Co-production of renewable-based linear alkylbenzene and hydrocarbon compositions

Abstract

The present invention relates to a production method and apparatus for alkylbenzenes from natural oils and kerosene and the co-production of a renewable content hydrocarbon composition, e.g. a renewable content hydrocarbon fluid composition and / or a renewable content fuel composition, without a hydrocracking or isomerization step. The invention also relates to a hydrocarbon fluid composition, to the use of said composition as hydrocarbon fluid and to an apparatus for the manufacture of linear alkylbenzene and a hydrocarbon composition.

Description

[0001] CO-PRODUCTION OF RENEWABLE-BASED LINEAR ALKYLBENZENE AND HYDROCARBON COMPOSITIONS

[0002] DESCRIPTION

[0003] TECHNICAL FIELD OF THE INVENTION

[0004] The present invention relates to a process and an apparatus for the production of linear alkylbenzenes (LAB) from natural oils and kerosene and the co-production of a renewable content hydrocarbon composition, e.g. a renewable content hydrocarbon fluid composition and / or a renewable content hydrocarbon fuel composition. Advantageously, the linear alkylbenzene can be produced in a conventional industrial alkylbenzene production plant without substantial modification. Another benefit is that the heavy normal paraffin fraction (C14-C18) which results from the hydrodeoxygenation of the natural oils is upgraded into the renewable content hydrocarbon composition without any hydrocracking and / or isomerization step. The invention also relates to a hydrocarbon fluid composition, to the use of said composition as hydrocarbon fluid and to an apparatus for the manufacture of linear alkylbenzene and a hydrocarbon composition.

[0005] Linear alkylbenzenes (LAB) are extensively used as a chemical intermediate to form linear alkylbenzene sulfonates (LAS), substances widely employed in detergents and cleaning products as well as in a variety of other applications, whereas hydrocarbon fluids may be used as solvents and base oils in a variety of applications including lubricants, agricultural chemical applications (e.g. spray oil applications), etc. and hydrocarbon fuels (e.g. diesel or jet fuel) are mainly used as energy source for propulsion in transport.

[0006] BACKGROUND OF THE INVENTION

[0007] Linear alkylbenzenes are organic compounds with the formula CeHsCnHhn+i. While n can have any practical value, current commercial use of alkylbenzenes requires that n lies in the range of 10 to 16, or in the range of 8 to 15, or in the range of 10 to 13, or in the range of 12 to 15, or in the range of 9 to 14. These specific ranges are often required when the alkylbenzenes are used as intermediates in the production of surfactants for detergents. Because the surfactants created from alkylbenzenes are biodegradable, the production of alkylbenzenes has grown rapidly since their initial uses in detergent production in the 1960s. The linearity of the paraffin chain in the alkylbenzenes is key to the material's biodegradability and effectiveness as a detergent. A major factor in the final linearity of the alkylbenzenes is the linearity of the paraffin component.

[0008] While detergents made utilizing alkylbenzene-based surfactants are biodegradable, processes for creating alkylbenzenes are not based on renewable sources. Specifically, alkylbenzenes are currently produced from kerosene extracted from the earth. Due to the growing environmental concerns over fossil fuel extraction and economic concerns over exhausting fossil fuel deposits, there may be support for using an alternate source for biodegradable surfactants in detergents and in other industries. To date industrial processes for the manufacture of detergent range alkylbenzenes are entirely based on fossil resources extracted from gaseous or liquid resources extracted from the ground from fossil deposits. Current process units to produce linear alkylbenzene do not usually intrinsically comprise a unit that performs hydrocracking or hydroisomerization reactions of paraffinic intermediates.

[0009] In EP1857525 the hydrotreatment (HDT) of combined streams of fossil kerosene and natural oils to obtain N-paraffins suitable for detergent production is described. In particular, short chain lauric natural oils are described to be able to be hydrotreated in the invention, among which palm kernel oil, obtained from oleaginous palm trees (Elaeis guineensis, Jacq.), babassu oil (Orbignya speciosa, Mart.) Barb. Rodr., and ouricuri oil or licuri oil also obtained from a palm tree (Syagrus Coronata (Martius) Beccari) are preferred. The proposed hydrotreatment process is described as involving hydrocracking reactions to reduce the number of carbon atoms in the chains of the vegetable oils used, followed by hydrotreatment to remove the oxygenated compounds, and followed by hydrogenation of olefins to remove double bonds. Suitable catalysts for the process are described as commercial sulfided NiMo catalysts and sulfided CoMo catalysts supported in gamma alumina.

[0010] In US2014364355 a method for the production of linear alkylbenzenes from natural oils is described. In the preferred embodiments, the natural oils include one or more of coconut oil, babassu oil, castor oil, cooking oil, and other vegetable, nut or seed oils. The natural oils typically comprise triglycerides, free fatty acids, or a combination of triglycerides and free fatty acid. Hydrodeoxygenation of the natural oil is effected in a hydrodeoxygenation unit. Catalysts may include those containing one or more of Ni, Mo, Co, P, such as Ni — Mo, Ni — Mo — P, Ni — Co — Mo, or Co — Mo, on aluminas, silica, titania, zirconia, and mixtures thereof. The paraffin stream after hydrodeoxygenation is subjected to separation to obtain a first and a second portion of paraffins, wherein the first portion of paraffins is directed to a unit for the production of linear alkylbenzene to generate a renewable linear alkylbenzene product and the second portion of paraffins is isomerized or hydrocracked to form a biofuel.

[0011] In LIS2013253240 a method for the production of linear alkylbenzenes from fossil kerosene and natural oil is described. The kerosene is pre-fractionated before to a stream preferably comprising C10-C13 paraffins before it is fed to a kero-hydrotreater (KHT). The same KHT additionally receives a stream of natural oil. In certain embodiments, the natural oils include one or more of coconut oil, babassu oil, castor oil, algae byproduct, beef tallow oil, borage oil, camelina oil, Canola® oil, choice white grease, coffee oil, corn oil, Cuphea Viscosissima oil, evening primrose oil, fish oil, hemp oil, hepar oil, jatropha oil, Lesquerella Fendleri oil, linseed oil, Moringa Oleifera oil, mustard oil, neem oil, palm oil, perilla seed oil, poultry fat, rice bran oil, soybean oil, stillingia oil, sunflower oil, tung oil, yellow grease, cooking oil, and other vegetable, nut, or seed oils. In the KHT reactions of hydrotreating of the fossil kerosene-based stream and the natural oil are carried out simultaneously. After the hydrotreating I hydrodeoxygenation step, the resulting stream may be directed to a separator to separate desired normal paraffins from branched or cyclic compounds. The normal paraffin stream is subsequently fed to a fractionator, where a first stream of paraffins and a second stream of paraffins is obtained. The first stream of normal paraffins is then directed to a production unit for normal alkylbenzene. The second stream of normal paraffins is directed to a process for the manufacture of other alkylbenzenes or olefins, or alternatively directed to a manufacturing process that forms biofuels by hydroisomerization.

[0012] In US2023137687 processes for producing product streams from renewable feed streams are described, especially for linear alkylbenzene from renewable feedstocks, comprising two reactors, one for hydrodeoxygenation of the biorenewable feed that is concentrated in free fatty acids with 10-13 carbon atoms and the other for hydrotreating a traditional biorenewable feed or a mineral feed operated at a higher deoxygenation ratio. The hydrodeoxygenated stream is fractionated to provide a light normal paraffin stream and a heavy normal paraffin stream, and then a portion of the hydrotreated stream is mixed with the light normal paraffin stream or the heavy normal paraffin stream. The light normal paraffin stream may be applied to the production of linear alkylbenzene whereas the hydrotreated stream mixed with the heavy normal paraffin stream may be subjected to hydroisomerization conditions to hydroisomerize the normal paraffins to branched paraffins so as to improve the cold flow properties and generate a green fuel stream.

[0013] It is highly desirable to increase the production of linear alkylbenzene from renewable resources instead of fossil resources, as can be seen by literature precedents. However, existing alkylbenzene production plants generally require important constructive modifications to have the capability to produce paraffins from natural oils in significant quantities. For a rapid transition towards the production of linear alkyl benzene with a high content in renewable resources, it would thus be desirable to use the currently existing assets for the manufacture of traditional (fossil-based) linear alkylbenzene and at the same time increase the renewable carbon in side-products that are accompanying the linear alkylbenzene manufacture while using available feedstocks from triglycerides of vegetable, animal, nut and / or seed oil origin.

[0014] BRIEF DESCRIPTION OF THE INVENTION

[0015] The present invention relates to a process and an apparatus for the co-production of biobased linear alkylbenzene and hydrocarbon compositions (e.g. fluids or fuels). The proposed invention advantageously allows utilizing the existing conventional assets for linear alkyl benzene production without energy and labor-intensive modifications and also brings about a practical valorization of side streams produced during the process. In particular, the inventors have found an advantageous way to valorize the heavy normal paraffins (C14-C18), that are formed by hydrodeoxygenation of natural oils, into novel hydrocarbon products without further chemical reaction.

[0016] Thus, a first aspect of the present invention relates to a process for the manufacture of linear alkylbenzene and a hydrocarbon composition comprising: combining a stream of fossil kerosene comprising hydrocarbons C9-C16 with a stream of natural oil comprising fatty acid chains of C10, C12 and C14 to obtain a mixture; hydrotreating and hydrodeoxygenating the mixture to form a hydrotreated and hydrodeoxygenated stream; separating said hydrotreated and hydrodeoxygenated stream to obtain a stream enriched in normal paraffins and a stream depleted in normal paraffins; fractionating said stream enriched in normal paraffins to obtain a first fraction of normal paraffins comprising normal paraffins in the range between C9-C14 and a second fraction of normal paraffins comprising normal paraffins in the range between C14-C18; producing linear alkylbenzene from said first fraction of normal paraffins; and combining at least a part of the second fraction of normal paraffins, without being subjected to a hydrocracking or hydroisomerization reaction, with: either at least a part of the stream depleted in normal paraffins or a fraction of said stream depleted in normal paraffins; and / or a product of hydrodearomatization of at least a part of the stream depleted in normal paraffins or a product of hydrodearomatization of a fraction of said stream depleted in normal paraffins; and / or at least a part of the stream depleted in normal paraffins or a fraction of said stream depleted in normal paraffins to form a combined stream, and hydrodearomatizing said combined stream; to form at least a hydrocarbon composition.

[0017] The apparatus suitable for carrying out the process typically comprises a common recipient, preferably comprising one or more storage tanks, for the natural oil and the fossil kerosene to form a mixture, more preferably a homogeneous mixture. An advantage of this feature is that existing recipients within a conventional linear alkylbenzene manufacture plant can be repurposed to hold up the mixture of natural oil and fossil kerosene without further modifications of the process stream.

[0018] The method then hydrodeoxygenates and hydrotreats in a hydrodeoxygenation I hydrotreating unit (HDO-HT) a stream comprising the natural oil / fossil kerosene mixture to provide a stream comprising a mixture of renewable n-paraffins, typically with carbon chains comprising C9-C18, and fossil-based n-paraffins, cyclo-paraffins, iso-paraffins, aromatics and olefins.

[0019] The resulting stream after the deoxygenation I hydrotreating process is directed to a separation process in a separator unit (N / l SEP) to form a stream enriched in n-paraffins and a stream depleted in n-paraffins, mainly comprising cyclo-paraffins, iso-paraffins and aromatics. The normal paraffin stream is further fractionated in a fractionation unit (FRAC) to form a stream mainly comprising n-paraffins C9-C14 and a stream mainly comprising n-paraffins C14-C18. The stream of C9-C14 n-paraffins is used for producing linear alkylbenzene whereas at least a part of the C14-C18 n-paraffins is used, without hydrocracking or isomerization, for producing a hydrocarbon composition (such as a fluid and / or a fuel), as described herein.

[0020] In one embodiment, at least a part of the n-paraffins C14-C18 is mixed with at least a part of the stream depleted in n-paraffins or a fraction of said stream depleted in n- paraffins, thus forming a stream of a hydrocarbon composition with enhanced content of biological matter which is suitable for use as a hydrocarbon fuel.

[0021] In another alternative or complementary embodiment, at least a part of the stream depleted in n-paraffins or a fraction of the stream depleted in n-paraffins is directed to a hydrodearomatization unit (HDA) and subsequently combined with the n-paraffins C14- C18, thus forming a stream of a hydrocarbon composition with enhanced content of biological matter which is dearomatized and is suitable for use as a hydrocarbon fluid. Said hydrocarbon fluids are preferably suitable for an application as hydrocarbon solvents and / or base oils in various industries.

[0022] In another alternative or complementary embodiment, at least a part of the n-paraffins C14-C18 is mixed with at least a part of the stream depleted in n-paraffins or a fraction of said stream depleted in n-paraffins and the mixture is directed to a hydrodearomatization unit (HDA), thus forming a stream of a hydrocarbon composition with enhanced content of biological matter which is dearomatized and is suitable for use as a hydrocarbon fluid. Said hydrocarbon fluids are preferably suitable for an application as hydrocarbon solvents and / or base oils in various industries.

[0023] Thus, the resulting hydrocarbon composition(s) from the process and the apparatus of the invention may be used for instance as a hydrocarbon fluid or as a hydrocarbon fuel (e.g. diesel or jet fuel). The fluids obtained by the present methods may be used as specialty fluids in a variety of applications. For example, the fluids may be used as solvents and base oils for instance in lubricants, agricultural chemical applications (e.g. spray oil applications), coolant and / or heat transfer fluids, electric vehicle fluids, acrylic and silicone mastics and sealants, printing inks, paints, coatings, adhesives, drilling fluids, metalworking fluids, cleaning fluids, and consumer products. A second aspect of the present invention refers to a hydrocarbon composition consisting of: from 75 wt.% to 99 wt.% of a mix of n-paraffins, iso-paraffins and cyclic paraffins in the C12-C16 range; from 1 wt.% to 20 wt.% of n-paraffins in the C17-C18 range; from 0-5 wt.% of other paraffins; and less than 1000 ppm by weight of aromatics; wherein the hydrocarbon composition has a flash point between 90-130 °C and the boiling range is between 220-320 °C.

[0024] The composition of the second aspect is suitable as a hydrocarbon fluid. In a third aspect the present invention relates to the use of the composition described in the second aspect as a hydrocarbon fluid such as solvents and / or base oils.

[0025] A further aspect of the present invention relates to an apparatus (or process plant) for the manufacture of linear alkylbenzene and a hydrocarbon composition according to the first aspect of the present invention, said apparatus comprising a hydrodeoxygenation I hydrotreating unit (HDO-HT), a separator unit (N / l SEP), a fractionation unit (FRAC), and alkylbenzene production unit, and optionally a hydrodearomatization unit (HDA).

[0026] These aspects and preferred embodiments thereof are additionally also defined hereinafter in the detailed description and in the claims.

[0027] All the features described in this specification (including the claims, description and drawings) can be combined in any combination, with the exception of combinations of such mutually exclusive features.

[0028] BRIEF DESCRIPTION OF THE DRAWINGS

[0029] To better understand the invention, its objects and advantages, the following figures are attached to the specification:

[0030] Fig. 1 General Schematic view of a process or apparatus according to the present invention for the manufacture, from natural oils and fossil kerosene, of linear alkylbenzene (243) and a hydrocarbon composition. At least a part of the second fraction of normal paraffins (209) is unified with at least a part of the stream depleted in normal paraffins (204) or a fraction (215) of said stream depleted in normal paraffins (204) or a product of hydrodearomatization thereof to form a hydrocarbon composition, wherein the second fraction of normal paraffins (209) is not subjected to a hydrocracking or hydroisomerization reaction.

[0031] Fig. 2 Embodiment according to the present invention for the production of linear alkylbenzene (243) from the first fraction of normal paraffins (206) in an alkylbenzene production unit (104).

[0032] Fig. 3 Embodiment according to the present invention for the manufacture, from natural oils and fossil kerosene, of linear alkylbenzene (243) and a hydrocarbon composition. At least a part of the stream of hydrocarbons depleted in normal paraffins (204) is unified with at least a part of the heavy normal paraffin stream (209) to form a hydrocarbon composition (211) suitable for use as a fuel product.

[0033] Fig. 4 Embodiment according to the present invention for the manufacture, from natural oils and fossil kerosene, of linear alkylbenzene (243) and a hydrocarbon composition. At least a part of the stream of hydrocarbons depleted in normal paraffins (204) may be separated into two different streams. The first part of the stream (204) may be directed to a unit for hydrodearomatization (106) to form a hydrocarbon composition (212) suitable as a hydrocarbon fluid and the second part of the stream (204) may be directed to a fractionation unit (107) generating a light hydrocarbon stream (213) typically comprising C9-C12 iso-paraffins, cyclic paraffins and aromatics, a middle paraffin stream (214) typically comprising C12-C14 iso-paraffins, cyclic paraffins and aromatics and a heavy paraffin stream (215) typically comprising C13-C16 iso-paraffins, cyclic paraffins and aromatics. Each of the fractionated hydrocarbon streams (213), (214), (215) may be directed to a dearomatization unit (106’), (106”), (106”’) to reduce the aromatic contents in said streams, generating streams (216), (217), (218), respectively, suitable as hydrocarbon fluids. Heavy dearomatized stream (218) is then combined with heavy normal paraffin stream (209) to form a hydrocarbon composition (220) suitable as a hydrocarbon fluid that has a superior flash point and a higher boiling range end point.

[0034] Fig. 5 Embodiment for the manufacture, from natural oils and fossil kerosene, of linear alkylbenzene (243) and a hydrocarbon composition. At least a part of the stream of hydrocarbons depleted in normal paraffins (204) may be separated into two different streams. The first part of the stream (204) may be directed to a unit for hydrodearomatization (106) to form a hydrocarbon composition (212) suitable as hydrocarbon fluid and the second part of the stream (204) may be directed to a fractionation unit (107) generating a light hydrocarbon stream (213) typically comprising C9-C12 iso-paraffins, cyclic paraffins and aromatics, a middle paraffin stream (214) typically comprising C12-C14 iso-paraffins, cyclic paraffins and aromatics and a heavy paraffin stream (215) typically comprising C13-C16 iso-paraffins, cyclic paraffins and aromatics. Heavy paraffin stream (215) is then combined with heavy normal paraffin stream (209) to form stream (221). Each of the hydrocarbon streams (213), (214), (221) may be directed to a dearomatization unit (106’), (106”), (106”’) to reduce the aromatic contents in said streams, generating streams (216), (217), (222), respectively, suitable as hydrocarbon fluids. Hydrocarbon composition (222) has a superior flash point and a higher boiling range end point.

[0035] Fig. 6 Embodiment for the manufacture, from natural oils and fossil kerosene, of linear alkylbenzene (243) and a hydrocarbon composition. At least a part of the stream of hydrocarbons depleted in normal paraffins (204) is unified with at least parts of the heavy normal paraffins stream (209) to form a combined stream (223). Part of the combined stream (223) may be directed to a unit for hydrodearomatization (106) and part of the combined stream (223) may be directed to a fractionation unit (107) generating a light hydrocarbon stream (225) typically comprising C9-C12 iso-paraffins, cyclic paraffins and aromatics, a middle paraffin stream (226) typically comprising C12-C14 iso-paraffins, cyclic paraffins and aromatics and a heavy paraffin stream (227) typically comprising C13-C16 iso-paraffins, cyclic paraffins and aromatics. Each of the fractionated hydrocarbon streams (225), (226), (227) may be directed to a dearomatization unit (106’), (106”), (106’”) to reduce the aromatic contents in said streams, generating streams (228), (229), (230), respectively, suitable as hydrocarbon fluids. Hydrocarbon composition (230) has a superior flash point and a higher boiling range end point.

[0036] DETAILED DESCRIPTION OF THE INVENTION

[0037] The following detailed description is just an exemplary description and is not intended to limit the invention or the uses and applications of the invention described herein.

[0038] Definitions Unless defined otherwise, all technical and scientific terms and expressions used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this disclosure belongs.

[0039] As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and / or "comprising”, when used in this specification, specify the presence of stated features, steps, operations, elements, and / or components, but do not preclude the presence or addition of one or more other features, steps, operations, elements, and / or components thereof. The term “comprises” encompasses the terms “consisting essentially of” and “consisting of”. The term “consisting essentially of” preferably means that the specified components represent at least 98wt%, or even at least 99wt%, of the total weight of the corresponding composition, solution or mixture.

[0040] As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items and may be abbreviated as " / ".

[0041] As used herein, the term "approximately" or "about" as applied to one or more values of interest, refers to a value that is similar to a stated reference value. In certain embodiments, the term "approximately" or "about" refers to a value that can vary up to ± 20 %, preferably within ± 10 %, and more preferably within ± 5 % of the stated reference value. When “approximately" or "about" is used before a numerical range, it applies to the upper and lower range end-points.

[0042] Indeed, the skilled person knows that numerical values relating to measurements are subject to measurement errors which place limits on their accuracy. Where terms such as "about" or "approximately" are applied to a particular value (e.g., "about 200 °C" or "approximately 200 °C") or to a range (e.g., "about x to approximately y"), the value or range may be interpreted as being as accurate as the method used to measure it. Unless explicitly stated otherwise, the general convention in the scientific and technical literature may be applied so that the last digit of numerical values preferably indicates the precision of measurement. Thus, unless other error margins are given, the maximum margin is preferably ascertained by applying the rounding-off convention to the last decimal place. For instance, a value of 3.5 preferably has an error margin of 3.45 to 3.54 and a range of 2% to 10% preferably covers a range of 1.5% to 10.4%. Said variations of a specified value are understood by the skilled person and are within the context of the present invention. Further, to provide a more concise description, some of the quantitative expressions given herein are not qualified with the term “about”. It is understood that, whether the term “about” is used explicitly or not, every quantity given herein is meant to refer to the actual given value, and it is also meant to refer to the approximation to such given value that would reasonably be inferred based on the ordinary skill in the art, including equivalents and approximations due to the experimental and / or measurement conditions for such given value.

[0043] Concentrations, amounts, and other numerical data may be expressed or presented herein in a range format. It is to be understood that such a range format is used merely for convenience and brevity and thus should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. As an illustration, a numerical range of "about 1 % to about 5 %" should be interpreted to include not only the explicitly recited values of about 1 % to about 5 %, but also include individual values and sub-ranges within the indicated range. Thus, included in this numerical range are individual values such as 2, 3 and 4 and sub-ranges such as from 1-3, from 2-4, and from 3-5, etc. This same principle applies to ranges reciting only one numerical value. It should also be understood that ranges formed by combination of any of the end points of different disclosed ranges and / or particular values therein are included in the present disclosure.

[0044] Concentrations expressed in parts (e.g. ppm), ratios and percentages are by weight (w / w) and are further based on the total weight of the product / composition, unless otherwise indicated.

[0045] As used herein, the term a stream enriched in a given compound (e.g. normal paraffins) means that the stream coming out of a vessel has a greater concentration of the given compound (e.g. normal paraffins) than the feed to the vessel and the term a stream depleted in a given compound (e.g. normal paraffins) means that the stream coming out of a vessel has a smaller concentration of the given compound (e.g. normal paraffins) than the feed to the vessel. As used herein, the term linear paraffin and normal paraffin shall be treated as meaning one and the same type of molecules. The skilled person understands that both termini refer to a straight-chain, saturated hydrocarbon molecule.

[0046] As used herein, the term iso-paraffins and branched paraffins shall be treated as meaning one and the same type of molecules. The skilled person understands that both termini refer to a branched-chain saturated hydrocarbon molecule.

[0047] As used herein, any expression that refers to a range of carbon atoms (e.g. Ca-Cb; Ca or shorter) for a given compound (hydrocarbon, paraffin...) means at least a single compound having a number of carbon atoms within such a range, or a mixture of two or more compounds having a number of carbon atoms within such a range. By way of illustration, a paraffin in the range of C9-C14 includes a C9 paraffin, a C10 paraffin, a C11 paraffin, a C12 paraffin, a C13 paraffin, a C14 paraffin or only one or more of such paraffins.

[0048] The skilled person also understands that these ranges are to be interpreted to essentially include the referred compounds (hydrocarbons, paraffins...) in the specified range, but however may also include certain amounts of the referred compounds (hydrocarbons, paraffins...) outside such range. For instance, a range C9-C14 may comprise a low amount (typically lower than 5%, 4%, 3%, 2%, or 1 %) of compounds close to such range (e.g. C8 and / or C15).

[0049] Unless otherwise stated, all the Standard Test Methods (e.g. ASTM, UOP, etc.) and all the regulatory requirements I specifications (e.g. NC 27101921) recited herein correspond to the latest version as in force at the priority date of the present patent application.

[0050] In the present disclosure, density values are determined according to ASTM D4052, cloud point values are measured according to ASTM D2386, flash point values are measured according to ASTM D93 and boiling point values are determined according to ASTM D86.

[0051] As used in the present disclosure, the terms "renewably-based" or "renewable" denote that the hydrocarbon (paraffins, olefins, aromatics, alkylbenzene, linear alkylbenzene or subsequent products prepared from renewable hydrocarbons) contains a carbon content from a "new carbon" source as measured by ASTM test method D6866, " Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis".

[0052] A partly renewable linear alkylbenzene product is provided which has the general chemical formula CeHsCnHLn+i of which the carbon is partly modern carbon, as defined and measured by ASTM D6866 and has a linearity of the paraffin alkyl group preferably of at least 80 mass percent but more preferably of at least 90 mass percent and most preferably of at least 92 mass percent. Thus, the alkylbenzene product contains at least 80 mass percent of linear alkylbenzenes meaning alkylbenzenes wherein the paraffin alkyl group is a linear paraffin alkyl group. The renewable linear alkylbenzene consists of a benzene ring which comprises the portion of the chemical formula of CeHsthat is alkylated with a normal paraffin which is described by the CnH2+i portion of the formula. Often, linear alkylbenzenes are sulfonated to produce a linear alkylbenzene sulfonate as a surfactant for use in detergents. For the purposes of use as material to produce a linear alkylbenzene sulfonate it is preferable that the paraffins carbon chain length (n in the chemical formula) of the alkyl group is in the range of 10 to 16, or in the range of 8 to 15, or in the range of 10 to 13, or in the range of 12 to 15, or in the range of 9 to 14.

[0053] The linearity of alkylbenzene product is mostly dependent on the linearity of the paraffins used to alkylate the benzene. It is a common rule of thumb by those skilled in the art that the linearity of a paraffin feed drops by about 5-7 mass percent after dehydrogenation and alkylation. Therefore, paraffin with 97 mass percent linearity (or alternatively 3 mass percent of non-linear paraffins) would result in an alkylbenzene product with linearity around 90-92 mass percent. This sets the requirement for paraffin linearity about 5-7 mass percent higher than the specification for the alkylbenzene product. Typically, the linearity of the paraffin product is measured by UOP 621 , UOP411 , or UOP732 standard test method available from ASTM. Linear alkylbenzenes may be analyzed using ASTM Standard Test Method D4337.

[0054] A General Schematic view of the process and apparatus according to the invention for the manufacture of linear alkylbenzene (243) and a hydrocarbon composition from natural oils and fossil kerosene is shown in FIG. 1 . At least a part of the second fraction of normal paraffins (209) is unified with at least a part of the stream depleted in normal paraffins (204) or a fraction (215) of said stream depleted in normal paraffins (204) or a product of hydrodearomatization thereof to form a hydrocarbon composition, wherein the second fraction of normal paraffins (209) is not subjected to a hydrocracking or hydroisomerization reaction prior to said combination.

[0055] The apparatus of the present invention typically comprises a recipient (100), where the fossil kerosene and the natural oil are mixed to form a mixture (200). A person skilled in the art will understand that not all combinations are homogeneously miscible when combining a natural oil and a fossil kerosene feedstock. Therefore, in the preferred embodiments concentrations of natural oil are chosen in which the mixture (200) in the recipient or storage system (100) is fully miscible, i.e. homogeneous. Preferably, the recipient (100) comprises one or more storage tanks. Optionally, the recipient (100) comprises a continuous circulation system to guarantee efficient and rapid mixing of both fluids. The inventors have found that the mixture of fossil kerosene with natural oil still may fulfill the regulatory requirements to classify it as middle oil, which is used commonly for linear alkylbenzene production, thus minimizing lengthy regulatory procedures and evaluations. In a preferred embodiment the mixture of kerosene and natural oil (200) is fully miscible and preferably complies with the regulatory requirements of kerosene in NC 27101921 c) so that no regulatory requirements need to be introduced into the production process.

[0056] In a preferred embodiment, the mixture (200) comprises less than 30 wt.% natural oil, more preferably less than 20 wt.% natural oil, most preferably less than 10 wt.% natural oil. Further, the natural oil comprises fatty acid chains C10, C12 and C14. Preferably, the sum of fatty acid chains C10, C12 and C14 in the natural oil is at least 20 wt.%, at least 30 wt.%, at least 40 wt.%, at least 50 wt.%, or at least 60 wt.%. In this way the process generates a preferred chain lengths distribution of normal paraffins for the manufacture of linear alkylbenzene.

[0057] In a more preferred embodiment, the natural oil / fossil kerosene mixture (200) comprises less than 30 wt.%, less than 20 wt.% or less than 10 wt.% natural oil, said natural oil comprising at least 20 wt.%, at least 30 wt.%, at least 40 wt.%, at least 50 wt.%, or at least 60 wt.% fatty acid moieties of carbon chain lengths C10, C12 and C14. Natural oils are not based on kerosene or other fossil fuels. A person skilled in the art will understand that a natural oil comprises fatty acid residues of different chain length in mono-, di- and triglyceride molecules and / or as free fatty acids. Therefore, it shall be understood that the weight percentage of fatty acid carbon chain lengths shall be the global percentage over all the fatty acids comprised in the natural oil either in mono-, di- and triglyceride molecules and / or as free fatty acids.

[0058] The natural oil typically comprises fatty acids with carbon chain lengths ranging from C10 to C18, with a high content of fatty acid chains of C10, C12 and C14. As previously described, preferably a mix of fatty acid chains C10, C12 and C14 represents at least 20 wt.%, at least 30 wt.%, at least 40 wt.%, at least 50 wt.%, or at least 60 wt.% of the fatty acid chains of the natural oil.

[0059] In the preferred embodiment of the invention lauric oils are used as natural oils. The term lauric oils refers to those oils containing a high proportion of lauric acid, a C12 saturated fatty acid. These natural oils possess a high significance for the manufacture of surfactants and soaps due to their advantageous chain length distribution. Furthermore, lauric oils regularly comprise C10 and C14 fatty acid chains that also find various applications in the surfactants and other industries. More preferably, the natural oil feed is selected from the group consisting of coconut oil, palm kernel oil, babassu oil, macauba kernel oil, animal derived lauric oils and mixtures thereof. Even more preferably, the natural oil is selected from the group of palm kernel oil, coconut oil and mixtures thereof.

[0060] In most cases natural lauric oils as well as other natural oils contain certain degrees of fatty acid chains greater than C14 which do not give an acceptable range for manufacture of paraffins suitable for the manufacture of detergent range linear alkylbenzene. Thus, in an industrially applicable process the resulting paraffins from higher carbon chain fatty acids need to be valorized in a suitable manner through chemical reaction or blending with other process streams.

[0061] The fossil kerosene is typically obtained as a fraction of petroleum distillates. Depending on the source of the crude oil utilized for its manufacture, the composition of fossil kerosene can vary largely. Typically, kerosene fractions have a boiling range between 140-275 °C. The kerosene stream comprises any hydrocarbon in the range of C9-C16, among which there are normal paraffins, iso-paraffins, cyclic paraffins, aromatics and olefins.

[0062] The mixed feed (200) is delivered to a hydrodeoxygenation I hydrotreating unit (HDO- HT) (101) which also receives a hydrogen feed (not shown in figures). In the hydrodeoxygenation I hydrotreating unit (101), the glycerides and fatty acids in the feed (200) are deoxygenated and converted into normal paraffins and the fossil kerosene comprising normal paraffins, iso-paraffins, cyclic paraffins, aromatics and olefins is hydrotreated. The fossil kerosene feed comprises among others heteroatom impurities, with heteroatoms selected from the group of sulfur, nitrogen, oxygen and phosphorous. Both feedstocks, once mixed, need to be submitted to a hydrodeoxygenation I hydrotreating process before they can be used in the subsequent productive processes according to the invention. Preferably, both reactions are carried out in one reactor over one catalytic body that is at the same time suitable to carry out hydrodeoxygenation of the natural oil and hydrotreating of the fossil-based kerosene feedstock.

[0063] Structurally, triglycerides are formed by three, typically different, fatty acid molecules that are bonded together with a glycerol bridge. The glycerol molecule includes three hydroxyl groups (HO-) and each fatty acid molecule has a carboxyl group (COOH). In triglycerides, the hydroxyl groups of the glycerol join the carboxyl groups of the fatty acids to form ester bonds. Therefore, during deoxygenation, the fatty acids are freed from the triglyceride structure and are converted into normal paraffins. The glycerol is converted into propane, and the oxygen in the hydroxyl and carboxyl groups is converted into water, carbon dioxide, or carbon monoxide. The deoxygenation reaction for fatty acids and triglycerides are respectively illustrated as:

[0064] 3H»+RCOOH — * RCHj + 2H»O

[0065] RCOOH • - ► III + COj The deoxygenation reaction of mono- and diglycerides is analogous.

[0066] During the deoxygenation reaction, the length of a paraffin chain Rn created will vary by a value of one depending on the exact reaction pathway. It is understood that deoxygenation includes at least one of hydrodeoxygenation, decarboxylation, and decarbonylation, or any combination thereof. For instance, if carbon dioxide is formed, then the chain will have one fewer carbon than the fatty acid source. If water is formed, then the chain will match the length of the fatty acid source. For clarity sake, in this disclosure, hydrodeoxygenation or simply deoxygenation shall be used synonymously for processes that involve hydrodeoxygenation (i.e. mechanistically the removal of all oxygen atoms by formation of water), decarboxylation, and decarbonylation mechanisms.

[0067] During the hydrotreating reaction, heteroatom impurities are removed from the feed stream by action of hydrogen. Preferably, the heteroatom is removed from the alkyl chain forming among others but not limited to hydrogen sulfide, ammonia, water. As an exemplary reaction occurring during the hydrotreating process, carbon bound sulfur is reacted with hydrogen under action of a catalytic body:

[0068] H3C-CH2-CH2-SH + H2H3C-CH2-CH3 + H2S

[0069] The challenge of the above-mentioned process is that conditions need to be found in which hydrodeoxygenation and hydrotreatment can be carried out in the same hydrotreating unit, preferably in a kero-hydrotreater unit (KHT), preferably under the action of hydrogen and a single catalytic body.

[0070] Surprisingly, the inventors found that including less than 30% natural oil, more preferably less than 20% natural oil, most preferably less than 10% natural oil to the kerosene feed in the process leads to a particularly high deoxygenation activity of the combined stream while maintaining the catalysts hydrotreating activity towards impurities comprised in the fossil kerosene stream.

[0071] Accordingly, the hydrodeoxygenation I hydrotreating unit (101) is preferably a KHT which is also configured to deoxygenate the natural oil feed to produce paraffins. The triglycerides and fatty acids in the combined feed (200) are thus deoxygenated and converted into normal paraffins in the KHT (101), using a catalyst that is suitable for both hydrodeoxygenation and hydrotreating or a mix of catalysts that each accomplish one or more of hydrodeoxygenation or hydrotreating.

[0072] Operating conditions for the deoxygenating and hydrotreating unit (101) preferably include pressures in the range of from about 15 to about 80 bar, about 30 to about 70 bar, about 40 to about 60 bar and temperatures in the range of from about 274 °C to about 371 °C, from about 274 °C to about 338 °C, from about 274 °C to about 310 °C. Catalysts may include those containing one or more of Ni, Mo, Co, P, such as Ni-Mo, Ni- Mo-P, Ni-Co-Mo, or Co-Mo, on alumina, silica, titania, zirconia, and mixtures thereof. Suitable hydrogen to hydrocarbon volume ratios include from about 100 to about 2000, from about 120 to about 1500, and from about 140 to about 1200 standard cubic meters per cubic meter of feedstock (Nm3 / m3). Suitable space velocities include about 0.2-4.0 hr1LHSV.

[0073] In specific embodiments, two or more effluent streams exit the KHT (101), a light stream (201) comprising water, CO2, H2S, hydrogen and C1-C8 hydrocarbons and a heavy stream (202) comprising hydrocarbons C9-C18 derived from hydrodeoxygenation and hydrotreating of stream (200). Stream (202) comprises normal paraffins, iso-paraffins, cyclic paraffins and aromatics. The treated stream of hydrocarbons (202) exiting KHT (101) may be fed to a separator unit (N / l SEP) (102) to separate the desired normal paraffins from branched and cyclic paraffins and aromatics that may be included in the stream (202). A suitable separator for this purpose is a separator that operates using the UOP LLC Molex™ process, which is a liquid-state separation of normal paraffins from branched and cyclic components using UOP LLC Sorbex™ technology employing suitable molecular sieves. Other separators known in the art are suitable for use herein as well.

[0074] The separator generates a stream of hydrocarbons enriched in normal paraffins (203) and a stream of hydrocarbons depleted in normal paraffins (204). The hydrocarbon stream enriched in normal paraffins (203) comprises essentially a higher amount of normal paraffins than the stream (202) before entering the separator (102) and the hydrocarbon stream depleted in normal paraffins (204) comprises essentially a lower amount of normal paraffins than the stream (202) before entering the separator (102). The hydrocarbon stream (204) comprises iso-paraffins, cyclic paraffins and aromatics. The normal paraffin stream (203) exiting the separator (102) is fed to a fractionator (FRAC) (103). The natural oil feed includes hydrocarbons that are heavier than the carbon chains acceptable for detergent range linear alkylbenzene manufacture, and as such the fractionator (103) is provided to fractionate hydrocarbons in the normal paraffin feed (203). The stream of normal paraffins (203) is fractionated into at least two streams, a first stream (206) comprising normal paraffins in the range between C9-C14 which are suitable for the manufacture of linear alkylbenzene and a second stream of normal paraffins comprising normal paraffins in the range between C14-C18. A skilled person in the art is aware that fractionation techniques only guarantee enrichment of one component, a complete separation is usually not pursued. In particular embodiments, the first stream (206) comprises more than 70 wt.%, more than 75 wt.%, more than 80 wt.%, more than 85 wt.%, or more than 90 wt.% of normal paraffins in the C9-C14 range, more preferably in the C10-C13 range. In particular embodiments, the second stream (209) comprises more than 70 wt.%, more than 75 wt. %, more than 80 wt.%, more than 85 wt.%, more than 90 wt.% of normal paraffins in the C14-C18 range, more preferably in the range C15-C18. A skilled person in the art understands that stream (209) comprises paraffins derived from fatty acid chains of the natural oil with carbon numbers C14-C18. Optionally, at least three further streams are separated, a light stream (205) comprising normal paraffins of C9 and two intermediate normal paraffin streams (207) and (208) comprising normal paraffins of C14 and C14+C15 respectively.

[0075] The first fraction of paraffins (206) is introduced to an alkylbenzene production unit (104). FIG. 2 shows an embodiment for the production of linear alkylbenzene (243) from the first fraction of normal paraffins (206) in an alkylbenzene production unit (104). As can be seen in FIG. 2, specifically, the first fraction of paraffins (206) is fed into a dehydrogenation unit (109) in the alkylbenzene production unit (104). In the dehydrogenation unit (109), the first portion of paraffins (206) is dehydrogenated into mono-olefins of the same carbon numbers as the first portion of paraffins (206). Typically, dehydrogenation occurs through known catalytic processes, such as the commercially popular Pacol process. Di-olefins (i.e., dienes) and aromatics are also produced as an undesired result of the dehydrogenation reactions as expressed in the following equations:

[0076] Mono-olefin formation: CnH2n+2 -> CnH2n+H2

[0077] Di-olefin formation: CnH2n -> CnH2n-2+H2 Aromatic formation: CnH2n-2 -> CnH2n-6+2H2

[0078] Operating conditions for the dehydrogenation unit (109) include space velocities from about 5 hr1to about 50 hr1LHSV and from about 20 hr1to about 32 hr1LHSV; pressures from about 0.3 bar to about 4 bar and from about 1 bar; to about 2 bar; temperatures from about 400-500 °C and from about 440 to about 490 °C, and hydrogen to hydrocarbon mole ratios from about 1-12 and from about 5-7. An example of a suitable catalyst is a Pt on alumina catalyst where platinum is attenuated with an attenuator metal. Another suitable catalyst is described in U.S. Pat. No. 6,177,381. The unit may be operated dry or with water injection up to about 2000 mass-ppm water.

[0079] In FIG. 2, a dehydrogenated stream (231) exits the dehydrogenation unit (109) comprising mono-olefins and hydrogen, and any unreacted normal paraffins, as well as some di-olefins and aromatics. The dehydrogenated stream (231) is delivered to a phase separator (110) for removing the hydrogen (232) from the dehydrogenated stream (231). As shown, the hydrogen exits the phase separator (110) in a recycle stream of hydrogen (232) that may be added to the hydrogen feed to support the deoxygenation process upstream.

[0080] At the phase separator (110), a liquid stream (233) is formed and comprises the monoolefins and any di-olefins and aromatics formed during dehydrogenation and unreacted normal paraffins. The liquid stream (233) exits the phase separator (110) and enters a selective hydrogenation unit (111), such as a DeFine reactor. The hydrogenation unit (111) selectively hydrogenates at least a portion of the di-olefins in the liquid stream (233) to form additional mono-olefins. As a result, an enhanced stream (234) is formed with an increased mono-olefin concentration and decreased content in di-olefins.

[0081] As shown, the enhanced stream (234) passes from the hydrogenation unit (111) to a lights separator (112), such as a stripper column, which removes a light end stream (235) containing any lights, such as butane, propane, ethane and methane, that resulted from cracking or other reactions during upstream processing. With the light ends (235) removed, stream (236) is formed and may optionally be delivered to an aromatic removal apparatus (113). The aromatic removal apparatus (113) removes aromatics from the stream (236) and forms a stream of mono-olefins (237). Preferably, the aromatic removal apparatus contains an absorbent selected from the group of clays, activated charcoal and silica.

[0082] In FIG. 2, the stream of mono-olefins (237) and a stream of benzene (238) are fed into an alkylation unit (114). The alkylation unit (114) holds a catalyst, such as a solid acid catalyst, that supports alkylation of the benzene (238) with the mono-olefins (237). Fluorided silica-alumina, hydrogen fluoride (HF), aluminum chloride (AlCh), and zeolitic catalysts are examples of major catalysts in commercial use for the alkylation of benzene with linear mono-olefins and may be used in the alkylation unit (114). As a result of alkylation, alkylbenzene, typically called linear alkylbenzene (LAB), is formed according to the reaction: and are present in an alkylation effluent (239).

[0083] Suitable operating conditions for the alkylation unit (114) include space velocities from about 1 hr1to about 10 hr1LHSV, pressures to maintain liquid phase operation such as about 10 to about 45 bar, temperatures in the range of from about 80 °C to about 200°C and 100 °C to about 170 °C, benzene to olefin mole ratios of about 3 to about 40 and about 8 to about 35.

[0084] Surplus amounts of benzene (238’) are supplied to the alkylation unit (114) to achieve high degree of desired alkylation. Therefore, the alkylation effluent (239) exiting the alkylation unit (114) contains alkylbenzene and unreacted benzene. Further the alkylation effluent (239) may also include unreacted paraffins. In FIG. 2, the alkylation effluent (239) is passed to a benzene separation unit (115), such as a fractionation column, for separating the unreacted benzene from the alkylation effluent (239). This unreacted benzene exits the benzene separation unit (115) in a benzene recycle stream (238’) that is delivered back into the alkylation unit (114) to reduce the volume of fresh benzene needed in stream (238).

[0085] As shown, a benzene-stripped stream (240) exits the benzene separation unit (115) and enters a paraffinic separation unit (116), such as a fractionation column. In the paraffinic separation unit (116), unreacted paraffins are removed from the benzene-stripped stream (240) in a recycle paraffin stream (206’), and are routed to and mixed with the first portion of paraffins (206) before dehydrogenation as described above. Further, an alkylbenzene stream (242) is separated by the paraffinic separation unit (116) and is fed to an alkylate separation unit (117). The alkylate separation unit (117), which may be, for example, a multi-column fractionation system, separates a heavy alkylate bottoms stream (244) from the alkylbenzene stream (242).

[0086] As a result of the post-alkylation separation processes, the linear alkylbenzene product (243) is isolated and exits the alkylbenzene production unit (104). It is noted that such separation processes are not necessary in all embodiments in order to isolate the alkylbenzene product (243). For instance, the alkylbenzene product (243) may be desired to have a wide range of carbon chain lengths and not require any fractionation to eliminate carbon chains longer than desired, i.e., heavies or carbon chains shorter than desired, i.e., lights.

[0087] In a particular embodiment, the manufacture of linear alkylbenzene comprises: dehydrogenating the first fraction of normal paraffins (206) to obtain a dehydrogenated stream (231) comprising mono-olefins, di-olefins, and aromatics; selectively hydrogenating said dehydrogenated stream (231) to obtain a stream enriched in mono-olefins (234); alkylating said stream enriched in mono-olefins (234) with benzene under alkylation conditions to obtain a stream comprising linear alkylbenzene (237); and isolating a linear alkylbenzene product (243) from the linear alkylbenzene stream (237).

[0088] The product produced herein is a linear alkylbenzene product comprising alkylbenzenes having the formula CeHsCnbkn+i wherein n is from 9 to 14, more preferably from 10 to 13. In some embodiments, at least 80 mass percent of the alkylbenzenes have linear alkyl groups. In other embodiments at least 90 mass percent of the alkylbenzenes have linear alkyl groups or at least 92 mass percent of the alkylbenzenes have linear alkyl groups.

[0089] The linear alkylbenzene may be sulfonated to provide a linear alkylbenzene sulfonate product comprising: alkylbenzene sulfonate compounds having the formula Cnbkn+iCeF SOsH wherein n is from 9 to 14, more preferably from 10 to 13; wherein at least 80 mass percent of the alkylbenzene sulfonate compounds have linear alkyl groups. In other embodiments at least 90 mass percent of the linear alkylbenzene sulfonates have linear alkyl groups or at least 92 mass percent of the linear alkylbenzene sulfonates have linear alkyl groups.

[0090] The linear alkylbenzene sulfonate may be neutralized to provide a linear alkylbenzene sulfonate salt product comprising: alkylbenzene sulfonate compounds having the formula CnH2n+iC6H4SO3M wherein n is from 9 to 14, more preferably from 10 to 13, M is a cationic species selected from sodium, potassium, calcium, magnesium, quaternary ammonium; wherein at least 80 mass percent of the alkylbenzene sulfonate compounds have linear alkyl groups. In other embodiments at least 90 mass percent of the linear alkylbenzene sulfonates have linear alkyl groups or at least 92 mass percent of the linear alkylbenzene sulfonates have linear alkyl groups. The neutralized linear alkylbenzene sulfonate may be added to a detergent formulation.

[0091] The hydrocarbon stream (204) or at least a part thereof may be further processed to obtain a number of valuable products including hydrocarbon compositions suitable as fuels or fluids, as will be explained hereinafter in different embodiments. In particular, the apparatus comprises means for combining at least a part of the second fraction of normal paraffins (209), without being subjected to a hydrocracking or hydroisomerization reaction, with: either at least a part of the stream depleted in normal paraffins (204) or a fraction of said stream depleted in normal paraffins; and / or a product of hydrodearomatization of at least a part of the stream depleted in normal paraffins (204) or a product of hydrodearomatization of a fraction of said stream depleted in normal paraffins (204); and / or at least a part of the stream depleted in normal paraffins (204) or a fraction of said stream depleted in normal paraffins (204) to form a combined stream, and hydrodearomatizing said combined stream; to form at least a hydrocarbon composition.

[0092] As shown in FIG. 3, in specific embodiments at least a part of the stream of hydrocarbons depleted in normal paraffins (204) may be unified with at least a part of the heavy normal paraffin portion (209) from fractionation unit (103) to form a hydrocarbon composition (211) suitable for use as a fuel product. The stream (209) is not further chemically modified, especially no hydroisomerization or hydrocracking processes are effected on stream (209) before the unification, i.e. before it is mixed with hydrocarbon stream (204). The hydrocarbon composition (211) suitable for use as fuel contains preferably up to 10%, more preferably up to 5%, most preferably up to 1 % of normal paraffins in the range C14-C18.

[0093] In preferred embodiments of the present invention the fuel composition of stream (211) contains 0.1 to 10% of normal paraffins of carbon chain number between C14-C18. The present inventors found surprisingly, that the fuel composition fulfills all specifications for jet fuel according to ASTM-D1655 if the second stream of paraffins (209) is added in a fraction of up to 10%, up to 5%, up to 1 %.

[0094] Thus, the process and the apparatus of the invention may provide a composition of fuel with a content of biological matter without employing processes of hydrocracking or hydroisomerization in existing linear alkylbenzene production facilities. The invention thus offers a procedure to increase the biological matter derived content in conventional fuel compositions while producing renewable linear alkylbenzene. The composition is a hydrocarbon composition that preferably has a boiling range between 140 °C and 270 °C and a cloud point below -47 °C and a content of normal paraffins in the range C14- C18 of up to 10%.

[0095] In a particular embodiment, at least a part of the second fraction of normal paraffins (209) is combined with at least a part of the stream depleted in normal paraffins (204) to form a hydrocarbon composition (211) suitable as fuel, preferably a jet fuel that has a boiling range between 140 °C and 270 °C, a cloud point below -47 °C and a content of normal paraffins in the range C14-C18 of up to 10%.

[0096] As shown in FIG. 4, in another specific embodiment the stream of hydrocarbons depleted in normal paraffins (204) comprising iso-paraffins, cyclic paraffins and aromatics may be separated into two different streams.

[0097] The first part of the stream (204) may be directed to a unit for hydrodearomatization (106) to obtain a hydrocarbon stream (212) that comprises preferably less than 1000 ppm, more preferably less than 500 ppm, most preferably less than 250 ppm of aromatics. The hydrocarbon stream (212) preferably has a flash point of 70-90 °C and a boiling range from 160-290 °C and can be used as a dearomatized hydrocarbon fluid composition. The second part of the stream (204) may be directed to a fractionation unit (107) generating at least two fractionated streams. More preferably three streams of hydrocarbons are generated through fractionation unit (107), a light hydrocarbon stream (213) typically comprising C9-C12 iso-paraffins, cyclic paraffins and aromatics, a middle paraffin stream (214) typically comprising C12-C14 iso-paraffins, cyclic paraffins and aromatics and a heavy paraffin stream (215) typically comprising C13-C16 iso-paraffins, cyclic paraffins and aromatics. Each of the fractionated hydrocarbon streams (213), (214), (215) may be directed to a dearomatization unit (106’), (106”), (106”’) to reduce the aromatic contents in said streams. The dearomatization unit may be a different unit for each stream including the first part of the stream (204), or may be the same unit operating in flexible production campaigns. After dearomatization, one or more different hydrocarbon streams comprising preferably less than 1000 ppm, more preferably less than 500 ppm, most preferably less than 250 ppm of aromatics are obtained. Light hydrocarbon fraction

[0098] (213) may give after dearomatization rise to a stream of hydrocarbons (216) that preferably has a flash point of 50-70 °C and a boiling range from 160-230 °C and can be used as a dearomatized hydrocarbon fluid composition. Middle hydrocarbon fraction

[0099] (214) may give after dearomatization rise to a stream of hydrocarbons (217) that preferably has a flash point of 70-90 °C and a boiling range from 210-250 °C and can be used as a dearomatized hydrocarbon fluid composition. Heavy hydrocarbon fraction

[0100] (215) may give after dearomatization rise to a stream of hydrocarbons (218) that preferably has a flash point of 90-110 °C and a boiling range from 220-290 °C and can be used as a dearomatized hydrocarbon fluid composition. Heavy dearomatized stream (218) is then combined with heavy normal paraffin stream (209) to form a hydrocarbon stream (220) that has a superior flash point and a higher boiling range end point. Hydrocarbon stream (220) may preferably have a flash point of 90-130 °C, 100-120 °C or 105-115 °C and a boiling range from 220-320 °C or 230-300 °C and can be used as a dearomatized hydrocarbon fluid composition.

[0101] Hydrodearomatization conditions in the present invention involve a temperature in the interval of about 100-250°C, a pressure in the interval of about 15-100 bar, and a liquid hourly space velocity (LHSV) in the interval of about 0.5-8. Further, a material catalytically active in hydrodearomatization is used, wherein said material catalytically active in hydrodearomatization comprises an active metal taken from the group comprising platinum, palladium, nickel, cobalt, tungsten and molybdenum, preferably one or more elemental noble metals such as platinum or palladium and a refractory support, preferably amorphous silica-alumina, alumina, silica or titania, or combinations thereof, with the associated benefit of such process conditions being suitable for hydrogenation of aromatics. Said material catalytically active in hydrodearomatization under hydrodearomatization conditions may be a material catalytically active in hydrocracking or material catalytically active hydroisomerization operating at moderate temperatures favoring hydrodearomatization. Hydrodearomatization conditions preferably involve at least 50% or 80% conversion of aromatics.

[0102] In a particular embodiment, at least part of the stream depleted in normal paraffins (204) is subjected to fractionation to obtain at least a first fraction (215) comprising C13-C16 iso-paraffins, cyclic paraffins and aromatics, and said fraction (215) is subjected to hydrodearomatization prior to combination with at least part of the second fraction of normal paraffins (209) so as to form a hydrocarbon composition (220) suitable as fluid that preferably has a flash point between 90-130 °C, 100-120 °C or 105-115 °C and a boiling range between 220-320 °C or 230-300 °C.

[0103] As shown in FIG. 5, in another specific embodiment the stream of hydrocarbons depleted in normal paraffins (204) comprising iso-paraffins, cyclic paraffins and aromatics may be separated into two different streams.

[0104] The first part of the stream (204) may be directed to a unit for hydrodearomatization

[0105] (106) to obtain a hydrocarbon stream (212) that comprises preferably less than 1000 ppm, more preferably less than 500 ppm, most preferably less than 250 ppm of aromatics. The hydrocarbon stream (212) preferably has a flash point of 70-90 °C and a boiling range from 160-290 °C and can be used as a dearomatized hydrocarbon fluid composition. The second part of the stream (204) may be directed to a fractionation unit

[0106] (107) generating at least two fractionated streams. More preferably three streams of hydrocarbons are generated through fractionation unit (107), a light hydrocarbon stream (213) typically comprising C9-C12 iso-paraffins, cyclic paraffins and aromatics, a middle paraffin stream (214) typically comprising C12-C14 iso-paraffins, cyclic paraffins and aromatics and a heavy paraffin stream (215) typically comprising C13-C16 iso-paraffins, cyclic paraffins and aromatics. Hydrocarbon stream (215) is combined with at least a portion of heavy normal paraffin stream (209) to form a new paraffin stream (221). Each of the fractionated hydrocarbon streams (213), (214), (221) may be directed to a dearomatization unit (106’), (106”), (106”’) to reduce the aromatic contents in said streams. The dearomatization unit may be a different unit for each stream including the first part of the stream (204), or may be the same unit operating in flexible production campaigns. After dearomatization, one or more different hydrocarbon streams comprising preferably less than 1000 ppm, more preferably less than 500 ppm, most preferably less than 250 ppm of aromatics are obtained. Light hydrocarbon fraction (213) may give after dearomatization rise to a stream of hydrocarbons (216) that preferably has a flash point of 50-70 °C and a boiling range from 160-230 °C and can be used as a dearomatized hydrocarbon fluid composition. Middle hydrocarbon fraction (214) may give after dearomatization rise to a stream of hydrocarbons (217) that preferably has a flash point of 70-90 °C and a boiling range from 210-250 °C and can be used as a dearomatized hydrocarbon fluid composition. Heavy hydrocarbon fraction (221) may give after dearomatization rise to a stream of hydrocarbons (222) that has a superior flash point and a higher boiling range end point. Hydrocarbon stream (222) preferably has a flash point of 90-130 °C, 100-120 °C or 105-115 °C and a boiling range from 220- 320 °C or 230-300 °C and can be used as a dearomatized hydrocarbon fluid composition.

[0107] In a particular embodiment, at least part of the stream depleted in normal paraffins (204) is subjected to fractionation to obtain at least a first fraction (215) comprising C13-C16 iso-paraffins, cyclic paraffins and aromatics prior to combination with at least part of the second fraction of normal paraffins (209), and the combined stream (221) is subjected to hydrodearomatization so as to form a hydrocarbon composition (222) suitable as fluid that preferably has a flash point between 90-130 °C, 100-120 °C or 105-115 °C and a boiling range between 220-320 °C or 230-300 °C.

[0108] As shown in FIG. 6, in another specific embodiment the stream of hydrocarbons depleted in normal paraffins (204) comprising iso-paraffins, cyclic paraffins and aromatics may be unified with at least a portion of the heavy normal paraffins (209) to form a combined stream (223). A part of the combined stream (223) may be directed to a unit for hydrodearomatization (106) to obtain a hydrocarbon stream (224) that comprises preferably less than 1000 ppm, more preferably less than 500 ppm, most preferably less than 250 ppm of aromatics. The hydrocarbon stream (224) preferably has a flash point of 70-90 °C and a boiling range from 160-320 °C and can be used as a dearomatized hydrocarbon fluid composition. The other part of the combined stream (223) may be directed to a fractionation unit (107) generating at least two fractionated streams. More preferably three streams of hydrocarbons are generated through fractionation unit (107), a light hydrocarbon stream (225) typically comprising C9-C12 iso-paraffins, cyclic paraffins and aromatics, a middle paraffin stream (226) typically comprising C12-C14 iso-paraffins, cyclic paraffins and aromatics and a heavy paraffin stream (227) typically comprising C13-C16 iso-paraffins, cyclic paraffins and aromatics. Each of the fractionated hydrocarbon streams (225), (226), (227) may be directed to a dearomatization unit (106’), (106”), (106”’) to reduce the aromatic contents in said streams. The dearomatization unit may be a different unit for each stream including the first part of stream (223), or may be the same unit operating in flexible production campaigns. After dearomatization, one or more different hydrocarbon streams comprising preferably less than 1000 ppm, more preferably less than 500 ppm, most preferably less than 250 ppm of aromatics are obtained. Light hydrocarbon fraction (225) may give after dearomatization rise to a stream of hydrocarbons (228) that preferably has a flash point of 50-70 °C and a boiling range from 160-230 °C and can be used as a dearomatized hydrocarbon fluid composition. Middle hydrocarbon fraction (226) may give after dearomatization rise to a stream of hydrocarbons (229) that preferably has a flash point of 70-90 °C and a boiling range from 210-250 °C and can be used as a dearomatized hydrocarbon fluid composition. Heavy hydrocarbon fraction (227) may give after dearomatization rise to a stream of hydrocarbons (230) that has a superior flash point and a higher boiling range end point. Hydrocarbon stream (230) preferably has a flash point of 90-130 °C, 100-120 °C or 105-115 °C and a boiling range from 220- 320 °C or 230-300 °C and can be used as a dearomatized hydrocarbon fluid composition.

[0109] In a particular embodiment, at least part of the second fraction of normal paraffins (209) is combined with at least part of the stream of hydrocarbons depleted in normal paraffins (204) and the combined stream is subjected to fractionation and hydrodearomatization so as to form a hydrocarbon composition (230) suitable as fluid that preferably has a flash point between 90-130 °C, 100-120 °C or 105-115 °C and a boiling range between 220-320 °C or 230-300 °C.

[0110] Thus, the process may provide hydrocarbon fluid compositions. Most paraffinic hydrocarbon fluid products to date originate exclusively from petroleum based, nonrenewable raw materials. Therefore, it is highly desirable to find methods to increase the content of carbon of biological origin in paraffinic hydrocarbon fluid products in industry. A second aspect of the present invention refers to a hydrocarbon composition (220, 222, 230) consisting of: from 75 % to 99% of n-paraffins, iso-paraffins, cyclic paraffins in the C12-C16 range; from 1% to 20% of n-paraffins in the C17-C18 range; from 0-5% of other paraffins; and less than 1000 ppm of aromatics, and wherein the hydrocarbon composition has a flash point between 90-130 °C and the boiling range is between 220-320 °C.

[0111] Preferably, the present invention refers to a hydrocarbon composition (220, 222, 230) consisting of: from 75 wt.% to 99 wt.% of a mix of n-paraffins, iso-paraffins and cyclic paraffins in the C12-C16 range, where the content of iso-paraffins plus cyclic paraffins in the C12-C16 range is higher than 90 wt.% based on the total weight of the sum of n- paraffins, iso-paraffins and cyclic paraffins in the C12-C16 range; from 1 wt.% to 20 wt.% of n-paraffins in the C17-C18 range; from 0-5 wt.% of other paraffins; and less than 1000 ppm by weight of aromatics, and wherein the hydrocarbon composition has a flash point between 90-130 °C and the boiling range is between 220-320 °C.

[0112] In a particular embodiment, the invention refers to a hydrocarbon composition (220, 222, 230) consisting of: from 80% to 99% of n-paraffins, iso-paraffins, cyclic paraffins in the C12-C16 range; from 1% to 15% of n-paraffins in the C17-C18 range; from 0-5% of other paraffins; and less than 1000 ppm of aromatics, and wherein the hydrocarbon composition has a flash point between 90-130 °C and the boiling range is between 220-320 °C.

[0113] In a particular embodiment, the invention refers to a hydrocarbon composition (220, 222, 230) consisting of: from 80 wt.% to 99 wt.% of a mix of n-paraffins, iso-paraffins and cyclic paraffins in the C12-C16 range, where the content of iso-paraffins plus cyclic paraffins in the C12-C16 range is higher than 90 wt.% based on the total weight of the sum of n- paraffins, iso-paraffins and cyclic paraffins in the C12-C16 range; from 1 wt.% to 15 wt.% of n-paraffins in the C17-C18 range; from 0-5 wt.% of other paraffins; and less than 1000 ppm by weight of aromatics, and wherein the hydrocarbon composition has a flash point between 90-130 °C and the boiling range is between 220-320 °C.

[0114] The composition of the second aspect (220, 222, 230) is suitable as a hydrocarbon fluid. In a third aspect the present invention relates to the use of the composition described in the second aspect as a hydrocarbon fluid such as solvents and / or base oils.

[0115] The applications for hydrocarbon fluids in the industry are wide and each requires a specific product profile. Therefore, the hydrocarbon fluid of the invention will help industrial entities to choose from a wider array of available hydrocarbon fluids for their unique purposes. Furthermore, the industry is moving to HCF with higher flash points, therefore these arrangements permit not only increase the renewable content, but also the production of higher boiling range and flash point HCF which otherwise could not be produced in the existing facilities. Especially, the hydrocarbon fluid of the invention provides access to an array of new solvent products with higher flash points, a requirement that may contribute to the innate safety of the products fabricated. The claimed hydrocarbon fluid composition preferably has a flash point of 100-120 °C or 105- 115 °C and / or a boiling range from 230-300 °C and can be used as a dearomatized hydrocarbon fluid composition.

[0116] A further aspect of the present invention relates to an apparatus (or process plant) comprising a hydrodeoxygenation I hydrotreating unit (HDO-HT) (101), a separator unit (N / l SEP) (102), a fractionation unit (FRAC) (103), and alkylbenzene production unit (104), and optionally a hydrodearomatization unit (HDA) (106”’), said apparatus being configured for carrying out a process for the manufacture of linear alkylbenzene (243) and a hydrocarbon composition comprising: combining a stream of fossil kerosene comprising hydrocarbons C9-C16 with a stream of natural oil comprising fatty acid chains of C10, C12 and C14 to obtain a mixture (200); hydrotreating and hydrodeoxygenating in the hydrodeoxygenation I hydrotreating unit (HDO-HT) (101) the mixture (200) to form a hydrotreated and hydrodeoxygenated stream (202); separating said hydrotreated and hydrodeoxygenated stream (202) in the separator unit (N / l SEP) (102) to obtain a stream enriched in normal paraffins (203) and a stream depleted in normal paraffins (204); fractionating said stream enriched in normal paraffins (203) in the fractionation unit (FRAC) (103) to obtain a first fraction of normal paraffins (206) comprising normal paraffins in the range between C9-C14 and a second fraction of normal paraffins (209) comprising normal paraffins in the range between C14-C18; producing linear alkylbenzene (243) in the alkylbenzene production unit (104) from said first fraction of normal paraffins (206); and combining at least a part of the second fraction of normal paraffins (209), without being subjected to a hydrocracking or hydroisomerization reaction, with: either at least a part of the stream depleted in normal paraffins or a fraction of said stream depleted in normal paraffins; and / or a product of hydrodearomatization of at least a part of the stream depleted in normal paraffins or a product of hydrodearomatization of a fraction of said stream depleted in normal paraffins; and / or at least a part of the stream depleted in normal paraffins or a fraction of said stream depleted in normal paraffins to form a combined stream, and hydrodearomatizing said combined stream; to form at least a hydrocarbon composition.

[0117] In a preferred embodiment, the apparatus also comprises a recipient (100) where the stream of fossil kerosene comprising hydrocarbons C9-C16 and the stream of natural oil comprising fatty acid chains of C10, C12 and C14 are combined to obtain the mixture (200).

[0118] The different elements and operation of the apparatus of the invention have been already disclosed above when describing the process for the manufacture of linear alkylbenzene (243) and a hydrocarbon composition.

[0119] While at least one exemplary embodiment has been presented in the foregoing Detailed Description, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration of the invention in any way. Rather, the foregoing Detailed Description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment of the invention, it being understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope of the invention as set forth in the appended Claims and their legal equivalents.

[0120] EXAMPLES

[0121] Example 1 - Mixture of CPKO with Kerosene Fraction

[0122] Crude palm kernel oil (CPKO) was mixed with a stream of heavy kerosene (boiling range 140-245 °C) in different relations in a recipient (100). The combined stream (200) was classified according to its distillation curve and its homogeneity.

[0123] According to the specification NC 27101921 , a hydrocarbon composition needs to have less than 90% of the composition volume that boils at a temperature of 210 °C and more than 65% of the composition volume that boils at 250 °C. The mixtures (200) of this example comply with the specification according to NC 27101921 c). Furthermore, all investigated compositions are homogeneous at ambient temperature, signifying that they can easily employed in the process without phase separation risk.

[0124] Example 2 - Deoxygenation of Kerosene CPKO mixture under hydrodeoxygenation / hydrotreatment conditions

[0125] Stream of different mixtures of kerosene and crude palm kernel oil (200) were hydrotreated I hydrodeoxygenated in a flow reactor (KHT) (101) using a catalyst comprising cobalt and molybdenum under admixture of hydrogen. The unit was operated under a constant supply of kerosene and crude palm kernel oil in adiabatic conditions. The effluent (202) was characterized by its conversion, sulfur impurities and residual oxygen by infrared spectroscopy.

[0126] As can be seen from the table above all conditions are effectively sufficient to both reduce the content of C=O and oxygenates as well as the sulfur content stemming from the fossil kerosene stream.

[0127] Example 3 - Mixture of second portion of normal paraffins (209) with hydrodearomatized stream (218) for formation of hydrocarbon fluid compositions A stream of heavy n-paraffins (comprising C14-C18 n-paraffins) (209) obtained from the process according to the process depicted in Fig. 4 was provided. Its composition was according to the table below.

[0128] A hydrodearomatized stream (218) was obtained in a process according to Fig. 4. It contains the following amounts of hydrocarbon compounds.

[0129] ■ Experiment 3a

[0130] The above stream (209) (10 wt.%) was mixed with the stream (218) (90 wt.%) to form hydrocarbon fluid (220). Various investigations were performed to evaluate the properties of hydrocarbon fluid (220).

[0131] ■ Experiment 3b

[0132] In a further experiment, the stream (209) (30 wt.%) was mixed with the stream (218) (70 wt.%) to obtain hydrocarbon fluid (220) with modified properties. The properties are summarized in the table below.

[0133] Example 4 - Mixture of second portion of normal paraffins (209) with nonhydrodearomatized stream (215) for formation of hydrocarbon fluid compositions A stream comprising heavy normal paraffins (C14-C18 n-paraffins) (209) was obtained according to the process illustrated in Fig. 5. The composition of stream (209) is provided in the table below.

[0134] A non-hydrodearomatized stream (215), was obtained according to the process illustrated in Fig. 5. The properties of stream (215) are summarized in the table below. ■ Experiment 4a

[0135] A mixture was prepared by combining the stream (209) (15 wt.%) with the stream (215) (85 wt.%) and hydrodearomatize the combined stream (221) to obtain hydrocarbon fluid (222). The properties of hydrocarbon fluid (222) are summarized in the table below.

[0136] Experiment 4b In a further experiment, the stream (209) (25 wt.%) was mixed with the stream (215) (75 wt.%) and hydrodearomatize the combined stream (221) to obtain hydrocarbon fluid (222) with modified properties. The properties are summarized in the table below.

[0137] The above examples show that the method of the present invention allows producing solvents with an elevated flash point through the co-processing of natural oils and fossil kerosene. Unlike conventional kerosene-based production routes — which are not industrially integrated to achieve such high flash points — the method provided herein offers a technically and industrially feasible alternative.

[0138] Some key advantages include:

[0139] 1. High Flash Point Performance

[0140] The combination of the heavy normal paraffin fraction (C14-C18) with a stream depleted in normal paraffins — after hydrodearomatization — results in a final product with a high flash point, as demonstrated in pilot-scale examples. This performance exceeds typical values for kerosene-based solvents and opens new application possibilities.

[0141] 2. Novel Production Route Using Renewable Feedstocks

[0142] Traditionally, solvents with flash points above 100 °C are derived from heavier petroleum cuts, such as gasoil fractions. The present invention introduces a new route to such products by leveraging the co-processing of renewable oils with kerosene, without requiring hydrocracking or isomerization. This innovation enables the use of existing industrial assets while achieving superior solvent properties.

[0143] 3. Incorporation of Renewable Carbon

[0144] The final product contains a significant proportion of biogenic carbon, derived from the natural oils used in the process. This allows for the integration of renewable content into solvent formulations, supporting sustainability goals and regulatory compliance in markets that favor or require renewable-based products. Environmental and Safety Benefits o Reduced VOC emissions, contributing to improved air quality and lower environmental impact. o Lower flammability, enhancing safety during handling, storage, and transportation. o Absence of aromatic compounds, eliminating regulatory concerns and improving compatibility with sensitive applications. Enhanced Chemical Stability and Industrial Versatility

[0145] The resulting solvent exhibits high chemical stability, which extends shelf life and broadens its applicability across industries such as lubricants, agricultural chemicals, coatings, and cleaning products.

Claims

38CLAIMS1. A process for the manufacture of linear alkylbenzene (243) and a hydrocarbon composition comprising: combining a stream of fossil kerosene comprising hydrocarbons C9-C16 with a stream of natural oil comprising fatty acid chains of C10, C12 and C14 to obtain a mixture (200); hydrotreating and hydrodeoxygenating the mixture (200) to form a hydrotreated and hydrodeoxygenated stream (202); separating said hydrotreated and hydrodeoxygenated stream (202) to obtain a stream enriched in normal paraffins (203) and a stream depleted in normal paraffins (204); fractionating said stream enriched in normal paraffins (203) to obtain a first fraction of normal paraffins (206) comprising normal paraffins in the range between C9-C14 and a second fraction of normal paraffins (209) comprising normal paraffins in the range between C14-C18; producing linear alkylbenzene (243) from said first fraction of normal paraffins (206); and combining at least a part of the second fraction of normal paraffins (209), without being subjected to a hydrocracking or hydroisomerization reaction, with: either at least a part of the stream depleted in normal paraffins or a fraction of said stream depleted in normal paraffins; and / or a product of hydrodearomatization of at least a part of the stream depleted in normal paraffins or a product of hydrodearomatization of a fraction of said stream depleted in normal paraffins; and / or at least a part of the stream depleted in normal paraffins or a fraction of said stream depleted in normal paraffins to form a combined stream, and hydrodearomatizing said combined stream; to form at least a hydrocarbon composition.

2. The process according to claim 1 , wherein the natural oil is a lauric oil, preferably selected from the group consisting of coconut oil, palm kernel oil, babassu oil, macauba kernel oil, animal derived lauric oils and mixtures thereof.

3. The process according to claim 2, wherein the natural oil is selected from the group consisting of coconut oil, palm kernel oil and mixtures thereof.

394. The process according to any one of claims 1 to 3, wherein at least a part of the second fraction of normal paraffins (209) is combined with at least a part of the stream depleted in normal paraffins (204) to form a hydrocarbon composition (211) suitable as fuel, preferably a jet fuel that has a boiling range between 140 °C and 270 °C, a cloud point below -47 °C and a content of normal paraffins in the range C14- C18 of up to 10%.

5. The process according to any one of claims 1 to 4, wherein at least part of the stream depleted in normal paraffins (204) is subjected to fractionation to obtain at least a first fraction (215) comprising C13-C16 iso-paraffins, cyclic paraffins and aromatics, and said fraction (215) is subjected to hydrodearomatization prior to combination with at least part of the second fraction of normal paraffins (209) so as to form a hydrocarbon composition (220) suitable as fluid that preferably has a flash point between 90-130 °C and a boiling range between 220-320 °C.

6. The process according to any one of claims 1 to 5, wherein at least part of the stream depleted in normal paraffins (204) is subjected to fractionation to obtain at least a first fraction (215) comprising C13-C16 iso-paraffins, cyclic paraffins and aromatics prior to combination with at least part of the second fraction of normal paraffins (209), and the combined stream (221) is subjected to hydrodearomatization so as to form a hydrocarbon composition (222) suitable as fluid that preferably has a flash point between 90-130 °C and a boiling range between 220-320 °C.

7. The process according to claim any of claims 1 to 6, wherein at least part of the second fraction of normal paraffins (209) is combined with at least part of the stream of hydrocarbons depleted in normal paraffins (204) and the combined stream is subjected to fractionation and hydrodearomatization so as to form a hydrocarbon composition (230) suitable as fluid that preferably has a flash point between 90-130 °C and a boiling range between 220-320 °C.

8. The process according to any one of claims 1 to 7, wherein the separation to form the stream enriched in normal paraffins (203) and the stream of hydrocarbons depleted in normal paraffins (204) is carried out using molecular sieves.

409. The process according to any one of claims 1 to 8, wherein in the fractionation of the stream enriched in normal paraffins (203) at least three further fractions are separated, said fractions being a light fraction comprising normal paraffins of C9 (205) and two intermediate normal paraffin fractions comprising normal paraffins of C14 (207) and C14+C15 (208) respectively.

10. The process according to any one of claims 1 to 9, further comprising the steps for the manufacture of linear alkylbenzene of: dehydrogenating the first fraction of normal paraffins (206) to obtain a dehydrogenated stream (231) comprising mono-olefins, di-olefins, and aromatics; selectively hydrogenating said dehydrogenated stream (231) to obtain a stream enriched in mono-olefins (234); alkylating said stream enriched in mono-olefins (234) with benzene under alkylation conditions to obtain a stream comprising linear alkylbenzene (237); and isolating a linear alkylbenzene product (243) from the linear alkylbenzene stream (237).11 . The process according to any one of claims 9 to 10, wherein the linear alkylbenzene product (243) is further sulfonated to form linear alkylbenzene sulfonic acid.

12. The process according to claim 11 wherein the linear alkylbenzene sulfonic acid is neutralized to form linear alkylbenzene sulfonate.

13. The process according to claim 12, wherein the linear alkylbenzene sulfonate is added to a detergent formulation.

14. A hydrocarbon composition consisting of: from 75 wt.% to 99 wt.% of a mix of n-paraffins, iso-paraffins and cyclic paraffins in the C12-C16 range; from 1 wt.% to 20 wt.% of n-paraffins in the C17-C18 range; from 0-5 wt.% of other paraffins, and less than 1000 ppm by weight of aromatics;wherein the hydrocarbon composition has a flash point between 90-130 °C and the boiling range is between 220-320 °C.

15. Use of a hydrocarbon composition as defined in claim 14 as a hydrocarbon fluid, preferably as a hydrocarbon solvent and / or base oil.

16. An apparatus for the manufacture of linear alkylbenzene (243) and a hydrocarbon composition according to the process of any one of claims 1 to 13, said apparatus comprising a hydrodeoxygenation I hydrotreating unit (HDO-HT) (101), a separator unit (N / l SEP) (102), a fractionation unit (FRAC) (103), and alkylbenzene production unit (104), and optionally a hydrodearomatization unit (HDA) (106”’).

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