liquids are only partially dissolved with low sulphur marine fuel blend stocks (RMG 180 ultra low sulphur fuel oil according to ISO8217(2012) standard). It is clear that such blended feedstocks have compatibility issues that lead to precipitation, separation and/or deposition of insoluble components, etc., if the blended feedstock is used directly in a blend with other marine fuels. Therefore, renewable mixing raw materials that do not have such compatibility issues are highly desirable.

Hansen solubility curve analysis was performed to identify a connecting substance that enables mixing of liquids in marine fuels. As shown in fig. 14a and 14b, the solubility spheres of each oil are overlapping, meaning that they are partially soluble despite their different hansen solubility parameters and the RED distance between their centers of solubility greater than 1.

The solvent mixtures which have been identified as possible connecting substances consist essentially of sulfur-containing solvents, ketones, alkanes and alcohols, and aromatics such as toluene, xylene and creosol.

Example 13: low sulfur fuel blend including a first fuel blend component containing a renewable component

Based on the solubility profile described in example 12, the first fuel mixture component containing renewable components is composed of a boiling point of 350+ ° c and a hansen solubility parameter (δ ° c)_D:17-18.5,δ_P:7-9.5,δ_H:7-10.5；R₀4-8) and a concentration of 0 to 10 wt.% of a heavy fraction comprising an upgraded renewable crude oil having a hansen solubility parameter (δ)_D:18-19.7,δ_P:3-6,δ_H:3-6；R₀4-6) and RMG380 High Sulfur Fuel Oil (HSFO) having a sulfur content of 2.49 wt.%.

The concentration of the extract can reach up to 10 wt%Is mixed with a second fuel component comprising an Ultra Low Sulfur Fuel Oil (ULSFO) having a hansen solubility parameter (δ) according to ISO8217, RMG 180 ultra low sulfur fuel oil_D:18-19.7,δ_P:3-6,δ_H:3-4.5；R₀:4-6.5)。

As expected, the first fuel mixture component without tie-up was found to be incompatible when the upgraded heavy fraction was mixed with two marine fuels (i.e., ultra low sulfur and high sulfur marine fuels) in a ratio of 5 wt% to 50 wt% upgraded renewable fraction. However, for the first fuel blend component containing 2 wt% or more of the high sulfur bonding material, the blend was found to be compatible. It was further found that the low sulfur fuel blend remains compatible at all ratios by dilution with Ultra Low Sulfur Fuel Oil (ULSFO), e.g., Ultra Low Sulfur Fuel Oil (ULSFO) can be added to the same tank as the low sulfur fuel blend according to the present invention without any compatibility issues.

An example of the properties of a low sulfur fuel mixture according to the present disclosure is shown in fig. 15, which is a mixture of 62 vol% of a first fuel component that includes a renewable component (Steeper HF, 350+ ° c boiling fraction).

Example 14: low sulfur mixtures comprising a partially upgraded heavy fraction (3 wt.% oxygen) and a first fuel blend component of a marine gas oil

Blending tests were conducted using the first fuel blend component from example 10 comprising a heavy fraction with an oxygen content of 3 wt% (boiling point 350+ ° c) and a second fuel blend component comprising a Marine Gas Oil (MGO) according to ISO8217 DMA standard. The heavy fraction has a Hansen solubility parameter (delta)_D:17-19,δ_P:7.5-12,δ_H:7-10；R₀5-9), and Marine Gas Oils (MGO) having a Hansen solubility parameter (delta)_D:18-19.7，δ_P：3-6，δ_H：3-5；R₀: 4.5-6.5). Since the RED center of solubility is higher than 1, the mixture is expected to be only partially soluble in the absence of the linking species according to the present invention. From the spot test and the microscopic test in FIG. 16It is seen that a blend test with a ratio of 50 wt% heavy fraction from partially upgraded renewable oil (hfpou)/50 wt% Marine Gas Oil (MGO) and 25 wt% hfpou/75 wt% MGO was also observed.

Example 15: low sulfur blends comprising a first fuel blend component comprising a portion of heavy fraction of upgraded oil (3 wt.% oxygen) and High Sulfur Fuel Oil (HSFO)

Blending tests were conducted using the first fuel blend component from example 10 comprising a heavy fraction with an oxygen content of 3 wt% (boiling point 350+ ° c) and the second fuel blend component comprising a marine gas oil (ultra low sulfur fuel) according to ISO8217 DMA standard. The heavy fraction has a Hansen solubility parameter (delta)_D:17-19,δ_P:7.5-12,δ_H:7-10；R₀5-9), and high sulfur fuel oils have a Hansen solubility parameter (delta)_D:18-19.7，δ_P：3-6，δ_H：3-5；R₀: 3-6). Since the RED center of solubility is close to 1, the mixture is expected to be soluble or compatible without the linking species according to the present invention. As can be seen from the spot and microscopic tests in fig. 17, it was also observed in the blend test with a ratio of 50 wt% heavy fraction of partially upgraded oil (hfpouo)/50 wt% High Sulfur Fuel Oil (HSFO) and 25 wt% hfpouo/75 wt% HSFO, which means that HSFO is a suitable linking substance to achieve the main goal of the invention (to achieve a low sulfur fuel blend of the first fuel blend component containing a renewable hydrocarbon component as described in example 14).