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
  • 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
• • 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
  • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
• • 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
  • C10G45/44—Hydrogenation of the aromatic hydrocarbons
• • 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
  • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
  • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

• the invention relates to a biobased isoparaffinic fluid having particularly interesting properties, for example in applications as a solvent.
• Special fluids are liquids used as industrial fluids, agricultural fluids, and fluids for domestic use generally obtained from fossil hydrocarbons transformed by refining routes but also from numerous products resulting from the polymerization or oligomerization of olefins from 3 to 4 carbons, and also synthetic hydrocarbons resulting from the transformation of natural gas or synthetic gas from biomass and/or coal.
• drilling fluids include drilling fluids, lubricants for industry, fluids for automotive formulations, phytosanitary products, base fluids for ink formulations, fuels for domestic applications, oils extenders for mastics, viscosity reducers for resin-based formulations, pharmaceutical compositions and compositions for food contact, fluids intended for cosmetic formulations, heat transfer fluids, dielectric fluids, lubricating base fluids, degreasing fluids.
• the aim of the present invention is to provide a biobased volatile hydrocarbon fluid having properties suitable for the intended applications.
• the invention relates to a hydrocarbon fluid comprising 75 to 95% by weight of isoparaffins and less than 500 ppm by weight of aromatics relative to the total weight of the hydrocarbon fluid, said fluid having an initial boiling point and an end point of boiling in the range from 120 to 240°C and a flash point below 90°C.
• the difference between the final boiling point and the initial boiling point ranges from 10 to 60°C, preferably from 25 to 45°C.
• the fluid according to the invention comprises: a content by weight of isoparaffins ranging from 80 to 93%, preferably from 85 to 90%, relative to the total weight of the hydrocarbon fluid; and/or a content by weight of n-paraffins ranging from 5 to 25% by weight, preferably from 7 to 20%, relative to the total weight of the hydrocarbon fluid; and/or a content by weight of aromatic compounds less than or equal to 300 ppm, 200 ppm, preferably less than or equal to 100 ppm, relative to the total weight of the hydrocarbon fluid; and/or a content by weight of naphthenic compounds less than or equal to 1%, preferably less than or equal to 0.5% and preferably less than or equal to 100 ppm relative to the total weight of the hydrocarbon fluid.
• the hydrocarbon fluid according to the invention has a biodegradability at 28 days measured according to the OECD 306 standard greater than or equal to 60%.
• the hydrocarbon fluid according to the invention has a flash point of less than or equal to 80°C, preferably less than or equal to 70°C, more preferably less than or equal to 60°C.
• the hydrocarbon fluid according to the invention comprises, relative to the total weight of the hydrocarbon fluid: from 90 to 98% by weight of paraffins having from 9 to 10 carbon atoms, or from 90 to 98% by weight of paraffins having 11 to 13 carbon atoms.
• the invention also relates to a process for the preparation of a hydrocarbon fluid according to the invention, comprising at least one stage of catalytic hydrogenation at a temperature of 80 to 180° C. and at a pressure of 50 to 160 bars of a feed of deoxygenated and isomerized biological origin having a boiling range from 120 to 340°C, preferably from 150 to 340°C.
• the method further comprises a fractionation step at the end of the hydrogenation step.
• the feed of deoxygenated and isomerized biological origin has an initial boiling point ranging from 120 to 200° C., preferably ranging from 140 to 170° C.
• the deoxygenated and isomerized feedstock (before hydrogenation) has a flash point ranging from 40 to 90°C, preferably from 50 to 80°C, more preferably from 55 to 70°C.
• the deoxygenated and isomerized feedstock (before hydrogenation) has a pour point less than or equal to 5°C, preferably less than or equal to 0°C, more preferably less than or equal to -5°C , or even less than or equal to -10°C.
• the invention also relates to the use of a hydrocarbon fluid according to the invention as a solvent, for example in a paint, material coating, material treatment, putty, polymerization, aerosol, cleaning or water treatment.
• the invention makes it possible to provide a biosourced volatile isoparaffinic fluid.
• the invention makes it possible to provide a volatile isoparaffinic fluid having a low flash point, which is particularly useful for applications as a solvent.
• the invention relates to a hydrocarbon fluid comprising 75 to 95% by weight of isoparaffins and less than 500 ppm by weight of aromatics relative to the total weight of the hydrocarbon fluid, said fluid having an initial boiling point and an end point of boiling in the range from 120 to 240°C and a flash point below 90°C.
• paraffins includes isoparaffins and n-paraffins.
• isoparaffins denotes non-cyclic branched alkanes.
• n-paraffins denotes non-cyclic linear alkanes.
• naphthenes denotes cyclic (non-aromatic) alkanes.
• the hydrocarbon fluid according to the invention comprises from 75 to 95% by weight of isoparaffins, preferably from 80 to 93% by weight of isoparaffins, preferably from 85 to 90% by weight of isoparaffins, relative to the total weight of the hydrocarbon fluid.
• the hydrocarbon fluid according to the invention preferably comprises from 5 to 25% by weight of n-paraffins, preferably from 7 to 20%, more preferably from 10 to 15% by weight of n-paraffins, relative to the total weight hydrocarbon fluid.
• the hydrocarbon fluid according to the invention comprises a content by weight of aromatic compounds of less than 500 ppm by weight, preferably a content by weight of compounds aromatics less than or equal to 300 ppm, preferably less than or equal to 200 ppm, preferably less than or equal to 100 ppm, preferably less than or equal to 50 ppm, preferably less than or equal to 20 ppm.
• the hydrocarbon fluid according to the invention preferably comprises a content by weight of naphthenic compounds less than or equal to 1%, preferably less than or equal to 0.5% and preferably less than or equal to 500 ppm relative to the total weight of the hydrocarbon fluid. .
• the hydrocarbon fluid according to the invention comprises from 85 to 89% by weight of isoparaffins, from 11 to 15% by weight of n-paraffins, and less than 0.5% by weight of compounds naphthenic, relative to the total weight of the hydrocarbon fluid.
• the hydrocarbon fluid according to the invention comprises from 85 to 89% by weight of isoparaffins, from 11 to 15% by weight of n-paraffins, less than 0.5% by weight of naphthenic compounds and less than 500 ppm by weight of aromatic compounds, based on the total weight of the hydrocarbon fluid.
• the hydrocarbon fluid according to the invention comprises from 85 to 89% by weight of isoparaffins, from 11 to 15% by weight of n-paraffins, less than 0.5% by weight of naphthenic compounds and less than 100 ppm by weight of aromatic compounds, based on the total weight of the hydrocarbon fluid.
• the contents of isoparaffins, n-paraffins and naphthenes can be measured according to methods well known to those skilled in the art, for example by gas phase chromatography.
• the aromatics content can be determined for example by UV spectrometry.
• the hydrocarbon fluid according to the invention has an initial boiling point and a final boiling point in the range from 120 to 240° C., preferably from 125 to 210° C., more preferably from 130 to 210° C. .
• the boiling range can be determined according to ASTM D86.
• the difference between the final boiling point and the initial boiling point ranges from 10 to 60°C, preferably from 25 to 45°C.
• the hydrocarbon fluid according to the invention comprises from 90 to 98% by weight of paraffins having from 9 to 13 carbon atoms.
• the hydrocarbon fluid comprises:
• the hydrocarbon fluid according to the invention has a flash point of less than 90° C., preferably a flash point of less than or equal to 80° C., preferably a flash point of less than or equal to 70° C., more preferably a flash point of less or equal to 65°C, or even less than or equal to 60°C.
• the flash point can be measured for example according to the ASTM D93 standard.
• the hydrocarbon fluid according to the invention has a viscosity at 40° C. of less than or equal to 2 mm 2 /s, preferably less than or equal to 1.7 mm 2 /s, preferably less than or equal to 1 .5 mm 2 /s, more preferably less than or equal to 1.2 mm 2 /s, or even less than or equal to 1 mm 2 /s.
• the kinematic viscosity at 40°C can be measured according to the ASTM D445 standard.
• the hydrocarbon fluid according to the invention comprises from 85 to 89% by weight of isoparaffins, from 11 to 15% by weight of n-paraffins, less than 0.5% by weight of naphthenic compounds and less of 500 ppm by weight of aromatic compounds, relative to the total weight of the hydrocarbon fluid, and has a flash point of less than or equal to 70°C.
• the hydrocarbon fluid according to the invention comprises from 85 to 89% by weight of isoparaffins, from 11 to 15% by weight of n-paraffins, less than 0.5% by weight of naphthenic compounds and less of 100 ppm by weight of aromatic compounds, relative to the total weight of the hydrocarbon fluid, and has a flash point of less than or equal to 70°C.
• the hydrocarbon fluid according to the invention comprises from 85 to 89% by weight of isoparaffins, from 11 to 15% by weight of n-paraffins, less than 0.5% by weight of naphthenic compounds and less of 500 ppm by weight of aromatic compounds, relative to the total weight of the hydrocarbon fluid, and has a viscosity at 40° C. of less than or equal to 1.7 mm 2 /s.
• the hydrocarbon fluid according to the invention comprises from 85 to 89% by weight of isoparaffins, from 11 to 15% by weight of n-paraffins, less than 0.5% by weight of naphthenic compounds and less of 100 ppm by weight of aromatic compounds, relative to the total weight of the hydrocarbon fluid, and has a viscosity at 40° C. of less than or equal to 1.7 mm 2 /s.
• the hydrocarbon fluid according to the invention comprises: from 90 to 98% by weight of paraffins having from 9 to 10 carbon atoms and has a viscosity at 40°C of less than or equal to 1 mm 2 /s, or from 90 to 98% by weight of paraffins having from 11 to 13 carbon atoms and has a viscosity at 40° C. of less than or equal to 1.2 mm 2 /s.
• the hydrocarbon fluid according to the invention comprises: from 90 to 98% by weight of paraffins having from 9 to 10 carbon atoms, has a flash point ranging from 25 to 50° C. and has a viscosity of 40 °C less than or equal to 1 mm 2 /s, or from 90 to 98% by weight of paraffins having 11 to 13 carbon atoms, has a flash point ranging from 50 to 65°C and has a viscosity at 40°C less than or equal to 1.2 mm 2 /s.
• the hydrocarbon fluid according to the invention also preferably has an extremely low content by weight of sulfur compounds, typically less than or equal to 5 ppm, preferably less than or equal to 3 ppm and more preferably less than or equal to 0.5 ppm, it that is, at a level too low to be detected by conventional low-sulphur analyzers.
• the hydrocarbon fluid according to the invention has a biodegradability at 28 days of at least 60%, preferably of at least 70%, preferentially of at least 75% and even more preferentially of at least less than 80% measured according to the OECD 306 standard.
• the hydrocarbon fluid according to the invention has a biodegradability after 28 days of at least 60%, measured according to the OECD 306 method, and a flash point less than or equal to 60°C.
• the hydrocarbon fluid according to the invention has a biodegradability at 28 days of at least 60%, measured according to the OECD 306 method, and a flash point of less than 90° C. and comprises from 85 to 89% by weight of isoparaffins relative to the total weight of the hydrocarbon fluid.
• the hydrocarbon fluid according to the invention has a biodegradability at 28 days of at least 60%, measured according to the OECD 306 method, and a flash point of less than 90° C. and comprises from 85 to 89% by weight of isoparaffins and less than 100 ppm by weight of aromatic compounds relative to the total weight of the hydrocarbon fluid.
• the hydrocarbon fluid according to the invention has a biodegradability at 28 days of at least 60%, measured according to the OECD 306 method, and a flash point of less than 90° C. and comprises from 85 to 89% by weight of isoparaffins relative to the total weight of the hydrocarbon fluid, and said fluid has an initial boiling point and an end boiling point in the range from 120°C to 240°C.
• the hydrocarbon fluid according to the invention has a biodegradability at 28 days of at least 60%, measured according to the OECD 306 method, and a flash point less than or equal to 65° C. and comprises from 85 to 89 % by weight of isoparaffins relative to the total weight of the hydrocarbon fluid, and said fluid has an initial boiling point and an end boiling point in the range from 125°C to 210°C.
• the hydrocarbon fluid according to the invention has a biodegradability at 28 days of at least 60%, measured according to the OECD 306 method, and a flash point less than or equal to 65° C. and comprises from 85 to 89 % by weight of isoparaffins and less than 100 ppm by weight of aromatic compounds based on the total weight of the hydrocarbon fluid, and said fluid has an initial boiling point and an end boiling point in the range from 125°C at 210°C.
• the hydrocarbon fluid according to the invention has a biodegradability at 28 days of at least 60%, measured according to the OECD 306 method, and a flash point less than or equal to 60° C. and comprises from 80 to 90 % by weight of isoparaffins relative to the total weight of the hydrocarbon fluid, and said fluid has an initial boiling point and an end boiling point in the range from 125°C to 210°C.
• the hydrocarbon fluid according to the invention has a biodegradability at 28 days of at least 60%, measured according to the OECD 306 method, and a flash point less than or equal to 50° C. and comprises from 80 to 90 % by weight of isoparaffins relative to the total weight of the hydrocarbon fluid, and said fluid has an initial boiling point and an end boiling point in the range from 130°C to 190°C.
• the hydrocarbon fluid according to the invention has a pour point less than or equal to -20°C, preferably less than or equal to -40°C, more preferably less than or equal to -50°C , even more preferably less than or equal to -70°C, or even less than or equal to -80°C.
• the hydrocarbon fluid according to the invention has a flash point of less than 90° C., a pour point of less than or equal to -50° C. and comprises from 80 to 89% by weight of isoparaffins and 11 to 15% by weight of n-paraffins, relative to the total weight of the hydrocarbon fluid.
• the hydrocarbon fluid according to the invention has a flash point of less than or equal to 65° C., a pour point of less than or equal to -70° C. and comprises from 80 to 89% by weight of isoparaffins and from 11 to 15% by weight of n-paraffins, based on the total weight of the hydrocarbon fluid.
• the hydrocarbon fluid according to the invention has a flash point of less than or equal to 65° C., a pour point of less than or equal to -70° C. and comprises from 80 to 89% by weight of isoparaffins , from 11 to 15% by weight of n-paraffins and less than 100 ppm by weight of aromatic compounds, relative to the total weight of the hydrocarbon fluid.
• the hydrocarbon fluid according to the invention is a hydrocarbon cut, typically resulting from the conversion of biomass.
• a hydrocarbon fraction produced from raw materials of biological origin can be chosen from vegetable oils, animal fats, fish oils and their mixtures.
• the invention also relates to a method for preparing a hydrocarbon fluid according to the invention, said method comprising at least one stage of catalytic hydrogenation at a temperature of 80 to 180° C. and at a pressure of 50 to 160 bars of a charge (or cut) of deoxygenated and isomerized biological origin having a boiling range ranging from 120 to 340°C, preferably from 150 to 340°C.
• the method comprises a preliminary step of preparing a deoxygenated and isomerized cut by a hydrodeoxygenation step (HDO) followed by an isomerization step (ISO).
• HDO hydrodeoxygenation step
• ISO isomerization step
• the method for preparing a hydrocarbon fluid comprises: a) a step of hydrodeoxygenation of a feed (or cut) of biological origin in order to obtain a feed (or cut) of hydrodeoxygenated biological origin, b) a step of hydroisomerization of the hydrodeoxygenated biomass, in order to obtain a feed (or cut) of deoxygenated and isomerized biological origin, c) optionally a step of distillation of the feed (or cut) of biological origin deoxygenated and isomerized in order to obtain a filler (or cut) of deoxygenated and isomerized biological origin having a boiling range from 120 to 340°C, preferably from 150 to 340°C, d) a catalytic hydrogenation step at a temperature of 80 to 180°C and at a pressure of 50 to 160 bars of the feed (or cut) of deoxygenated and isomerized biological origin resulting from stage b) or from stage c) when it is present.
• the filler (or cut) of biological origin is chosen from vegetable oils, animal fats, fish oils and mixtures thereof.
• vegetable oils that can be used, mention may be made of rapeseed oil, canola oil, tall or tall oil, sunflower oil, soybean oil, hemp oil, olive oil, flaxseed oil, mustard oil, palm oil, peanut oil, castor oil, coconut oil.
• the hydrodeoxygenation (HDO) step leads to the decomposition of the structures of biological esters or triglyceride constituents, the elimination of oxygenated, phosphorus and sulfur compounds and the hydrogenation of olefinic bonds.
• the product from the hydrodeoxygenation reaction is then isomerized.
• the feedstock of deoxygenated and isomerized biological origin has an initial boiling point ranging from 120 to 200° C., preferably ranging from 140 to 170° C., before the hydrogenation step.
• fractions of interest are then subjected to hydrotreatment and then distillation steps in order to obtain the specifications of the hydrocarbon fluid according to the invention.
• This HDO/ISO process is implemented on a raw biological load, also called biomass or raw material of biological origin, selected from the group consisting of vegetable oils, animal fats, fish oils and their mixture.
• Suitable raw materials of biological origin are, for example, rapeseed oil, canola oil, tall or tall oil, sunflower oil, soybean oil, hemp oil, olive oil, linseed oil, mustard oil, palm oil, peanut oil, castor oil, coconut oil, animal fats such as tallow, recycled edible fats, genetically engineered raw materials, and biological raw materials produced from microorganisms such as algae and bacteria. Condensation products, esters or other derivatives obtained from raw biological materials can also serve as raw materials.
• the raw material of biological origin is an ester or a triglyceride derivative.
• This material is first subjected to a hydrodeoxygenation (HDO) step to decompose the structure of the constituent esters or triglycerides and eliminate the oxygenated, phosphorus and sulfur compounds concomitantly with the hydrogenation of the olefinic bonds.
• HDO hydrodeoxygenation
• This step of hydrodeoxygenation (HDO) of the original raw material biological is followed by an isomerization of the product thus obtained leading to the branching of the hydrocarbon chain and to an improvement in the properties of the paraffin at low temperatures.
• the hydrogen and the raw material of biological origin are passed over a catalytic hydrodeoxygenation bed simultaneously, in the same direction or in countercurrent.
• the pressure and the temperature are between 20 and 150 bars and between 200 and 500°C respectively.
• Conventional and known hydrodeoxygenation catalysts are used during this step.
• the raw material of biological origin can be subjected to pre-hydrogenation under mild conditions to avoid side reactions of the double bonds before the HDO step.
• the product resulting from the reaction is subjected to an isomerization step (ISO) where the hydrogen and the product, and optionally a mixture of n-paraffins, are passed over catalytic beds of isomerization simultaneously, in the same direction or against the current.
• ISO isomerization step
• the pressure and temperature are between 20 and 150 bars and between 200 and 500°C respectively.
• Conventional and known isomerization catalysts are used during this step.
• Additional secondary processes can also be implemented (such as intermediate mixtures, trappings or other such processes).
• Patent application WO2014/033762 describes a process comprising a pre-hydrogenation step, a hydrodeoxygenation (HDO) step and an isomerization step operated in countercurrent.
• Patent application EP1728844 describes a process for producing hydrocarbon compounds from a mixture of compounds of plant and animal origin. This process includes a pre-treatment step of the mixture to remove contaminants, such as alkali metal salts, for example, followed by a hydrodeoxygenation (HDO) step and an isomerization step.
• HDO hydrodeoxygenation
• Patent application EP2084245 describes a method for producing a hydrocarbon mixture which can be used as gas oil or in a gas oil composition by hydrodeoxygenation of a mixture of biological origin containing fatty acid esters optionally mixed with acids free fats, for example vegetable oils such as sunflower oil, rapeseed oil, canola oil, palm oil or tall oil, followed by hydroisomerization on specific catalysts.
• Patent application EP2368967 describes such a process and the product obtained by this process.
• the raw material of biological origin contains less than 15 ppm of sulphur, preferably less than 8 ppm, preferably less than 5 ppm and more preferably less than 1 ppm according to the EN ISO 20846 standard.
• sulfur as raw material of biosourced origin.
• the deoxygenated and isomerized feed from the HDO/ISO process is then hydrogenated.
• the hydrogen used in the hydrogenation unit is typically highly purified hydrogen.
• the term “highly purified” means hydrogen of a purity for example greater than 99%, even if other grades can also be used.
• the hydrogenation step is carried out using catalysts.
• Typical hydrogenation catalysts can be either bulk or supported and can include the following metals: nickel, platinum, palladium, rhenium, rhodium, nickel tungstate, nickel-molybdenum, molybdenum, cobalt-molybdenum.
• the supports can be silica, alumina, silica-alumina or zeolites.
• a preferred catalyst is a catalyst based on nickel on an alumina support whose specific surface area varies between 100 and 200 m 2 /g of catalyst or a mass catalyst based on nickel.
• the hydrogenation conditions are typically the following:
• -Temperature 80 to 180° C., preferably 120 to 160° C. and more preferably 150 to 160° C.;
• WH Hourly volume velocity
• the temperature in the reactors is typically between 150 and 160°C with a pressure of around 100 bars, while the hourly volumetric speed is around 0.6 hr 1 with a treatment rate adapted according to the quality of the load to be treated and parameters of the first hydrogenation reactor.
• Hydrogenation can take place in one or more reactors in series.
• the reactors can comprise one or more catalytic beds.
• the catalytic beds are generally fixed catalytic beds.
• the hydrogenation process preferably comprises two or three reactors, preferably three reactors and is more preferably carried out in three reactors in series.
• the first reactor allows the trapping of sulfur compounds and the hydrogenation of essentially all the unsaturated compounds and up to around 90% of the aromatic compounds.
• the product from the first reactor contains substantially no sulfur compound.
• the hydrogenation of the aromatics continues and up to 99% of the aromatics are therefore hydrogenated.
• the third stage in the third reactor is a finishing stage making it possible to obtain aromatics contents of less than or equal to 500 ppm, preferably less than or equal to 300 ppm, preferably less than or equal to 100 ppm, plus preferably less than or equal to 50 ppm, and ideally less than or equal to 20 ppm even in the case of products with a high boiling point, for example greater than 300° C.
• a reactor which comprises two or three or more catalytic beds.
• the catalysts may be present in varying or substantially equal amounts in each reactor; for three reactors, the quantities according to the weight can for example be 0.05-0.5/0.10-0.70/0.25-0.85, preferably 0.07-0.25/0 15-0.35/0.4-0.78 and more preferably 0.10-0.20/0.20-0.32/0.48-0.70.
• the first reactor is composed of twin reactors implemented in an alternative way. This mode of operability allows in particular easy loading and unloading of the catalysts: when the first reactor includes the saturated catalyst first (substantially all the sulfur is trapped on and/or in the catalyst) it must be changed often.
• a single reactor can also be used in which two, three or more catalytic beds are installed.
• quench boxes in the English sense of "reaction quenching"
• reaction quenching it may be necessary to insert quench boxes (in the English sense of "reaction quenching") in the recycling system or between the reactors to cool the effluents from one reactor to another or from a catalytic bed to another to control the temperatures and hydrothermal equilibrium of each reaction.
• quench boxes in the English sense of "reaction quenching"
• the product resulting from the process and/or the gases separated are at least partly recycled in the supply system of the hydrogenation reactors. This dilution helps to keep the exothermicity of the reaction within controlled limits, especially in the early stage. Recycling further allows heat exchange prior to the reaction and also better temperature control.
• the effluent from the hydrogenation unit mainly contains the hydrogenated product and hydrogen. Flash separators are used to separate effluents in gas phase, mainly residual hydrogen, and in liquid phase, mainly hydrogenated hydrocarbon cuts. The process can be carried out using three flash separators, one at high pressure, one at intermediate pressure and one at low pressure very close to atmospheric pressure.
• the hydrogen gas that is collected at the top of the flash separators can be recycled into the hydrogenation unit feed system or at various levels in the hydrogenation units between the reactors.
• the final product is separated at atmospheric pressure. It then directly feeds a vacuum fractionation unit.
• the Fractionation will take place at a pressure of between 10 and 50 mbar and more preferably at about 30 mbar.
• Fractionation can be carried out in such a way that various hydrocarbon fluids can be simultaneously removed from the fractionation column and their boiling point can be predetermined.
• the hydrogenation reactors, the separators and the fractionation unit can therefore be directly connected without the need to use intermediate tanks.
• This integration of hydrogenation and fractionation allows an optimized thermal integration associated with a reduction in the number of devices and an energy saving.
• the hydrocarbon fluid according to the invention typically comes from the treatment of raw materials of biological origin.
• the hydrocarbon fluid according to the invention typically has a biomaterial content of at least 90% by weight, relative to the total weight of the carbon atoms. This content is advantageously higher, in particular greater than or equal to 95% by weight, relative to the total weight of the carbon atoms, preferably greater than or equal to 98% by weight, relative to the total weight of the carbon atoms and advantageously equal 100% by weight, based on the total weight of the carbon atoms.
• biomaterial content also referred to as biogenic carbon content
• ASTM D6866 can be determined according to ASTM D6866.
• the hydrocarbon fluid according to the invention has particularly good biodegradability.
• Biodegradation of an organic chemical refers to the reduction in complexity of chemical compounds through the metabolic activity of microorganisms. Under aerobic conditions, microorganisms transform organic substances into carbon dioxide, water and biomass.
• the OECD 306 method is used for the evaluation of the biodegradability of individual substances in seawater.
• the hydrocarbon fluid according to the invention has a biodegradability at 28 days of at least 60%, preferably at least 70%, more preferably at least 75% and advantageously at least 80%.
• hydrocarbon fluid according to the invention is a solvent, for example in a composition for painting, for coating a material (for example wood), for treating material (for example wood), putty, polymerization, aerosol, cleaning or water treatment.
• the hydrocarbon fluids according to the invention can be used: as drilling fluids, in hydraulic fracturing, in mining, in water treatment, as industrial solvents, in the composition of paints, for decorative coatings, in coating fluids, in the automotive industry, in the textile industry, in metal mining, in explosives, in oil dispersants, in concrete release formulations, in adhesives, in printing inks printing, in metalworking fluids, in coating fluids, in rolling oils, in particular for aluminum, as cutting fluids, as rolling oils, as electrical discharge machining (EDM) fluids, as rust inhibitors, as industrial lubricants, as extender oils, in sealing products such as sealants or polymers, in particular based on silicone, as viscosity reducers in the formulations of e plasticized polyvinyl chloride, in resins, in varnishes, in polymers used in water treatment, papermaking or printing pastes, in particular as thickeners, cleaning and/or degreasing solvents, for suspension polymerization, in the food processing industry, for food grade
• Table 1 groups together the physicochemical properties of three hydrocarbon fluids according to the invention and of hydrotreated vegetable oil (HVO) before hydrogenation.
• the fluids were prepared by hydrogenation of a hydrotreated vegetable oil (HVO).
• HVO hydrotreated vegetable oil
• the hydrogenation was carried out at a temperature of 150-160° C., a pressure of 100 bars and an hourly volume rate of 0.6 lr 1 .
• the catalyst used for the hydrogenation is nickel on alumina.
• a distillation is implemented at the end of the hydrogenation step in order to recover the cut of interest (Fluids 1 to 3).

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Paints Or Removers (AREA)

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• 2021
  • 2021-06-17 FR FR2106461A patent/FR3124188A1/fr active Pending
• 2022
  • 2022-06-16 CN CN202280041581.6A patent/CN117460807A/zh active Pending
  • 2022-06-16 WO PCT/EP2022/066516 patent/WO2022263609A1/fr active Application Filing
  • 2022-06-16 KR KR1020237042932A patent/KR20240022485A/ko unknown
  • 2022-06-16 EP EP22735139.2A patent/EP4355841A1/fr active Pending

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