PROCESS FOR PRODUCING MIDDLE DISTILLATES BY CO-PROCESSING MINERAL CHARGE WITH OPTIMIZATION OF CUTTING POINTS TO MAXIMIZE BIOGENIC CARBON IN KEROSENE

Abstract

A process for producing middle distillates from a fossil hydrocarbon feedstock is described, in which at least 50% by weight of the compounds have an initial boiling point above 250°C and a final boiling point below 800°C, mixed with at least one renewable feedstock selected from vegetable oils, algal oils, cooking oils, and animal fats, fresh or used, alone or in mixtures, comprising: a) a hydrotreating step of said feedstock mixture; b) a hydrocracking step of at least a portion of the hydrotreated feedstock from step a); c) gas / liquid separation of the effluent from step b); d) sending the gaseous effluent, comprising at least hydrogen, to a compression step; e) fractionation of at least a portion to produce at least one naphtha cut comprising compounds having a boiling point less than or equal to 180°C, and preferably between 80 and 130°C,at least one first cut comprising compounds with a boiling point between 130°C and 220°C, at least one second cut comprising compounds with a boiling point between 130°C and 300°C, at least one third cut comprising compounds with a boiling point between 250°C and 400°C, and at least one unconverted heavy liquid cut comprising compounds with a boiling point above 400°C; f) mixing at least part of the first cut and at least part of the third cut and sending the mixture to a diesel storage unit; g) sending at least part of the third cut to a kerosene storage unit. Figure 1 to be published.

Description

Title of the invention: METHOD FOR PRODUCING MIDDLE DISTILLATES BY CO-PROCESSING OF MINERAL CHARGE WITH OPTIMIZATION OF CUTTING POINTS TO MAXIMIZE BIOGENIC CARBON IN KEROSENE Technical field

[0001] The present invention relates to a process for producing middle distillates comprising a hydrotreatment step and a hydrocracking step.

[0002] This process converts a set of hydrocarbon feedstocks into products of interest (naphtha, jet, diesel). These hydrocarbon feedstocks contain, for example, aromatic, and / or olefinic, and / or naphthenic, and / or paraffinic compounds, including so-called fossil feedstocks, such as vacuum distillate cuts (VDC) or Vacuum Gas Oil (VGO) from the direct distillation of crude oil or from conversion units such as FCC, coker, H-Oil or visco-reduction, feedstocks from the Fischer-Tropsch process, feedstocks from the processing of oil sands and shale oils, mixed with at least one renewable feedstock chosen from vegetable oils, algal oils, cooking oils, animal fats, fresh or used, alone or in a mixture, and feedstocks from the reprocessing of biomass / plastics / tires / and household waste, alone or in mixtures.These charges may possibly contain metals, and / or nitrogen, and / or oxygen and / or sulfur.

[0003] In particular, the present invention relates to a process for producing middle distillates from a hydrocarbon feedstock, preferably of the vacuum distillate type, mixed with at least one renewable feedstock chosen from vegetable oils, algal oils, cooking oils, animal fats, fresh or used, alone or as a mixture, and feedstocks resulting from the reprocessing of biomass / plastics / tires / and household waste, alone or as a mixture, said process comprising a hydrotreatment step and a hydrocracking step.

[0004] The objective of the process according to the invention is essentially the production of a middle distillate cut, comprising a kerosene cut having initial and final boiling points in a range from 130 to 300°C and a diesel cut having initial and final boiling points in a range from 130 to 400°C. The applicant has shown that it is judicious to extract not two but three middle distillate type cuts. They are then mixed for on the one hand maximize the Biogenic Carbon of the kerosene cut to maximize the SAF (Sustainable Aviation Fuel) and on the other hand improve the product qualities of the diesel cut and in particular the cloud point.

[0005] Throughout the rest of the text, biogenic carbon is understood to mean carbon fixed by the plant following photosynthesis from CO2 in the air. The determination of biogenic carbon is carried out using the ASTM D6866 method B (AMS) standard. Prior art

[0006] The process for producing middle distillates including a step of hydrocracking heavy petroleum fractions is now an essential refining process which makes it possible to produce, from excess and poorly recoverable heavy feedstocks, lighter fractions such as gasoline, jet fuels and diesel fuels which the refiner is looking for to adapt its production to the structure of demand. Certain hydrocracking processes also make it possible to obtain a highly purified residue which can provide excellent bases for the production of oils. Compared to catalytic cracking (FCC), the advantage of catalytic hydrocracking is that it provides very good quality middle distillates. Conversely, the gasoline produced has a much lower octane number than that resulting from catalytic cracking.

[0007] This process derives its flexibility from three main elements, which are the operating conditions used, the types of catalysts employed and the fact that the hydrocracking of hydrocarbon feedstocks can be carried out in one or two stages. It is thus suitable for treating and transforming any type of hydrocarbon feedstock as long as it is compatible with injection in liquid form into catalytic reactors. In particular, it is capable of using, alone or in a mixture, feedstocks resulting from the distillation of crude oil, but also vegetable oils, animal fats for example.

[0008] It can be carried out in one step in one or more reactors in series in the presence of a single catalyst which not only hydrocracks the hydrocarbon feedstock into lower boiling products but also converts residual organic compounds comprising sulfur and nitrogen into hydrogen sulfide and ammonia respectively.

[0009] The hydrocracking catalysts used in the processes for producing middle distillates are said to be bifunctional, i.e. combining an acid function with a hydro-dehydrogenating function. The acid function is provided by oxides whose surface areas generally vary from 150 to 1,000 m2.g 1 such as halogenated aluminas (chlorinated or fluorinated in particular), combinations of boron and aluminum oxides, amorphous silica-alumina and zeolites. The hydro-dehydrogenating function is provided either by one or more metals from group VIB of the periodic table of elements, either by a combination of at least one metal from group VIB of the periodic table and at least one metal from group VIII.

[0010] The balance between these two functions is one of the parameters that governs the activity and selectivity of the catalyst. A weak acid function and a strong hydro-dehydrogenating function give catalysts that are not very active, working at generally high temperatures (greater than or equal to 390-400°C), and at low feed space velocity (the WH expressed in volume of feed to be treated per unit of catalyst volume and per hour is generally less than or equal to 2 h1), but with very good selectivity for middle distillates (jet fuels and diesels). Conversely, a strong acid function and a weak hydro-dehydrogenating function give active catalysts, but with lower selectivities for middle distillates.

[0011] One type of conventional hydrocracking catalyst is based on moderately acidic amorphous oxides, such as silica-aluminas for example. These systems are used to produce good quality middle distillates, and possibly oil bases. The disadvantage of these amorphous support-based catalysts is their low activity.

[0012] Catalysts comprising, for example, Y zeolite, or catalysts comprising, for example, Beta zeolite, have a catalytic activity greater than that of silica-aluminas, but have generally lower selectivities for middle distillates (jet fuels and diesels).

[0013] In order to specifically maximize the production of middle distillates and reduce the carbon footprint of refining processes, it may also prove advantageous to work with renewable feedstocks, in addition to fossil feedstocks, which are likely to lead to a reduction in the carbon footprint. Among the renewable feedstocks, we can cite, for example, vegetable oils, animal fats, or used cooking oils which, after hydrotreatment, generally lead to long linear paraffins comprising mainly nCi5 to nCi8 hydrocarbons. In the total effluent leaving the reactor, the n-paraffins from the oils will be mainly found in fuel cuts such as kerosene and diesel and will therefore have an impact on the cold properties such as the crystal disappearance point of the kerosene cut and the cloud point of the diesel cut.However, these are key properties of fuels, determining their approval and commercial use. It is therefore essential to control the flow properties of the products and to manage operating conditions to comply with the product specifications, i.e. concretely the crystal disappearance point below -40°C for Jet kerosene and the cloud point below 5°C for summer diesel fuel or below -5°C for winter diesel fuel (Euro V standard).

[0014] In order to limit the negative impact of linear paraffins on cold properties, a first solution is to isomerize these compounds to achieve the required fuel specifications. Another advantageous solution is also to convert these linear paraffins by selective hydrocracking for direct incorporation into the kerosene fraction.

[0015] Thus, in the context of reducing greenhouse gas emissions, refiners must increase the proportion of biologically derived components in fuels. The public authorities aim to promote the use of biofuels in transport, not only road transport (diesel and gasoline engines) but also air transport. For example, the roadmap of the Ancre (national alliance for the coordination of research for energy), published in June 2018, assesses the French potential of biofuel production sectors for aviation, taking into account the maturity and development time of these industrial sectors. The following deployment trajectory therefore reflects the French ambition for 2030 of an incorporation of aviation biofuels in France of 5%.In addition, the National Low Carbon Strategy (SNBC) revised in 2018 sets a long-term direction for air transport by 2050, aiming at a 50% substitution of conventional fossil fuels with biofuels. Biofuel production has therefore been promoted in recent years and will continue to be significantly increased in the years to come.

[0016] An advantageous solution to maximize the biogenic carbon content and optimize cold properties is to cleverly play on the cutting points. This also allows the introduction of renewable carbon into this fossil cut. The production of biokerosene, or also called SAF according to the Anglo-Saxon terminology ("Sustainable Aviation Fuel"), is particularly sought after to decarbonize the aviation sector, whether civil or military.

[0017] State of the art

[0018] In the literature, there are many studies on the molecular understanding of cold properties in fuels. These studies systematically evoke the determining role of normal paraffins on cold properties. Indeed, normal paraffins, due to their linear and flexible structure, can easily align and form stable crystals with cooling. Another important factor is the length of the normal paraffins. The longer a paraffin is (typically normal paraffins having a carbon number in the chain greater than 15 carbon atoms), the more axial interactions by Van der Waals forces between n-paraffins are important in the crystals. On the other hand, for short linear paraffins, the interactions between the ends are also important and not negligible and disrupt the organization of the crystals.

[0019] Disappearance point of crystals (kerosene)

[0020] The freezing point (FP) of a kerosene corresponds to the lowest temperature at which the fuel does not contain any solid crystals. The FP measurement is carried out using the D5972, D7153, D7154 (automated methods) or D2386 (manual method) standards. These four standards are accepted for the certification of a kerosene fuel according to ASTM D1655-20d. However, the minimum and maximum temperature limits for the application of these four methods are not the same. The recommended methods for certification or re-certification are the ASTM D5972 and / or ASTM D7153 automated methods.

[0021] In the determination of the FP, the sample is cooled in a standardized apparatus, being vigorously stirred, thus simulating the cooling conditions that may be encountered during a flight. The temperature at which the crystals appear is the crystallization temperature and is detected using the optical detection system (opacity and crystal). The sample is then heated until the opacity disappears.

[0022] At this stage, the temperature is increased until the crystal detector detects the disappearance of the crystals. If this temperature is higher than the formation temperature of the first crystals, the disappearance point of the crystals is obtained.

[0023] Cloudy point (Diesel)

[0024] The cold resistance of a diesel can be characterized by three properties: the filterability limit temperature (FLT), the cloud point (CP) and the pour point (FP). These properties generally follow the same trend with the concentration of normal paraffins present in the diesel and are fairly well correlated with each other. In general, the crystallization of a fluid occurs in two stages: the first is nucleation with the appearance of crystals and the second stage is agglomeration and growth of the crystals. The CP therefore characterizes the first stage when the first crystals appear; the FLT characterizes the moment during cooling from which the size of the crystals becomes too large for them to pass through a filter and the FP characterizes the temperature from which the product can no longer flow because it becomes solid. Consequently, the following order of temperature is observed: CP > FLT > FP.It should be noted that PT and TLF are defined in diesel specifications according to ASTM D975-20c "Standard Specification for Diesel Fuel" unlike pour point.

[0025] The measurement of the PT or "cloud point" according to the Anglo-Saxon terminology is carried out according to the standards ASTM D2500-11 or NF ISO EN 23015. These methods are used for PTs below 49°C. In the determination, the sample is heated at least 15°C above the assumed PT and introduced into a test tube closed with a cap. A thermometer inside the tube touches the bottom of the tube. It is then cooled gradually, using increasingly cold cooling baths and the clarity of the product is manually checked every degree. The PT is the temperature at which a distinct cloudiness appears at the bottom of the test tube. It is reported from degree to degree. There are other equivalent automated methods that are also accepted for diesel certification (ASTM D975-20c), including AFNOR ISO 3015 and ASTM D5773. However, in the event of a discrepancy between two values ​​given by different standards, the ASTM D2500 method is used. This method is expensive and also requires distillation, particularly by hydrocracking.

[0026] Biogenic Carbon

[0027] The determination of Biogenic Carbon is carried out via the ASTM D6866 method B (AMS) standard.

[0028] Numerous patent applications describe the co-processing of renewable feedstocks with a fossil feedstock with the aim of producing either a diesel cut, or a kerosene cut, or both, cuts incorporating a portion of biogenic carbon.

[0029] For example, the incorporation of renewable lipid feedstocks containing triglycerides with diesel cuts that are fossil petroleum feedstocks in the co-treatment hydrotreatment process has been described in documents FR 2 949 475, EP 1 693 432 and EP 2 046 917 B1. This incorporation makes it possible to produce a renewable diesel cut and to integrate it directly into the diesel pool from fossil resources without investing in a dedicated hydrotreatment unit. The advantages of co-treatment of a feedstock containing triglycerides with a fossil petroleum cut compared to the treatment of a pure lipid feedstock are well detailed in document FR 2 949 475 A1, such as for example:

[0030] - Limitation of polymerizations linked to the thermal instability of the renewed charges velables,

[0031] - Reduction by dilution effect of the sulfur, nitrogen and aromatic contents,

[0032] - Limitation of exotherms linked to the hydrotreatment of biological loads,

[0033] - Reduction of the CO and CO2 content in the gaseous effluent: limitation of the effect inhibition of catalytic activity by CO and limitation of corrosion risks in the presence of water and CO2,

[0034] - Increase in the solubility of hydrogen in the mixture to be treated.

[0035] The hydrotreatment process essentially produces a fraction of renewable diesel depending on the rate of incorporation at the input of the process, i.e. cuts with an initial boiling point of 250°C or 280°C and a final boiling point of up to 340°C, or even 370°C.

[0036] The hydrocracking process makes it possible to produce, in addition to renewable diesel, lighter biogenic products such as biokerosene and bionaphtha.

[0037] The production of biokerosene (or S AF) is attracting more and more attention compared to the production of renewable diesel in the context of the energy transition. On the other hand, the valorization of biological resources in bio naphtha for petrochemicals (for the production of olefins, BTX aromatics, polymers and cosmetic products, etc.) is also increasingly interesting. Refiners are therefore increasingly interested in technical solutions allowing the incorporation of biokerosene into fossil kerosene and the production of bionaphtha for petrochemicals.

[0038] It is described in the invention WO 2009 / 148909 A2, that pure feedstocks containing triglycerides such as palm oil and animal fat can be converted on the sequence of hydrotreatment steps (on a sulfurized NiMo catalyst supported on alumina) and hydrocracking (on a Pt-Pd catalyst supported on amorphous silica-alumina) for the production of bio naphtha, for yields up to 28% by weight.

[0039] Patent application WO 2011 / 012439 A1 describes that lipid feedstocks can be converted into n-paraffins and propane by hydrodeoxygenation and decarbonylation on a conventional hydrotreatment catalyst. These n-paraffins with fossil naphtha are then mixed and injected into the steam cracking unit for the production of olefins, diolefins and aromatics.

[0040] Document EP 2 143 777 A1 describes a process for hydrocracking a feedstock consisting of a mixture of a vacuum distillate with vegetable feedstocks or animal fats, with a sequence of hydrotreatment catalysts (NiMo / Al2O3 type), followed by a hydrocracking catalyst (NiMo / zeolite type) and then by a post-treatment catalyst (hydrodesulfurization type) making it possible to obtain a diesel with a very low sulfur content. The incorporation of a biological feedstock with the vacuum distillate, according to this invention, makes it possible to significantly increase the yield of the diesel cut but unfortunately this results in a reduction in the kerosene yield. For example, it notes an increase of 6% in the yield of the diesel cut but a reduction of more than 3% in the kerosene cut with the incorporation of 10% by weight of soybean oil mixed with a DSV.On the other hand, the diesel cut obtained has degraded cold properties: cloud point 3°C ​​higher than fossil diesel obtained without the incorporation of soybean oil.

[0041] The applicant discovered that it was judicious to extract not two but three middle distillate type cuts. They are then mixed to, on the one hand, maximize the Biogenic Carbon of the kerosene cut to thus maximize the SAF and, on the other hand, improve the product qualities of the diesel cut and in particular the cloud point. Summary of the invention

[0042] The subject of the present invention is a process for producing middle distillates from at least one fossil hydrocarbon feedstock of which at least 50% by weight of the compounds have an initial boiling point above 250°C and a final boiling point below 800°C, said fossil hydrocarbon feedstock being co-treated in a mixture with at least one renewable feedstock chosen from vegetable oils, algal oils, cooking oils and animal fats, fresh or used, alone or in a mixture, and feedstocks from the reprocessing of biomass / plastics / tires / and household waste, alone or in mixtures, said process comprising at least the following steps:

[0043] a) a step of hydrotreating said feed mixture in the presence of hydrogen and at least one hydrotreating catalyst at a temperature of between 200 and 450°C, under a pressure of between 2 and 25 MPa, at a space velocity of between 0.1 and 6 h-1 and at a quantity of hydrogen introduced such that the volume ratio liter of hydrogen / liter of hydrocarbon is between 100 and 5000 L / L,

[0044] b) a step of hydrocracking at least a portion and preferably all of the hydrotreated feed from step a), in the presence of hydrogen and a hydrocracking catalyst, the hydrocracking step being carried out at a temperature of between 200°C and 480°C,at a total pressure of between 1 MPa and 25 MPa with a ratio of hydrogen volume to hydrocarbon feed volume of between 80 and 5000 liters per liter and at an Hourly Volume Speed ​​(WH) defined by the ratio of the volume flow rate of liquid hydrocarbon feed to the volume of catalyst loaded into the reactor of between 0.1 and 50 h1, ,

[0045] c) The gas / liquid separation of the effluent from step b) to produce a liquid effluent and a gaseous effluent comprising at least hydrogen,

[0046] d) Sending the gaseous effluent comprising at least hydrogen to a compression stage before recycling it to at least the hydrotreatment stage a) and the hydrocracking stage b),

[0047] e) The fractionation of at least a part and preferably all of the liquid effluent from step c), in a fractionation section, to produce:

[0048] - at least one naphtha cut comprising compounds having a boiling point less than or equal to 180°C, and preferably between 80 and 130°C,

[0049] - at least a first cut in the range of middle distillates comprising compounds having a boiling point between 130°C and 220°C, and preferably between 130°C and 180°C,

[0050] - at least one second cut in the range of middle distillates comprising compounds having a boiling point between 130°C and 300°C, and preferably between 190°C and 300°C,

[0051] - at least a third cut in the range of middle distillates comprising compounds having a boiling point between 250°C and 400°C and preferably between 300 and 370°C,

[0052] - and at least one unconverted heavy liquid cut comprising compounds having a boiling point above 400°C and preferably above 370°C

[0053] a) mixing at least a portion of the first cut in the middle distillate range comprising compounds having a boiling point between 130°C and 220°C and at least a portion of the third cut in the middle distillate range comprising compounds having a boiling point between 250°C and 400°C and sending the mixture to a diesel storage unit,

[0054] b) Sending at least a portion and preferably all of the third cut in the middle distillate range comprising compounds having a boiling point between 250°C and 400°C into a kerosene storage unit.

[0055] An advantage of the present invention is to provide a process for producing a kerosene cut comprising compounds having a boiling point between 180°C and 300°C, and preferably between 190°C and 300°C, maximizing the biogenic carbon content while meeting the jet specification. Surprisingly, the cloud point of the diesel cut is also improved.

[0056] In particular, an advantage of the present invention is to provide a hydrocracking process making it possible to improve the Biogenic Carbon content of the kerosene cut, while also making it possible to comply with the jet specification for the kerosene cut and to obtain improved cold properties for the diesel cut compared to the use of catalysts or a chain of catalysts of the prior art.

[0057] Throughout the remainder of the text, the term “naphtha cut” means a hydrocarbon cut comprising compounds having a boiling point generally less than or equal to 180°C, and preferably between 80 and 130°C.

[0058] The term "middle distillate cut" means a hydrocarbon cut comprising compounds having a boiling point generally between 130 and 370°C. The middle distillate cut generally comprises a kerosene cut having a boiling point between 130 and less than 300°C and / or a diesel cut having a boiling point between 250 and 370°C.

[0059] The term “unconverted heavy liquid cut” means a hydrocarbon cut comprising compounds having a boiling point generally higher than 370°C which presents the part of the unconverted charge (also called UCO for Unconverted Oil according to Anglo-Saxon terminology).

[0060] Within the meaning of the present invention, the various embodiments presented can be used alone or in combination with each other, without limitation of combination.

[0061] In the sense of the present invention, the different parameter ranges for a given step such as pressure ranges and temperature ranges may be used alone or in combination. For example, in the sense of the present invention, a preferred range of pressure values ​​may be combined with a more preferred range of temperature values.

[0062] In the following text, the groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, publisher CRC press, editor-in-chief DR Lide, 81st edition, 2000-2001). For example, group VIII according to the CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUP AC classification, and group VIB to the metals of column 6.

[0063] In the remainder of the text, the expressions "between ... and..." and "between .... and ..." are equivalent and mean that the limit values ​​of the interval are included in the range of values ​​described. If this were not the case and the limit values ​​were not included in the range described, such precision will be provided by the present invention.

[0064] In the present description, the expression "greater than..." is understood as strictly greater than, and symbolized by the sign ">", and the expression "less than" as strictly less than, and symbolized by the sign "<". List of figures

[0065] [Fig.l]

[0066] [Fig.l] schematically illustrates an embodiment of the hydroconversion process according to the invention. Description of the embodiments

[0067] In accordance with the invention, the process treats at least one fossil hydrocarbon feedstock of which at least 50% by weight of the compounds have an initial boiling point above 250°C and a final boiling point below 800°C, said fossil hydrocarbon feedstock being co-treated in a mixture with at least one renewable feedstock chosen from vegetable oils, algal oils, cooking oils and animal fats, fresh or used, alone or in a mixture, and feedstocks resulting from the reprocessing of biomass / plastics / tires / and household waste, alone or in mixtures.

[0068] Charges

[0069] A wide variety of hydrocarbon feedstocks can be treated by the hydrocracking processes according to the invention.

[0070] In accordance with the invention, the fossil hydrocarbon feedstock used in the hydrocracking process according to the invention is a hydrocarbon feedstock of which at least 50% by weight of the compounds have an initial boiling point above 250°C and a final boiling point below 800°C, preferably of which at least 60% by weight, more preferably of which at least 75% by weight and more preferably of which at least 80% by weight of the compounds have an initial boiling point above 250°C and a final boiling point below 800°C.

[0071] The fossil hydrocarbon feedstock is advantageously chosen from diesel fuels from a catalytic cracking unit or LCO (Light Cycle Oil) according to the English terminology, atmospheric distillates, vacuum distillates from the direct distillation of crude oil or from conversion units such as FCC, coker, H-Oil or visbreaking, feedstocks from units for extracting aromatics from lubricating oil bases or from solvent dewaxing of lubricating oil bases, distillates from desulfurization or hydroconversion processes in a fixed bed or in a bubbling bed of RAT (atmospheric residues) and / or RSV (vacuum residues) and / or deasphalted oils. The above list is not exhaustive.Said fillers preferably have a boiling point T5 greater than 200°C, preferably greater than 340°C, that is to say that 95% by weight of the compounds present in the filler have a boiling point greater than 250°C, and preferably greater than 340°C.

[0072] In accordance with the invention, the fossil hydrocarbon feedstock is treated in the process according to the invention in a mixture with at least one renewable feedstock chosen from vegetable oils, cooking oils, algal oils and animal fats, fresh or used, alone or in a mixture, and feedstocks resulting from the reprocessing of biomass / plastics / tires / and household waste, alone or in mixtures.

[0073] Vegetable oils can advantageously be crude or refined, totally or partially, and derived from the following plants: rapeseed, sunflower, soybean, palm, palm kernel, olive, coconut, jatropha, this list not being exhaustive. Algal or fish oils are also relevant. Animal fats are advantageously chosen from lard or fats composed of residues from the food industry or from the catering industries.

[0074] These fillers essentially contain chemical structures of the triglyceride type that the skilled person also knows under the name fatty acid triester as well as free fatty acids. A fatty acid triester is thus composed of three fatty acid chains. These fatty acid chains in the form of triester or in the form of free fatty acids, have a number of unsaturations per chain, also called the number of carbon-carbon double bonds per chain, generally between 0 and 3 but which can be higher, in particular for oils derived from algae which generally have a number of unsaturations per chain of 5 to 6.

[0075] More generally, the method according to the invention is capable of treating the charges aforementioned alone or in mixture whatever the proportions.

[0076] Preferably, the content of renewable filler in the filler mixture is between 0.5 and 40% by weight relative to the total mass of the filler treated in the process according to the invention, and preferably between 1 and 35% by weight, preferably between 2 and 30% by weight and more preferably between 5 and 25% by weight.

[0077] These feedstocks may possibly contain metals, and / or nitrogen, and / or oxygen and / or sulfur. Where appropriate, the process according to the invention may advantageously comprise or not a liquid / gas separation step between the hydrotreatment step of said feedstock and the hydrocracking step.

[0078] The nitrogen content of the feedstocks treated in the processes according to the invention is generally greater than 200 ppm by weight, preferably between 500 and 10,000 ppm by weight, more preferably between 700 and 4,000 ppm by weight and even more preferably between 1,000 and 4,000 ppm by weight. The sulfur content of the feedstocks treated in the processes according to the invention is advantageously between 0.01 and 5% by weight, preferably between 0.2 and 4% by weight and even more preferably between 0.5 and 3% by weight.

[0079] The charge may optionally contain metals. The cumulative nickel and vanadium content of the charges treated in the processes according to the invention is preferably less than 5 ppm, preferably less than 3 ppm and preferably less than 1 ppm by weight.

[0080] The feedstock may optionally contain asphaltenes. The asphaltene content is generally less than 3000 ppm by weight, preferably less than 1000 ppm by weight, even more preferably less than 300 ppm by weight.

[0081] Due to the presence of renewable feedstocks derived from biomass, said feedstock treated in the process according to the invention may also contain oxygenated compounds. Their content varies greatly depending on the feedstock that it is desired to transform in the process according to the invention. It is generally less than 50% by weight, and preferably less than 15%, very preferably less than 5% by weight, even more preferably less than 2% by weight.

[0082] Embodiment

[0083] In accordance with the invention, the process comprises a step a) of hydrotreatment of said feedstocks of the Vacuum Distillates type in a mixture with renewable feedstocks operating, in the presence of hydrogen and at least one hydrotreatment catalyst, at a temperature of between 200 and 450°C, under a pressure of between 2 and 25 MPa, at a space velocity of between 0.1 and 6 h-1 and at a quantity of hydrogen introduced such that the volume ratio liter of hydrogen / liter of hydrocarbon is between 100 and 5000 L / L.

[0084] Operating conditions such as temperature, pressure, recycling rate hydrogen, hourly space velocity, may vary greatly depending on the nature of the load, the quality of the desired products and the facilities available to the refiner.

[0085] Preferably, the hydrotreatment step a) according to the invention operates at a temperature of between 250 and 450°C, very preferably between 300 and 430°C, under a pressure of between 5 and 20 MPa, at a space velocity of between 0.2 and 5 h-1, and at a quantity of hydrogen introduced such that the volume ratio liter of hydrogen / liter of hydrocarbon is between 300 and 3000 NL / L.

[0086] The hydrocarbon feedstocks treated in the process according to the invention are sent to the hydrotreatment step a) before being sent to the hydrocracking step b) of said process. In this step a), said feedstocks are advantageously desulfurized and denitrogenated.

[0087] The effluent from step a) is sent to a hydrocracking step b) according to the invention which operates at a temperature of between 320 and 450°C, very preferably between 330 and 435°C, under a pressure of between 3 and 20 MPa, and very preferably between 6 and 20 MPa, at a space velocity of between 0.2 and 6 h-1, very preferably between 0.3 and 5 h-1 and at a quantity of hydrogen introduced such that the volume ratio liter of hydrogen / liter of hydrocarbon is between 200 and 2000 L / L.

[0088] These operating conditions used in step a) of the process according to the invention generally make it possible to achieve nitrogen levels in the effluent of between 0 and 500 ppm and preferably between 5 and 300 ppm.

[0089] These operating conditions used in steps a) and b) of the process according to the invention make it possible to obtain conversions per pass, into products having boiling points lower than 400°C, and better still lower than 370°C, greater than 15% by weight and even more preferably between 20 and 95% by weight.

[0090] According to the invention, the hydrotreatment step a) operates in the presence of at least one hydrotreatment catalyst. Preferably, the hydrotreatment catalyst is chosen from conventional hydrotreatment catalysts known to those skilled in the art.

[0091] Conventional hydrotreatment catalysts can advantageously be used in supported or unsupported form, preferably containing at least one amorphous support and at least one hydro-dehydrogenating element chosen from at least one non-noble element from groups VIB and VIII, and most often at least one element from group VIB (from molybdenum or tungsten taken alone or in a mixture) and at least one non-noble element from group VIII (from nickel or cobalt taken alone or in a mixture).

[0092] Preferably, the amorphous support is alumina or silica-alumina.

[0093] Preferred catalysts are selected from NiMo, NiW, NiMoW or CoMo catalysts supported on alumina and NiMo, NiW or NiMoW catalysts supported on silica-alumina.

[0094] The effluent from the hydrotreatment stage, part of which and preferably all of which enters the hydrocracking stage a), generally comprises a nitrogen content preferably less than 300 ppm by weight, less than 200 ppm by weight, preferably less than 100 ppm by weight and preferably less than 50 ppm by weight.

[0095] The process according to the invention can advantageously comprise a separation step between the hydrotreatment step and the hydrocracking step.

[0096] In one embodiment, the process according to the invention does not comprise a separation step between the hydrotreatment step and the hydrocracking step.

[0097] According to the invention, the process comprises a step b) of hydrocracking at least a portion and preferably all of the hydrotreated feedstock from step a), in the presence of hydrogen and a hydrocracking catalyst, the hydrocracking step being carried out at a temperature of between 200°C and 480°C, at a total pressure of between 1 MPa and 25 MPa with a ratio of hydrogen volume to hydrocarbon feedstock volume of between 80 and 5000 liters per liter and at an Hourly Volume Velocity (WH) defined by the ratio of the volume flow rate of liquid hydrocarbon feedstock to the volume of catalyst loaded into the reactor of between 0.1 and 50 h-1.

[0098] Preferably, the hydrocracking catalyst is chosen from conventional hydrocracking catalysts known to those skilled in the art.

[0099] The hydrocracking catalysts used in hydrocracking processes are all of the bifunctional type combining an acid function with a hydrogenating function. The acid function is provided by supports with large surfaces (generally 150 to 800 m2.gl) having a surface acidity, such as halogenated aluminas (chlorinated or fluorinated in particular), combinations of boron and aluminum oxides, amorphous silica-aluminas and zeolites. The hydrogenating function is provided either by one or more metals from group VIII of the periodic table of elements, or by a combination of at least one metal from group VIB of the periodic table and at least one metal from group VIII.

[0100] Preferably, the hydrocracking catalyst(s) comprise a hydrogenating function comprising at least one metal from group VIII chosen from iron, cobalt, nickel, ruthenium, rhodium, palladium and platinum and preferably cobalt and nickel and / or at least one metal from group VIB chosen from chromium, molybdenum and tungsten, alone or as a mixture and preferably from molybdenum and tungsten.

[0101] Preferably, the content of group VIII metal in the hydrocracking catalyst(s) is advantageously between 0.5 and 15% by weight and preferably between 2 and 10% by weight, the percentages being expressed as a percentage by weight of oxides.

[0102] Preferably, the content of group VIB metal in the hydrocracking catalyst(s) is advantageously between 5 and 25% by weight and preferably between 15 and 22% by weight, the percentages being expressed as a percentage by weight of oxides.

[0103] The catalyst(s) may also optionally contain at least one promoter element deposited on the catalyst and chosen from the group formed by phosphorus, boron and silicon, optionally at least one element from group VIIA (chlorine, fluorine preferred), and optionally at least one element from group VIIB (manganese preferred), optionally at least one element from group VB (niobium preferred).

[0104] Preferably, the hydrocracking catalyst(s) comprise an acid function chosen from alumina, silica alumina and zeolites, preferably chosen from Y zeolites and preferably chosen from silica alumina and zeolites.

[0105] A preferred catalyst comprises and preferably consists of at least one Group VI metal and / or at least one non-noble Group VIII metal, and a Y zeolite and an alumina binder.

[0106] An even more preferred catalyst comprises and preferably consists of nickel, molybdenum, a Y zeolite and alumina.

[0107] Another preferred catalyst comprises and preferably consists of nickel, tungsten and alumina or silica alumina.

[0108] In step b) of the process according to the invention, the conversion, during the first step, into products having boiling points below 340°C, and better still below 370°C, is greater than 20% and preferably greater than 30% and even more preferably between 30 and 90% and preferably between 50 and 85%.

[0109] The effluent from hydrotreatment step a) and entering hydrocracking step b) comprises a nitrogen content preferably less than 500 ppm by weight and preferably less than 30 ppm by weight.

[0110] The hydrotreatment step a) and the hydrocracking step b) can advantageously be carried out in the same reactor or in different reactors. In the case where they are carried out in the same reactor, the reactor comprises several catalytic beds, the first catalytic beds comprising the hydrotreatment catalyst(s) and the following catalytic beds comprising the hydrocracking catalyst(s).

[0111] According to the invention, the process comprises a step c) of gas / liquid separation of the effluent from step b) to produce a liquid effluent and a gaseous effluent comprising at least hydrogen.

[0112] Preferably, step c) of gas / liquid separation is carried out in a se high temperature high pressure parateur operating at a temperature between 50 and 450°C, preferably between 100 and 400°C, even more preferably between 200 and 300°C, and a pressure corresponding to the outlet pressure of b) less the pressure losses.

[0113] According to the invention, the process comprises a step d) of sending the gaseous effluent comprising at least hydrogen into a compression step before its recycling into at least the hydrotreatment and hydrocracking steps a) and b). This step is necessary to allow the gas to be recycled upstream, i.e. into the hydrotreatment and hydrocracking steps a), therefore at higher pressure.

[0114] The gaseous effluent comprising at least hydrogen can advantageously be mixed with make-up hydrogen before or after its introduction into compression step d), preferably via a make-up hydrogen compressor.

[0115] According to a variant, a portion of the gaseous effluent comprising at least compressed hydrogen can also advantageously be sent to the hydrocracking step f).

[0116] According to the invention, the process comprises a fractionation step e), fed with at least part and preferably all of the liquid effluent from step c), in a fractionation section, to produce:

[0117] - at least one naphtha cut comprising compounds having a boiling point less than or equal to 180°C, and preferably between 80 and 130°C.

[0118] - at least a first cut in the range of middle distillates comprising compounds having a boiling point between 130°C and 200°C, and preferably between 130°C and 180°C,

[0119] - at least a second cut in the range of middle distillates comprising compounds having a boiling point between 180°C and 320°C, and preferably between 190°C and 300°C,

[0120] - at least a third cut in the range of middle distillates comprising compounds having a boiling point between 280°C and 400°C and preferably between 300 and 370°C,

[0121] - and at least one unconverted heavy liquid fraction comprising compounds having a boiling point above 400°C and preferably above 370°C.

[0122] Fractionation step e) is carried out in at least one distillation column. The distillation column operates at a pressure of between 0.1 and 0.4 MPa absolute.

[0123] Step e) of fractionation by distillation advantageously also makes it possible to extract a gaseous fraction,

[0124] Preferably, said unconverted heavy liquid cut, and having a point boiling point above 370°C, said fraction is withdrawn at the lower end of the column.

[0125] Depending on the destination or use of the cuts from the fractionation step, a person skilled in the art will adjust the cut points in the separation and / or distillation operations. For example, it may be necessary to adjust the end point of the naphtha cut to 125, 150, 175 or 200°C.

[0126] The cutting points of the first, second and third cuts resulting from fractionation step e), judiciously chosen, make it possible to maximize the Biogenic carbon in the kerosene cut while improving the cloud point of the diesel cut.

[0127] In particular, the cutting points of the second cut in the range of middle distillates comprising compounds having a boiling point between 180°C and 320°C, and preferably between 190°C and 300°C correspond to the cutting points of the jet cut.

[0128] The diesel cut preferably corresponds to the mixture of at least a part and preferably all of the first cut in the range of middle distillates comprising compounds having a boiling point between 130°C and 200°C, and preferably between 130°C and 180°C and at least a part and preferably all of the third cut in the range of middle distillates comprising compounds having a boiling point between 280°C and 400°C.

[0129] According to the invention, the process comprises a step f) of mixing at least a portion and preferably all of the first cut in the middle distillate range comprising compounds having a boiling point of between 130°C and 220°C and at least a portion and preferably all of the third cut in the middle distillate range comprising compounds having a boiling point of between 250°C and 400°C and sending at least a portion and preferably all of the mixture to a diesel storage unit.

[0130] According to the invention, the process comprises a step g) of sending at least a part and preferably all of the third cut in the range of middle distillates comprising compounds having a boiling point between 250°C and 400°C into a kerosene storage unit.

[0131] The mixing of at least a part and preferably all of the first cut and at least a part and preferably all of the third cut can be carried out by any technique known to those skilled in the art (paddle mixer, static mixer, etc.). It can be carried out within the limits of the unit or at the diesel storage, including the shipping system.

[0132] The naphtha cut can be sent to a fuel storage unit, for example a naphtha storage unit, from conventional petroleum feedstocks.

[0133] The product obtained by the process, which can therefore be a naphtha cut, a middle distillate cut (kerosene cut and / or diesel cut) or even the unconverted heavy liquid cut, can include a biogenic carbon content according to ASTM D6866 of between 3 and 35% by weight.

[0134] According to a variant, the liquid fraction, unconverted residue, (UCO) resulting from step e) containing products whose boiling point is higher than 370°C and resulting from the distillation is at least partly and preferably entirely introduced into the second hydrocracking step h) of the process according to the invention.

[0135] A purge can advantageously be carried out on the residual liquid fraction in order to avoid the accumulation of heavy polyaromatic products (HPNA) present in the heavy cuts recycle loop. Indeed, the HPNAs are gradually formed during their recycling in the second hydrocracking stage and the recycling of these heavy aromatic components in the loop of the second hydrocracking stage h) has the consequence of increasing their molecular weight. The presence of HPNAs in said recycle loop ultimately leads to a significant pressure drop. A purge is therefore necessary in order to limit the accumulation of these HPNA products.

[0136] According to this variant, the process comprises a step h) of hydrocracking said unconverted liquid fraction from step e), optionally purged, operating in the presence of hydrogen and a hydrocracking catalyst, at a temperature of between 250 and 480°C, under a pressure of between 2 and 25 MPa, at a space velocity of between 0.1 and 8 h-1 and at a quantity of hydrogen introduced such that the volume ratio liter of hydrogen / liter of hydrocarbon is between 100 and 2000 L / L.

[0137] Preferably, the hydrocracking step h) according to the invention operates at a temperature of between 300 and 450°C, very preferably between 320 and 435°C, under a pressure of between 3 and 20 MPa, and very preferably between 9 and 20 MPa, at a space velocity of between 0.2 and 5 h-1, and at a quantity of hydrogen introduced such that the volume ratio liter of hydrogen / liter of hydrocarbon is between 100 and 2000 L / L.

[0138] These operating conditions used in step h) of the process according to the invention generally make it possible to achieve conversions per pass, into products having boiling points below 330°C, preferably below 350°C and preferably below 380°C, of ​​greater than 15% by weight and even more preferably between 20 and 80% by weight. Nevertheless, the conversion per pass in step h) is kept low in order to maximize the selectivity of the process into products having boiling points between 130 and 370°C. The conversion per pass is limited by the use of a high recycle rate on the second hydrocracking stage loop. This rate is defined as the ratio between the feed flow rate of step e) and the flow rate of the load from step a), preferably this ratio is between 0.2 and 4, preferably between 0.5 and 2.

[0139] According to a variant, the hydrocracking step h) operates in the presence of at least one hydrocracking catalyst. Preferably, the second-stage hydrocracking catalyst is chosen from conventional hydrocracking catalysts known to those skilled in the art. The hydrocracking catalyst used in said step h) may be identical to or different from that used in step b) and preferably different.

[0140] The hydrocracking catalysts used in hydrocracking processes are all of the bifunctional type combining an acid function with a hydrogenating function. The acid function is provided by supports with large surfaces (generally 150 to 800 m2.gl) having a surface acidity, such as halogenated aluminas (chlorinated or fluorinated in particular), combinations of boron and aluminum oxides, amorphous silica-aluminas and zeolites. The hydrogenating function is provided either by one or more metals from group VIII of the periodic table of elements, or by a combination of at least one metal from group VIB of the periodic table and at least one metal from group VIII.

[0141] Preferably, the hydrocracking catalyst(s) used in step h) comprise a hydrogenating function comprising at least one metal from group VIII chosen from iron, cobalt, nickel, ruthenium, rhodium, palladium and platinum and preferably cobalt and nickel and / or at least one metal from group VIB chosen from chromium, molybdenum and tungsten, alone or as a mixture and preferably from molybdenum and tungsten.

[0142] Preferably, the content of group VIII metal in the hydrocracking catalyst(s) is advantageously between 0.5 and 15% by weight and preferably between 2 and 10% by weight, the percentages being expressed as a percentage by weight of oxides.

[0143] Preferably, the content of noble metal from group VIII in the hydrocracking catalyst(s) is advantageously between 0.05 and 2% by weight and preferably between 0.1 and 1% by weight and very preferably between 0.2 and 0.5%, the percentages being expressed as a percentage by weight of oxides.

[0144] Preferably, the content of group VIB metal in the hydrocracking catalyst(s) is advantageously between 5 and 25% by weight and preferably between 15 and 22% by weight, the percentages being expressed as a percentage by weight of oxides.

[0145] The catalyst(s) used in step h) may also optionally comprise at least one promoter element deposited on the catalyst and chosen from the group formed by phosphorus, boron and silicon, optionally at least one element from group VIIA (chlorine, fluorine preferred), and optionally at least one element from group VIIB (manganese preferred), optionally at least one element from group VB (niobium preferred).

[0146] Preferably, the hydrocracking catalyst(s) used in step h) comprise an acid function chosen from alumina, silica alumina and zeolites, preferably chosen from Y zeolites and preferably chosen from silica alumina and zeolites.

[0147] Thus, in a first particular embodiment, at least part and preferably all of the effluent from hydrocracking step h) can advantageously be recycled into gas / liquid separation step c).

[0148] This configuration allows the use of a single compressor on the hydrogen recycle loop. Indeed, in this case, the recycle of gas containing hydrogen to step h) is provided by the same compressor as the recycle of gas containing hydrogen to steps a) and b).

[0149] In a second particular embodiment, at least a portion and preferably all of the effluent from hydrocracking step h) can advantageously be sent to a second gas / liquid separation step to produce a liquid effluent and a gaseous effluent comprising at least hydrogen.

[0150] Preferably, said second gas / liquid separation step is implemented in a high-temperature, high-pressure separator operating at a pressure and temperature compatible with the outlet temperature and pressure of step h). Said second separation step is preferably implemented at a temperature of between 200 and 390°C, under a pressure of between 2 and 16 MPa.

[0151] In this case, the liquid effluent from the second separation stage can advantageously be recycled into the hydrocracking stage h).

[0152] According to a variant, the gaseous effluent comprising at least hydrogen from the second separation step can advantageously be sent to compression step d). In this case, the method uses two gas / liquid separators and a single compressor on the hydrogen recycle loop, as well as a single make-up hydrogen compressor, which reduces the cost of the installation.

[0153] According to another variant, the gaseous effluent comprising at least hydrogen from the second separation stage can be sent to a second compression stage before being recycled in stage h).

[0154] These operating conditions used in the processes according to the invention generally make it possible to achieve conversions per pass, into products having boiling points lower than 340°C, and better still lower than 370°C, greater than 15% by weight and even more preferably between 20 and 95% by weight.

[0155] Furthermore, the kerosene fraction produced by the process according to the invention has a crystal disappearance point of less than -20°C, preferably less than -30°C and even more preferably less than -40°C. The diesel cut produced by the process has a cloud point less than 15°C, preferably less than 5°C and very preferably less than 0°C. Description of the figure

[0156] [Fig. 1] represents the diagram of a particular embodiment of the method of the present invention, comprising:

[0157] - an optional pretreatment step (1-a') of the renewable load (2), by example by filtration and / or stripping with nitrogen so as to obtain a pretreated oil (3);

[0158] - a step a) of hydrotreatment (2-a) of a feed comprising a fraction of the pretreated renewable feedstock (3) and a heavy majority fraction of hydrocarbons of fossil origin (5), in the presence of a hydrogen-rich gas (6), carried out in at least one fixed-bed reactor comprising at least one hydrotreatment catalyst, to obtain a hydrotreated effluent (7);

[0159] - a step b) of hydrocracking (8-b) of at least part of the hydrotreated effluent (7) resulting from step a), in the presence of hydrogen (9) carried out in at least one fixed bed reactor comprising at least one hydrocracking catalyst, to obtain a hydrocracked effluent (10);

[0160] - a step c) of separation (11 -c) of the hydrocracked effluent (10) carried out optionally- only in the presence of an aqueous washing solution (12) and making it possible to obtain at least one gaseous effluent comprising hydrogen (13), at least one liquid effluent (14) and optionally an aqueous effluent (15) containing dissolved salts.

[0161] - a step e) of fractionation (16-e) of the liquid effluent (14) allowing to obtain: - at least one naphtha cut (17) comprising compounds having a boiling point less than or equal to 180°C, and preferably between 80 and 130°C.

[0162] - at least one first cut (19a) in the middle distillate range comprising compounds having a boiling point between 130°C and 220°C, and preferably between 130°C and 180°C,

[0163] - at least one second cut (18) in the middle distillate range comprising compounds having a boiling point between 180°C and 300°C, and preferably between 190°C and 300°C,

[0164] - at least one third cut (19b) in the middle distillate range comprising compounds having a boiling point between 300°C and 370°C,

[0165] - and at least one unconverted heavy liquid fraction (20) comprising compounds having a boiling point above 370°C.

[0166] The first and third cuts 19a and 19b are mixed by any means known to those skilled in the art to form a cut 19c corresponding to the diesel cut. 19c mixture is then sent to a diesel storage unit at the refinery.

[0167] Optionally, the unconverted heavy liquid cut having a boiling point above 370°C (20) can be recycled in the hydrotreatment step a) and / or in the hydrocracking step b) (not shown).

[0168] Optionally, the unconverted heavy liquid cut having a boiling point above 370°C (20) can be sent to a second hydrocracking stage (21-f) which is carried out in at least one fixed-bed reactor comprising at least one hydrocracking catalyst and is supplied with hydrogen (22). The second hydrocracked effluent (23) is sent to the separation stage c) (11-c).

[0169] Only the main steps, with the main flows, are shown in [Fig.l], in order to allow a better understanding of the invention. It is understood that all the equipment necessary for operation is present (balloons, pumps, exchangers, furnaces, columns, etc.), even if not shown. It is also understood that flows of hydrogen-rich gas (make-up or recycle), as described above, can be injected at the inlet of each reactor or catalytic bed or between two reactors or two catalytic beds. Means well known to those skilled in the art for purifying and recycling hydrogen can also be implemented.

[0170] The examples illustrate the invention without limiting its scope. Examples

[0171] Example 1 (comparative): hydrocracking of a mixture comprising 83% by weight of vacuum distillate and 17% by weight of animal fat, on the hydrotreatment catalyst sequence followed by the hydrocracking catalyst based on a USY zeolite and a Beta zeolite with standard cutting points: [130; 250] for the kerosene cut and [250; 370°C] for the diesel cut.

[0172] Example 2 (compliant): hydrocracking of a mixture comprising 83% by weight of vacuum distillate and 17% by weight of animal fat, on the hydrotreatment catalyst sequence followed by the hydrocracking catalyst based on a USY zeolite and a Beta zeolite with judiciously chosen cutting points: [190; 280] for the kerosene cut and the blend [130; 190] + [280; 370°C] for the diesel cut. This makes it possible to maximize the biogenic carbon content of the kerosene cut while respecting the jet specification of the cut and improving the cloud point of the diesel cut.

[0173] For both examples, the characteristics of the mixture feed comprising 83% by weight of vacuum distillate and 17% by weight of animal fat are given in Table 1.

[0174] The feedstock, before being injected into the hydrocracking stage, is pretreated with a hydrotreatment catalyst, at a total pressure of 14 MPa and at a temperature of temperature and WH allowing to obtain an organic nitrogen content of 10 ppm in the hydrotreated feed, that is to say, at the inlet of the hydrocracking catalytic beds.

[0175] All of the hydrotreated effluent from the hydrotreatment section is sent directly to the hydrocracking section without an intermediate separation step. The temperatures of the hydrocracking catalysts are controlled to achieve a total conversion of the 370°C+ cut of 86% by weight.

[0176] All examples are compared at iso total pressure of 14 MPa, at iso total volume of catalysts and at iso charge flow rate.

[0177] Product yields, biogenic carbon flow rate in kerosene and diesel cuts, and cold flow properties (kerosene crystal disappearance point and diesel cloud point) are compared between two examples in Table 2.

[0178] The yields of main products given in Table 2 are calculated relative to the liquid feed, i.e. the mixture comprising 83% by weight of vacuum distillate and 17% by weight of animal fat before the hydrotreatment step. It should be noted that the sum of the yields given in Table 2 is not completed to 100% (but to 98.7%) because the yields of co-products (H2S, NH3, CO, CO2 and water) and the hydrogen consumption are not reported in Table 4, which are identical between two examples.

[0179] Characteristics of the mixture of DSV and animal fat:

[0180] [Tables 1] Animal Fat (AF) DSV DSV+AF (83 / 17 wt. %) Density at 15°C g / ml 0.9165 0.9284 0.9262 Carbon %wt. ds 77.00 85.6 84.3 Hydrogen %wt. ds 11.89 12.32 12.18 Oxygen %wt. ds 11.06 0.17 2.00 Sulphur ppm 6.3 18920 15200 Nitrogen ppm 9.2 1395 903 Monoglycerides %wt. ds <0.1 Diglycerides %wt. ds 3.1 Triglycerides %wt. ds 93.1 Acid Number 10.2 Free Fatty Acid %wt. ds 3.3 C16:0 %wt. ds 21.1 C16:1,C16:2 %weight ds 3.9 C18:0 %weight ds 5.9 C18:1,C18:2 %weight ds 50.0 C18:2 %weight ds 12.6 C18:3 %weight ds 1.0 C20:l %wt ds 1.0 E C16, % %wt ds 25.0 EC18, % %wt ds 69.5 DS 0.5 %wt °C 340 316 316 DS 5 %wt °C 523 394 394 DS 10 %wt °c 569 413 415 DS 20 %wt °c 600 436 438 DS 30 %wt °c 607 450 455 DS 40 %wt °c 609 466 473 DS 50 %wt °c 611 480 493 DS 60 %wt °c 612 498 515 DS 70 %wt °c 613 515 540 DS 80 %wt °c 616 537 572 DS 90% weight °c 618 563 605 DS 95% weight °c 619 581 610 DS 99.5% weight °c 628 625 628

[0181] Operating conditions and process performance:

[0182] [Tables2] Example 1: Comparative Example 2: in accordance with the invention Hydrotreatment section Catalyst NiMoP / Al2O3 NiMoP / Al2O3 Temperature, °C °C 372 372 WH, h 1 h-1 1 1 Hydrocracking section 1 Catalyst NiMoP / USY+BEA on A12O3 NiMoP / USY+BEA on A12O3 Temperature, °C °C 395 395 WH, h 1 h-1 2.25 2.25 Process performance Nitrogen at the outlet of the HDT section, ppm PPm 10 10 Total conversion of the 370°C+ cut, % % 86 86 Heavy gasoline cut points [°C - °C] [80-130] [80-130] Kerosene cut points [°C - °C] [130-250] [190-280] Diesel Cut Points [°C - °C] [250-370] [130-190]+ [280-370] Middle Distillate Cut Points [°C - °C] [130-370] [130-370] Yield 98.9 98.9 Gas C1-C4 % m / m 6.5 6.5 Light Gasoline (PI-80°C) % m / m 6.7 6.7 Heavy Gasoline % m / m 11.7 11.7 Middle Distillate % m / m 60.7 60.7 Kerosene % m / m 30.7 22.9 Diesel % m / m 30.0 37.7 Unconverted (370°C+), %m / m charge % m / m 13.3 13.3 Product Quality Biogenic Carbon flow rate in kerosene g / 100 g VGO 1.8 3.5 Biogenic Carbon content in kerosene % m / m 7.1 18.4 Kerosene Freezing Point °C -70.0 -41.9 Biogenic Carbon flow rate in diesel g / 100 g VGO 14.2 12.4 Biogenic Carbon content in diesel % m / m 57.0 39.6 Diesel Cloud Point °C 1.4 -2.0

[0183] Table 2 shows both the strong increase in the mass flow rate of Biogenic Carbon in kerosene (from 1.8 g / h to 3.5 g / h), the kerosene thus produced meeting the jet specification and the improvement in the cloud point of diesel which goes from 1.4°C to -2°C.

Claims

Claims

1. Process for producing middle distillates from at least one fossil hydrocarbon feedstock of which at least 50% by weight of the compounds have an initial boiling point above 250°C and a final boiling point below 800°C, said fossil hydrocarbon feedstock being co-treated in a mixture with at least one renewable feedstock chosen from vegetable oils, algal oils, cooking oils and animal fats, fresh or used, alone or in a mixture, and feedstocks from the reprocessing of biomass / plastics / tires / and household waste, alone or in mixtures, said process comprising at least the following steps: a) a step of hydrotreating said feedstock mixture in the presence of hydrogen and at least one hydrotreatment catalyst at a temperature of between 200 and 450°C, under a pressure of between 2 and 25 MPa, at a space velocity of between 0,1 and 6 h-1 and at a quantity of hydrogen introduced such that the volume ratio liter of hydrogen / liter of hydrocarbon is between 100 and 5000 L / L, b) a step of hydrocracking at least a part and preferably all of the hydrotreated feedstock from step a), in the presence of hydrogen and a hydrocracking catalyst, the hydrocracking step being carried out at a temperature between 200°C and 480°C, at a total pressure between 1 MPa and 25 MPa with a ratio of volume of hydrogen per volume of hydrocarbon feedstock between 80 and 5000 liters per liter and at an Hourly Volume Velocity (WH) defined by the ratio of the volume flow rate of liquid hydrocarbon feedstock to the volume of catalyst loaded into the reactor between 0.1 and 50 h1, c) The gas / liquid separation of the effluent from step b) to produce a liquid effluent and a gaseous effluent comprising at least hydrogen,d) Sending the gaseous effluent comprising at least hydrogen to a compression stage before recycling it to at least the hydrotreatment stage a) and the hydrocracking stage b), e) Fractionating at least part and preferably all of the liquid effluent from stage c), in a fractionation section, to produce:, - at least one naphtha fraction comprising compounds having a boiling point less than or equal to 180°C, and preferably between 80 and 130°C, - at least one first cut in the middle distillate range comprising compounds having a boiling point between 130°C and 220°C, and preferably between 130°C and 180°C, - at least one second cut in the middle distillate range comprising compounds having a boiling point between 130°C and 300°C, and preferably between 190°C and 300°C, - at least one third cut in the middle distillate range comprising compounds having a boiling point between 250°C and 400°C and preferably between 300 and 370°C,- and at least one unconverted heavy liquid cut comprising compounds having a boiling point above 400°C and preferably above 370°C f) mixing at least a portion of the first cut in the middle distillate range comprising compounds having a boiling point between 130°C and 220°C and at least a portion of the third cut in the middle distillate range comprising compounds having a boiling point between 250°C and 400°C and sending the mixture to a diesel storage unit, g) Sending at least a portion and preferably all of the third cut in the middle distillate range comprising compounds having a boiling point between 250°C and 400°C to a kerosene storage unit.,

2. Process according to claim 1 in which the hydrocarbon feedstock is chosen from light gas oils from a catalytic cracking unit, atmospheric distillates, vacuum distillates from direct distillation of crude or from conversion units such as FCC, coker, H-Oil or visbreaking, feedstocks from units for extracting aromatics from lubricating oil bases or from solvent dewaxing of lubricating oil bases, distillates from fixed bed or ebullated bed desulfurization or hydroconversion processes of RAT (atmospheric residues) and / or RSV (vacuum residues) and / or deasphalted oils.

3. Process according to one of claims 1 or 2 in which the vegetable oils are crude or refined, totally or in part, and derived from the following plants: rapeseed, sunflower, soybean, palm, palm kernel, olive, coconut, jatropha, and the animal fats are chosen from lard or fats composed of residues from the food industry or derived from catering industries.

4. Process according to one of the preceding claims in which the hydrotreatment step a) operates at a temperature of between 250 and 450°C, very preferably between 300 and 430°C, under a pressure of between 5 and 20 MPa, at a space velocity of between 0.2 and 5 h-1, and at a quantity of hydrogen introduced such that the volume ratio liter of hydrogen / liter of hydrocarbon is between 300 and 3000 NL / L.

5. Process according to claim 4 in which the hydrotreatment catalysts used in step a) are in supported or unsupported form, preferably containing at least one amorphous support and at least one hydro-dehydrogenating element chosen from at least one non-noble element from groups VIB and VIII, and preferably at least one element from group VIB chosen from molybdenum or tungsten taken alone or in a mixture, and at least one non-noble element from group VIII chosen from nickel or cobalt taken alone or in a mixture.

6. Process according to one of claims 1 to 5 in which the hydrocracking catalyst used in step b) comprises and preferably consists of at least one metal from group VI and / or at least one non-noble metal from group VIII, and a Y zeolite and an alumina binder.

7. Process according to one of the preceding claims in which the liquid fraction, unconverted residue, (UCO) from step e) containing products whose boiling point is higher than 370°C and from the distillation is at least partly and preferably entirely introduced into the second hydrocracking step h) of the process.

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