Paraffin-based compositions for renewable jet fuels and high yield production of renewable paraffin bases

Abstract

The invention relates to a paraffin-based composition comprising at least 90% by weight of paraffin, relative to the total weight of the paraffin-based composition, in which:-the weight ratio between the weight content of Cx isoparaffin and the weight content of C (x-1) normal paraffin is greater than or equal to 2.0, x is an integer selected from 14, 15, 16 and 17, and-the weight content of C (x-1) normal paraffin, relative to the total weight of the paraffin-based composition, is at least 90% by weight of paraffin, relative to the total weight of the paraffin-based composition. The weight content of C14 normal paraffin is greater than or equal to 1.0%. The invention also relates to a method for preparing such a paraffin-based composition.

Description

Technical Field

[0001] This invention relates to the field of refining biologically derived raw materials, particularly for the manufacture of paraffin-based materials, especially for jet engines. More specifically, this invention relates to a novel method for obtaining biological (or renewable) paraffin-based materials in improved yields. Background Technology

[0002] Conventional aviation fuels of the jet fuel type (also known as "jet fuel" or "kerosene") are produced from crude oil and typically contain a complex mixture of hydrocarbons with 6 to 18 carbon atoms. These hydrocarbons include straight-chain and branched alkanes, cycloalkanes, and aromatics. Jet fuel fractions typically have cut points between 140°C and 240°C, and final boiling points of up to 300°C.

[0003] Due to the scarcity of fossil resources and increasingly important environmental issues, there is a growing search for using bio-derived molecules to replace fossil-derived molecules. However, the preparation of jet fuel from bio-derived molecules that can be directly used in jet fuel formulations presents significant economic and environmental challenges. Existing technology

[0004] Aviation fuels derived from bio- or renewable feedstocks can be produced in part by hydrotreating esters and fatty acids from oils and / or fats. Typically, bio-based feedstocks (usually oils and / or fats) are hydrodeoxygenated, then isomerized, and subsequently fractionated to obtain a kerosene fraction that meets jet fuel specifications, particularly its cryogenic properties. This fraction corresponds to the light fraction of the hydrodeoxygenation / isomerization product to remove long-chain paraffins, especially nC17-nC18 compounds known to reduce the cryogenic properties of jet fuels. However, the yield in the kerosene fraction can be relatively low, and accounts for 40% by weight or less of the hydrotreated and isomerized bio-based effluent, especially when the latter has a relatively high cloud point (particularly -35°C to 0°C). In other words, the higher the cloud point of the hydrotreated and isomerized bio-based feedstock (the lower the isomerization rate of the feedstock), the lower the yield of the kerosene fraction obtained from that feedstock. However, it is not always possible to reduce the n / i ratio and thus increase jet fuel yield by changing isomerization conditions, especially when it is desirable to use conventional, cheaper catalysts that result in less isomerization feedstock formation.

[0005] Therefore, a method is needed to solve the above problems. In particular, a method is needed to obtain paraffin-based compositions in high yield from bio-based effluents with high cloud points (especially -35°C to 0°C).

[0006] There is also a need for a paraffin-based composition derived from bio-based effluents with high turbidity points (particularly -35°C to 0°C), which is particularly suitable for blending with fossil-derived jet fuels. Summary of the Invention

[0007] This invention provides a paraffin-based composition comprising, by weight, at least 90% paraffin, preferably at least 90% C7-C18 paraffin, relative to the total weight of the paraffin-based composition, wherein:

[0008] - The weight ratio between the weight content of Cx isoparaffin and the weight content of C(x-1) normal paraffin is greater than or equal to 2.0, where x is an integer selected from 14, 15, 16, and 17.

[0009] - The weight content of C14 orthoparaffin is greater than or equal to 1.0% relative to the total weight of the paraffin-based composition.

[0010] The paraffin-based composition according to the invention can be equivalently defined as comprising at least 90% by weight of paraffin relative to the total weight of the paraffin-based composition, and having a weight ratio R (i-Cx / n-C(x-1)) The set (Ens) where x is 14 to 17, each R (i-Cx / n-C(x-1)) The weight ratio between the weight content of Cx isomer paraffin and the weight content of C(x-1) normal paraffin, wherein:

[0011] - The ratio R of the set (Ens) (i-Cx / n-C(x-1)) At least one of them is greater than or equal to 2.0, and

[0012] - The weight content of C14 orthoparaffin is greater than or equal to 1.0% relative to the total weight of the paraffin-based composition.

[0013] The inventors discovered that the freezing point of the above composition is less than or equal to -40°C, thus meeting the specifications, particularly those defined by standard D7566-21, while the density is greater than or equal to 755 kg / m³. 3 Achieving this density is not obvious, as it typically implies the presence of numerous long chains (usually containing at least 15 carbon atoms), which in principle means a freezing point above -40°C, thus falling outside this specification. However, renewable paraffinic materials are commonly blended with fossil-derived jet fuels, but with a lower density. Therefore, the incorporation rate of renewable paraffinic materials into fossil jet fuels is limited by the density of the resulting blend, which necessarily decreases as the proportion of renewable paraffinic materials increases. Thus, it is possible to obtain a freezing point that meets specifications but with a higher density (typically greater than or equal to 755 kg / m³) than those in the prior art. 3 The renewable paraffin base makes it possible to incorporate a larger proportion of this renewable paraffin base into fossil jet fuels in the form of blends.

[0014] The present invention also relates to a jet fuel composition comprising the paraffin-based composition as described above, optionally blended with a fossil-derived jet fuel.

[0015] The present invention also relates to a method for producing a paraffin-based composition, comprising at least the following steps:

[0016] a) Provides a biologically derived hydrocarbon effluent containing at least 95% by weight paraffin, preferably at least 95% by weight C7-C24 paraffin, wherein:

[0017] - The weight ratio between the weight content of Cx isoparaffin and the weight content of C(x-1) normal paraffin is greater than or equal to 2.0, where x is an integer selected from 14, 15, 16, 17, and 18.

[0018] - The weight content of C14 n-paraffin is greater than or equal to 1.0% relative to the total weight of the hydrocarbon effluent, and

[0019] b) Fractionate the bio-derived hydrocarbon effluent provided in step a) to obtain a paraffinic base.

[0020] The method for producing the paraffin-based composition according to the present invention can be equivalently defined as including at least the following steps:

[0021] a) Provides a biologically derived hydrocarbon effluent containing at least 95% by weight paraffin, preferably at least 95% by weight C7-C24 paraffin, having a weight ratio R' (i-Cx / n-C(x-1)) The set (Ens2), where x is 14 to 18, each R' (i-Cx / n-C(x-1)) The weight ratio between the weight content of Cx isoparaffin and the weight content of C(x-1) normal paraffin in the hydrocarbon effluent, wherein:

[0022] - R' of set (Ens2) (i-Cx / n-C(x-1)) At least one of them is greater than or equal to 2.0, and

[0023] - The weight content of C14 n-paraffin is greater than or equal to 1.0% relative to the total weight of the hydrocarbon effluent, and

[0024] b) Fractionate the bio-derived hydrocarbon effluent provided in step a) to obtain a paraffinic base.

[0025] The method according to the invention advantageously allows for an increase in the yield of aviation fuel obtained from bio-based effluents, particularly the yield of aviation fuel produced by the hydrotreating and isomerization of bio-based feedstocks. Surprisingly, the yield can be increased by at least 10% by weight, preferably at least 15% by weight, without reducing the cryogenic properties of the jet fuel, while simultaneously increasing its density, without altering the isomerization conditions of the bio-based feedstock. Therefore, the yield of paraffinic components in bio-based hydrocarbon effluents can be increased regardless of the manufacturing conditions, particularly even when they have high cloud points (especially -35°C to 0°C). Detailed Implementation

[0026] As used herein, the terms “comprising” and “comprises” are synonymous with “including”, “includes”, “contains”, and “containing”, and are inclusive or open-ended, and do not exclude additional features, elements, or method steps not specified.

[0027] Unless otherwise stated, weight content throughout the specification is expressed relative to the total weight of the paraffin-based composition or the total weight of the hydrocarbon effluent.

[0028] The terms mass% and weight% have equivalent meanings and refer to the ratio of the weight of the product to 100g of the composition containing it.

[0029] As used herein, “carbon number” or “Cx” (where “x” is an integer) describes a hydrocarbon or molecule, where “x” represents the number of carbon atoms, regardless of whether it is linear or branched. A carbon number range (e.g., C6 to C18 or C19+) refers to a molecule having a number of carbons within the indicated range (6 to 18 carbon atoms or 19 carbon atoms or more), including the extreme members of that range. However, not every carbon number within the range must be present in the molecule described.

[0030] "Cx normal paraffin" refers to a straight-chain paraffin containing x carbon atoms and is equivalent to "n-Cx".

[0031] "Cx isomeric paraffin" refers to branched paraffin containing x carbon atoms and is equivalent to "i-Cx".

[0032] The carbon number distribution was determined by true boiling point distribution and gas chromatography. As used in this specification, the total amount of normal and isoparaffins at a given carbon number was determined by gas chromatography (“GC”) or equivalent gas chromatography using ASTM D-5442 analysis of petroleum waxes. For example, this can be done as described in the following publication: Marko R. Djokic et al., Quantitative analysis of crude and stabilized bio-oils by comprehensive two-dimensional gas chromatography (Journal of Chromatography A, 1257 (2012) pp131-140).

[0033] The compounds or paraffins (or optionally isoparaffins or n-paraffins) of the compositions of the present invention, or biologically derived hydrocarbon effluents, or specific fractions (e.g., C12-C18 fractions) of the compositions of the present invention or biologically derived hydrocarbon effluents, having an average carbon number of C12-C18, are described. moy The average carbon number of the compound set corresponding to the composition of the present invention or biologically derived hydrocarbon effluent, or biologically derived hydrocarbon effluent, or the composition of the present invention or biologically derived hydrocarbon effluent, or paraffin (or optionally isomer or n-paraffin). This average value can be calculated according to the following formula:

[0034] [Mathematical Expression 1]

[0035]

[0036] i is an integer.

[0037] i min The carbon number of the compound or paraffin (or optionally isoparaffin or normal paraffin) having the lowest carbon number among the compositions according to the invention, or biologically derived hydrocarbon effluents, or a specific fraction of the compositions according to the invention or biologically derived hydrocarbon effluents, is the carbon number of the compound or paraffin (or optionally isoparaffin or normal paraffin) having the lowest carbon number among the compositions according to the invention, or biologically derived hydrocarbon effluents, or a specific fraction of the compositions according to the invention or biologically derived hydrocarbon effluents.

[0038] i maxThe carbon number of the compound or paraffin (or optionally isoparaffin or n-paraffin) having the highest carbon number in a specific fraction of a composition, biological hydrocarbon effluent, or composition or biological hydrocarbon effluent according to the invention, and...

[0039] x i It is the weight fraction of a group of compounds or paraffins (or optionally isomers or normal paraffins) having a carbon number equal to i, which are compounds of the present invention, or of a specific fraction of a biological hydrocarbon effluent, or of the present invention or of a biological hydrocarbon effluent.

[0040] In particular, when determining a specific C of the composition of the present invention or a bio-derived hydrocarbon effluent... x -C y When the average carbon number of the fraction's compounds or paraffins, or optionally isomers or normal paraffins, i min =x and i max =y. For example, if the fraction under consideration is C12-C18, then i min =12 and i max =18.

[0041] The contents of aromatic compounds and cycloalkanes can be determined by gas chromatography (GC×GC reversed phase).

[0042] Unless otherwise stated, the boiling points described herein are measured at atmospheric pressure. The initial boiling point is defined as the temperature at which the first vapor bubble forms. The final boiling point is the highest temperature achievable during distillation. At this temperature, no more vapor can be carried to the condenser. The determination of the initial and final boiling points uses techniques known to those skilled in the art, and various methods adapted to the distillation temperature range are applicable, such as NF EN 15199-1 (2020 edition) or ASTM D2887-19 for determining the boiling points of petroleum fractions by gas chromatography, ASTM D7169-05 for heavy hydrocarbons, and ASTM D7500-15 (2019), D86-12, or D1160-18 for distillate oils.

[0043] The freezing point of injectable fuel hydrocarbons can be measured according to the standard ASTM D2386-19 / D7153-15e1 / D5972-16 / IP435(2016).

[0044] The density of injectable fuel hydrocarbons can be measured according to standard ASTM D4052-18.

[0045] The turbidity point of biologically derived hydrocarbon effluents can be measured according to standard ASTM D2500-17a.

[0046] Paraffin-based compositions according to the present invention

[0047] According to the paraffin-based composition of the present invention, the weight ratio between the weight content of Cx isoparaffin and the weight content of C(x-1) normal paraffin is greater than or equal to 2.0, where x is an integer selected from 14, 15, 16 and 17, preferably selected from 14, 15 and 16.

[0048] Preferably, the weight ratio between the weight content of Cx isoparaffin and the weight content of C(x-1) normal paraffin is greater than or equal to 2.5, more preferably greater than or equal to 3.0, more preferably greater than or equal to 5.0, more preferably greater than or equal to 6.0, more preferably greater than or equal to 7.0, more preferably greater than or equal to 8.0, and more preferably 2.0 to 20, where x is an integer selected from 14, 15, 16 and 17, more preferably selected from 14, 15 and 16.

[0049] In other words (equivalent to the definition above), the paraffin-based composition has a weight ratio R (i-Cx / n-C(x-1)) The set (Ens), where x is 14 to 17, preferably x is 14 to 16, each R (i-Cx / n-C(x-1)) It is the weight ratio between the weight content of Cx isomer paraffin and the weight content of C(x-1) normal paraffin, and the ratio R of this set (Ens) (i-Cx / n-C(x-1)) At least one of them is greater than or equal to 2.0, preferably greater than or equal to 2.5, preferably greater than or equal to 3.0, preferably greater than or equal to 4.0, preferably greater than or equal to 5.0, preferably greater than or equal to 6.0, preferably greater than or equal to 7.0, preferably greater than or equal to 8.0, and more preferably 2.0 to 20.

[0050] Preferably, the ratio R of the set (Ens) as defined above (i-Cx / n-C(x-1)) At least two of them are greater than or equal to 2.0, preferably greater than or equal to 2.5, preferably greater than or equal to 3.0, preferably greater than or equal to 4.0, preferably greater than or equal to 5.0, preferably greater than or equal to 6.0, preferably greater than or equal to 7.0, preferably greater than or equal to 8.0, and more preferably 2.0 to 20.

[0051] Preferably, the ratio R of the set (Ens) as defined above (i-Cx / n-C(x-1)) At least three (or three) of them are greater than or equal to 2.0, preferably greater than or equal to 2.5, preferably greater than or equal to 3.0, preferably greater than or equal to 4.0, preferably greater than or equal to 5.0, preferably greater than or equal to 6.0, preferably greater than or equal to 7.0, preferably greater than or equal to 8.0, and most preferably 2.0 to 20.

[0052] The ratio R of the set (Ens)(i-Cx / n-C(x-1)) The higher the number, greater than or equal to 2.0 (or 2.5 or 3.0, or 4.0, or 5.0, or 6.0, or 7.0 or 8.0, or 2.0 to 20), the lower the freezing point and the higher the density of the composition according to the invention.

[0053] Preferably, in the paraffin-based composition:

[0054] - The weight ratio between the weight content of C15 isoparaffin and the weight content of C14 normal paraffin is greater than or equal to 2.0, preferably greater than or equal to 2.5, preferably greater than or equal to 3.0, preferably greater than or equal to 4.0, preferably greater than or equal to 5.0, preferably greater than or equal to 6.0, and more preferably from 2.0 to 20, and / or

[0055] - The weight ratio between the weight content of C16 isoparaffin and the weight content of C15 normal paraffin is greater than or equal to 2.0, preferably greater than or equal to 2.5, preferably greater than or equal to 3.0, preferably greater than or equal to 4.0, preferably greater than or equal to 5.0, preferably greater than or equal to 6.0, preferably greater than or equal to 7.0, preferably greater than or equal to 8.0, and more preferably 2.0 to 20, and / or

[0056] - The weight ratio between the weight content of C14 isoparaffin and the weight content of C13 normal paraffin is greater than or equal to 2.0, preferably greater than or equal to 2.5, preferably greater than or equal to 3.0, preferably greater than or equal to 4.0, preferably greater than or equal to 5.0, preferably greater than or equal to 6.0, preferably greater than or equal to 7.0, and more preferably 2.0 to 20.

[0057] The paraffinic composition contains, relative to the total weight of the paraffinic composition, a C14 n-paraffin content of greater than or equal to 1.0% by weight. Preferably, the C14 n-paraffin content of the paraffinic composition, as defined relative to the total weight of the paraffinic composition, is greater than or equal to 1.1% by weight, preferably greater than or equal to 1.5% by weight, preferably greater than or equal to 2.0% by weight, preferably greater than or equal to 2.5% by weight, preferably greater than or equal to 3.0% by weight, and more preferably from 1.0% by weight to 10.0% by weight.

[0058] Preferably, the paraffin-based composition has a C14 paraffin content (i.e., all C14 ortho-paraffins and C14 iso-paraffins) of 7.0% or more by weight relative to the total weight of the paraffin-based composition, preferably 8.0% or more by weight, preferably 8.5% or more by weight, preferably 10.0% or more by weight, preferably 12.0% or more by weight, preferably 15.0% or more by weight, and more preferably from 7.0% to 25.0% by weight.

[0059] Preferably, the weight content of C7-C13 compounds in the paraffinic composition is less than or equal to 60% by weight, preferably less than or equal to 50% by weight, preferably less than or equal to 45% by weight, and more preferably from 20% to 60% by weight, relative to the total weight of the paraffinic composition.

[0060] Preferably, the paraffin-based composition may have one or more of the following characteristics:

[0061] - The weight ratio of normal paraffin to isoparaffin is greater than or equal to 0.140, preferably greater than or equal to 0.145, preferably greater than or equal to 0.150, preferably greater than or equal to 0.155, preferably greater than or equal to 0.160, preferably greater than or equal to 0.165, and most preferably from 0.140 to 0.50, and / or

[0062] - The weight ratio of C14-C18 ortho-paraffin to C14-C18 iso-paraffin is greater than or equal to 0.105, preferably greater than or equal to 0.110, preferably greater than or equal to 0.115, preferably greater than or equal to 0.120, preferably greater than or equal to 0.125, preferably greater than or equal to 0.130, and most preferably from 0.105 to 0.50, and / or

[0063] - The average carbon number of the C14-C18 fraction of paraffin contained in the paraffin-based composition is less than or equal to 16.0, preferably less than or equal to 15.8, preferably less than or equal to 15.5, preferably less than or equal to 15.2, preferably less than or equal to 15.0, and preferably from 12.0 to 16.0.

[0064] Preferably, relative to the total weight of the paraffinic composition, the paraffinic composition may contain C8-C16 paraffin at a weight content of greater than or equal to 95% by weight, preferably greater than or equal to 97% by weight, preferably greater than or equal to 98% by weight, preferably greater than or equal to 99% by weight, and preferably from 95% to 99.99% by weight.

[0065] Preferably, relative to the total weight of the paraffinic composition, the paraffinic composition may contain less than or equal to 5% by weight of C17-C18 paraffin, preferably less than or equal to 2% by weight, preferably less than or equal to 1% by weight, preferably less than or equal to 0.5% by weight, and more preferably from 0.001% by weight to 5% by weight.

[0066] Paraffin-based compositions may have one or more of the following characteristics:

[0067] - Density greater than or equal to 730 kg / m³ 3 Preferably greater than or equal to 740 kg / m 3 Preferably greater than or equal to 750 kg / m 3The preferred value is 750 kg / m³. 3 Up to 770kg / m 3 , and / or

[0068] - Freezing point less than or equal to -40°C, preferably less than or equal to -41°C, more preferably less than or equal to -42°C, more preferably -42°C to -40°C, and / or

[0069] - The final boiling point is less than or equal to 300°C, preferably less than or equal to 290°C, and more preferably between 250°C and 290°C.

[0070] The paraffin-based composition may also have one or more of the following characteristics:

[0071] - The weight content of ortho-C16 is less than or equal to 2% by weight, preferably less than or equal to 1.5% by weight, and more preferably from 0.001% by weight to 2% by weight, and / or

[0072] - The weight content of isomeric C16 is greater than or equal to 10% by weight, preferably greater than or equal to 15% by weight, and more preferably from 10% to 30% by weight, and / or

[0073] - The weight ratio between the weight content of isomeric C16 and the weight content of normal C16 is greater than or equal to 3, preferably greater than or equal to 4, preferably greater than or equal to 5, preferably greater than or equal to 10, preferably greater than or equal to 15, and / or

[0074] - The content of normal C17 and normal C18 is zero (or not detected, or less than 0.01 wt%).

[0075] Typically, paraffin-based compositions may have one or more of the following characteristics:

[0076] - The initial point measured according to standard D86-12 is 130°C to 170°C, and / or

[0077] - The final cut point, measured according to standard D86-12, is 250°C to 300°C.

[0078] Method for preparing paraffin-based compositions according to the present invention

[0079] The present invention also relates to a method for producing a paraffin-based composition, comprising at least the following steps:

[0080] a) Provides a biologically derived hydrocarbon effluent containing at least 95% by weight paraffin, preferably at least 95% by weight C7-C24 paraffin, wherein:

[0081] - The weight ratio between the weight content of Cx isoparaffin and the weight content of C(x-1) normal paraffin is greater than or equal to 2.0, where x is an integer selected from 14, 15, 16, 17, and 18.

[0082] - The weight content of C14 n-paraffin is greater than or equal to 1.0% relative to the total weight of the hydrocarbon effluent, and

[0083] b) Fractionate the bio-derived hydrocarbon effluent provided in step a) to obtain a paraffinic base.

[0084] Preferably, this method enables the preparation of paraffin-based compositions as defined in the preceding sections.

[0085] Biological hydrocarbon effluent

[0086] The biologically derived hydrocarbon effluents used in this invention contain absolutely no fossil-derived components.

[0087] It contains at least 95% by weight of paraffin relative to the total weight of the biologically derived hydrocarbon effluent, and the weight ratio between the weight content of Cx isoparaffin and the weight content of C(x-1) n-paraffin is greater than or equal to 2.0, where x is an integer selected from 14, 15, 16, 17 and 18, and the weight content of C14 n-paraffin is greater than or equal to 1.0% relative to the total weight of the hydrocarbon effluent.

[0088] The invention is particularly advantageous when the weight ratio between the weight content of Cx isoparaffin and the weight content of C(x-1) normal paraffin in the hydrocarbon effluent is greater than or equal to 2.0, where x is an integer selected from 14, 15, 16, 17 and 18, as defined above, because this allows for a significant increase in the paraffin-based yield obtained from the hydrocarbon effluent.

[0089] Preferably, the hydrocarbon effluent has a weight ratio between the weight content of Cx isoparaffin and the weight content of C(x-1) normal paraffin, which is greater than or equal to 2.5, preferably greater than or equal to 3.0, preferably greater than or equal to 5.0, preferably greater than or equal to 6.0, preferably greater than or equal to 7.0, preferably greater than or equal to 8.0, and more preferably from 2.0 to 20, where x is an integer selected from 14, 15, 16, 17 and 18, preferably from 14, 15, 16 and 18, and more preferably from 14, 15 and 16.

[0090] In other words (equivalent to the definition above), the hydrocarbon effluent has a weight ratio R' (i-Cx / n-C(x-1)) The set (Ens2), where x is 14 to 18, preferably x is 14 to 16, each R' (i-Cx / n-C(x-1)) It is the weight ratio between the Cx isoparaffin content and the C(x-1) normal paraffin content in the hydrocarbon effluent, and the ratio R' of the aggregate (Ens2).(i-Cx / n-C(x-1)) At least one of them is greater than or equal to 2.0, preferably greater than or equal to 2.5, preferably greater than or equal to 3.0, preferably greater than or equal to 5.0, preferably greater than or equal to 6.0, preferably greater than or equal to 7.0, preferably greater than or equal to 8.0, and more preferably 2.0 to 20.

[0091] Preferably, the ratio R' of the set (Ens2) as defined above (i-Cx / n-C(x-1)) At least two of them are greater than or equal to 2.0, preferably greater than or equal to 2.5, preferably greater than or equal to 3.0, preferably greater than or equal to 4.0, preferably greater than or equal to 5.0, preferably greater than or equal to 6.0, preferably greater than or equal to 7.0, preferably greater than or equal to 8.0, and more preferably 2.0 to 20.

[0092] Preferably, the ratio R' of the set (Ens2) as defined above (i-Cx / n-C(x-1)) At least three (or three) of them are greater than or equal to 2.0, preferably greater than or equal to 2.5, preferably greater than or equal to 3.0, preferably greater than or equal to 4.0, preferably greater than or equal to 5.0, preferably greater than or equal to 6.0, preferably greater than or equal to 7.0, preferably greater than or equal to 8.0, and most preferably 2.0 to 20.

[0093] Preferably, in the hydrocarbon effluent:

[0094] - The weight ratio between the weight content of C15 isoparaffin and the weight content of C14 normal paraffin is greater than or equal to 2.0, preferably greater than or equal to 2.5, preferably greater than or equal to 3.0, preferably greater than or equal to 4.0, preferably greater than or equal to 5.0, preferably greater than or equal to 6.0, and more preferably from 2.0 to 20, and / or

[0095] - The weight ratio between the weight content of C16 isoparaffin and the weight content of C15 normal paraffin is greater than or equal to 2.0, preferably greater than or equal to 2.5, preferably greater than or equal to 3.0, preferably greater than or equal to 4.0, preferably greater than or equal to 5.0, preferably greater than or equal to 6.0, preferably greater than or equal to 7.0, preferably greater than or equal to 8.0, and more preferably 2.0 to 20, and / or

[0096] - The weight ratio between the weight content of C14 isoparaffin and the weight content of C13 normal paraffin is greater than or equal to 2.0, preferably greater than or equal to 2.5, preferably greater than or equal to 3.0, preferably greater than or equal to 4.0, preferably greater than or equal to 5.0, preferably greater than or equal to 6.0, preferably greater than or equal to 7.0, and more preferably 2.0 to 20.

[0097] The hydrocarbon effluent also contains a C14 n-paraffin content of 1.0% or more by weight relative to the total weight of the hydrocarbon effluent. Preferably, the C14 n-paraffin content of the hydrocarbon effluent, as defined by the total weight of the hydrocarbon effluent, is 1.1% or more by weight, preferably 1.2% or more by weight, preferably 1.3% or more by weight, preferably 1.4% or more by weight, and more preferably from 1.0% to 3% by weight.

[0098] Preferably, in the hydrocarbon effluent, the weight content of C7-C13 compounds is less than or equal to 25% by weight, more preferably less than or equal to 22% by weight, more preferably less than or equal to 21% by weight, and more preferably 10% to 25% by weight, relative to the total weight of the hydrocarbon effluent.

[0099] Relative to the total weight of the hydrocarbon effluent, the hydrocarbon effluent may also have:

[0100] - The weight content of isoparaffin is 50% to 95% by weight, preferably 60% to 90% by weight, preferably 70% to 85% by weight, and / or

[0101] - The weight content of orthoparaffin is 5% to 50% by weight, preferably 10% to 40% by weight, and more preferably 15% to 30% by weight.

[0102] Hydrocarbon effluents may also have the following characteristics:

[0103] - The content of cycloalkanes is less than 5% by weight, preferably less than 3% by weight, typically from 0.1% to 4% by weight, or even from 0.1% to 3% by weight, and / or

[0104] - The content of aromatic compounds is less than 5% by weight, preferably less than 3% by weight, typically from 0.1% to 4% by weight, or even from 0.1% to 3% by weight.

[0105] Advantageously, the biogenic hydrocarbon effluent comprises or consists of the following: normal paraffin, isoparaffin, optional cycloalkanes and aromatic compounds, in particular the amounts presented above, and optional impurities, in amounts of up to 0.2% by weight, preferably up to 0.1% by weight, the sum of which equals 100% by weight.

[0106] Preferably, the hydrocarbon effluent has the following characteristics:

[0107] - The content of paraffin wax of C8 to C24, preferably C8 to C20, is 95% to 100% by weight, preferably at least 97% by weight, preferably at least 98% by weight, preferably at least 99% by weight, and / or

[0108] - The weight ratio between the weight content of isoparaffin and the weight content of normal paraffin is 1.0 to 8.0, preferably 2.0 to 6.0, more preferably 3.0 to 5.0, and more preferably 3.5 to 4.5.

[0109] Biologically derived hydrocarbon effluents, particularly containing the aforementioned amounts of n-paraffins, isoparaffins, and optionally cycloalkanes and aromatic compounds, or even impurities, may have at least one of the following physical properties:

[0110] - The initial distillation point, measured according to standard D86-12, is 130°C to 160°C, preferably 140°C to 150°C, and / or

[0111] - The final boiling point, measured according to standard D86-12, is 280°C to 380°C, preferably 280°C to 320°C, and / or

[0112] - The cloud point, as measured according to standard ASTM D2500-17a, is at most 0°C, for example -35°C to 0°C, preferably -25°C to 0°C, and more preferably -20°C to 0°C.

[0113] Step a) Provide bio-derived hydrocarbon effluent

[0114] Biological hydrocarbon effluents are advantageously produced by the hydrogenation of esters and fatty acids.

[0115] Step a) may therefore include the following steps:

[0116] a1) Provides oils or mixtures of oils of natural origin containing fatty acids and fatty acid esters.

[0117] a2) Hydrogenate the naturally sourced oil or mixture of naturally sourced oils provided in step a1) to obtain a bio-based hydrocarbon effluent as defined above.

[0118] Naturally sourced oils are defined as oils derived from biomass and free of fossil-derived mineral oils. In the product description, "naturally sourced oils" refers to any oil, fat, or mixture thereof.

[0119] Vegetable oils may be selected from pine oil, rapeseed oil, sunflower seed oil, castor oil, peanut oil, flaxseed oil, babassu oil, hemp oil, linola oil, jatropha oil, peanut oil, rice bran oil, mustard oil, carinata oil, coconut oil, coconut meat oil, olive oil, palm oil, cottonseed oil, corn oil, palm kernel oil, soybean oil, pumpkin seed oil, grapeseed oil, argan oil, jojoba oil, sesame oil, walnut oil, hazelnut oil, tung oil, rice bran oil, safflower oil, seaweed oil, used oils, nut shell oils (especially cashew shell oil), and any combination thereof.

[0120] Used oils include used cooking oils (used food oils) and oils recovered from wastewater, such as intercepted and discharged fats / oils, drain oil, sewer oil (e.g. from wastewater treatment plants), and used fats from the food industry.

[0121] Animal fats can be selected from beef tallow, lard, fats (yellow and brown fats), fish oil / fat, and milk fat.

[0122] In particular, animal fats and used cooking oils may be used that are animal by-products and that meet the requirements of European Parliament and Council Regulation 1069 / 2009 of 21 October 2009 and Commission Regulation 142 / 2011 (EU) (the implementing rules of EC Regulation 1069 / 2009).

[0123] Animal fat is an animal byproduct, which is the fat residue of animals other than the cooking oils used in food, such as those from the food industry or from animal byproduct processing facilities.

[0124] The cooking oil used is an animal by-product, specifically used food cooking oil (used cooking oil or UCO), which is the residue of plant or animal-derived fats used in agricultural industries, collective or commercial catering for human food.

[0125] Naturally derived oils can also be produced by natural or genetically modified microorganisms, such as bacteria, yeasts (especially oleophobic yeasts), algae, prokaryotes, or eukaryotes. In particular, these oils can be recovered using well-known mechanical or chemical extraction methods.

[0126] In a preferred embodiment, the naturally sourced oil may be selected from animal fats and / or used oils, particularly from animal fats and / or used oils in a waste state.

[0127] Naturally derived oils may contain 50% by weight or more fatty acid esters (monoglycerides, diglycerides, triglycerides of fatty acids) and / or free fatty acids, preferably 60% by weight or more, and most preferably 70% by weight or more. Typically, naturally derived oils or mixtures of naturally derived oils may contain fatty acid esters and free fatty acids, which contain one to three saturated or unsaturated C8-C24 acyl groups. When multiple acyl groups are present, they may be the same or different.

[0128] Then the naturally sourced oil or mixture of naturally sourced oils provided in step a1) is subjected to hydrogenation treatment a2) to obtain a bio-derived hydrocarbon effluent.

[0129] This hydrotreating step can be carried out in one or more hydrotreating reactors. Any type of reactor commonly used for this type of reaction can be used, such as a fixed-bed reactor, stirred tank reactor, fluidized bed reactor, slurry reactor, etc., with a fixed-bed reactor being preferred.

[0130] Hydrotreating can be carried out in the presence of hydrogen at temperatures ranging from 100°C to 550°C and pressures ranging from 0.01 MPa to 10 MPa. The ratio of hydrogen to feed can be from 100 to 2,000 Nl / l.

[0131] The hydrogenation process can carry out one or more reactions selected from hydrodeoxygenation, decarboxylation, and decarbonylation.

[0132] Hydrodeoxygenation is preferably carried out in a continuous fixed-bed reactor, a continuous stirred tank reactor, or a slurry reactor containing a solid catalyst. The solid catalyst may be selected from oxides or sulfides of Ni, Mo, W, and Co, or mixtures such as NiW, NiMo, CoMo, NiCoW, NiCoMo, NiMoW, and CoMoW as the catalytic phase, preferably supported on carbon, alumina, silica, zeolite, titanium dioxide, or zirconium oxide, or mixtures thereof.

[0133] Hydrodeoxygenation can be carried out at a temperature of 200°C to 500°C, preferably 220°C to 400°C, at a pressure of 1 MPa to 10 MPa (10 to 100 bar), for example 6 MPa, with a hydrogen / oil ratio of 100 to 2,000, but preferably 350 to 1,500, for example 800 Nl of H2 / l oil.

[0134] Decarboxylation and / or decarbonylation are preferably carried out in the presence of a solid catalyst in a batch reactor, a continuous fixed-bed reactor, a continuous stirred-tank reactor, or a slurry reactor. Decarboxylation and / or decarbonylation can be carried out directly with glycerides, any esters, or with free fatty acids.

[0135] The catalyst can be selected from:

[0136] - Oxides or sulfides of Ni, Mo, W, Co, NiW, NiMo, CoMo, NiCoW, NiCoMo, NiMoW and CoMoW are used as the catalyst phase, preferably supported on carbon, alumina, silica, titanium dioxide, zirconium oxide, zeolite or a mixture thereof.

[0137] - A mixture of Group 10 (Ni, Pt, and Pd) and Group 11 (Cu and Ag) metals or alloys supported on carbon, magnesium oxide, zinc oxide, spinel (Mg2Al2O4, ZnAl2O4), perovskite (BaTiO3, ZnTiO3), calcium silicate (such as calcite), alumina, silicon dioxide, or a mixture of silicon dioxide and alumina, or the latter.

[0138] - Basic oxides, such as alkali metal oxides, alkaline earth metal oxides, lanthanide oxides, zinc oxide, spinel (Mg2Al2O4, ZnAl2O4), perovskite (BaTiO3, ZnTiO3), and calcium silicate (such as diaspore), can be in bulk or dispersed on neutral or basic supports, on basic zeolites (such as alkali metal or alkaline earth metal zeolites with low silica / alumina content obtained by exchange or impregnation).

[0139] To achieve optimal performance and stable continuous operation, the active metal component of the catalyst (preferably in the case of Ni, Mo, W, Co, or a mixture thereof) is preferably in the form of a sulfide. Therefore, it is preferable that trace amounts of decomposable sulfur compounds (thermally or catalytically) are present or intentionally added to the feedstock to maintain the metal sulfide in its sulfide state. For example, these sulfur compounds can be H₂S, COS, CS₂, thiols (e.g., methyl sulfide), thioethers (e.g., dimethyl sulfide), disulfides (e.g., dimethyl disulfide), thiophene, and tetrahydrothiophene compounds.

[0140] Decarboxylation and / or decarbonylation occur in the presence of hydrogen, which stabilizes catalytic activity by removing strongly adsorbed unsaturated substances from the catalyst surface via hydroaddition reactions (e.g., when decarbonylation is the dominant reaction pathway). The presence of hydrogen can also hydrogenate double bonds present in the acyl moieties of fatty acids to obtain paraffinic reaction products from the decarboxylation process.

[0141] Decarboxylation and / or decarbonylation can be carried out at temperatures from 100°C to 550°C, pressures from 0.01 MPa to 10 MPa, and in the presence of hydrogen. The ratio of hydrogen to feedstock can be from 100 to 2,000 Nl / l.

[0142] Liquid effluents produced by the hydrotreating of oils from natural sources typically contain hydrocarbon fractions consisting essentially of orthoparaffins having about 8 to about 24 carbon atoms.

[0143] After separation, a portion of the hydrocarbon fraction can be recycled to the inlet of the hydrotreating process, particularly upstream of the deoxygenation reaction, to absorb the heat of reaction, dilute remaining impurities, or provide more dissolved forms of hydrogen.

[0144] According to one embodiment, step a2) provides a biologically derived hydrocarbon effluent of the method, and the liquid effluent produced by hydrogenation treatment of a2) corresponds to the biologically derived hydrocarbon effluent.

[0145] If it is desired to improve the low-temperature characteristics of the hydrocarbon fraction, the liquid effluent produced by hydrogenation treatment a2) can be isomerized under isomerization conditions to at least partially isomerize the normal paraffin into the isomerized paraffin.

[0146] Therefore, in another embodiment, the effluent leaving the hydrotreating step a2) is subjected to a wholly or partially isomerization step a3), typically in the presence of an isomerization catalyst and optionally in the presence of hydrogen. In the latter case, this is referred to as hydroisomerization.

[0147] Isomerization catalysts are typically bifunctional catalysts containing acid functional groups and (de)hydrogenation functional groups.

[0148] Acid functional groups are typically provided by amorphous or crystalline supports, which usually have a molecular weight of 100 to 700 μm. 2 A specific surface area of ​​ / g, and having an acidic surface, such as halogenated (especially fluorinated or chlorinated) or phosphorylated or sulfated alumina, amorphous silica-alumina (optionally containing boron), amorphous silica-alumina-titanium dioxide, sulfated zircon, tungsten-containing zircon and zeolite, or mixtures thereof. Suitable support materials include amorphous alumina, amorphous silica-alumina, amorphous silica-borosilicate, amorphous silica-alumina-titanium dioxide, zeolite, or modified zeolite having the following structures: magnesium alkali zeolite, β-zeolite, Y-zeolite, mordenite, and ALPO-31, SAPO-11, SAPO-31, SAPO-37, SAPO-41, SM-3, MgAPSO-31, FU-9, NU-10, NU-23, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM Molecular sieves of -48, ZSM-50, ZSM-57, θ-1, EU-1, EU-13, ISI-1, KZ-2, ISI-4 and KZ-1, MeAPO-11, MeAPO-31, MeAPO-41, MeAPSO-11, MeAPSO-31, MeAPSO-41, MeAPSO-46, ELAPO-11, ELAPO-31, ELAPO-41, ELAPO-11, ELASO-31, and ELASO-41 can be used alone or in combination. The acidity of the support can be measured by methods well known to those skilled in the art. It can be, for example, by temperature-programmed desorption (TPD) with ammonia, by infrared measurement of absorbed molecules (pyridine, CO, etc.), by catalytic cracking testing, or by hydrogenation conversion using model molecules.

[0149] The (de)hydrogenation function is ensured by one or more metals from Group 6 of the periodic table, or by a combination of at least one metal from Group 6 and at least one metal from Groups 8-10.

[0150] Suitable isomerization catalysts therefore typically contain zeolites, alumina, and / or metals selected from Groups 6 and 8-10 of the periodic table, and optionally a support.

[0151] Examples of catalysts with isomerization capabilities include nickel oxide catalysts or nickel and tungsten oxides on acidic supports, such as amorphous silica / alumina, zeolites, magnesium alkali zeolites, phosphorylated alumina, phosphorylated silica / alumina, etc.

[0152] Preferably, the isomerization catalyst contains SAPO-11 or SAPO-41 or ZSM-22 or ZSM-23 or magnesium alkali zeolite and Pt, Pd or Ni and Al2O3 or SiO2. Typical isomerization catalysts are, for example, Pt / SAPO-11 / Al2O3, Pt / ZSM-22 / Al2O3, Pt / ZSM-23 / Al2O3 and Pt / SAPO-11 / SiO2. The catalyst can be used alone or in combination. The presence of hydrogen is particularly preferred to reduce catalyst deactivation. Particularly preferably, the isomerization catalyst can be a noble metal-based bifunctional catalyst, such as Pt-SAPO and / or Pt-ZSM catalysts, and used in combination with hydrogen.

[0153] The isomerization step (a3) ​​can be carried out, for example, at a temperature of 150°C to 500°C, preferably 220°C to 450°C, and a pressure of 1 to 15 MPa, preferably 1 to 9 MPa or 2 to 6 MPa (absolute).

[0154] Airspeed can range from 0.1 to 20 h / h. -1 More preferably 0.2 to 10h -1 More preferably 0.3 to 4 hours -1 The hydrogen-containing gas is introduced simultaneously with the feedstock at a ratio of 75 to 2,500 NL(H2) / L liquid feedstock, more preferably 150 to 1,500, or even more preferably 250 to 1,000 NL(H2) / L liquid feedstock.

[0155] Furthermore, the isomerization step (a3) ​​is preferably a step primarily used for isomerizing the liquid effluent from the hydrotreating process (a2). In other words, although hydrotreating typically results in low isomerization (usually less than 5% by weight), isomerization leads to a significant increase in the content of isomerized paraffins. More specifically, it is preferable to increase the content (by weight) of isomerized paraffins by at least 30 percentage points, more preferably at least 50 percentage points, more preferably at least 60 percentage points, and even more preferably at least 70 percentage points through the isomerization step.

[0156] The isomerization step (a3) ​​can be performed at the end of the hydrotreatment step (a2), for example, by placing the isomerization catalyst bed downstream of the hydrotreatment catalyst bed.

[0157] The effluent produced by the hydrotreating step (a2) or the isomerization step (a3) ​​can be fractionated to separate the liquid fraction and the non-condensable fraction and / or unreacted hydrogen, and then reused.

[0158] In this invention, the diesel fraction from the hydrotreating step (a2) or the isomerization step (a3) ​​is used as a renewable component.

[0159] This diesel fraction typically corresponds to the liquid fraction of hydrotreated or hydrotreated and isomerized effluents.

[0160] Alternatively, step a) includes:

[0161] a1′) provides a first hydrocarbon effluent of biological origin comprising at least 95% by weight paraffin, preferably at least 95% by weight C7-C24 paraffin, and the weight ratio between the weight content of Cx isoparaffin and the weight content of C(x-1) n-paraffin is strictly less than 2.0, where x is an integer selected from 14, 15, 16, 17, and 18, preferably selected from 14, 15, and 16 (or equivalently having a weight ratio R1′). (i-Cx / n-C(x-1)) The set (Ens2-1), where x is 14 to 18, preferably 14 to 16, each R1′ (i-Cx / n-C(x-1)) R1′ is the weight ratio between the weight content of Cx isoparaffin and the weight content of C(x-1) normal paraffin in the first hydrocarbon effluent. (i-Cx / n-C(x-1)) At least one of the components must be strictly less than 2.0%, and the weight content of C14 n-paraffin must be greater than or equal to 1.0% relative to the total weight of the first hydrocarbon effluent.

[0162] a2′) provides a biogenic second hydrocarbon effluent comprising at least 95% by weight paraffin, preferably at least 95% by weight C7-C24 paraffin, and the weight ratio between the weight content of Cx isomer paraffin and the weight content of C(x-1) n-paraffin is strictly greater than 2.0, where x is an integer selected from 14, 15, 16, 17, and 18, preferably selected from 14, 15, and 16 (or equivalently having a weight ratio R2′). (i-Cx / n-C(x-1)) The set (Ens2-2), where x is 14 to 18, preferably 14 to 16, each R2′ (i-Cx / n-C(x-1)) R2′ is the weight ratio between the weight content of Cx isoparaffin and the weight content of C(x-1) normal paraffin in the second hydrocarbon effluent, representing the ratio of the aggregate (Ens2-2). (i-Cx / n-C(x-1)) At least one of the components must be strictly greater than 2.0%, and the weight content of C14 n-paraffin must be greater than or equal to 1.0% relative to the total weight of the second hydrocarbon effluent.

[0163] a3') The first effluent and the second effluent are mixed in a certain proportion to obtain a biogenic hydrocarbon effluent containing at least 95% by weight paraffin, and the weight ratio between the weight content of Cx isoparaffin and the weight content of C(x-1) n-paraffin is greater than or equal to 2.0, preferably greater than or equal to 2.5, where x is an integer selected from 14, 15, 16, 17, and 18, preferably selected from 14, 15, and 16 (or equivalently having a weight ratio R'). (i-Cx / n-C(x-1)) The set (Ens2), where x is 14 to 18, preferably 14 to 16, each R' (i-Cx / n-C(x-1)) R' is the weight ratio between the weight content of Cx isoparaffin and the weight content of C(x-1) normal paraffin in the hydrocarbon effluent, representing the ratio of the aggregate (Ens2). (i-Cx / n-C(x-1)) At least one of the components is greater than or equal to 2.0, preferably greater than or equal to 2.5), and the weight content of C14 n-paraffin is greater than or equal to 1.0% relative to the total weight of the hydrocarbon effluent.

[0164] Preferably, the first and second hydrocarbon effluents of biological origin are produced by hydrotreating a naturally sourced oil, optionally followed by an isomerization step, hydrotreating, isomerization, and the oil as defined above.

[0165] Therefore, step a) may include:

[0166] a1') provides at least one oil from a first natural source containing fatty acids and fatty acid esters.

[0167] a2'') Hydrogenate the first naturally sourced oil provided in step a1') to obtain a first biogenic hydrocarbon effluent containing at least 95% by weight paraffin, preferably at least 95% by weight C7-C24 paraffin, and the weight ratio between the weight content of Cx isoparaffin and the weight content of C(x-1) n-paraffin is strictly less than 2.0, where x is an integer selected from 14, 15, 16, 17, and 18, preferably selected from 14, 15, and 16 (or equivalently having a weight ratio R1'). (i-Cx / n-C(x-1)) The set (Ens2-1), where x is 14 to 18, preferably 14 to 16, each R1' (i-Cx / n-C(x-1)) R1' is the weight ratio between the weight content of Cx isoparaffin and the weight content of C(x-1) normal paraffin in the first hydrocarbon effluent, representing the ratio of aggregate (Ens2-1). (i-Cx / n-C(x-1)) At least one of the components must be strictly less than 2.0%, and the weight content of C14 n-paraffin must be greater than or equal to 1.0% relative to the total weight of the first hydrocarbon effluent.

[0168] a3') provides at least one oil from a second natural source containing fatty acids and fatty acid esters.

[0169] a4′) Hydrogenate the second naturally sourced oil provided in step a3′) to obtain a second biogenic hydrocarbon effluent containing at least 95% by weight paraffin, preferably at least 95% by weight C7-C24 paraffin, and having a weight ratio between the weight content of Cx isomer paraffin and the weight content of C(x-1) n-paraffin strictly greater than 2.0, where x is an integer selected from 14, 15, 16, 17, and 18, preferably selected from 14, 15, and 16 (or equivalently having a weight ratio R2′) (i-Cx / n-C(x-1)) The set (Ens2-2), where x is 14 to 18, preferably 14 to 16, each R2′ (i-Cx / n-C(x-1)) R2′ is the weight ratio between the weight content of Cx isoparaffin and the weight content of C(x-1) normal paraffin in the second hydrocarbon effluent, representing the ratio of the aggregate (Ens2-2). (i-Cx / n-C(x-1)) At least one of them is strictly greater than 2.0, and the weight content of C14 n-paraffin is greater than or equal to 1.0% relative to the total weight of the second hydrocarbon effluent, and

[0170] a5') The first effluent and the second effluent are mixed in a certain proportion to obtain a biogenic hydrocarbon effluent containing at least 95% by weight paraffin, and having a weight ratio between the weight content of Cx isoparaffin and the weight content of C(x-1) n-paraffin greater than or equal to 2.0, preferably greater than or equal to 2.5, where x is an integer selected from 14, 15, 16, 17, and 18, preferably selected from 14, 15, and 16 (or equivalently having a weight ratio R') (i-Cx / n-C(x-1)) The set (Ens2), where x is 14 to 18, preferably 14 to 16, each R' (i-Cx / n-C(x-1)) R' is the weight ratio between the weight content of Cx isoparaffin and the weight content of C(x-1) normal paraffin in the hydrocarbon effluent, representing the ratio of the aggregate (Ens2). (i-Cx / n-C(x-1)) At least one of the components is greater than or equal to 2.0, preferably greater than or equal to 2.5), and the weight content of C14 n-paraffin is greater than or equal to 1.0% relative to the total weight of the hydrocarbon effluent.

[0171] Step b) Fractionation

[0172] Step b) can fractionate the hydrocarbon effluent obtained in step a).

[0173] In particular, step b) can be carried out by vacuum distillation.

[0174] This type of distillation can be carried out in any distillation column, especially a vacuum distillation column.

[0175] Therefore, appropriate cutoff points can be selected to obtain paraffin-based compositions. These cutoff points can be defined, for example, based on the analysis of the paraffin (normative and isoparaffin content) contained in the biogenic hydrocarbon effluent to be separated. Those skilled in the art know how to determine appropriate cutoff points based on the composition of the hydrocarbon feedstock in n-paraffin and isoparaffin.

[0176] Therefore, the present invention also relates to paraffin-based compositions that can be obtained or acquired by the method according to the present invention.

[0177] Preferably, the paraffin-based composition that can be obtained or is obtained by the method according to the invention has the characteristics defined above for the paraffin-based composition according to the invention.

[0178] The present invention also relates to a jet fuel composition comprising a paraffin-based composition as defined in this specification, optionally blended with a fossil-derived jet fuel.

[0179] Preferably, the fossil-derived jet fuel is jet fuel that conforms to standard ASTM D1655-21-c.

[0180] Preferably, the jet fuel conforming to standard ASTM D1655-21-c is Jet A1 or Jet A.

[0181] Jet A1 or Jet A is typically produced by atmospheric distillation of crude oil, followed by additional processing such as desulfurization or hydrodesulfurization to produce a hydrocarbon fraction with reduced mercaptan content. It may also contain fractions from the hydrocracking process of vacuum gas oil.

[0182] Preferably, the jet fuel composition comprises up to 50% by volume of a paraffin-based composition and at least 50% by volume of a fossil-derived jet fuel.

[0183] The following examples illustrate the invention but do not limit its scope.

[0184] Example

[0185] Example 1: Simulation of fractionation of hydrotreated oil (according to the present invention)

[0186] Using conventional distillation simulation software (such as Aspen Hysys), HVO (hydrotreated and isomerized vegetable oils) with the composition shown in Table 1, especially HVO with an i-C15 / n-C14 ratio greater than 2.0 and an iC14 content greater than 1.0% by weight, was separated into light and heavy fractions.

[0187] Adjust simulation parameters, namely the cutoff point and the characteristics of the fractionation column (number of stages, flow rate, reflux ratio, etc.), to maximize the amount of product recovered from the light fraction (paraffin-based fraction) while keeping the freezing point below -41°C.

[0188] [Table 1]

[0189]

[0190] *: Cycloalkanes (monoaromatic hydrocarbons)

[0191] The composition of the recovered light fraction is detailed in Table 2.

[0192] [Table 2]

[0193]

[0194] The calculated freezing point of this light fraction is -41℃.

[0195] The calculated density of this light fraction (paraffin-based) is 760.7 kg / m³. 3

[0196] The distillation curve for D86 is as follows:

[0197] [Table 3]

[0198]

[0199] Before separation, the light fraction (paraffinic) accounts for approximately 45% by weight of HVO.

[0200] Example 2 - Fractionation Simulation of Another Hydrotreated Oil (Comparative Example)

[0201] HVO (hydrotreated and isomerized vegetable oils) with the compositions shown in Table 3, especially those with i-C15 / n-C14 ratios and i-C16 / n-C15 ratios less than 2, were separated into light and heavy fractions using conventional distillation simulation software (e.g., Aspen Hysys).

[0202] Adjust simulation parameters, namely the cutoff point and the characteristics of the fractionation column (number of stages, flow rate, reflux ratio, etc.), to maximize the amount of product recovered from the light fraction (paraffin-based fraction) while keeping the freezing point below -41°C.

[0203] [Table 4]

[0204]

[0205] *: Cycloalkanes and monoaromatics

[0206] The composition of the recovered light fraction is detailed in Table 4.

[0207] [Table 5]

[0208]

[0209] The calculated freezing point of this light fraction is -41℃.

[0210] The calculated density of this light fraction is 752 kg / m³. 3

[0211] Before separation, this light fraction accounted for approximately 26% by weight of HVO.

[0212] The results of this embodiment clearly demonstrate that, starting with hydrotreated oil having a high cloud point (-12°C), the yield of kerosene fraction obtained from this feedstock is relatively low. A comparison with Example 1 of the present invention shows that, starting with hydrotreated oil having the same cloud point of -12°C, but further having a weight ratio between the weight content of Cx isoparaffin and the weight content of C(x-1) n-paraffin greater than or equal to 2.0, where x is an integer selected from 14, 15, 16, 17, and 18, and the weight content of C14 n-paraffin greater than or equal to 1.0%, the kerosene fraction yield is significantly increased (+19%), and the density increases, while still maintaining a freezing point below -40°C.

Claims

1. A paraffin-based composition comprising at least 90% by weight paraffin relative to the total weight of the paraffin-based composition, exhibiting a weight ratio R (i-Cx / n-C(x-1)) The set (Ens), where, x is 14 to 17, for each R (i-Cx / n-C(x-1)) The weight ratio between the weight content of Cx isomer paraffin and the weight content of C(x-1) normal paraffin, wherein: - The ratio R of the set (Ens) (i-Cx / n-C(x-1)) At least one of them is greater than or equal to 2.0, and - The weight content of C14 orthoparaffin is greater than or equal to 1.0% relative to the total weight of the paraffin-based composition.

2. The paraffin-based composition according to claim 1, wherein, The set (Ens) has at least two ratios R (i-Cx / n-C(x-1)) Greater than or equal to 2.0, preferably greater than or equal to 2.5, preferably greater than or equal to 3.0, preferably greater than or equal to 5.

0.

3. The paraffin-based composition according to claim 1 or 2, wherein: - The weight ratio between the weight content of C15 isoparaffin and the weight content of C14 normal paraffin is greater than or equal to 2.0, preferably greater than or equal to 2.5, preferably greater than or equal to 3.0, preferably greater than or equal to 4.0, preferably greater than or equal to 5.0, preferably greater than or equal to 6.0, and / or - The weight ratio between the weight content of C16 isoparaffin and the weight content of C15 normal paraffin is greater than or equal to 2.0, preferably greater than or equal to 2.5, preferably greater than or equal to 3.0, preferably greater than or equal to 4.0, preferably greater than or equal to 5.0, preferably greater than or equal to 6.0, preferably greater than or equal to 7.0, preferably greater than or equal to 8.

0.

4. The paraffin-based composition according to any one of the preceding claims, wherein, The weight content of the C7-C13 compound relative to the total weight of the paraffin-based composition is less than or equal to 60% by weight, preferably less than or equal to 50% by weight, preferably less than or equal to 45% by weight, and more preferably from 20% to 60% by weight.

5. The paraffin-based composition according to any one of the preceding claims, having one or more of the following characteristics: - The weight ratio of normal paraffin to isoparaffin is greater than or equal to 0.140, preferably greater than or equal to 0.145, preferably greater than or equal to 0.150, preferably greater than or equal to 0.155, preferably greater than or equal to 0.160, preferably greater than or equal to 0.165, and most preferably from 0.140 to 0.50, and / or - The weight ratio of C14-C18 ortho-paraffin to C14-C18 iso-paraffin is greater than or equal to 0.105, preferably greater than or equal to 0.110, preferably greater than or equal to 0.115, preferably greater than or equal to 0.120, preferably greater than or equal to 0.125, preferably greater than or equal to 0.130, and most preferably from 0.105 to 0.50, and / or - The average carbon number of the C14-C18 fraction of paraffin contained in the paraffin-based composition is less than or equal to 16.0, preferably less than or equal to 15.8, preferably less than or equal to 15.5, preferably less than or equal to 15.2, preferably less than or equal to 15.0, and most preferably 12.0 to 16.

0.

6. The paraffin-based composition according to any one of the preceding claims, having one or more of the following characteristics: - Density greater than or equal to 730 kg / m³ 3 Preferably greater than or equal to 740 kg / m 3 Preferably greater than or equal to 750 kg / m 3 The preferred value is 750 kg / m³. 3 Up to 770kg / m 3 , and / or - Freezing point less than or equal to -40°C, preferably less than or equal to -41°C, more preferably less than or equal to -42°C, more preferably -42°C to -40°C, and / or - The final boiling point is less than or equal to 300°C, preferably less than or equal to 290°C, and more preferably between 250°C and 290°C.

7. A method for producing a paraffin-based composition according to any one of claims 1 to 6, comprising at least the following steps: a) Provides a biologically derived hydrocarbon effluent containing at least 95% by weight paraffin, preferably at least 95% by weight C7-C24 paraffin, exhibiting a weight ratio R' (i-Cx / n-C(x-1)) The set (Ens2), where, x is 14 to 18, for each R' (i-Cx / n-C(x-1)) The weight ratio between the weight content of Cx isoparaffin and the weight content of C(x-1) normal paraffin in the hydrocarbon effluent, wherein: - R' of set (Ens2) (i-Cx / n-C(x-1)) At least one of them is greater than or equal to 2.0, and - The weight content of C14 n-paraffin is greater than or equal to 1.0% by weight relative to the total weight of the hydrocarbon effluent, and b) Fractionate the bio-derived hydrocarbon effluent provided in step a) to obtain a paraffinic base.

8. The method according to claim 7, wherein, In the bio-derived hydrocarbon effluent, at least two ratios R' of the set (Ens2) (i-Cx / n-C(x-1)) Greater than or equal to 2.0, preferably greater than or equal to 2.5, preferably greater than or equal to 3.0, preferably greater than or equal to 5.

0.

9. The method according to claim 7 or 8, wherein, The hydrocarbon effluent has the following characteristics: - The weight ratio between the weight content of C15 isoparaffin and the weight content of C14 normal paraffin is greater than or equal to 2.0, preferably greater than or equal to 2.5, preferably greater than or equal to 3.0, preferably greater than or equal to 4.0, preferably greater than or equal to 5.0, preferably greater than or equal to 6.0, and / or - The weight ratio between the weight content of C16 isoparaffin and the weight content of C15 normal paraffin is greater than or equal to 2.0, preferably greater than or equal to 2.5, preferably greater than or equal to 3.0, preferably greater than or equal to 4.0, preferably greater than or equal to 5.0, preferably greater than or equal to 6.0, preferably greater than or equal to 7.0, preferably greater than or equal to 8.

0.

10. The method according to any one of claims 7 to 9, wherein, The hydrocarbon effluent has a C7-C13 compound content of less than or equal to 25% by weight, preferably less than or equal to 22% by weight, preferably less than or equal to 21% by weight, and more preferably 10% to 25% by weight, relative to the total weight of the hydrocarbon effluent.

11. The method according to any one of claims 7 to 10, wherein, Step a) includes: a1) Provides oils or mixtures of oils of natural origin containing fatty acids and fatty acid esters. a2) Hydrogenate the naturally sourced oil provided in step a1) to obtain a bio-based hydrocarbon effluent.

12. The method according to any one of claims 7 to 10, wherein, Step a) includes a1') Provides a first hydrocarbon effluent of biological origin containing at least 95% by weight paraffin, which presents: - Weight ratio R1′ (i-Cx / n-C(x-1)) The set (Ens2-1), where x is 14 to 18, each R1′ (i-Cx / n-C(x-1)) R1′ is the weight ratio between the weight content of Cx isoparaffin and the weight content of C(x-1) normal paraffin in the first hydrocarbon effluent, and the ratio of the aggregate (Ens2-1). (i-Cx / n-C(x-1)) At least one of them is strictly less than 2.0, and - The weight content of C14 n-paraffin is greater than or equal to 1.0% relative to the total weight of the first hydrocarbon effluent. a2') Provides a second hydrocarbon effluent of biological origin containing at least 95% by weight paraffin, which presents as: - Weight ratio R2' (i-Cx / n-C(x-1)) The set (Ens2-2), where x is 14 to 18, each R2' (i-Cx / n-C(x-1)) It is the weight ratio between the Cx isoparaffin content and the C(x-1) normal paraffin content in the second hydrocarbon effluent, and the ratio R2' of the aggregate (Ens2-2). (i-Cx / n-C(x-1)) At least one of them is strictly greater than 2.0, and - The weight content of C14 n-paraffin is greater than or equal to 1.0% relative to the total weight of the second hydrocarbon effluent. a3') The first effluent and the second effluent are mixed in a certain proportion to obtain a bio-derived hydrocarbon effluent containing at least 95% by weight paraffin, and exhibiting: - Weight ratio R' (i-Cx / n-C(x-1)) The set (Ens2), where x is 14-18, preferably 14-16, each R' (i-Cx / n-C(x-1)) It is the weight ratio between the weight content of Cx isoparaffin and the weight content of C(x-1) normal paraffin in the hydrocarbon effluent, and the ratio R' of the aggregate (Ens2). (i-Cx / n-C(x-1)) At least one of them is greater than or equal to 2.0, and - The weight content of C14 n-paraffin is greater than or equal to 1.0% relative to the total weight of the hydrocarbon effluent.

13. A paraffin-based composition obtained by the method according to any one of claims 7 to 12.

14. A jet fuel composition comprising a paraffinic composition according to any one of claims 1 to 6, or a paraffinic composition obtained by the method according to any one of claims 7 to 12, and optionally a jet fuel of a fossil source.

15. The jet fuel composition of claim 14, comprising up to 50% by volume of a paraffinic composition and at least 50% by volume of a fossil-derived jet fuel.

Images