Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
  • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
  • C07C29/1516—Multisteps
  • C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
  • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
  • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
  • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
  • C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
  • C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
  • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
  • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1011—Biomass
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1037—Hydrocarbon fractions
  • C10G2300/1048—Middle distillates
  • C10G2300/1051—Kerosene having a boiling range of about 180 - 230 °C
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/08—Jet fuel
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0913—Carbonaceous raw material
  • C10J2300/0916—Biomass
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0913—Carbonaceous raw material
  • C10J2300/0916—Biomass
  • C10J2300/092—Wood, cellulose
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
  • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
  • C10J2300/1656—Conversion of synthesis gas to chemicals
  • C10J2300/1665—Conversion of synthesis gas to chemicals to alcohols, e.g. methanol or ethanol
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels

Definitions

• TITLE PROCESS FOR MANUFACTURING A JET FUEL FROM FEEDS OF RENEWABLE ORIGIN
• the present invention relates to the technical field of refining petroleum feedstocks of fossil origin and feedstocks of biological origin, particularly for the manufacture of jet fuel. More particularly, the invention relates to a process for obtaining a jet fuel having a component of biological (or renewable) origin.
• jet fuels also called jet fuel, jet fuel or kerosene
• jet fuel are produced from crude oil and contain a complex mixture of hydrocarbons that typically have 6 to 18 carbon atoms. These hydrocarbons include linear and branched alkanes, cycloalkanes and aromatic hydrocarbons.
• the cut points of the jet-fuel fraction typically vary between 140°C and 240°C.
• fuel bases can be crude oil distillation cuts, possibly hydrotreated or sometimes subjected to a softening treatment (MEROX process for example). These bases can also be cuts from a hydrocracker effluent or an effluent from a catalytic cracker (often after hydrotreatment). Other fuel bases can be prepared by other routes such as Fischer Tropsch synthesis followed by a cracking step. The choice of fuel bases as well as their relative proportions are made so that the final properties of the mixture meet the desired specifications.
• MEOX process softening treatment
• Other fuel bases can be prepared by other routes such as Fischer Tropsch synthesis followed by a cracking step. The choice of fuel bases as well as their relative proportions are made so that the final properties of the mixture meet the desired specifications.
• a solution for obtaining a jet fuel with a component of biological origin consists of mixing a conventional jet with a paraffin base derived from renewable feedstocks as provided for by standard D7566-21, thus allowing the production of alternative aviation fuels.
• Bases for aviation fuel derived from renewable feedstocks that can be incorporated into fossil fuels are
• Synthetic paraffinic kerosenes [SPK] resulting from processes such as the Fischer-Tropsch process, hydrotreatment of esters and fatty acids [HEFA-SPK] or produced by the Alcohol-to-jet route (transformation of alcohol into kerosene) [ATJ-SPK]
• SPK Synthetic paraffinic kerosenes
• Another solution consists of co-treating a hydrocarbon of fossil origin with a feed of renewable origin, as provided in particular in standard ASTM D1655-21 c.
• document EP2346962 describes a process making it possible to obtain a kerosene cut, part of which is of biological origin.
• a feed of petroleum origin mixed with a feed of biological origin is subjected to a hydrotreatment step, then fractionated in order to recover a kerosene cut.
• the filler of biological origin used is an animal oil and/or fat, or a mixture of these oils/fats.
• the oils and/or fats used are not transesterified.
• Document EP2533895 describes a specific catalyst for producing biodiesel. It describes in particular the use of this catalyst to treat a load which is a mixture of a hydrocarbon of fossil origin (kerosene, diesel, etc.) and a biomass chosen from vegetable or animal oils and fats. The oils and/or fats used are not trans-esterified. Jet production is not mentioned.
• document EP3813539 describes a process for producing a purified biodiesel from renewable raw materials (such as fats and oils) containing unsaponifiable materials.
• the process involves the esterification of vegetable oils or fats to obtain a crude biodiesel which is then subjected to distillation to produce a purified biodiesel and a distillation base.
• the latter contains more than 2% by mass of unsaponifiables as well as soaps, phospholipids, proteins, colored compounds, sulfur compounds, high boiling point compounds containing acidic or basic groups, and mono-, diet triglycerides.
• This distillation bottom is then diluted with a filler of fossil origin of the middle distillate type, before being subjected to a hydrodeoxygenation step in order to produce hydrocarbons of the diesel type. Jet production is not mentioned.
• the invention proposes a process for manufacturing a jet fuel comprising at least the steps consisting of: a) providing methyl esters of fatty acids resulting from the reaction of animal fats and/or used cooking oils with methanol in a transesterification reactor, b) supplying hydrocarbons of fossil origin, c) preparing a hydrocarbon feed containing the hydrocarbons of fossil origin supplied by step b) and the fatty acid methyl esters supplied by step a ) in a content of at most 5% vol relative to the hydrocarbon feed, d) subject the hydrocarbon feed prepared during step c) to hydrotreatment and obtain a treated hydrocarbon feed, e) fractionate the treated hydrocarbon feed obtained in step d) and recover a kerosene fraction as jet fuel, said kerosene fraction having a final boiling point below 300°C, measured in particular according to the ASTM D86-12 standard.
• the process according to the invention thus makes it possible to obtain an aviation fuel, part of which is of renewable origin, also called SAF for “Sustainable Aviation Fuel” in English.
• the kerosene fraction obtained meets the specifications of an A1 jet according to standard ASTM D1655-21, in particular when the methyl esters are obtained from animal fats which are animal by-products. This makes it possible to increase the production of kerosene by using this type of fat.
• process according to the invention can be implemented in existing hydrotreatment units.
• % by weight and % by mass have an equivalent meaning and refer to the proportion of the mass of a product compared to 100g of a composition comprising it.
• Boiling points as mentioned here are measured at atmospheric pressure unless otherwise noted.
• An initial boiling point is defined as the temperature value at which a first vapor bubble is formed.
• a final boiling point is the highest temperature achievable during distillation. At this temperature, no more vapor can be transported to a condenser.
• the determination of the initial and final points uses techniques known in the trade and several methods adapted depending on the range of distillation temperatures are applicable, for example NF EN 15199-1 (version 2020) or ASTM D2887-19 for the measurement of boiling points of petroleum fractions by gas chromatography, ASTM D7169-05 for heavy hydrocarbons, ASTM D7500-15(2019), D86-12 or D1160-18 for distillates.
• the animal fats and used cooking oils, from which the methyl esters used in the present invention are derived, are advantageously animal fats and used cooking oils having the status of animal by-products, in particular within the meaning of Regulation (EC) No. °1069/2009 of the European Parliament and of the Council of October 21, 2009 and Commission Regulation (EU) No. 142/2011 (Regulation implementing EC Regulation No. 1069/2009).
• Animal fats with the status of animal by-product are fatty residues of animal origin, other than used cooking oils, for example from the food industries or rendering installations.
• Used cooking oils having the status of animal by-products are used cooking oils (used cooking oils or UCO), namely residues of fats of plant or animal origin used for human food, in food industry, collective or commercial catering.
• the fatty acid methyl esters provided in step a) come from the reaction of animal fats and/or used cooking oils with methanol in a trans-esterification reactor.
• this step a) may thus include, or consist of, a step of transesterification of animal fats and/or used cooking oils with methanol to obtain methyl esters of the fatty acids initially contained in the animal fats and/or used cooking oils, and glycerin, followed by a separation step by distillation, decantation or centrifugation of the methyl esters produced.
• the triglycerides contained in animal fats and/or used cooking oils react with methanol to obtain methyl esters of fatty acids in a transesterification reactor.
• This reaction is usually carried out in the presence of a catalyst, by an acid or basic, homogeneous or heterogeneous catalysis process, typically at a temperature of 25°C to 110°C or 35°C. °C to 90°C and a reaction time of 30 minutes to 50 hours.
• a catalyst/oil mass ratio typically 0.25 to 8% and a methanol/oil molar ratio of 3:1 to 15:1.
• This reaction is for example carried out in the presence of acid catalysts (hydrochloric acid, sulfuric acid, sulfonic acid, boron trifloride, zinc chloride, acid ion exchangers, aluminum trioxide, iron trioxide, etc.) or in the presence basic catalysts such as alkali metal alkoxides and hydroxides as well as sodium or potassium carbonates (sodium hydroxide, potassium hydroxide, sodium ethanolate, potassium ethanolate, etc.).
• acid catalysts hydroochloric acid, sulfuric acid, sulfonic acid, boron trifloride, zinc chloride, acid ion exchangers, aluminum trioxide, iron trioxide, etc.
• basic catalysts such as alkali metal alkoxides and hydroxides as well as sodium or potassium carbonates (sodium hydroxide, potassium hydroxide, sodium ethanolate, potassium ethanolate, etc.).
• the transesterification reaction can also be carried out under supercritical conditions can also be used, the reaction being carried out at high pressures of 15-35MPa, and, in some cases, at high temperatures of 250 to 280°C, or even higher (300-350°C). Under these supercritical conditions, the reaction can be carried out in the absence or presence of catalyst.
• the methyl esters of fatty acids used in the present invention are therefore free of impurities such as unsaponifiable compounds, soaps, or other compounds originating from animal fats or used cooking oils used as raw material.
• their unsaponifiable content is advantageously less than or equal to 1% m/m (measured according to standard ISO 3596:2001).
• the fatty acid methyl esters provided in step a) may comprise at least one of the following characteristics :
• the fatty acid methyl esters provided in step a) may comprise at least one of the following characteristics:
• the content of methyl esters of fatty acids whose carbon chain contains 20 to 22 carbon atoms will be as low as possible, zero preference, in order to improve the cold properties and in particular the freezing point.
• esters produced from animal fats which are animal by-products and having one or more of the characteristics mentioned above, are produced from animal fats originating from category 1 materials and/or from materials of category 2, category 1 and 2 materials being defined in articles 8 and 9 respectively of European Regulation 1069/2009.
• Step a) of supplying methyl esters of fatty acids may in particular comprise (i) obtaining methanol of renewable origin, (ii) followed by the reaction of animal fats and/or used cooking oils with the methanol obtained in step (i) in a transesterification reactor.
• methanol of renewable origin we mean methanol obtained from biomass.
• Step (i) can thus include:
• synthesis gas comprising CO/H2 comprising one of the following steps: o a biomass gasification step, o a biomass pyrolysis step, o a step of producing biogas containing methane and CO2, optionally by anaerobic digestion of biomass in the presence of one or more microorganisms, followed by partial oxidation of the biogas in the presence of dioxygen, a step of converting a synthesis gas comprising CO/H2 into methanol, in particular into presence of a catalyst.
• Biomass may include wood fuels from natural forests and woodlands (e.g. sawdust), agricultural residues (e.g. rice husks, straw manure), energy crops that are grown exclusively for energy production (e.g. corn and oil palm), urban waste (e.g. wood waste, rice, straw manure), energy crops that are grown exclusively for energy production (e.g. corn and oil palm), urban waste (e.g. municipal solid waste and sewage) and waste-derived biomass fuel (e.g. pellets Of wood).
• wood fuels from natural forests and woodlands e.g. sawdust
• agricultural residues e.g. rice husks, straw manure
• energy crops that are grown exclusively for energy production e.g. corn and oil palm
• urban waste e.g. wood waste, rice, straw manure
• energy crops that are grown exclusively for energy production e.g. corn and oil palm
• urban waste e.g. municipal solid waste and sewage
• waste-derived biomass fuel e.g. pellets Of wood
• Methanol of renewable origin can in particular be obtained by conversion of a synthesis gas comprising CO/H2, this synthesis gas being derived from biomass.
• the conversion of a synthesis gas into methanol is well known to those skilled in the art.
• Biomass can for example be gasified to produce a synthesis gas (or “syngas” in English) rich in CO/H2, this synthesis gas then being converted into methanol in the presence of a catalyst.
• a synthesis gas or “syngas” in English
• CO/H2 a synthesis gas
• a method of this type is for example described in the document WO2018134853A1.
• Synthesis gas suitable for further conversion to methanol can also be obtained by pyrolysis of biomass.
• a synthesis gas suitable for subsequent conversion into methanol can also be obtained by partial oxidation in the presence of dioxygen of a biogas containing methane and CO2, this biogas resulting for example from the anaerobic digestion of biomass in the presence of one or several microorganisms.
• a process of this type is for example described in document W02019060988A1.
• the fossil hydrocarbons which can be used in the present invention can be chosen from kerosene cuts.
• a kerosene cut of fossil origin has boiling points ranging from 130°C to 300°C. It typically has an initial boiling point according to the ASTM D86-12 standard of 130 to 160°C and a final boiling point according to the ASTM D86-12 standard of 220°C to 300°C. These kerosene cuts can be :
• the hydrocarbons of fossil origin are advantageously a kerosene cut or a mixture of kerosene cuts, preferably coming from the direct distillation of crude oil or from hydrocracking.
• the hydrocarbon feed prepared in step c) contains the hydrocarbons of fossil origin provided by step b) and the methyl esters of fatty acids provided by step a) in a content of at most 5% by volume relative to the hydrocarbon filler, advantageously at most 0.9% or 0.6% or 0.5% or 0.4% or 0.3% by volume.
• the content of fatty acid methyl esters in the hydrocarbon feedstock can be from 0.1% by volume to 1% by volume, preferably from 0.1% by volume to 0.9% by volume, or from 0 .1% to 0.6% by volume, more preferably 0.1% to 0.5% by volume or 0.1 to 0.4% by volume or 0.1 to 0.3% by volume , or in any inclusive interval defined by two of these limits.
• This preparation step can be carried out by simply mixing the constituents of the hydrocarbon feed supplied in steps a) and b), in particular upstream of the hydrotreatment step of step d), or during step d. ).
• Step d) of hydrotreatment of the hydrocarbon feed can be implemented in one or more reactors.
• Any type of reactor usually used for this type of reaction can be used, for example a fixed bed reactor, a bubbling bed reactor, a slurry reactor, etc., preferably a fixed bed reactor.
• step d) is carried out under a pressure of 15 to 130 bars and at a temperature of 250 to 380°C, preferably 280 to 340°C, in the presence of a hydrotreatment catalyst and dihydrogen. .
• an hourly space velocity of the liquid (WH in French, LHSV in English - Liquid Hourly Space Velocity): from 0.2 to 9 hr 1 , preferably 0.5 to 7, and more preferably 0.8 to 1 .8, and a dihydrogen ratio: 50 to 1500 Nm 3 /m 3 of charge, preferably 120 to 250 Nm 3 /m 3 and more preferably 120 to 200 Nm 3 /m 3 .
• Step d) is typically carried out in a fixed bed reactor, comprising one or more catalyst beds.
• step d) can be carried out under a pressure of 15 to 50 bars and at a temperature of 280°C to 340°C, in the presence of a hydrotreatment catalyst and dihydrogen, typically with a dihydrogen rate from 120 to 180 Nm 3 /m 3 of charge.
• a hydrotreatment catalyst and dihydrogen typically with a dihydrogen rate from 120 to 180 Nm 3 /m 3 of charge.
• the hydrotreatment catalyst is a conventional hydrotreatment catalyst.
• Conventional hydrotreatment catalysts include in particular an active metal compound such as nickel, platinum, palladium, rhenium, rhodium, nickel tungstate, nickel molybdenate, molybdenum, cobalt molybdenate, nickel molybdenate, nickel, this metallic compound may or may not be deposited on a support.
• This support can generally comprise oxides such as silicas, aluminas, aluminosilicates (in particular zeolites), oxides of titanium, or even carbon, molecular sieves, salts or alkaline earth metals.
• a support When a support is present, it advantageously has a specific surface area varying from 100 to 250 m 2 /g, preferably from 150 to 200 m 2 /g.
• the catalyst comprises at least two metals from groups 6, 9, 10, 11 of the periodic table of elements, preferably at least two metals such as NiMo, CoMo, or even CoNiMo, preferably on an alumina support.
• conventional hydroprocessing catalysts When supported, conventional hydroprocessing catalysts typically include a metal content of 0.01 to 25% by weight based on mass. total mass of the catalyst, preferably 15 to 20% by mass, for example 20% by mass relative to the total mass of the catalyst.
• the catalyst used does not have an isomerizing function or has negligible isomerizing activity under the reaction conditions. In other words, the catalyst does not promote the isomerization of the hydrocarbon compounds present in the feed.
• a support is present, it is preferably slightly or not acidic.
• a catalyst not having an isomerizing function can comprise at least one metal from groups 6, 9, 10, 11 of the periodic table of elements, optionally on a support chosen from alumina, silica alumina, phosphated alumina, borated alumina, phosphated alumina silica, alone or in a mixture.
• Hydrotreatment step d) produces an effluent containing a liquid fraction containing the kerosene fraction, and a gaseous fraction.
• the hydrotreated feedstock obtained at the outlet of step d) undergoes fractionation.
• This fractionation can be carried out by distillation or stripping, in particular by adding a separation column, for example a distillation column, or even a stripping column.
• the effluent leaving the reactor is fractionated, typically by stripping, in order to recover a kerosene cut.
• This fractionation can be implemented so that the kerosene cut forms a jet fuel, respecting in particular the desired specifications.
• the recovered kerosene fraction has a final boiling point less than or equal to 300°C, in particular measured according to the ASTM D86-12 standard.
• the initial boiling point according to ASTM D86-12 can be 120 to 185°C.
• the final boiling point according to ASTM D86-12 can be 220 to 300°C.
• step e) makes it possible to obtain a kerosene fraction meeting one or more of the required specifications, in particular those of an A1 jet according to standard ASTM D1655-21, in particular the incorporation contents of the methyl esters in the hydrocarbon filler prepared in step c) above.
• the fractionation step also makes it possible to recover the gas produced, in particular methane, during the hydrotreatment step.
• Fig. 1 simplified diagram of a hydrotreatment unit making it possible to implement the process according to one embodiment of the invention.
• Figure 1 represents a simplified diagram of a hydrotreatment unit 1 making it possible to implement the process according to the invention.
• This unit 1 comprises a reactor 2 into which the feed to be treated is introduced by means of a line 3.
• This reactor contains one or more beds of hydrotreatment catalysts.
• the filler (C), in the present invention, is a mixture of a kerosene filler of fossil origin and methyl esters of fatty acids of renewable origin.
• a line 4 recovers the effluent leaving reactor 2 and leads it to a separation section 5.
• a heat exchanger 6 is placed downstream of the reactor on line 4 in order to heat the charge circulating in line 3, upstream of the reactor.
• a line 7, connected to line 3 supplies a gas rich in H2 to the load to be treated.
• the feed mixed with the H2-rich gas circulating in line 3 is heated by a furnace 8.
• the feed is mixed with the hydrogen-rich gas, then brought to the reaction temperature by the heat exchanger 6 and the oven 8 before entering reactor 2. It then passes into reactor 2.
• the mixture obtained is cooled, then separated in the separation section 5, for example by stripping, which makes it possible to obtain:
• G a gaseous fraction (G), containing in particular water from stripping, gaseous hydrocarbons, an acid gas rich in H2S, part of which is reinjected into the gas rich in H2 mixed with the load, by means of a line 9,
• a kerosene cut taken at the outlet of an atmospheric crude distillation unit was mixed with different charges of renewable origin.
• Ke The characteristics of the kerosene cut of fossil origin used, denoted “Kero” are presented in table 1 below.
• the different charges of renewable origin used are as follows:
• EMAG GA Methyl ester of animal fat
• EMAG UCO Methyl ester of UCO
• the catalyst used is a CoMo type catalyst.
• the operating conditions are presented in Table 3.
• FP The freezing point
• Table 4 The freezing point (denoted FP) was determined for the effluents obtained for each load, the results are presented in Table 4 below. Each of these effluents corresponds to the liquid fraction leaving the reactor, after separation of the gases.
• AFP corresponds to the difference (noted) between the freezing point of hydrotreated kerosene alone and mixed with a filler with the filler of renewable origin considered. AFP thus represents the degradation of the freezing point of the effluent produced for the different loads of renewable origin.
• the different fillers of renewable origin do not all have the same impact on the freezing point: the more the filler contains long carbon chains, the more it degrades the cold properties of the product.
• GA FAME which contains 29% C16, is the most favorable filler since it only degrades the freezing point by 1.7°C at 0.3% m of incorporation and by 6.2° C at 0.5%m.
• Table 5 brings together the other properties of the effluents obtained during coprocessing with FAMEs, more precisely of the 140°C+ fraction of the effluent leaving the hydrotreatment reactor. It can be seen that the 140°C+ fractions of the effluents obtained comply with most of the specifications of an A1 jet.

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