WO2023194338A1 - Carburant kérosène renouvelable ayant d'excellentes propriétés à froid - Google Patents
Carburant kérosène renouvelable ayant d'excellentes propriétés à froid Download PDFInfo
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- WO2023194338A1 WO2023194338A1 PCT/EP2023/058742 EP2023058742W WO2023194338A1 WO 2023194338 A1 WO2023194338 A1 WO 2023194338A1 EP 2023058742 W EP2023058742 W EP 2023058742W WO 2023194338 A1 WO2023194338 A1 WO 2023194338A1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/10—Catalytic processes with metal oxides
-
- 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
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
-
- 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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
- C10G69/126—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step polymerisation, e.g. oligomerisation
-
- 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
- C10G2300/1088—Olefins
- C10G2300/1092—C2-C4 olefins
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- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
- C10L2270/00—Specifically adapted fuels
- C10L2270/04—Specifically adapted fuels for turbines, planes, power generation
Definitions
- the present invention is part of the field of biosourced fuels and more particularly relates to a kerosene base, preferably renewable and meeting the specifications in force, in particular those defined in standard ASTM D7566 and in particular in Annex 5, and very advantageously presenting particularly satisfactory cold properties.
- the present invention also relates to any composition which comprises such a kerosene base.
- US patent 8,373,012 proposes a method for preparing mixtures of renewable fuels, comprising the conversion of fermentative isobutanol into synthetic paraffinic kerosene (or Synthesized Paraffinic Kerosene, SPK, according to Anglo-Saxon terminology) which meet the specifications of the standard ASTM D7566-10a, Annex 1, and therefore have in particular a cold point of at most -40°C.
- synthetic paraffinic kerosene or Synthesized Paraffinic Kerosene, SPK, according to Anglo-Saxon terminology
- Application WO13085980 discloses a renewable kerosene fuel derived at least in part from biomass which comprises between 5 and 20% by weight of iso-paraffins and between 15 and 95% by weight of naphthenes. More particularly, document WO13085980 describes a renewable kerosene fuel derived from biomass having a cold point which can be equal to approximately -39°C, -40°C or -70°C and in particular a density at 15°C (ie 60 °F) between 819 and 839 kg/m 3 (between 0.8192 g/cc and 0.8393 g/cc).
- Said kerosene fuel comes from a predominantly n-paraffinic fuel composition (more than 40% by weight), comprising approximately 7% by weight of C9 compounds, 12% by weight of C10 compounds, 8% by weight of C1 compounds 1, 9 % by weight of C12 compounds and approximately 11% of C14+ compounds, which corresponds to a C9+ mixture comprising approximately 35% by weight of C9 and C12 compounds.
- Application WO18224730 discloses a renewable kerosene fuel compound, in particular obtained by a Fischer-Tropsch process, comprising mainly isoparaffins and typically mainly C15 to C18 paraffins, C15- paraffins (i.e.
- compositions comprising such a renewable kerosene component mixed with a kerosene of fossil origin (that is to say from petroleum) and having a cold point less than or equal to -40°C, in particular varying between approximately -53°C and approximately -55°C.
- Patent application W02022/008534 describes renewable fuel products composed mainly of isoparaffins (at least 86.7% by weight) and comprising between 35.4 and 69.8% by weight of paraffins (n- and iso-paraffins) in C9 -C12, that is to say comprising between 9 and 12 carbon atoms, in other words C9, C10, C11 and C12.
- document W02022/008534 describes a renewable kerosene component comprising 86.7% by weight of isoparaffins and compounds containing 69.8% by weight of paraffins (n- and iso-paraffins) in C9-C12 including 33.5% by weight of C9 and C12 paraffins, 19.5% by weight of C10 paraffins, 16.8% by weight of C1 1 paraffin, having a cold point equal to - 54°C and a density of 750.7 kg/m3.
- kerosenes and in particular kerosenes that are at least partly biosourced, meeting all the specifications in force, in particular a density between 730 and 770 kg/m 3 at 15°C. and a flash point greater than or equal to 38°C, and in particular having excellent cold properties, more particularly having a very low cold point and in particular less than or equal to - 60°C, preferably less than or equal to - 80 °C.
- the present invention relates to a kerosene base comprising at least 60.0% by weight of a mixture composed of C3n hydrocarbons and C4n hydrocarbons, with n being a natural number chosen between 3 and 4, the kerosene base comprising at least 80% by weight of isoparaffins relative to the total weight of the kerosene base.
- the interest of the present invention lies in the consequent improvement in the cold properties of kerosenes, in particular mixtures of kerosenes for aircraft engines, meeting all the other specification criteria for kerosenes, in particular intended for aviation. , and more particularly the specifications of the ASTMD7566 standard and in particular those of Annex 5 of the ASTMD7566 standard, such as in particular a flash point greater than or equal to 38°C, a density between 730 and 770 kg/m 3 at 15° vs.
- the kerosene base according to the present invention has a very low cold point, in particular less than or equal to - 60°C, more particularly less than or equal to - 70°C, preferably less than or equal to - 80°C, and the mixtures which comprise it have cold points satisfactory cold temperatures and meeting the specification in force, with a cold point less than or equal to - 40°C.
- Another advantage of the present invention lies in the fact that the kerosene base according to the invention, used alone or in mixture with other biosourced kerosenes and/or of fossil origin, is advantageously at least partly biosourced, which will help airlines to achieve their objective of reducing their CO2 emissions and therefore their carbon footprint.
- 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 is not the case and the limit values are not included in the range described, such precision will be provided by the present invention.
- biosourced means that the product/compound it describes is an organic product/compound whose carbon comes from CO2 present in the atmosphere recently fixed (on a human scale) thanks to solar energy (photosynthesis) .
- this CO2 is captured or fixed by plant life (for example, agricultural crops or forest materials).
- plant life for example, agricultural crops or forest materials.
- CO2 is captured or fixed by photosynthesizing bacteria or phytoplankton.
- a biosourced material has a 14 C/ 12 C isotopic ratio greater than 0.
- a material of fossil origin has a 14 C/ 12 C isotopic ratio of approximately 0.
- the terms “renewable” or “from renewable sources” can also be used.
- T95 or “temperature T95” are interchangeable and designate the temperature at which 95% by weight of the product considered is evaporated. It is determined according to the standardized ASTM D2887 method.
- T5 or “T5 temperature” is the temperature at which 5% by weight of the product considered is evaporated, determined according to the same standardized ASTM D2887 method.
- Cx designates compounds containing x carbon atoms.
- a chemical compound C3 contains 3 carbon atoms.
- the term “Cx+” designates compounds having at least x carbon atoms.
- C9+ compounds are compounds containing at least 9 carbon atoms (i.e. 9 or more carbon atoms).
- the term “Cx-” designates compounds having at most x carbon atoms.
- olefin and “mono-olefin” are used interchangeably and refer to hydrocarbons comprising a single double bond.
- the smoke point (or “smoke point” according to Anglo-Saxon terminology) is a parameter determined by a standardized test described in standard ASTM D1322 / IP 598, which consists of measuring the maximum height of a flame not emitting smoke in an oil lamp (wick lamp). The smoke point is expressed in mm. The higher the smoke point, indicating a lower C/H ratio between carbon atoms C and hydrogen atoms H, the better the qualities of the kerosene, in particular the more thermally stable the product.
- the smoke point is the temperature from which oils or fats emit fumes continuously. Above this temperature, the products begin to decompose and denature.
- a low C/H ratio (or a high H/C ratio) is preferred because kerosenes must have a high calorific value (or “specific energy” according to Anglo-Saxon terminology).
- a high C/H ratio implies higher flame radiation, increased carbon deposition in aircraft engines and generation of black smoke and therefore elevation of the smoke point.
- the cold point (or freezing point according to Anglo-Saxon terminology) of a substance defines a temperature at which the liquid and solid states of the substance can coexist in equilibrium (ASTM D5972 and/or D7153).
- kerosene base comprising, preferably consisting of:
- the kerosene base mainly comprises hydrocarbons, aliphatic, that is to say mainly non-cyclic and non-aromatic; preferably the kerosene base comprises at least 90% by weight, preferably at least 95% by weight, preferably at least 99% by weight of aliphatic hydrocarbons.
- the kerosene base comprises less than 10% by weight, preferably less than 5% by weight, preferably less than 1.0% by weight, and very preferably less than 0.5% by weight of cyclic and/or aromatic hydrocarbon compounds, such as naphthene, benzene and/or naphthalene compounds.
- the kerosene base comprises strictly less than 10% by weight of naphthene compounds (also called cyclo-paraffins), preferably less than 5% by weight, preferably less than 1.0% by weight, very preferably less than 0.5%. weight, and very preferably is free of naphthene compounds.
- naphthene compounds also called cyclo-paraffins
- naphthene compounds increase the density of kerosene produced and have a C/H ratio between carbon and hydrogen atoms higher than that of paraffins.
- the kerosene base mainly comprises hydrogenated aliphatic hydrocarbons, called alkanes or even paraffins, that is to say that the kerosene base preferably comprises at least 90% by weight, preferably at least 95% by weight, preferably at least 95% by weight. less 99% by weight, of paraffins, that is to say linear paraffins (or n-paraffins) and branched paraffins (or iso-paraffins).
- the C3n and C4n hydrocarbons of the mixture of the kerosene base are predominantly hydrogenated aliphatic hydrocarbons, that is to say preferably at least 90% by weight, preferably at least 95% by weight, preferably at least 99% by weight. % weight, C3n and C4n paraffins.
- the kerosene base may optionally comprise olefins, in particular C3n and C4n olefins, preferably at a weight content of less than 5% by weight, preferably less than 1.0% by weight, very preferably less than 0.5%. weight.
- olefins in particular C3n and C4n olefins, preferably at a weight content of less than 5% by weight, preferably less than 1.0% by weight, very preferably less than 0.5%. weight.
- the kerosene base mainly comprises branched paraffins (or isoparaffins), that is to say it comprises at least 80% by weight, preferably at least 90% by weight, very preferably at least 95% by weight, of branched paraffins (or isoparaffins).
- the C3n and C4n hydrocarbons of the mixture of the kerosene base according to the invention are mainly branched hydrogenated hydrocarbons, that is to say they are at least 80% by weight, preferably at least 90% by weight, very preferably at least 95% by weight, C3n and C4n iso-paraffins, in particular C9 and C12 iso-paraffins or C12 and C16 iso-paraffins.
- isoparaffins or branched paraffins
- the kerosene base comprises at least 80% by weight, preferably at least 90% by weight, very preferably at least 95% by weight, of iso-paraffins, and advantageously at least 40% by weight, preferably at least 50% by weight, preferably at least 70% by weight, of multi-branched paraffins.
- multi-branched paraffins means that said paraffins have a branching index greater than or equal to 2, and preferably less than or equal to 9, very preferably less than or equal to 6.
- the base kerosene comprises at least 60.0% by weight, preferably at least 70.0% by weight, preferably at least 80.0% by weight, preferably at least 90.0% by weight, of a mixture of iso-paraffins in C3n and C4n, and in particular a mixture of C9 and C12 iso-paraffins or a mixture of C12 and C16 iso-paraffins, and very advantageously at least 40% by weight, preferably at least 50% weight, preferably at least 70% by weight, of multi-branched C3n and C4n paraffins and in particular of a mixture of multi-branched C9 and C12 paraffins or of a mixture of multi-branched C12 and C16 iso-paraffins. plugged in.
- the kerosene base comprises at most 10% by weight of n-paraffins, preferably at most 7% by weight of n-paraffins and preferably at most 5% by weight of n-paraffins, and can for example comprise at least 2 % weight of n-paraffins.
- the hydrocarbons containing 3n and 4n carbon atoms are present in the kerosene base at weight contents such that the C4n/C3n weight ratio between the C4n hydrocarbons and the C3n hydrocarbons is greater than or equal to 0.10, and preferably less than or equal to 1.1, preferably less than or equal to 0.9, preferably less than or equal to 0.5.
- the kerosene base preferably comprises less than 40% by weight, preferably less than 30% by weight, optionally less than 25% by weight, preferably less than 20% by weight, or even less than 10% by weight, of hydrocarbons containing m carbon atoms, m being a natural number different from the integers 3n and 4n, n being as defined above, that is to say a natural number chosen between 3 and 4, that is to say m different from 9 and 12 or 12 and 16.
- the kerosene base preferably comprises less than 40% by weight, preferably less than 30% by weight, optionally less than 25% by weight, preferably less than 20% by weight, or even less than 10% by weight, of hydrocarbons in Cm, Cm being different from C9 and C12 or from C12 and C16.
- the kerosene base preferably comprises less than 40% by weight, preferably less than 30% by weight, optionally less than 25% by weight, preferably less than 20% by weight, or even less than 10% by weight, of hydrocarbons in C8-, C10, C11 and C13+ or C11-, C13, C14, C15 and C17+, respectively when the mixture comprises, preferably consists of, C9, C12 or C12, C16 hydrocarbons.
- the kerosene base may optionally comprise C5n hydrocarbons, n being as defined above, which corresponds to C15 or C20 hydrocarbons, preferably at a content less than or equal to 15% by weight, preferably less than or equal to 10% weight, preferably less than or equal to 5% weight.
- the kerosene base according to the invention has an initial boiling temperature greater than or equal to 140°C.
- the kerosene base is advantageously at least partly, preferably entirely, biosourced.
- the kerosene base according to the invention has a percentage of modern carbon (pMC) greater than or equal to 1%, preferably greater than or equal to 50%, preferably greater than or equal to 75%, in particular greater than or equal to 90%, or even greater than or equal to 100%.
- pMC percentage of modern carbon
- the kerosene base described above is obtained by a process comprising a step of oligomerization of C3 (containing 3 carbon atoms) to C6 (containing 6 carbon atoms) olefins, preferably C3 and/or C4 , in the presence of a catalyst oligomerization, preferably heterogeneous, and a step of hydrogenation of at least part of the reaction effluent resulting from the oligomerization step.
- Said olefins advantageously come from a process for dehydrating alcohols in particular C3 to C6, preferably C3 and/or C4, said alcohols preferably being biosourced, for example produced by fermentation of sugars.
- the oligomerization step can be carried out in the presence of silica-alumina, used as an oligomerization catalyst, at a temperature between 20°C and 300°C, preferably between 25 and 220°C, preferred manner between 30°C and 200°C, a pressure between 1.5 and 6.5 MPa, preferably between 2.0 and 4.0 MPa, and a WH (hourly volume velocity, corresponding to the volume flow rate of the load olefin relative to the volume of catalyst in operation) between 0.1 and 0.5 h -1 , preferably between 0.2 and 0.3 h -1 .
- silica-alumina used as an oligomerization catalyst
- the reaction effluent obtained at the end of the oligomerization step is fractionated into at least a first fraction comprising the dimers and trimers and a second fraction advantageously having a T5 greater than or equal to 140°C, said first fraction being advantageously at least partly recycled at the entrance to the oligomerization stage and the second fraction advantageously being at least partly sent to the hydrogenation stage.
- Those skilled in the art will also know how to adjust the operating conditions of the hydrogenation step, for example at a temperature between 50 and 300°C, preferably between 60 and 200°C, a pressure between 0.5 and 5, 0 MPa, preferably between 1.0 and 5.0 MPa, and preferably in the presence of hydrogen preferably at a content between 0.5 and 3% by weight relative to the weight of the part of the second fraction supplying the hydrogenation stage.
- the kerosene base described above can be obtained by a preparation process comprising, preferably consisting of: a') optionally a step of pretreatment of a C3 to C6 olefinic filler, preferably C3 and/or C4, preferably implementing at least one adsorption section and/or a water washing section and/or a hydrotreatment section and/or a selective hydrogenation section; a”) optionally a step of separating the olefinic feedstock to at least partially separate the C5 and C6 compounds present in said olefinic feedstock; a) an oligomerization step supplied at least by the olefinic feedstock, optionally pretreated and/or separated, a first recycle and a second recycle, the first recycle preferably being in a weight ratio of between 0.3 and 1.5, preferably between 0.5 and 1.2, relative to the olefinic charge, and the second recycle preferably being in a weight ratio of between 0.5 and 10.0, preferably between 1.0 and 5.0 and
- a recycling step comprising: the preparation of a first recycle comprising, preferably consisting of, at least part of the light fraction resulting from step b; the preparation of a second recycle comprising, preferably consisting of, at least part of the intermediate fraction resulting from step b); and transferring the first recycle and the second recycle to step a) of oligomerization; d) a step of hydrogenating at least part of the heavy fraction separated in step b) in the presence of hydrogen, to obtain a hydrogenated heavy fraction comprising at least one kerosene base; e) optionally a step of separating the heavy hydrogenated fraction, to separate at least said kerosene base according to the invention.
- the kerosene base according to the invention meets the specifications in force for kerosenes in particular for aviation, and more particularly the specifications of the ASTM D7566 standard and in particular those defined in Appendix 5 of ASTM D7566.
- the kerosene base has a final boiling temperature less than or equal to 300°C and advantageously a temperature difference T90-T10 (difference between the boiling temperature making it possible to recover 10% of the product tested and the temperature of boiling to recover 90% of the product tested) greater than or equal to 21 °C, preferably greater than or equal to 40°C.
- the kerosene base according to the invention has a flash point (or flash point according to Anglo-Saxon terminology) advantageously greater than or equal to 38°C and a density at 15°C preferably between 730 and 770 kg /m 3 .
- the kerosene base according to the invention has a cold point (or freezing point according to Anglo-Saxon terminology) less than or equal to -40°C, in particular less than or equal to -50°C, more particularly less than or equal to -50°C. equal to -60°C, even more particularly less than or equal to -70°C, or even less than or equal to -80°C.
- the present invention also relates to any composition
- any composition comprising the kerosene base described above, preferably a composition comprising at least 5% by weight of said kerosene base, preferably at least 10% by weight of the kerosene base, preferably at least 30% by weight. of the kerosene base, very preferably at least 50% by weight of the kerosene base, and optionally preferably less than 90% by weight, preferably less than 60% by weight of the kerosene base.
- Said composition comprises, in addition to the kerosene base, one or more biosourced kerosene product(s) different from the kerosene base according to the invention and/or one or more kerosene product(s). of fossil origin (also called fossil kerosene product(s) or non-renewable kerosene product(s), for example so-called aromatic kerosene products.
- the present invention also relates to a process for preparing such a composition
- a process for preparing such a composition comprising mixing the kerosene base according to the invention with at least one kerosene product other than said kerosene base, in particular with a biosourced and/or fossil kerosene product, of preferably in a proportion of the kerosene base of at least 5% by weight, preferably at least 10% by weight, preferably at least 30% by weight, very preferably at least 50% by weight, relative to to the total weight of the composition.
- said process for preparing the composition also comprises all of the steps for preparing the kerosene base according to the invention as described above, prior to mixing said kerosene base with said at least one kerosene product other than said kerosene base.
- compositions and their preparation processes have the advantage of being able to improve, advantageously in a simple manner, the cold properties of kerosene fuels, particularly intended for aviation applications, while maintaining the other characteristics and properties of kerosenes in the specifications. in force.
- Another advantage of these compositions lies in the fact that they have a percentage of modern carbon (pMC) greater than or equal to 1%, preferably greater than or equal to 10%, preferably greater than or equal to 25%, in particular greater than or equal to equal to 50%.
- pMC modern carbon
- the compositions prepared, which comprise the kerosene base according to the invention will be able to help airlines achieve the CO2 emissions reduction objectives set, in particular a reduction in CO2 emissions of 50% in 2050 compared to 2005 levels, and therefore to achieve carbon neutrality.
- the present invention thus also relates to the use of a composition as described above, as fuel for aircraft engines.
- a biosourced olefinic feedstock comprising 94.5% by weight of isobutene and 5.5% by weight of isobutane is oligomerized in the presence of a silica-alumina catalyst, at a temperature between 30 and 90°C, a pressure of 3.5 MPa and at a WH of 0.3 h -1 .
- the oligomerization reaction is carried out in three reactors in series, with an intermediate exchanger between each reactor. A part of the hydrogenated finished product obtained after hydrogenation is recycled to the oligomerization stage, in order to control the exotherm in the reactors.
- reaction effluent obtained at the end of the oligomerization step is separated by distillation into:
- Hydrogenation is carried out in the presence of a nickel catalyst on an alumina support, at 180°C under 3.0 MPa of hydrogen with a WH of 0.5 h -1 and a hydrogen flow rate of 50 NL/h.
- the rate of olefins observed after hydrogenation is very low (bromine number ⁇ 0.8 g/100g), i.e. a high hydrogenation rate.
- the hydrogenation effluent then obtained is then sent to a distillation section.
- a kerosene cut, with a distillation interval of 140°C- 300°C is obtained: it corresponds to a kerosene base.
- the kerosene base obtained is analyzed; its characteristics and properties are presented in Table 1.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
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Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP23717473.5A EP4504876A1 (fr) | 2022-04-05 | 2023-04-04 | Carburant kérosène renouvelable ayant d'excellentes propriétés à froid |
| US18/854,280 US20250243418A1 (en) | 2022-04-05 | 2023-04-04 | Renewable kerosene fuel having excellent low-temperature properties |
| JP2024558988A JP2025511371A (ja) | 2022-04-05 | 2023-04-04 | 優れた低温特性を有する再生可能ケロセン燃料 |
| CA3245577A CA3245577A1 (fr) | 2022-04-05 | 2023-04-04 | Renewable kerosene fuel having excellent properties at low temperatures |
| KR1020247034989A KR20240169649A (ko) | 2022-04-05 | 2023-04-04 | 우수한 저온 특성을 갖는 재생 가능한 등유 연료 |
| AU2023249904A AU2023249904A1 (en) | 2022-04-05 | 2023-04-04 | Renewable kerosene fuel having excellent properties at low temperatures |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR2203113A FR3134111B1 (fr) | 2022-04-05 | 2022-04-05 | Carburant kérosène renouvelable ayant d’excellentes propriétés à froid |
| FRFR2203113 | 2022-04-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2023194338A1 true WO2023194338A1 (fr) | 2023-10-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2023/058742 Ceased WO2023194338A1 (fr) | 2022-04-05 | 2023-04-04 | Carburant kérosène renouvelable ayant d'excellentes propriétés à froid |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US20250243418A1 (fr) |
| EP (1) | EP4504876A1 (fr) |
| JP (1) | JP2025511371A (fr) |
| KR (1) | KR20240169649A (fr) |
| AR (1) | AR128983A1 (fr) |
| AU (1) | AU2023249904A1 (fr) |
| CA (1) | CA3245577A1 (fr) |
| FR (1) | FR3134111B1 (fr) |
| TW (1) | TW202403025A (fr) |
| WO (1) | WO2023194338A1 (fr) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2025247756A1 (fr) | 2024-05-29 | 2025-12-04 | Shell Internationale Research Maatschappij B.V. | Composant de carburéacteur |
Citations (8)
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|---|---|---|---|---|
| EP1664249A1 (fr) * | 2003-09-17 | 2006-06-07 | Shell Internationale Researchmaatschappij B.V. | Melange de kerosene derive du petrole et d'une synthese de fischer-tropsch |
| US8373012B2 (en) | 2010-05-07 | 2013-02-12 | Gevo, Inc. | Renewable jet fuel blendstock from isobutanol |
| WO2013085980A1 (fr) | 2011-12-06 | 2013-06-13 | Phillips 66 Company | Carburant pour avion renouvelable issu de biomasse |
| FR2995306A1 (fr) * | 2012-09-12 | 2014-03-14 | IFP Energies Nouvelles | Procede de production de kerosene a partir de butanols |
| WO2018224730A1 (fr) | 2017-06-07 | 2018-12-13 | Neste Oyj | Composition de carburant et procédé de production d'une composition de carburant |
| US20190194559A1 (en) * | 2016-09-01 | 2019-06-27 | The Petroleum Oil & Gas Corporation Of South Africa (Pty) Ltd | Method to produce an alternative synthetically derived aviation turbine fuel - synthetic paraffinic kerosene (spk) |
| US20210363448A1 (en) * | 2020-05-22 | 2021-11-25 | Exxonmobil Research And Engineering Company | High napthenic content kerosene compositions |
| WO2022008534A1 (fr) | 2020-07-08 | 2022-01-13 | Total Raffinage Chimie | Composition de carburéacteur et procédé de production d'une composition de carburéacteur |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9567541B2 (en) * | 2012-11-12 | 2017-02-14 | Uop Llc | Jet-range hydrocarbons |
| US10577291B2 (en) * | 2012-11-12 | 2020-03-03 | Uop Llc | Methods for producing jet-range hydrocarbons |
| WO2021154440A1 (fr) * | 2020-01-29 | 2021-08-05 | Exxonmobil Research And Engineering Company | Oligomérisation d'isobutanol en présence de catalyseurs acides solides de type zéolite mww |
-
2022
- 2022-04-05 FR FR2203113A patent/FR3134111B1/fr active Active
-
2023
- 2023-03-31 TW TW112112530A patent/TW202403025A/zh unknown
- 2023-04-03 AR ARP230100830A patent/AR128983A1/es unknown
- 2023-04-04 US US18/854,280 patent/US20250243418A1/en active Pending
- 2023-04-04 WO PCT/EP2023/058742 patent/WO2023194338A1/fr not_active Ceased
- 2023-04-04 CA CA3245577A patent/CA3245577A1/fr active Pending
- 2023-04-04 JP JP2024558988A patent/JP2025511371A/ja active Pending
- 2023-04-04 EP EP23717473.5A patent/EP4504876A1/fr active Pending
- 2023-04-04 AU AU2023249904A patent/AU2023249904A1/en active Pending
- 2023-04-04 KR KR1020247034989A patent/KR20240169649A/ko active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1664249A1 (fr) * | 2003-09-17 | 2006-06-07 | Shell Internationale Researchmaatschappij B.V. | Melange de kerosene derive du petrole et d'une synthese de fischer-tropsch |
| US8373012B2 (en) | 2010-05-07 | 2013-02-12 | Gevo, Inc. | Renewable jet fuel blendstock from isobutanol |
| WO2013085980A1 (fr) | 2011-12-06 | 2013-06-13 | Phillips 66 Company | Carburant pour avion renouvelable issu de biomasse |
| FR2995306A1 (fr) * | 2012-09-12 | 2014-03-14 | IFP Energies Nouvelles | Procede de production de kerosene a partir de butanols |
| US20190194559A1 (en) * | 2016-09-01 | 2019-06-27 | The Petroleum Oil & Gas Corporation Of South Africa (Pty) Ltd | Method to produce an alternative synthetically derived aviation turbine fuel - synthetic paraffinic kerosene (spk) |
| WO2018224730A1 (fr) | 2017-06-07 | 2018-12-13 | Neste Oyj | Composition de carburant et procédé de production d'une composition de carburant |
| US20210363448A1 (en) * | 2020-05-22 | 2021-11-25 | Exxonmobil Research And Engineering Company | High napthenic content kerosene compositions |
| WO2022008534A1 (fr) | 2020-07-08 | 2022-01-13 | Total Raffinage Chimie | Composition de carburéacteur et procédé de production d'une composition de carburéacteur |
Non-Patent Citations (1)
| Title |
|---|
| See also references of EP4504876A1 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20240169649A (ko) | 2024-12-03 |
| EP4504876A1 (fr) | 2025-02-12 |
| CA3245577A1 (fr) | 2023-10-12 |
| US20250243418A1 (en) | 2025-07-31 |
| AU2023249904A1 (en) | 2024-10-03 |
| FR3134111B1 (fr) | 2025-06-20 |
| AR128983A1 (es) | 2024-07-03 |
| TW202403025A (zh) | 2024-01-16 |
| JP2025511371A (ja) | 2025-04-15 |
| FR3134111A1 (fr) | 2023-10-06 |
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