阅读说明：本技术 含烃化石和可再生组分的混合物和生产这种混合物的方法 (Mixture comprising hydrocarbon fossil and renewable components and method for producing such a mixture ) 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：本发明涉及一种用于输入炼油厂的烃混合物,包括含有可再生烃组分的第一混合物组分和含有石油衍生烃的第二混合物组分,以形成用于在炼油厂进行加工的最终的烃混合物的至少一部分,其中,所述第一混合物组分的特征在于包含至少70重量％的沸点高于220℃且具有特性(δ-(d1),δ-(p1),δ-(h1))＝(17-20,6-12,6-12)的烃物质；以及其中,所述第二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),其中,所述第一混合物组分以至多80重量％的相对量存在于所述最终的烃混合物中。(The invention relates to a hydrocarbon mixture for input to a refinery, comprising a first mixture component comprising a renewable hydrocarbon component and a second mixture component comprising a petroleum-derived hydrocarbon to form at least a portion of a final hydrocarbon mixture for processing at the refinery, wherein the first mixture component is characterized by comprising at least 70 wt% of a hydrocarbon having a boiling point above 220 ℃ and a property (delta) of d1 ,δ p1 ,δ h1 ) (ii) a hydrocarbon material of (17-20,6-12, 6-12); and wherein the second mixture component is characterized byTo have the characteristic (delta) d2 ,δ p2 ,δ h2 ) (17-20,3-5,4-7), wherein the first mixture component is present in the final hydrocarbon mixture in a relative amount of up to 80 wt%.)

1. A hydrocarbon mixture for input to a refinery comprising a first mixture component comprising a renewable hydrocarbon component and a second mixture component comprising a petroleum-derived hydrocarbon to form at least a portion of a final hydrocarbon mixture for processing at the refinery, wherein the first mixture component is characterized by comprising at least 70 wt% of hydrocarbon material having a boiling point above 220 ℃ and by having the property (δ)_d1,δ_p1,δ_h1) (17-20,6-12, 6-12); and wherein the second mixture component is characterized by having a characteristic (δ)_d2,δ_p2,δ_h2) (17-20,3-5,4-7), wherein the first mixture component is present in the final hydrocarbon mixture in a relative amount of up to 80 wt%.

2. The hydrocarbon mixture of claim 1, wherein the first mixture component comprises: is characterized by having a characteristic (delta)_d,δ_p,δ_h) (17-20,6-15,6-12) and characterized by having the property (δ)_d3,δ_p3,δ_h3) (iii) a linker of (17-20,3-6, 4-6); wherein the hydrocarbon material is present in the first mixture component in a relative amount of 90 to 99.5 wt% and the connecting material is present in an amount of 0.5 to 99.5 wt%A relative amount of 10 wt% is present in the first mixture component.

3. A hydrocarbon mixture as claimed in claim 2, wherein the connecting substance is an oil having a sulphur content of at least 1 wt%, such as an oil having a sulphur content of at least 1.5 wt%, preferably an oil having a sulphur content of at least 2.0 wt%.

4. A hydrocarbon mixture as claimed in any one of claims 1 to 3, wherein the first mixture component containing renewable hydrocarbon components comprises hydrocarbon materials having a boiling point of at least 70 wt% above 300 ℃, such as at least 70 wt% above 350 ℃; preferably, the first mixture component comprises a hydrocarbon material having a boiling point above 370 ℃ in an amount of at least 70 wt%, for example above 400 ℃ in an amount of at least 70 wt%.

5. A hydrocarbon mixture as claimed in claim 4, wherein the first mixture component containing renewable hydrocarbon components comprises hydrocarbon materials having at least 50 wt% boiling points above 300 ℃, such as at least 50 wt% boiling points above 350 ℃; preferably, the hydrocarbon material of the first mixture component contains at least 50 wt.% of hydrocarbons having a boiling point above 370 ℃, for example, the hydrocarbon material of the first mixture component contains at least 50 wt.% of hydrocarbons having a boiling point above 400 ℃.

6. A hydrocarbon mixture as claimed in any one of claims 4 to 5, wherein the first mixture component containing renewable hydrocarbon components comprises hydrocarbon material having at least 10 wt% boiling points above 400 ℃, such as at least 10 wt% boiling points above 450 ℃.

7. A hydrocarbon mixture as claimed in any one of the preceding claims, wherein the first mixture component is present in the final hydrocarbon mixture in a relative amount of up to 10 to 75 wt%, and wherein the second mixture component is present in the final hydrocarbon mixture in a relative amount of 25 to 90 wt%.

8. A hydrocarbon mixture as claimed in any one of the preceding claims, wherein the hydrocarbon material of the first mixture component comprising renewable hydrocarbon components has a water content of less than 1 wt%, for example a water content of less than 0.5 wt%; preferably, the hydrocarbon material of the first mixture component comprising a renewable hydrocarbon component has a water content of less than 0.25 wt%, for example a water content of less than 0.1 wt%.

9. A hydrocarbon mixture as claimed in any one of the preceding claims, wherein the first mixture component is characterized by a property (δ)_d1,δ_p1,δ_h1)＝(17-20,7-12,7-12)。

10. A hydrocarbon mixture as claimed in claim 9, wherein the first mixture component is characterized by a characteristic (δ)_d1,δ_p1,δ_h1)＝(17-20,7-9,8.5-10)。

11. A hydrocarbon mixture as claimed in any one of the preceding claims, wherein the hydrocarbon species in the first mixture component comprising a renewable hydrocarbon component is characterised by having a characteristic (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)＝(17-20,4-6,4-7)。

12. A hydrocarbon mixture as claimed in any one of the preceding claims, wherein the first mixture component is present in the final hydrocarbon mixture in a relative amount of from 50 to 75 wt%, wherein the second mixture component is present in the final hydrocarbon mixture in a relative amount of from 25 to 50 wt%, and wherein further the connecting substance is optionally present in the final hydrocarbon mixture in a relative amount of from 0.5 to 5 wt%.

13. A hydrocarbon mixture as claimed in any one of the preceding claims, wherein the linking substance comprises or further comprises one or more components selected from each of the following: 1. ketones, 2 alcohols, 3 alkanes, 4 aromatics, such as toluene, xylene, creosol.

14. The hydrocarbon mixture of claim 13, wherein the linking substance comprises or further comprises 25 to 90 wt.% of a ketone, 0.1 to 40 wt.% of an alkane, 1 to 40 wt.% of an alcohol, and 0.1 to 20 wt.% of toluene and/or xylene and/or creosol.

15. A hydrocarbon mixture as claimed in any one of the preceding claims, having a viscosity at 50 ℃ in the range of from 160 to 180cSt, a flash point above 60 ℃, a pour point of less than 30 ℃ and a Total Acid Number (TAN) of less than 2.5mg KOH/g.

16. A hydrocarbon mixture as claimed in any one of the preceding claims, wherein the hydrocarbon species and/or the hydrocarbon species of the first mixture component are further characterised by having a conradson carbon residue number of less than 25.

17. A hydrocarbon mixture according to any one of the preceding claims, wherein the first mixture component of hydrocarbon substances and/or the substances is further characterized by having a TAN of less than 50mg KOH/g, such as less than 40mg KOH/g, preferably the first mixture component and/or the substances is further characterized by having a Total Acid Number (TAN) of less than 30mg KOH/g, such as less than 20mg KOH/g.

18. A hydrocarbon mixture as claimed in any one of the preceding claims, wherein the first mixture component and/or the 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 20,

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

19. A hydrocarbon mixture as claimed in any one of the preceding claims, wherein the hydrocarbon species of the first mixture component are further characterised by having an oxygen content of less than 15 wt%, such as less than 12 wt%; preferably, the first mixture component is further characterized as having an oxygen content of less than 10 wt.%, such as less than 8 wt.%.

20. A hydrocarbon mixture according to any one of the preceding claims, wherein the first hydrocarbon mixture component and/or the hydrocarbon species has an oxygen content of less than 5 wt%, such as less than 3 wt%.

21. A hydrocarbon mixture as claimed in claim 20, wherein the hydrocarbon species of the first mixture component is further characterised by a viscosity at 50 ℃ in the range 1000 to 10000cSt, for example a viscosity at 50 ℃ in the range 100 to 1000 cSt.

22. A hydrocarbon mixture as claimed in any one of the preceding claims, wherein the hydrocarbon material of the first mixture component is produced from biomass and/or waste material.

23. The hydrocarbon mixture of claim 22, wherein the production of the hydrocarbon material of the first mixture component is performed by a hydrothermal liquefaction process.

24. A hydrocarbon mixture as claimed in claim 23, wherein the hydrocarbon material of the first mixture component is 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 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 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 hydrocarbon component comprising high boiling compounds.

25. An intermediate mixture component for forming a hydrocarbon mixture as claimed in any one of the preceding claims, the intermediate mixture component comprising a hydrocarbon material comprising hydrocarbons and a linking material to form at least a portion of the intermediate mixture component, wherein the hydrocarbon material is characterized by having a characteristic (δ) by_d1,δ_p1,δ_h1) (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 hydrocarbon material is present in the intermediate mixture component in a relative amount of 90 to 99.5 wt.%, and wherein the linking material is present in the intermediate mixture component in a relative amount of 0.5 to 10 wt.%.

26. The intermediate mixture component of claim 25, wherein the hydrocarbon material is present in the intermediate mixture component in a relative amount of up to 95 wt.% to 99.5 wt.%, and wherein the linking material is present in the intermediate mixture component in a relative amount of up to 0.5 wt.% to 5 wt.%.

27. A process for producing a hydrocarbon mixture containing renewable hydrocarbons according to any of the preceding claims, wherein the process comprises the steps of:

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

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

-adding the first mixture component to the second mixture component to form the hydrocarbon mixture.

28. A method of producing a hydrocarbon mixture according to claim 27, wherein the method further comprises the steps of:

-providing a linking substance in a relative amount of 0.5 to 10% by weight of the final hydrocarbon mixture, having a characteristic (δ)_d3,δ_p3,δ_h3)＝(17-20,3-6,3-6)；

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

-adding the second mixture component or the first mixture component to the intermediate mixture component to form the hydrocarbon mixture.

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

30. The method according to any of the preceding claims, wherein an intermediate mixture component comprising the first mixture component or the second mixture component and the connecting substance is operated to form a homogeneous mixture before adding the second mixture component and/or the first mixture component to form the hydrocarbon mixture.

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

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

33. The method of claim 32, wherein compatibility is determined to exist based on the measured characteristic and the first component and the second component are accepted for direct mixing.

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

Technical Field

The present invention relates to the field of hydrocarbon processing in refineries, and in particular to the field of processing hydrocarbon mixtures comprising a first mixture component comprising a renewable hydrocarbon component and a second mixture component comprising a petroleum-derived hydrocarbon to form at least a portion of a final hydrocarbon mixture for processing at a refinery with increased efficiency.

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 and without the need for latent heat addition. Furthermore, the hydrothermal liquefaction process allows for a wide range of heat recovery processes. Renewable crude oils produced have many similarities to their petroleum counterparts and are typically much higher in quality than, for example, bio-oils produced by pyrolysis, which typically contain large 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-oils 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 by 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 drop-in-fuel. However, while renewable crude oils produced by hydrothermal 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

The boiling points of the oxygen and oxygen free differ greatly

Higher oxygen content than petroleum derived oils leads to higher exotherms in upgrading processes (e.g. by catalytic hydrogenation) due to higher oxygen content

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 considered during 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., conventional petroleum-derived oils or other oils) at the refinery.

For applications where the oil or fraction thereof is in a mixture, such as in the input stream to a refinery, either before entering the refinery or at a later stage during the refinery, including fossil hydrocarbons as well as hydrocarbon mixtures containing renewable components, it is important that all components are fully compatible, e.g., do not stratify upon use, storage and/or dilution with other fuel mixtures for the same application.

While this compatibility, along with improved efficiency and processability, is desirable, it is generally not available for oils containing renewable components.

One way to improve the compatibility of renewable crude oils with fossil counterparts is to deoxygenate the renewable crude oil by hydrogenation at high oxygen content. This would improve compatibility but is a very expensive way to achieve increased miscibility.

Energy & Fuels 2019,33, p.11135-11144(Ying et al), page 11135, show that bio-oils obtained from rapid pyrolysis processes are problematic in co-processing with petroleum because they are immiscible and very high in oxygen content, which has changed the focus on HTL derived bio-crude.

According to us patent application 2013/0174476, it is known to produce a bio-oil composition comprising a biomass-derived liquid, at least one petroleum-derived composition and optionally one or more additives to produce alternative bio-oil compositions. In this previously known technique, the biomass-derived liquid is a pyrolysis oil, which may have the disadvantages described above and further has a high water content. A large amount of residue is generated in the process, which significantly reduces the process efficiency.

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.

Object of the Invention

It is therefore an object of the present invention to provide a hydrocarbon mixture comprising a petroleum component and a renewable component which does not have the above-mentioned efficiency and compatibility problems and which produces minimal waste or residues.

Disclosure of Invention

According to one aspect of the invention, the object is achieved by a hydrocarbon mixture for input to a refinery comprising a first mixture component comprising a renewable hydrocarbon component and a second mixture component comprising a petroleum-derived hydrocarbon to form at least a portion of a final hydrocarbon mixture for processing at the refinery, wherein the first mixture component is characterized by comprising at least 70 wt% of hydrocarbon species having a boiling point above 220 ℃ and by having the property (δ ℃.) (δ)_d1,δ_p1,δ_h1) (17-20,6-12, 6-12); and wherein the second mixture component is characterized by having a characteristic (δ)_d2,δ_p2,δ_h2) (17-20,3-5,4-7), wherein the first mixture component is present in the final hydrocarbon mixture in a relative amount of up to 80 wt%.

By providing a specified first mixture component, the residue produced by the hydrocarbon mixture is minimized, thus achieving improved efficiency.

In one embodiment, the first mixture component comprises a first mixture characterized by having a property (δ)_d,δ_p,δ_h) (ii) a hydrocarbon material of (17-20,6-15, 6-12); and is characterized by having a characteristic (delta)_d3,δ_p3,δ_h3) (iii) a linker of (17-20,3-6, 4-6); wherein the hydrocarbon material is present in the first mixture component in a relative amount of 90 to 99.5 wt% and the linking material is present in the first mixture component in a relative amount of 0.5 to 10 wt%.

In one embodiment, the connecting substance is an oil having a sulphur content of at least 1 wt.%, for example an oil having a sulphur content of at least 1.5 wt.%, preferably an oil having a sulphur content of at least 2.0 wt.%.

In one embodiment, the first mixture component containing renewable hydrocarbon components comprises hydrocarbon materials having at least 70 weight percent boiling points above 300 ℃, e.g., at least 70 weight percent boiling points above 350 ℃; preferably, the hydrocarbon material of the first mixture component contains at least 70 wt.% of boiling point above 370 ℃, for example at least 70 wt.% of the first mixture component has boiling point above 400 ℃.

In one embodiment, the first mixture component containing a renewable hydrocarbon component comprises hydrocarbon material having at least 50 weight percent boiling point above 300 ℃, e.g., at least 50 weight percent of the hydrocarbon material has a boiling point above 350 ℃; preferably, the first mixture component comprises hydrocarbon material having a boiling point above 370 ℃ in an amount of at least 50 wt%, e.g., the first mixture component comprises at least 50 wt% of hydrocarbon material having a boiling point above 400 ℃ of the first mixture component.

In one embodiment, the first mixture component containing a renewable hydrocarbon component comprises hydrocarbon materials having at least 10 weight percent boiling points greater than 400 ℃, such as at least 10 weight percent boiling points greater than 450 ℃.

In one embodiment, the first mixture component is present in the final hydrocarbon mixture in a relative amount of up to 10 wt% to 75 wt%, wherein the second mixture component is present in the final hydrocarbon mixture in a relative amount of 25 wt% to 90 wt%.

In one embodiment, the first mixture component comprising a renewable hydrocarbon component comprises a hydrocarbon material having a water content of less than 1 weight percent, such as a water content of less than 0.5 weight percent; preferably, the first mixture component comprising a renewable hydrocarbon component comprises a hydrocarbon material having a water content of less than 0.25 wt%, for example a water content of less than 0.1 wt%.

In one embodiment, the first mixture component is characterized by having a characteristic (δ)_d1,δ_p1,δ_h1)＝(17-20,7-12,7-12)；

In one embodiment, the first mixture component is characterized by having a characteristic (δ)_d1,δ_p1,δ_h1)＝(17-20,7-9,8.5-10)。

In one embodiment, the hydrocarbon material in the first mixture component comprising a renewable component is characterized as having a characteristic (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)＝(17-20,4-6,4-7)。

In one embodiment, the first mixture component is present in the final hydrocarbon mixture in a relative amount of 50 to 75 wt%, wherein the second mixture component is present in the final hydrocarbon mixture in a relative amount of 25 to 50 wt%, and wherein further, the linking substance is optionally present in the final hydrocarbon mixture in a relative amount of 0.5 to 5 wt%.

In one embodiment, the linking substance comprises one or more components selected from each of the following groups: 1. ketones, 2. alcohols 3. alkanes, 4. aromatics, such as toluene, xylene, creosol.

In one embodiment, the linking species comprises or further comprises 25 to 90 wt.% of a ketone, 0.1 to 40 wt.% of an alkane, 1 to 40 wt.% of an alcohol, and 0.1 to 20 wt.% of toluene and/or xylene and/or creosol.

In one embodiment, the viscosity of the hydrocarbon mixture at 50 ℃ is in the range of 160cSt to 180cSt, the flash point of the hydrocarbon mixture is above 60 ℃, the pour point of the hydrocarbon mixture is less than 30 ℃, and the Total Acid Number (TAN) is less than 2.5mg KOH/g.

In one embodiment, the first mixture component and/or the hydrocarbon material is further characterized as having a conradson carbon residue number of less than 25.

In one embodiment, the first mixture component and/or the hydrocarbon material is further characterized as having a TAN of less than 50mg KOH/g, such as less than 40mg KOH/g, and preferably the first mixture component and/or the hydrocarbon material is further characterized as having a Total Acid Number (TAN) of less than 30mg KOH/g, such as less than 20mg KOH/g.

In one embodiment, the first mixture component and/or the hydrocarbon material 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 20,

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

In one embodiment, the hydrocarbon material of the first mixture component is further characterized as having an oxygen content of less than 15 wt.%, such as an oxygen content of less than 12 wt.%; preferably, the first mixture component is further characterized as having an oxygen content of less than 10 wt.%, such as less than 8 wt.%.

In one embodiment, the first mixture component and/or hydrocarbon material has an oxygen content of less than 5 wt.%, such as less than 3 wt.%.

In one embodiment, the first mixture component is further characterized by a viscosity at 50 ℃ in the range of from 1000cSt to 10000cSt, for example a viscosity at 50 ℃ in the range of from 100cSt to 1000 cSt.

In one embodiment, the hydrocarbon material of the first mixture component is produced from biomass and/or waste material.

In one embodiment, the production of the hydrocarbon material of the first mixture component is performed by a hydrothermal liquefaction process.

In one embodiment, the hydrocarbon material of the first mixture component is 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 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 to 30 minutes;

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

g. expanding (expand) the converted feed mixture to a pressure of 1 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 mixture component comprising high boiling compounds.

In another aspect of the invention, the object is achieved by an intermediate mixture component comprising hydrocarbon material containing hydrocarbons and connecting material to form at least part of the intermediate mixture component, wherein the hydrocarbon material is characterized by having the property (δ) to form a hydrocarbon mixture according to any of the preceding claims_d1,δ_p1,δ_h1)＝(17-20,6-12,7-10), and wherein the connecting substance is characterized by having a property (δ)_d3,δ_p3,δ_h3) (17-20,3-6, 3-6); wherein the hydrocarbon material is present in the intermediate mixture component in a relative amount of 90 to 99.5 wt.%, and wherein the linking material is present in the intermediate mixture component in a relative amount of 0.5 to 10 wt.%.

In one embodiment, the hydrocarbon material is present in the intermediate mixture component in a relative amount of up to 95 wt.% to 99.5 wt.%, and wherein the linking material is present in the intermediate mixture component in a relative amount of up to 0.5 wt.% to 5 wt.%.

In another aspect of the invention, the object of the invention is achieved by a process for producing a hydrocarbon mixture containing renewable components according to any one of the preceding claims, wherein the process comprises the following steps:

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

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

-adding the first mixture component to the second mixture component to form the hydrocarbon mixture.

In one embodiment, the method further comprises the steps of:

-providing a linking substance in a relative amount of 0.5 to 10% by weight of the final hydrocarbon mixture, having a characteristic (δ)_d3,δ_p3,δ_h3)＝(17-20,3-6,3-6)；

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

-adding the second mixture component or the first mixture component to the intermediate mixture component to form the hydrocarbon mixture.

In one embodiment, the first mixture component and/or the second mixture component and/or the intermediate mixture component are heated to a temperature in the range of from 70 ℃ to 150 ℃ prior to forming the hydrocarbon mixture.

In one embodiment, an intermediate mixture component comprising the first mixture component or the second mixture component and a connecting substance is manipulated to form a homogeneous mixture prior to adding the second mixture component and/or the first mixture component to form the hydrocarbon mixture.

In one embodiment, 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 hydrocarbon mixture according to any one of the preceding claims, comprising measuring a property (δ) of a first mixture component comprising a renewable hydrocarbon component_d1,δ_p1,δ_h1) Measuring a property (delta) of a component of the second mixture_d2,δ_p2,δ_h2) Determining the compatibility of the first component and the second component based on the measurement of the property.

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

In one embodiment, the first component and the second component are determined to be incompatible based on the measured property, wherein the first component is selected to have the property ((δ)_d3,δ_p3,δ_h3) And wherein the linking substance is added to the first component or the second 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 for producing oil in 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 shows a schematic of a refinery process with potential feed points (potential drop in points) for the first mixture component and/or the intermediate mixture component.

FIG. 6 is a photograph of solvent grades used in the solubility test;

fig. 7 shows a photograph of the field test used to evaluate solubility: (1) indicating complete dissolution of both solvents and (2) partial dissolution of both solvents.

Fig. 8 shows a 3D plot of hansen solubility parameters for renewable crude oil (oil a) produced in example 1.

Fig. 9a and 9b summarize solvents and solvent mixtures to determine hansen solubility parameters for estimating hansen solubility parameters for renewable crude oil produced in example 1.

Figure 10 summarizes the characteristics of the renewable liquids produced by the hydrothermal liquefaction and upgrading process.

Fig. 11 shows a 3D plot of hansen solubility parameters for renewable crude oils (oil a, oil B, and oil C produced in example 1).

Fig. 12 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. 13a, 13b, and 13c show 3D plots of hansen solubility parameters for fossil crude, VGO, and bitumen versus renewable crude, partially upgraded oil, and upgraded oil, respectively.

Fig. 14 summarizes hansen solubility parameters for different renewable liquids, fossil oils, VGO, and asphalt.

Fig. 15a and 15b show 3D plots of hansen solubility parameters for ultra low sulfur fuel oil and high sulfur fuel oil versus partial upgraded oil, partial upgraded heavy fraction, and upgraded heavy fraction.

Fig. 16 shows an example of a low sulfur fuel blend containing renewable components in accordance with a preferred embodiment of the present invention.

Figure 17 shows field tests and microscope images of the mixture between the partially upgraded heavy fraction (hfpou) and the Marine Gas Oil (MGO) described in example 14.

Figure 18 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) Alcohol and ketone), a crude oil phase, an aqueous phase (which contains 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 mixture 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

Based on MEK free (MEK free bases)

Example 2: providing a first mixture 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), wherein the sulfur saturation level was maintained at 45 bar at a hydrogen flow rate of 24L/hour at 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 mixture 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/hour, 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 temperatureFixed 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

Example 4: refinery process and potential blend points for first blend component and intermediate blend component

Conventional refinery processes involve several hydrotreating steps and separations to ensure high yields of fuel and maximum utilization of petroleum. Figure 5 illustrates a simplified conventional refinery process in which petroleum crude oil is first fractionated by atmospheric distillation into naphtha, jet fuel/kerosene, diesel, atmospheric gas oil and atmospheric tower bottoms. Each of these fractions is passed to further hydroprocessing stages as required to ensure compliance with fuel specifications. It is desirable to utilize existing infrastructure to co-process a first fuel mixture component comprising renewable hydrocarbons and a second mixture component comprising a refinery stream, i.e., to co-process petroleum at an existing refinery.

There are several potential feed points (drop in points) for a refinery. In all cases, the compatibility of the first blend component is critical to ensure smooth operation of the refinery during co-processing, e.g., the blend components should not delaminate when used, stored, and/or diluted with other blends in the same application. It has been shown in the prior art that certain fractions (distillates) of renewable crude oil (in this context hydrocarbon materials) can be co-processed with certain petroleum fractions (second mixture components) at least in relatively small mixing ratios and at acceptable catalyst deactivation rates, e.g., Ying (2019). However, the prior art co-processing methods also typically produce large amounts of residue. The residue typically contains heavy oil components that are difficult to further process into the desired higher value products and therefore constitute a process loss that reduces the overall process efficiency. Such residue in prior art processes may result from mixing a petroleum-derived composition with a renewable crude oil and separating the incompatible portion (i.e., residue), wherein the first mixture component typically comprises the lighter portion of the original first mixture component or as a result of fractionating the renewable crude oil into a lighter fraction and a heavier resid fraction.

For the hydrocarbon mixture according to the invention, the amount of residues is minimized or eliminated, i.e. the overall process efficiency is increased. Thus, due to the large amount of renewable energy, the hydrocarbon mixtures according to the invention typically have a greater amount of high boiling components than conventional petroleum derived products, which can be processed into higher value products with a low carbon footprint.

A particularly noteworthy feed point (drop in point) or mixing point for the inventive intermediate mixture components for the preparation of the inventive hydrocarbon mixtures is the mixing with gas oil and/or vacuum gas oil prior to the hydrotreatment, as further illustrated below by the solubility curve. Further advantages can be obtained by the hydrocarbon mixture according to the invention, such as enhanced processability, e.g. less tendency for reactor plugging, less catalyst deactivation, generally smoother and robust refinery operation, and higher proportions of the first fuel mixture component, due to the improved compatibility of the hydrocarbon mixture according to the invention. All of these are important decision-making factors for refineries to introduce an unconventional first blend component containing renewable components into a refinery.

Example 5: 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 phase solubility" principle, where a distance measure of the hansen solubility parameter measures 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 be determined by the sum of the volume or weight of the respective parameters (equation 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 fig. 9a/9 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. 6 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 evaluate the compatibility of marine fuel blends and has been used, for example, in the analysis of the hansen solubility parameters by Redelius [ p.redelius, "big solubility model using hansen solubility parameter," Energy and Fuels, vol.18, No.4, pp.1087-1092,2004 ]. 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. 7a, the mixture is considered to be completely soluble (i.e., category 1), while if two separate concentric spots are formed as shown in fig. 7b, the solvent is considered to be partially soluble (i.e., category 2).

Example 6: 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. 8) 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. 9a/9 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. 11. However, oil a has a higher polarity and stronger hydrogen bonding interactions than oil B and oil C. Comparing the parameters of the three biocrudes, it 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 9 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 processing conditions as described in example 1.

Example 7: partial upgraded oil and hansen solubility parameter of upgraded oil

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

As shown in FIGS. 9a/9b, a total of 18 solvents were used to determine the partially upgraded renewable oil II (. delta.). 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. 11, 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. 12, 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 values for the partially upgraded oil in the bio-crude solubility sphere range are 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 8: 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. 14 and visualized in fig. 13a, 13b and 13 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 9: 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) and VGO (. delta.))_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. 13a, FIG. 13b, and FIG. 13c 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 Hansen Solubility parameter for asphalt is given by Redelius, "Bitumen Solubility Model using Hansen Solubilityty 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. 12 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 with petroleum or derived heavy fractions in a ratio of 9:1 become soluble and compatible when heated to temperatures of 70 ℃ to 130 ℃, as analyzed by spot tests. Thus, in one advantageous embodiment of the invention, the first mixture component and the second 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 10: 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 4. 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. 15a and 15b 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. 15a and 15b, 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 11: 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

^aThe para-xylene may be substituted with toluene or with 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, and the hansen solubility parameters of the individual solvents and the combined connecting species I are as shown in table 10.

Example 12: synergistic treatment of biocrude and/or partially upgraded renewable and fossil 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 2 wt% of mixed MEK/m-cresol (70: 30) the solubility of the biological crude oil and the asphalt is increased. 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. 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% proportion of partial upgradant.

Example 13: 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. 15a and 15b, 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 14: low sulfur fuel blend including a first fuel blend component containing a renewable component

Based on the solubility profile described in example 13, 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.%.

A first fuel blend component containing different bridging substances in concentrations of up to 10 wt.% is blended with a second fuel component comprising an Ultra Low Sulfur Fuel Oil (ULSFO) having a Hansen solubility parameter (delta) according to ISO8217 for RMG 180 ultra low sulfur fuel oils_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. 16, which is a mixture of 62 vol% of a first fuel component that includes a renewable component (Steeper HF, 350+ ° c boiling fraction).

Example 15: low sulfur mixtures comprising a partially upgraded oil 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. As can be seen from the spot test and the microscopic test in fig. 17, it was also observed in the blend test at a ratio of 50 wt% heavy fraction from partially upgraded renewable oil (hfpouo)/50 wt% Marine Gas Oil (MGO) and 25 wt% hfpouo/75 wt% MGO.

Example 16: 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. 18, 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 15).