Hydrocarbon composition of biological origin containing aromatics

Abstract

New fuels produced from biological sources such as cashew nut shell liquid are disclosed, together with methods for producing such fuel by the conversion of phenol-lipids in ways avoiding oligomerization.

Description

DescriptionTitle of Invention:Hydrocarbon composition of biological origin containing aromaticsTechnical Field

[0001] The invention relates to the field of fuels produced from biological liquid material. In addition, the invention relates to methods for producing such fuels by the conversion of phenol-lipids in ways avoiding polymerization.Background Art

[0002] When a presence of aromatics is desired, substantial chemical modification of the products originating from triglycerides is required.

[0003] We have now identified that a compound comprising a cyclic structure with a paraffinic side chain may be beneficial in this respect, and furthermore we have identified that such a compound may be produced from phenol-lipids and hydrodeoxygenation.

[0004] For e.g. pyrolysis oil comprising reactive conjugated diolefins in aromatic compounds, an initial hydrotreatment at low temperatures may be carried out to avoid formation of oligomers which may solidify in the process. Oligomerization during the processing of such feeds may be avoided by dilution with a range of compounds, but pyrolysis oil from biological sources is dominated by oxygenates, and is commonly not miscible with diesel product, unless at least partially hydrodeoxygenated.

[0005] For triglycerides a higher reaction temperature is required to initiate the exothermic reaction, but to control reaction temperature, quenching and dilution with non-reactive product is employed, typically without miscibility issues.

[0006] Raw phenol-lipids may commonly contain reactive double-bonds and may in a manner similar to reactive pyrolysis oil feedstocks, produce oligomers which may solidify and block production equipment. From biological and medical research phenol-lipids are known to show preference for the aqueous phase, which leads to an expectation of poor miscibility with hydrocarbons as well as lipids, such as triglycerides in a biological setting.

[0007] However, we have surprisingly found that contrary to biological pyrolysis oil, phenol-lipids are miscible with diesel, triglycerides and hydrotreated products of such mixtures and pure hydrotreated phenol-lipids, and we have confirmed that this feature may be employed to direct diluted phenol-lipids to hydrodeoxygenation in a reactor operating at elevated temperature, such as 250°C and above. The dilution works as a safeguard against oligomerization, and the elevated temperature supports stepwise reaction, with saturation of double bonds at moderate temperature, releasing energy, supporting hydrodeoxygenation at an elevated temperature.Summary of Invention

[0008] Cyclic (aromatic or non-aromatic) compounds with an alkane side chain having biological origin, as well as compositions comprising such compounds are provided.

[0009] In addition, a simple process for upgrading phenol-lipids is provided, in which double bonds are saturated, oxygen is removed and oligomerization is minimized.Definitions

[0010] A material catalytically active in a chemical reaction such as hydrodeoxygenation shall be understood as a material having significant catalytic activity and preference for said chemical reaction under the conditions used. As it will be realized by the skilled person, most reactions will show an amount of side reactions, but unless otherwise specified the term a material catalytically active in a chemical reaction under active conditions shall be understood as a combination of feedstock composition and physical conditions under which a commercially relevant amount of conversion takes place with higher selectivity than any other chemical reaction.

[0011] As used herein, the term topology of a molecular sieve is used in the sense described in the 'Atlas of Zeolite Framework Types," Sixth Revised Edition, Elsevier, 2007, and three letter framework type codes are used in accordance herewith.

[0012] The severity of reaction conditions shall be understood as the extent to which a given reaction will take place. Hydrodeoxygenation severity, shall e.g. be understood as being increased if one or more physical or chemical conditions are changed in a way having the consequence that the degree of hydrodesulfurization is increased.

[0013] Pressure units such as “MPag”, shall in compliance with the practice of the field be used to denote MPa, gauge, i.e. the pressure relative to atmospheric pressure.

[0014] The gas to oil ratio (GOR) is defined as the ratio between gas entering a process step and oil (feedstock) entering the process step. For the present document the ratio is based on the total amount of gas (recycle and make-up gas in combination) relative to the fresh feedstock entering the same process step (i.e. excluding recycle). The gas to oil ratio is commonly given as a ratio between the volume of gas at normal conditions (Nm3- the volume at 0°C and 1 atmosphere) and the liquid at standard conditions (m3- typically at 60°F and 1 atmosphere). GOR is presented without compensation for hydrogen purity - unless stated as hydrogen to oil ratio. Commonly GOR reflects a need for excess hydrogen, which commonly is available by a safety factor of 6 as obtained by multiplication with the observed or the theoretical consumption of hydrogen, but a safety factor from 3 to 8 may be observed in practice.

[0015] Where concentrations in the gas phase are given, they are, unless otherwise specified, given as volume / volume concentration.

[0016] Where concentrations of oxygenates or other groups of molecules are referred to, they shall signify the concentration of all the molecules of such a group, and not to the functional group.

[0017] Where concentrations in the solid or liquid phase are given, they are, unless otherwise specified given as wt / wt concentration.

[0018] Where concentrations of elements in compounds or mixtures in any phase are given, they are, unless otherwise specified given as wt / wt concentrations.Technical Problem and Solution to Problem

[0019] In recent years conversion of biological liquid material to fuel has developed into an established industry, employing especially triglycerides as a feedstock. The drawbacks of earlier diesel fuels based on fatty acid methylated esters have been overcome by the technology of hydroprocessing, by which fuels absent of oxygen and with excellent fuel properties, especially for use in diesel engines, have been developed.

[0020] Fuels of biological origin are limited by the availability of feedstock, and therefore alternative feedstock is desired. This includes feedstock known as pyrolysis oil obtained by conversion via liquefaction methods such as pyrolysis and related thermochemical techniques. Products from pyrolysis of biological materials are polar due to their oxygen content, and thus commonly immiscible with non-polar liquids such as hydrocarbon fuels, such that recycle of product is not viable for their processing, and therefore a low temperature stabilization step saturating olefins is required.

[0021] A simpler approach is however to identify suitable feedstocks available without such conversion. One potential group of feedstocks are phenol-lipids, such as cardanol (shown below) and anacardic acids which may be extractedfrom a range of biological materials including waste from food production such as cashew shells and mango kernels. It is reported that for cashew nutshell liquid the alkane side chain in the raw feedstock has a dominant chain length of 15 carbon atoms, but other side-chain length may be found in other raw feedstocks. An additional methyl or ethyl substitute may also be found on the benzene ring. The content of oxygen in such feedstocks is approximately 5 wt%.

[0022] The raw biological source of phenol-lipids, e.g. crude cashew nut shell liquid (CNSL), commonly is anacardic acid (or similar structures) in which a carboxylic acid group is found between the phenol group and the side chain. This carboxylicacid group may beneficially be removed by pretreatment such as thermal reactions or by acid wash to provide what is known as 2ndboil CNSL, or alternatively by hydrotreatment, to provide acid free phenol-lipids.

[0023] During conversion, phenol-lipids have multiple challenges similar to those of products from pyrolysis of biological materials. The lipid chain is commonly unsaturated which may lead to oligomerization with formation of high boiling compounds. This may happen if phenol-lipids are used directly as fuels, and it may also happen during hydroprocessing at elevated temperatures.

[0024] Compounds having a tendency to polymerize, such as olefins, may preferentially be hydrotreated in dilution, since this will reduce the rate of polymerization. However, this approach requires that the diluent and the feedstock are miscible, and from treatment of pyrolysis products it is known that oxygenate feedstocks have poor miscibility with the hydrotreated hydrocarbon product.

[0025] The research related to phenol-lipids has mainly been in the life sciences, and here it has been reported that some phenol-lipids have poor miscibility with lipids. Based on this information it was expected that dilution with hydrotreated hydrocarbon product could be problematic, and that an initial stabilization reactor may be required, which could either operate at low temperature such as 120°C to 220°C on the pure phenol-lipids or possibly at a higher temperature such as 150°C to 250°C in combination with a dilution with partially hydrotreated feedstock.

[0026] Surprisingly we have identified that hydrocarbons such as fossil diesel, vegetable oil and hydrotreated phenol-lipids are suited for dilution of phenol- lipids, such that they may be processed together while reducing the risk of polymerization. This has the benefit of avoiding a stabilization reactor operating at low temperatures upstream the main hydrodeoxygenation reactor.

[0027] US 2024 / 0124791 has described the use of phenolic lipids for the production of renewable diesel. Here it is described favorably that release of small molecules is avoided, such that the full amount of the biological carbon can be used in the fuel, and it is demonstrated in experiments with up to 10 wt% phenolic lipids that a product with less than 4 wt% aromatics may be produced.

[0028] As mentioned above, we have, contrary to this, identified specific valuable properties including the presence of aromatics and cyclohexanes.

[0029] The hydrotreatment of oxygenates involves release of thermal energy, causing a temperature increase in the reactor. To ensure a robust process, to avoid thermal oligomerization of feedstock and to avoid damage to catalysts, it is commonly desired to keep the temperature increase over a catalyst bed below 55°C / m, such as below 50°C / m or even below 45°C / m, and in practice this may be implemented by dilution with a saturated hydrocarbon, to around 35 wt% fresh feed for a triglyceride feed. This will distribute the heat release across a larger volume of catalyst due to the increased heat capacity of the liquid.

[0030] We have observed that the hydrodeoxygenation of phenolic oxygen is less reactive than oxygen in triglycerides and fatty acids. Therefore, the heat release from hydrotreating phenol-lipids is slower than for triglycerides. In process design, this may be employed to provide the benefit of reducing the required recycle of product, resulting in reduced reactor size and energy required to circulate the feedstock. Based on moderate extrapolation of current experiments, we estimate that a dilution to 50 wt%, 60 wt% or even 70 wt% fresh feed may be operational, which translates into a total volume of fresh feed+diluent being reduced from about 300 % of the flow of fresh feed to perhaps less than 150 % of the flow of fresh feed, which also is reflected proportionally in reactor size and energy required to circulate the feedstock.

[0031] After hydrodeoxygenation, the oxygen is substantially removed, or at least commonly below 1 wt% such as below 200 ppmwt or 100 ppmwt. In addition, other hydrotreatment reactions occur simultaneously, such as saturation of double bonds in the side chain, and a partial saturation of the aromatic rings in the feedstock. For convenience we call this hydrocarbon composition C6C-R1 (where C6C is a cyclic structure comprising 6 carbon atoms in aromatic or saturated form and R1 is an alkane group comprising 13-18 carbon atoms) or Ph-C15 when cyclic group is aromatic, and the side chain has a length of 15 carbon atoms. Similarly, Cy-C15 would designate a compound with a cyclohexane cyclic groupand a side chain which has a length of 15 carbon atoms, as shown below.

[0032] Hydrodeoxygenation, as well as other processes removing heteroatoms (i.e. atoms other than C and H) from hydrocarbonaceous compounds is carried out in a so-called hydrotreatment step. The step may also be named hydrodemetalation, hydrodenitrogenation etc. from the heteroatoms released.

[0033] The material catalytically active in hydrotreatment, typically comprises an active metal (sulfided base metals such as nickel, cobalt, tungsten and / or molybdenum, but if the hydrocarbon is free of sulfur and nitrogen compounds possibly also elemental noble metals such as platinum and / or palladium and other metals of the platinum group) and a refractory support (such as alumina, silica or titania, or combinations thereof). Base metal catalysts are commonly tungsten and / or molybdenum promoted by presence of nickel and / or cobalt (2-20 wt% molybdenum and / or tungsten in combination with nickel and / or cobalt in an atomic ratio of 0.2-1 .0 (Ni+Co):(Mo+W)), and commonly the support is a simple refractive material such as alumina, silica, titania or activated carbon. Commonly the material is absent of more acidic materials such as molecular sieves and silica-alumina. In general all hydrotreatment catalysts are active in all hydrotreatment reactions, but for hydrodeoxygenation of especially triglycerides a molybdenum based catalyst with much lower concentration of promoter (such as ratios below 0.1 ), or even absence of promoters, may however be favorably used as such a material will favor selectivity toward hydrodeoxygenation, separating oxygen as water, over decarboxylation / decarbonylation separating oxygen as carbon oxides in feedstocks with carbonyl groups or carboxylic acids, thus avoiding a loss of biological carbon. In addition, the lower catalyst activity may slow down the reaction rate and thus distribute heat released by the exothermic reactions. Active hydrotreating conditions typically involve a temperature in the interval 250-460°C, a pressure in the interval 3-30 MPa, and a liquid hourly space velocity (LHSV) in the interval 0.1-5 hr-1 and a GOR (gas to oil ratio) of 300- 10000 Nm3 / m3optionally together with intermediate cooling by quenching withcold hydrogen, feed or product. The GOR would depend on the theoretical hydrogen consumption for hydrotreating the feedstock, multiplied by a safety factor which commonly may be at least 2 or 3 and less than 5, 8 or 10. The seventy of hydrotreatment is typically increased by increasing temperature, hydrogen availability (partial pressure and relative flow rate) and the metal content and dispersion on catalysts. An unpromoted catalytically active material comprising molybdenum and less than 0.5 wt% nickel and cobalt on a refractory support is commonly used in a first step, followed by a promoted catalytically active material comprising molybdenum or tungsten in combination with nickel or cobalt on a refractory support to support the reaction going to completion. The use of an unpromoted catalyst has been identified as not being necessary in the case of a less reactive feedstock with a molecular structure where the oxygen is bound as an alcohol to an aromatic ring (phenols) or cyclohexanes (cyclohexanols), and thus does not favor decarboxylation or decarbonylation.

[0034] When the heteroatom ic products of hydrotreatment are fluid, such as hydrocarbons and products comprising heteroatoms (such as water, ammonia, hydrochloric acid and hydrogen sulfide) these will leave the reactor and may be separated downstream. When the heteroatomic products are solid (such as released metals, silicon and phosphorous), they will commonly precipitate on the catalytically active material, which therefore preferably is designed to have a capacity for uptake of such solid heteroatomic compounds, e.g. by high void space, high surface areas and high pore diameters. This material is commonly called a guard catalyst, and may conveniently be placed in one or more separate reactors, operating at selected conditions, according to the heteroatoms to be captured. Hydrotreatment may thus be carried out in multiple guard reactors, and possibly also multiple hydrodeoxygenation reactors, but for small scale plants, it may also be beneficial to operate all hydrotreatment steps in a single reactor.

[0035] It has been observed that cashew nut shell liquid has a tendency to gum formation on surfaces of equipment and catalyst, which is assumed to be due to polymerization of phenol-lipids and subsequent dehydrogenation. When diluting the phenol-lipids with a saturated molecule such as n-hexadecane, similar gum formation has been observed, whereas dilution with soy oil prevented such gum formation. Without being bound by theory, one plausible theory is that at high gasrates, elevated temperature and pressure, the elevated partial pressure of a light boiling diluent such as n-hexadecane will effectively strip off a significant amount of n-hexadecane to the gas phase. As a consequence, the concentration of phenol-lipids in the liquid phase is increased, which will increase the rate of polymerization. Assuming this mechanism, it is preferred to employ a diluent having a moderate partial pressure at the reaction conditions. A practical guidance based on empirical experience is to use a diluent having an atmospheric boiling point above the process temperature, such as triglycerides, a light gas oil or a heavy kerosene fraction.

[0036] An alternative plausible theory is that double bonds and oxygen groups in triglycerides interact with reactive sites on the catalyst, and thus moderates the catalyst ability to catalyze polymerization. It is therefore preferred to dilute phenol-lipids with a reactive diluent, with the assumed effect of slowing the initial catalytic polymerization, until the concentration of polymerizable molecules is reduced.

[0037] An alternative means for moderating catalytic reactions by reducing the temperature in initial stages, which is assumed to allow saturation of reactive alcohol groups and double bonds, while keeping the temperature sufficient low for avoiding polymerization, until the concentration of polymerizable molecules is reduced.

[0038] As will be known to the skilled person the claimed processes require circulation of gaseous streams rich in hydrogen in addition to the liquid stream being the main focus of the invention. In general excess hydrogen is preferred to be present in the processes, to avoid formation of carbon on the surface of catalysts, but to save cost and environmental load, the recycle of hydrogen is practiced.

[0039] When the catalytically active material contains elemental noble metals substantial absence of sulfur is required, and contrary when the catalytically active material contains sulfided base metals a presence of sulfur is required, commonly 100 to 2000 ppmvoi. Therefore, as known to the skilled person, purification of recycled hydrogen rich gas may be required, and addition of highpurity make-up gas will commonly be made to the process stage which uses noble metal catalysts.Embodiments and Advantageous Effects

[0040] A first embodiment relates to a hydrocarbon composition comprising from 25 wt% to 100 wt% of a compound having the structure C6C-R, in which C6C is a cyclic structure comprising 6 carbon atoms in aromatic or saturated form and R is an alkane group comprising 13-18 carbon atoms, and wherein the14C content in the C isotopes in the hydrocarbon composition is at least 10% of the14C content in biological materials, and wherein the hydrocarbon composition comprises less than 100 ppmwt O. This has the associated benefit of such a hydrocarbon composition comprising an amount of cyclic compounds, supporting swelling of sealings.

[0041] A second embodiment relates to the hydrocarbon composition according to the first embodiment wherein the C6C-R compounds comprise 10 wt% to 50 wt% of aromatic C6 structures and the remainder of C6C-R compounds are saturated C6 rings. This has the associated benefit of such a hydrocarbon composition being a composition of sustainable origin while comprising a specific amount of aromatics supporting swelling of sealings.

[0042] A third embodiment relates to a method for producing a hydrotreated intermediate composition involving directing a hydrocarbonaceous mixture comprising one or more phenol-lipids of biological origin and an amount of hydrogen to contact a hydrodeoxygenation catalyst under active hydrodeoxygenation conditions to provide said hydrotreated intermediate composition, characterized in said hydrocarbonaceous mixture containing at least 1 wt% O, 2 wt% O or 5 wt% O and less than 15 wt% O or 25 wt% O and comprising from 25 wt% or 35 wt% to 50 wt% or 80 wt% phenol-lipids, and further characterized in said hydrodeoxygenation catalyst being a sulfided base metal catalyst on a support comprising alumina, and in said hydrodeoxygenation conditions involving an initial temperature above 250°C, such as above 270°C or 300°C and below 400°C, such as below 370°C, a pressure of at least 2 MPag such as 5 MPag and less than to 20 MPag such as 15 MPag, a gas to oil ratio of 500 Nm3 / m3to 2500 Nm3 / m3or 5000 Nm3 / m3and a space velocity above 0.1 hr1or 0.2 hr1and below 2 hr1or 5 hr1and in said hydrotreated intermediate composition having an oxygen content being less than 1 wt% 0. This has the associated benefit of such a method converting a specific feedstock of biological origin to a useful hydrocarbon. The temperature at the initial contact with the hydrotreatment catalyst may be limited to 250°C, and may be controlled to less than 400°C or 350°C by addition of quench hydrogen or cold feedstock.

[0043] A fourth embodiment relates to a method according to the third embodument, wherein said hydrodeoxygenation conditions involves an initial temperature above 250°C such as above 270°C or 300°C and below 320°C, such as below 300°C and wherein the reactions releases heat elevating the temperature to above 320°C, such as above 340°C and below 420°C such as below 410°C or below 400°C. This has the associated benefit of initial hydrodeoxygenation conditions stabilizing the hydrocarbonaceous mixture at low temperature, avoiding gum formation.

[0044] In a fifth embodiment relating to a method according to the third or fourth embodiment the hydrocarbonaceous mixture comprises more than 10 wt%, such as 20 wt% or 30 wt% and less than 80 wt%, such as 60 wt%, 50 wt% or 40 wt% of oxygenates, aromatics, nitrogen and sulfur compounds in combination, such as triglycerides or fatty acids. This has the associated benefit of moderating catalyst activity by competition while diluting with material which may contribute as a heat sink.

[0045] A sixth embodiment relates to the method according to the third, fourth, or fifth embodiment further comprises the step of providing said hydrocarbonaceous mixture by combining a biologically derived liquid with a diluent, said diluent comprising one or more of a hydrotreated hydrocarbonaceous composition and a fossil hydrocarbon. This has the associated benefit of providing a robust and simple method for conversion of phenol-lipids to intermediates useful as fuels, by dilution with a substantially saturated compound, optionally of biological origin such as hydrotreated triglycerides, hydrotreated fatty acids or hydrotreated phenol-lipids contributing as a heat sink.

[0046] An seventh embodiment relates to the method according to the sixth embodiment wherein said hydrotreated hydrocarbon comprises an amount ofsaid hydrotreated intermediate composition or a composition derived therefrom. This has the associated benefit of simplifying the feedstock supply, by providing the diluent at least in part as recycle.Examples

[0047] The reactivity and robustness of a process for deoxygenation of CNSL, as an example of a phenol-lipid was investigated.Example 1

[0048] Three oils were used for the evaluation. CNSL, Soy oil and light gasoil. Characteristics of these oils are shown in Table 1 .

[0049] The oils were in different ratios treated in a reactor setup comprising three different commercially available catalysts from Topsoe A / S, 19 ml TK-340, 7 ml TK-359 and 46 ml TK-569, at a temperature of 330-340°C with a space velocity of 0.9 hr1, a pressure of 7.5 MPag and a hydrogen to oil ratio being a factor 5 of the hydrogen consumption.

[0050] During the test feedstock mixtures of 0 wt%, 9 wt%, 18 wt%, 42 wt% and 100 wt% CNSL were tested, in combination with soy oil and light gas oil as shown in Table 2.

[0051] As the mixture of light gasoil and soy oil contained 11 wt% aromatic after hydrodeoxygenation, this was considered the basis contribution of 71 wt% light gas oil to hydrotreated product (as soy oil does not contain aromatics). These experimental data indicated that 10-40 wt% of the aromatic CNSL is maintained in aromatic form, without optimization of the aromatics yield. The experiments with absence of soy oil showed full hydrodeoxygenation and extremely low formation of CO and CO2, confirming absence of carboxylic acids and reactive carbonyls.

[0052] The experiment with 100 wt% CNSL showed some oligomerization, including formation of di-aromatic and tri-aromatic compounds, but other than the saturation of aromatics and oligomerization of 100 wt% CNSL the experiments indicate that hydrotreatment is quite selective, with few side reactions.

[0053] Therefore the experiments confirm a potential for recycling moderate amounts of hydrotreated product, such that it even is likely that after a short start-up periodhydrotreatment of a combination of CNSL with hydrotreated, recycled, CNSL is possible. The recycle to fresh feed ratio may be 1 :1 , considering the selective reactions with 42 wt% CNSL, but even a ratio of 1 :2 appears likely to lead to a robust process, since recycled CNSL product will only transfer moderately to the gas phase.

[0054] Example 2

[0055] Co-processing of cashew nutshell liquid (CNSL) with either n-hexadecane (nC16) or soybean oil (SOY) was evaluated in a pilot plant hydrotreating setup to assess process feasibility and supplement patent application data.

[0056] Three compositions were tested: 20 vol% and 42 vol% CNSL in n- hexadecane, and 20 vol% CNSL in soy oil. All compositions were doped with DMDS to approximately 500 wt ppm sulfur. The catalyst system comprised Topsoe TK-340 and TK-569, loaded in a stainless-steel trickle-bed reactor, and operated at 300-330°C, 5.0-7.5 MPag, LHSV 0.92 hr-1, and H2 / oil ratio of 990 Nl / I.

[0057] Severe gum formation and reactor plugging were observed during isothermal operation with CNSL / n-hexadecane blends at 330°C and 300°C. Implementing a temperature gradient with a lower reactor inlet temperature (~280°C) successfully prevented further gum formation and plugging, enabling stable operation for these compositions, with the temperature increasing to 300°C from exothermic reaction.

[0058] For CNSL / soy oil compositions, no reactor plugging occurred under any tested conditions, including isothermal operation at 300°C and 330°C. Monoaromatic content in the hydrotreated product increased with both temperature and CNSL content in soy oil compositions, reaching up to 3.23 wt% at 330°C and 20 vol% CNSL. In contrast, aromatic content in CNSL / n-hexadecane blends remained negligible (<0.5 wt%). Compared to Example 1 , while the apparent LHSV is the same, the fact that 58-80% of non-reacting n-hexadecane was present, the effective LHSV is actually much lower, which is a likely reason for the high extent of aromatic saturation.

[0059] Complete removal of oxygen (to <200 wt ppm), nitrogen (<2 wt ppm), and sulfur (<5 wt ppm) was achieved for all compositions and conditions.

[0060] Product boiling point distributions indicated that heavy-end (BP >400°C) formation increased with temperature but was not significantly affected by higher CNSL content in soy oil compositions.

[0061] The results demonstrate that co-processing of CNSL with n-hexadecane or soy oil is feasible, with complete heteroatom removal and manageable hydrogen consumption. Reactor plugging due to gum formation occurred, but surprisingly it was found to be mitigated by moderating catalyst activity, either by employing a temperature gradient with a lower inlet temperature, particularly for paraffinic diluents such as n-hexadecane or by dilution with a reactive compound. The hydrotreatment step yields hydrotreated intermediates.Patent Literature

[0062] PTL1 : US 2024 / 0124791Table 1Soy / LGO 9% CNSL 18% CNSL 42% CNSL 100% CNSL% CNSL 0 9 18 42 100 % Soy 29 18 9 0 0 % LGO 71 73. 73 58 0 I. BP [°C] 165 168 162 168 330 T30 [°C] 289 289 286 304 401 T50 [°C] 325 325 322 352 402 T70 [°C] 369 368 365 399 404 T90 [°C] 608 606 423 402 417Table 2Soy / LGO 9% CNSL 18% CNSL 42% CNSL 100% CNSL% CNSL0 9 18 42 100 % Soy 29 18 9 0 0 % LGO 71 73. 73 58 0 I. BP [°C] 150 154 159 166 260 T30 [°C] 282 282 282 299 368 T50 [°C] 311 314 316 349 370 T70 [°C] 320 331 347 368 371 T90 [°C] 353 366 368 371 530 % Aromatics 11.7 15.1 14.8 15.2 11.6Table 3% Soy 0 0 80 % nC16 80 58 0 I.BP [°C] 287 287 393 T30 [°C] 292 292 597 T50 [°C] 293 293 606 T70 [°C] 294 400 610 T90 [°C] 399 402 613Table 4

Claims

Claims

1. A hydrocarbon composition comprising from 25 wt% to 100 wt% of a compound having the structure C6C-R, in which C6C is a cyclic structure comprising 6 carbon atoms in aromatic or saturated form and R is an alkane group comprising 13 to 18 carbon atoms, and wherein the14C content in the C isotopes in the hydrocarbon composition is at least 10% of the14C content in biological materials, and wherein the hydrocarbon composition comprises less than 100 ppmwt O.

2. A hydrocarbon composition according to claim 1 , wherein the C6C-C15 compounds comprise 10 wt% to 50 wt% of aromatic C6 structures and the remainder of C6C-R compounds are saturated C6 rings.

3. A method for producing a hydrotreated intermediate composition, involving directing a hydrocarbonaceous mixture comprising one or more phenol-lipids of biological origin and an amount of hydrogen to contact a hydrodeoxygenation catalyst under active hydrodeoxygenation conditions to provide said hydrotreated intermediate composition characterized in said hydrocarbonaceous mixture containing at least 1 wt% O, 2 wt% 0 or 5 wt% 0 and less than 15 wt% 0 or 25 wt% 0 and comprising from 25 wt% or 35 wt% to 50 wt% or 80 wt% phenol-lipids wherein at least 50% of the C isotopes in the phenol lipids are14C, and further characterized in said hydrodeoxygenation catalyst being a sulfided base metal catalyst on a support comprising alumina, and in said hydrodeoxygenation conditions involving an initial temperature above 250°C such as above 270°C or 300°C and below 400°C, such as below 370°C, a pressure of at least 2 MPag such as 5 MPag and less than 20 MPag such as 15 MPag, a gas to oil ratio of 500 Nm3 / m3to 2500 Nm3 / m3or 5000 Nm3 / m3and a space velocity above 0.1 hr1or 0.2 hr1and below 2 hr1or 5 hr1and in said hydrotreated intermediate composition having an oxygen content being less than 1 wt% O.,

4. A method for producing a hydrotreated intermediate composition according to claim 3, wherein said hydrodeoxygenation conditionsinvolves an initial temperature above 250°C such as above 270°C or 300°C and below 320°C, such as below 300°C and wherein the hydrodeoxygenation reaction releases heat elevating the temperature to above 320°C, such as above 340°C and below 420°C such as below 410°C or below 400°C.

5. A method for producing a hydrotreated intermediate composition according to claim 3 or 4 wherein in the hydrocarbonaceous mixture comprises more than 10 wt%, such as 20 wt% or 30 wt% and less than 80 wt%, such as 60 wt%, 50 wt% or 40 wt% of oxygenates, aromatics, nitrogen and sulfur compounds in combination, such as triglycerides or fatty acids.

6. A method according to claim 3, 4 or 5 further comprising the step of providing said hydrocarbonaceous mixture by combining a biologically derived liquid with a diluent, said diluent comprising one or more of a hydrotreated hydrocarbonaceous composition and a fossil hydrocarbon.

7. A method according to claim 6 wherein said hydrotreated hydrocarbon comprises an amount of said hydrotreated intermediate composition or a composition derived therefrom.

8. A method according to claims 3 to 7, wherein said phenol-lipid comprises one or more of a cardanol species and an anacardic acid.

9. A method according to claims 3 to 8, wherein said phenol-lipid is derived from a biological material, such as cashew nut shells, cashew apples and mango kernels.

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