Classifications

• • 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
  • C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
  • C11C3/126—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on other metals or derivates
• • 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
  • C10G3/42—Catalytic treatment
  • C10G3/44—Catalytic treatment characterised by the catalyst used
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
  • B01D3/14—Fractional distillation or use of a fractionation or rectification column
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/12—Silica and alumina
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/888—Tungsten
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/08—Heat treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/20—Sulfiding
• • 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
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/54—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
• • 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
  • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
  • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
• • 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
  • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
  • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
• • 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
  • C10G49/002—Apparatus for fixed bed hydrotreatment processes
• • 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
  • C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
  • C11C3/123—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on nickel or derivates
• • 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

• fillers In this respect, the recovery of feedstocks from renewable sources into fuels has experienced a very strong resurgence of interest in recent years.
• these fillers mention may be made, for example, of vegetable oils, animal fats, raw or having undergone a prior treatment, as well as mixtures of such fillers.
• These fillers contain chemical structures of the triglyceride or ester or fatty acid type, the structure and the length of the hydrocarbon chain of the latter being compatible with the hydrocarbons present in gas oils and kerosene.
• the liquid effluent resulting from these hydrotreating processes after separation, essentially consists of n-paraffins and is substantially free of sulfur, nitrogen and oxygen impurities.
• the sulfur content is typically between 1 and 20 ppmw
• the nitrogen content is typically between 0.2 and 30 ppmw
• the oxygen content is typically less than 2000 ppm weight.
• Paraffins have a number of carbon atoms typically between 9 and 25, which is mainly dependent on the composition of the charge to be hydrotreated.
• this liquid effluent cannot generally be incorporated as such into the kerosene or diesel pool, in particular because of insufficient cold properties and/or too high boiling temperatures.
• the paraffins present lead to high pour points and therefore to congealing phenomena for uses at low temperatures.
• eicosane linear paraffin with 20 carbon atoms, C20H42
• C20H42 linear paraffin with 20 carbon atoms
• the boiling point of eicosane is thus compatible with incorporation into a diesel pool, but its melting point can cause freezing problems and limit its use.
• the filterability limit temperature for winter diesel is a maximum of -15°C.
• the boiling point of eicosane means that it cannot be incorporated into the kerosene pool, for which the final temperature of the distillation curve must be less than 300°C.
• hydroconversion step hydroisomerization and/or hydrocracking reactions
• hydroisomerization makes it possible to convert a linear paraffin into a branched paraffin with conservation of the number of carbon atoms in the molecule. This makes it possible to improve the cold properties of the effluent since branched paraffins have better cold properties than linear paraffins.
• nonadecane has a melting point of 32°C while one of its monobranched isomers, 7-methyl-octadecane has a melting point of -16°C.
• Hydrocracking makes it possible to convert a linear paraffin into linear or branched paraffins of lower molecular weight. This makes it possible to adjust the distillation curve of the effluent if necessary to make it compatible with the kerosene pool.
• the hydrocracking of one molecule of eicosane can lead to the production of two molecules of 2-methylnonane.
• the boiling point of 2-methylnonane is 167°C, which is compatible with incorporation into the kerosene pool.
• the hydroconversion step is carried out on a bifunctional catalyst having both a hydro/dehydrogenating function and a Bronsted acid function.
• the operating conditions can be adapted to promote the hydroisomerization or hydrocracking reactions as required.
• halogenated aluminas chlorinated or fluorinated in particular
• phosphorus-containing aluminas silica-aluminas or even siliceous aluminas
• siliceous aluminas can also be used.
• the olefins are hydrogenated to form the final reaction products. It is then necessary to have a hydro/dehydrogenating function that is sufficiently active with respect to the acid function in order, on the one hand, to quickly supply the acid phase with olefins and, on the other hand, to quickly hydrogenate the olefinic intermediates after their reaction on the acid phase. This makes it possible on the one hand to maximize the activity of the catalyst and on the other hand to promote hydroisomerization compared to hydrocracking when the first reaction is desired, or to limit the production of too light cracking products when the reaction hydrocracking is desired.
• a sufficiently active hydrogenating function is also desirable in order to limit the deactivation of the bifunctional catalyst by coking during the hydroconversion of n-paraffins (Alvarez et al., Journal of Catalysis, 162, 2, 179-189) for a range of fixed operating conditions.
• Noble metals Pt, Pd
• group VIA transition metals Mo, W
• group VIII transition metals Ni, Co
• Noble metals are used in their reduced form while transition metals are used in a sulphide form.
• Group VIA transition metals and Group VIII transition metals, generally attributed to decoration of Group VIA sulfide phases by Group VIII transition metals.
• CoMoS molybdenum or tungsten sulphide phase promoted by nickel or cobalt
• NiMoS nickel or cobalt
• the choice of the nature of the hydrogenating function, of the noble metal or sulphide type depends on various criteria, of an economic nature (the price of the noble metals is significantly higher than that of the transition metals of groups VIA and VIII) or of chemical nature (impact of the presence of contaminants).
• the hydrogenating activity of noble metals is higher than that of transition metal sulphides when the partial pressure of hydrogen sulphide (H 2 S) in the reaction medium is low or even zero.
• the hydrogenating activity of transition metal sulfides is higher than that of noble metals when the partial pressure of H 2 S in the reaction medium becomes high (C. Marcilly, Catalyse acido-basique, volume 2, 2003, editions Technip).
• transition metal sulphides requires the presence of H 2 S in the reaction medium to ensure their stability, and in particular the maintenance of the promotion of the molybdenum or tungsten sulphide phases by nickel. or cobalt under reaction conditions. Maintaining the promotion is desirable in order to retain the synergistic effect and to have maximum activity of the sulphide phase.
• a catalyst based on a nickel-promoted tungsten sulphide phase (“NiWS”) on silica-alumina exhibits an activity per tungsten atom 16 times greater than that of a catalyst based on non-nickel promoted tungsten sulfide (“WS”) on silica-alumina (M. Girleanu et al., ChemCatChem 2014, 6, 1594-1598). Maintaining the promotion depends on the operating conditions under which the catalyst works. Studies combining molecular modeling by DFT and thermodynamic model thus make it possible to propose diagrams of stability of the phases promoted according to a thermodynamic quantity called chemical potential in sulfur.
• the value of the chemical sulfur potential is itself calculated from the temperature of the medium and the ratio between the partial pressures of hydrogen sulphide (H 2 S) and hydrogen (H 2 ) and is available in the form of an abacus ( C. Arrouvel et al., Journal of Catalysis 2005, 232, 161-178).
• the chemical potential of sulfur decreases when the temperature increases, and when the ratio between the partial pressures of hydrogen sulphide and hydrogen decreases. It is thus possible to evaluate the thermodynamic stability of the promoted phases as a function of the operating conditions. Thus, it is reported that the NiWS phase is no longer thermodynamically stable (complete nickel segregation and loss of promotion) for sulfur chemical potential values below -1.27 eV.
• H 2 S content in the gas leaving the unit must be at least 100 ppm and preferably at least 200 ppm to maintain the catalyst in its sulfurized form.
• the composition of the exit gas is not specified. The values provided correspond to P(H2S)/P(H2) ratios at least greater than 1.10 -4 and preferably at least greater than 2.10 -4 in the case where it is assumed that the outlet gas consists only of 'hhS and hydrogen.
• Patent application FR2940144 A1 claims a process for the hydrodeoxygenation of feedstocks derived from renewables.
• the effluent resulting from the hydrodeoxygenation is subjected to a stage of separation and preferably a stage of gas/liquid separation and of separation of the water and of at least one liquid hydrocarbon base.
• said liquid hydrocarbon base is hydroisomerized on a bifunctional hydroisomerization catalyst. It is taught that it is possible to add a certain amount of sulfur compounds such as, for example, dimethyldisulfide to maintain the catalyst in its sulfurized form if necessary.
• the quantity of sulfur is such that the H 2 S content in the recycle gas which is sent to the hydroisomerization stage is at least 15 ppm by volume, preferably at least 0.1% by volume and preferably at least 0.2% volume.
• the composition of the recycle gas is not specified.
• the values provided correspond to P(H2S)/P(H2) ratios at least greater than 1.5.10 -5 , preferably at least greater than 1.10 -3 and preferably greater than 2.10 -3 in the case where it is assumed that the recycle gas consists only of h ⁇ S and hydrogen. No examples are provided.
• Patent application WO2009/156452 A1 claims a process for the production of paraffinic hydrocarbons from a feed containing triglycerides, diglycerides, monoglycerides and/or fatty acids.
• Said process comprises (a) a step of hydrodeoxygenation in the presence of hydrogen and a catalyst in order to obtain an effluent comprising water and paraffins, (b) a step of separating the effluent from ( a) to obtain a liquid effluent rich in paraffins and (c) a step of hydroisomerization of said effluent rich in paraffins in the presence of hydrogen and a catalyst comprising nickel sulphide and tungsten and/or molybdenum sulphide as hydrogenating phases and a support comprising silica-alumina and/or a zeolite.
• Step (c) of the example provided uses a hydroisomerization catalyst of the NiWS/silica-alumina type.
• Patent application U S2011/0219669 A1 claims a method for producing diesel fuel comprising mixing a feed of renewable origin and a fossil feed, said mixture then being transformed in contact with a dewaxing/isomerization catalyst putting a hydrogenating function and an acid function of the zeolite type are involved. It is taught that when the hydrogenating function of said catalyst is of the sulphide type, for example NiWS, the hydrocarbon feed must contain a minimum of sulfur to maintain the hydrogenating function in its sulphide form.
• the minimum recommended content of sulfur (present in sulfur molecules) in the feed is at least 50 ppm by weight, preferably at least 100 ppm by weight, more preferably at least 200 ppm by weight.
• the decomposition of these sulfur molecules in the deparaffinization/isomerization reactor makes it possible to generate a partial pressure of H 2 S necessary for maintaining the hydrogenating phase in its sulfide form.
• the sulfur can be supplied directly in the form of H 2 S, for example already present in the hydrogen-rich gas stream supplying the unit.
• the hydroconversion step can use hydrogen from different sources.
• the hydrogen used in the process according to the invention may or may not contain impurities.
• a catalytic reforming unit produces hydrogen during the dehydrogenation reactions of napthenes into aromatics and during the dehydrocyclization reactions.
• the hydrogen produced by a catalytic reforming unit is substantially free of CO and C0 2 .
• Hydrogen can also be produced by other methods such as, for example, by the steam reforming of light hydrocarbons or else by the partial oxidation of various hydrocarbons such as heavy residues.
• Steam reforming consists of transforming a light hydrocarbon charge into synthesis gas, that is to say into a mixture of hydrogen (H 2 ), carbon monoxide (CO), carbon dioxide (C0 2 ) , and water (H 2 0) by reaction with steam over a nickel-based catalyst.
• hydrogen H 2
• CO carbon monoxide
• C0 2 carbon dioxide
• H 2 0 water
• the production of hydrogen is also accompanied by the formation of carbon oxides which are substantially eliminated by the steam conversion of carbon monoxide (CO) to carbon dioxide (C0 2 ), then by elimination C0 2 by absorption for example by a solution of amines.
• CO residual carbon monoxide
• Other sources of hydrogen can also be used such as hydrogen from catalytic cracking gases which contains significant amounts of CO and CO2.
• the hydrogen used can also come from the outlet gas of a hydrotreating unit, in this case this hydrogen can undergo more or less extensive purification steps to eliminate impurities such as ammonia (NH 3 ) or hydrogen sulfur (H 2 S).
• An advantage of the method according to the present invention is therefore to provide a method for treating a feedstock from a renewable source which undergoes hydrotreatment before being sent to a hydroconversion step using a bifunctional catalyst comprising a phase molybdenum and/or tungsten sulfide promoted by nickel and/or cobalt, said catalyst operating under operating conditions such that the ratio between the H2S partial pressure and the hydrogen partial pressure entering said hydroconversion step is lower at 5.10 -5 .
• An advantage of the present invention is to provide a method making it possible to obtain a gain in activity and selectivity of the hydroconversion catalyst.
• the implementation of the operating conditions in accordance with the invention makes it possible, all other things being equal, to reduce the temperature necessary to obtain a cold property value targeted for the middle distillate cut (measured for example by a cloud point value ).
• the implementation of the operating conditions in accordance with the invention also makes it possible to improve the yield in the middle distillate cut for a targeted cold property value (measured for example by a cloud point value).
• an advantage of the process according to the invention is also to allow better resistance of the hydroconversion catalyst to deactivation when the operating conditions of the hydroconversion step, in particular in terms of total pressure and hydrogen ratio on load, promote deactivation.
• Another advantage of the process according to the invention is also to allow better resistance of the hydroconversion catalyst to the possible presence of oxygenated compounds.
• temporary operation of the hydroconversion unit under operating conditions not in accordance with the invention is not excluded. It may thus happen that the ratio between the hydrogen sulphide partial pressure and the hydrogen partial pressure is not in accordance with the invention during certain periods. For example due to occasional malfunctioning of any tools for purifying the hydrogen sent to the hydroconversion unit and/or the liquid hydrocarbon effluent from step c). In this case, the repair of any tools for purifying the hydrogen and/or the hydrocarbon effluent resulting from c) makes it possible to find an operating mode of the process in accordance with the invention.
• the present invention relates to a process for treating a feed from a renewable source comprising at least: a) a step of hydrotreating said feed in the presence of a fixed-bed catalyst, said catalyst comprising a function hydrogenating agent and an oxide support, at a temperature of between 200 and 450°C, at a pressure of between 1 MPa and 10 MPa, at an hourly space velocity of between 0.1 h 1 and 10 h -1 and in the presence of a total quantity of hydrogen mixed with the charge such that the hydrogen/charge ratio is between 70 and 1000 Nm 3 of hydrogen/m 3 of charge, b) a stage of separation of at least part of the effluent from step a) into at least one light fraction and at least one liquid hydrocarbon effluent, c) a step of removing at least part of the water from the liquid hydrocarbon effluent from step b ), d) a step of hydroconversion of at least a portion of the liquid hydrocarbon effluent from step c) in the presence of
• the present invention is particularly dedicated to the preparation of gas oil and/or kerosene fuel bases corresponding to the new environmental standards, from feedstocks originating from renewable sources.
• the fillers from renewable sources used in the process according to the present invention are advantageously chosen from oils and fats of vegetable or animal origin, or mixtures of such fillers, containing triglycerides and/or free fatty acids and/or esters.
• the vegetable oils can advantageously be crude or refined, totally or partly, and derived from the following plants: rapeseed, sunflower, soya, palm, palm kernel, olive, coconut, jatropha, this list not being exhaustive. Seaweed or fish oils are also relevant.
• the animal fats are advantageously chosen from lard or fats composed of residues from the food industry or from catering industries.
• fillers essentially contain chemical structures of the triglyceride type that those skilled in the art also know under the name fatty acid triester as well as free fatty acids.
• a fatty acid triester is thus composed of three chains of fatty acids. These fatty acid chains in triester form or in free fatty acid form have a number of unsaturations per chain, also called the number of carbon-carbon double bonds per chain, generally between 0 and 3 but which can be higher in particular for oils derived from algae which generally have a number of unsaturations per chain of 5 to 6.
• the molecules present in the fillers from renewable sources used in the present invention therefore have a number of unsaturations, expressed per molecule of triglyceride, advantageously between 0 and 18.
• the level of unsaturation, expressed as the number of unsaturation per hydrocarbon fatty chain is advantageously between 0 and 6.
• the feeds from renewable sources generally also contain various impurities and in particular heteroatoms such as nitrogen.
• Nitrogen contents in vegetable oils are generally between 1 ppm and 100 ppm by weight approximately, depending on their nature.
• the charge may undergo, prior to step a) of the process according to the invention, a pre-treatment or pre-refining step so as to eliminate, by an appropriate treatment, contaminants such as metals, such as alkaline compounds eg on ion exchange resins, alkaline earths and phosphorus.
• a pre-treatment or pre-refining step so as to eliminate, by an appropriate treatment, contaminants such as metals, such as alkaline compounds eg on ion exchange resins, alkaline earths and phosphorus.
• Appropriate treatments can for example be thermal and/or chemical treatments well known to those skilled in the art.
• the charge, optionally pretreated is brought into contact with a catalyst in a fixed bed at a temperature of between 200 and 450° C., preferably between 220 and 350° C. , preferably between 220 and 320°C, and even more preferably between 220 and 310°C.
• the pressure is between 1 MPa and 10 MPa, preferably between 1 MPa and 6 MPa and even more preferably between 1 MPa and 4 MPa.
• the hourly space velocity, ie the volume of charge per volume of catalyst and per hour is between 0.1 h 1 and 10 h 1 .
• the charge is brought into contact with the catalyst in the presence of hydrogen.
• the total quantity of hydrogen mixed with the charge is such that the hydrogen/charge ratio is between 70 and 1000 Nm 3 of hydrogen/m 3 of charge and preferably between 150 and 750 Nm 3 of hydrogen/m 3 load.
• the fixed-bed catalyst is advantageously a hydrotreating catalyst comprising a hydro-dehydrogenating function comprising at least one metal from group VIII and/or from group VI B, taken alone or as a mixture and a support chosen from the group formed by alumina, silica, silica-aluminas, magnesia, clays and mixtures of at least two of these minerals.
• This support can also advantageously contain other compounds and for example oxides chosen from the group formed by boron oxide, zirconia, titanium oxide, phosphoric anhydride.
• the preferred support is an alumina support and most preferably h, d or g alumina.
• Said catalyst is advantageously a catalyst comprising metals from group VIII preferably chosen from nickel and cobalt, taken alone or as a mixture, preferably in combination with at least one metal from group VI B preferably chosen from molybdenum and tungsten. , taken alone or in combination.
• the content of group VIII metal oxides and preferably of nickel oxide is advantageously between 0.5 and 10% by weight of nickel oxide (NiO) and preferably between 1 and 5% by weight of nickel oxide.
• nickel and the content of group VI B metal oxides and preferably of molybdenum trioxide is advantageously between 1 and 30% by weight of molybdenum oxide (MOO3), preferably from 5 to 25% by weight, the percentages being expressed in% by weight relative to the total mass of the catalyst.
• the total content of metal oxides of groups VI B and VIII in the catalyst used in step a) is advantageously between 5 and 40% by weight and preferably between 6 and 30% by weight relative to the mass. total catalyst.
• Said catalyst used in step a) of the process according to the invention must advantageously be characterized by a high hydrogenating power so as to direct the selectivity of the reaction as much as possible towards hydrogenation preserving the number of carbon atoms of the fatty chains. that is to say the hydrodeoxygenation route, in order to maximize the yield of hydrocarbons entering the field of distillation of kerosenes and/or gas oils. This is why it is preferred to operate at a relatively low temperature. Maximizing the hydrogenating function also makes it possible to limit the polymerization and/or condensation reactions leading to the formation of coke which would degrade the stability of the catalytic performances.
• a catalyst of the Ni or NiMo type is used.
• Said catalyst used in stage a) of hydrotreatment of the process according to the invention can also advantageously contain a doping element chosen from phosphorus and boron, taken alone or as a mixture.
• Said doping element can be introduced into the matrix or preferably be deposited on the support. It is also possible to deposit silicon on the support, alone or with phosphorus and/or boron and/or fluorine.
• the content by weight of oxide of said doping element is advantageously less than 20% and preferably less than 10% and it is advantageously at least 0.001%.
• Preferred catalysts are the catalysts described in patent application FR 2 943 071 describing catalysts having a high selectivity for hydrodeoxygenation reactions.
• catalysts described in patent application EP 2 210 663 describing supported or bulk catalysts comprising an active phase consisting of a sulphide element from group VI B, the element from group VI B being molybdenum.
• the metals of the catalysts used in stage a) of hydrotreatment of the process according to the invention are sulphide metals or metallic phases and preferably sulphide metals.
• step a) of the process according to the invention simultaneously or successively, a single catalyst or several different catalysts.
• This step can be carried out industrially in one or more reactors with one or more catalytic beds and preferably with a downflow of liquid.
• Said hydrotreatment step a) allows the hydrodeoxygenation, hydrodenitrogenation and hydrodesulphurization of said feed.
• stage b) of the process according to the invention a stage of separation of at least part and preferably all of the effluent resulting from stage a) is implemented. Said step b) makes it possible to separate at least one light fraction, at least one liquid hydrocarbon effluent.
• Said light fraction comprises at least one gaseous fraction which comprises the unconverted hydrogen and the gases containing at least one oxygen atom resulting from the decomposition of the oxygenated compounds during stage a) of hydrotreatment and the compounds C4, c ie the compounds C1 to C4 preferably exhibiting a final boiling point below 20°C.
• the purpose of this step is to separate the gases from the liquid, and in particular to recover the hydrogen-rich gases which may also contain gases such as CO and CO2 and at least one liquid hydrocarbon effluent.
• Said liquid hydrocarbon effluent preferably has a sulfur content of less than 10 ppm by weight, a nitrogen content of less than 2 ppm by weight.
• Separation step b) can advantageously be implemented by any method known to those skilled in the art such as for example the combination of one or more high and/or low pressure separators, and/or distillation and /or high and/or low pressure stripping.
• step c) of the process according to the invention at least a part and preferably all of the liquid hydrocarbon effluent resulting from step b) of separation undergoes a step of elimination of at least a part and preferably all of the water formed by the hydrodeoxygenation (HDO) reactions which take place during stage b) of hydrotreatment.
• the purpose of this water removal step is to separate the water from the liquid hydrocarbon effluent containing the paraffinic hydrocarbons.
• Step c) of eliminating at least part of the water and preferably all of the water can advantageously be carried out by all the methods and techniques known to those skilled in the art.
• said step c) is implemented by drying, by passing over a desiccant, by flash, by decantation or by a combination of at least two of these techniques.
• the atomic oxygen content of the liquid hydrocarbon effluent containing the paraffinic hydrocarbons resulting from step c) of the process according to the invention, expressed in part per million by weight (ppm) is preferably less than 500 ppm, more preferably less than 300 ppm, very preferably less than 100 ppm by weight.
• the content in ppm by weight of atomic oxygen in said liquid hydrocarbon effluent is measured by the infrared absorption technique such as for example the technique described in patent application US2009/0018374A1.
• step d) of the process according to the invention at least part and preferably all of the liquid hydrocarbon effluent resulting from step c) of the process according to the invention is converted in the presence of a catalyst bifunctional fixed bed hydroconversion, said catalyst comprising a molybdenum and/or tungsten sulphide phase in combination with at least nickel and/or cobalt, said hydroconversion step being carried out at a temperature between 250 and 500°C , at a pressure of between 1 MPa and 10 MPa, at an hourly space velocity of between 0.1 and 10 h 1 and in the presence of a total quantity of hydrogen mixed with the charge such that the hydrogen/charge ratio is comprised between 70 and 1000 Nm 3 /m 3 of charge, and in the presence of a total quantity of sulfur such that the ratio between the partial pressure of hydrogen sulphide and the partial pressure of hydrogen at the inlet of said hydroconversion stage is less than 5.10 -5 , preferably e less than 4.10 -5 , very preferably less than 3.10
• the sulfur present may come from the hydrocarbon effluent from stage c) and/or from the hydrogen flow mixed with the feed from stage d).
• the sulfur When the sulfur is provided by the hydrocarbon effluent, it is generally in the form of organic sulfur molecules, unconverted at the end of step a) of the process.
• sulfur When sulfur is supplied by hydrogen, it is generally in the form of hydrogen sulphide.
• sulfur can be provided by adding sulfur molecules to the charge and/or hydrogen to maintain the hydroconversion catalyst in sulfur form.
• the ratio of the partial pressures of hydrogen sulphide and hydrogen is calculated by considering the quantity of hydrogen and sulfur introduced at the inlet of the hydroconversion unit, and that all the hydrogen introduced is in the gas phase (the hydrogen possibly dissolved in the charge is not considered), that all the sulfur is in the form of hydrogen sulphide (the sulphur-containing molecules, if present, are transformed into hydrogen sulphide), and that all of the hydrogen sulfide is in the gas phase.
• said hydrogen stream undergoes a purification step in the case where the hydrogen sulphide content in said hydrogen stream entering step d) is greater than 50 ppm by volume.
• the hydrogen sulfide content in said hydrogen stream can be measured by any method known to those skilled in the art such as, for example, by gas phase chromatography or by laser infrared spectrometry, for example proposed by the company AP2E (ProCeas® analyzer H2 purity).
• the hydrogen content in said hydrogen flow can be measured by any method known to those skilled in the art such as for example measurement by thermal conductivity, for example proposed by the company WITT (Inline Gas Analyser).
• the presence of oxygenated compounds can induce a loss of activity of the hydroconversion catalyst.
• said hydrogen stream undergoes a purification step if the atomic oxygen content in said hydrogen stream entering the hydroconversion unit is greater than 250 ppm by volume.
• said hydrogen stream undergoes a purification step in the case where the atomic oxygen content in said hydrogen stream is greater than 50 ppm by volume.
• Said hydrogen flow used in the process according to the invention and preferably in step d) of the process according to the invention is advantageously generated by the processes known to those skilled in the art such as for example a catalytic reforming process or catalytic cracking of gases.
• the hydrogen used in the process according to the invention may or may not contain impurities.
• the atomic oxygen content in said hydrogen flow can be measured by any method known to those skilled in the art such as for example by gas phase chromatography.
• said hydrogen stream can be fresh hydrogen or a mixture of fresh hydrogen and recycled hydrogen, that is to say hydrogen not converted during step d) of hydroconversion and/or not converted during stage a) of hydrotreatment and recycled in said stage d).
• said hydrogen stream undergoes a purification step to eliminate the oxygenated compounds before being introduced into said step d). If said hydrogen stream contains a hydrogen sulphide content greater than 50 volume ppm, said hydrogen stream undergoes a purification step to remove the hydrogen sulphide before being introduced into said step d).
• Said hydrogen flow purification step can advantageously be carried out according to any method known to those skilled in the art (see for example Z. Du et al., Catalysts, 2021, 11, 393).
• said purification step is advantageously implemented according to the methods of pressure swing adsorption or PSA "Pressure Swing Adsorption” according to the English terminology, or temperature swing adsorption or TSA “Temperature Swing Adsorption” according to Anglo-Saxon terminology, washing with amines, methanation, preferential oxidation, membrane processes, cryogenic distillation, used alone or in combination.
• PSA Pressure Swing Adsorption
• TSA Temperatur swing adsorption
• a purge of the recycled hydrogen can also advantageously be carried out in order to limit the accumulation of molecules containing at least one oxygen atom such as carbon monoxide CO or carbon dioxide CO2 and thus to limit the atomic oxygen content in said hydrogen flow.
• the atomic oxygen content in said hydrogen stream used in the process according to the invention and preferably in step d) of the process according to the invention expressed in parts per million by volume (ppmv), must be less than 500 ppmv, preferably less than 250 ppmv and most preferably less than 50 ppmv.
• the atomic oxygen content in said hydrogen flow is calculated from the concentrations of molecules having at least one oxygen atom in said hydrogen flow, weighted by the number of oxygen atoms present in said oxygenated molecule.
• ppmv(O) ppmv (CO) + 2 * ppmv (CO2 ) with: ppmv (O) atomic oxygen content in the hydrogen stream in parts per million by volume, ppmv (CO) carbon monoxide content in the hydrogen stream in parts per million by volume, ppmv (CO2) carbon dioxide content in the hydrogen stream in parts per million by volume.
• step d) of hydroconversion of the process according to the invention operates at a temperature of between 250° C. and 450° C., and very preferably, between 250 and 400° C., at a pressure of between 2 MPa and 10 MPa and very preferably between 1 MPa and 9 MPa, at an hourly volume rate advantageously between 0.2 and 7 h 1 and very preferably between 0.5 and 5 h -1 , at a hydrogen flow rate such that the hydrogen/feed volume ratio is advantageously between 100 and 1000 normal m 3 of hydrogen per m 3 of feed and preferably between 150 and 1000 normal m 3 of hydrogen per m 3 of feed.
• Stage d) of hydroconversion of the process according to the invention operates with a ratio between the partial pressure of hydrogen sulphide and hydrogen of less than 5.10 -5 , preferably less than 4.10 5 , very preferably less than 3.10 5 , very preferably less than 2.10 5 and even more preferably less than 1.5.10 5
• the hydroconversion catalyst comprises at least tungsten and/or molybdenum in combination with at least nickel and/or cobalt.
• the tungsten and/or molybdenum content is advantageously comprised in oxide equivalent between 5 and 50% by weight relative to the finished catalyst, preferably between 10 and 40% by weight and very preferably between 15 and 35% by weight and the nickel and/or cobalt content of said catalyst is advantageously comprised in oxide equivalent between 0.5 and 10% by weight relative to the finished catalyst, preferably between 1 and 8% by weight and very preferably between 1.5 and 6% by weight.
• Said catalyst is used in its sulfurized form.
• the catalyst comprises tungsten in combination with nickel.
• the metals are advantageously introduced into the catalyst by any method known to those skilled in the art, such as for example comixing, dry impregnation or impregnation by exchange.
• the hydroconversion catalyst also advantageously comprises at least one acidic solid and optionally a binder.
• the acidic solid is a Bronsted acid preferably chosen from silica alumina, zeolite Y, SAPO-11, SAPO-41, ZSM-22, ferrierite, ZSM-23, ZSM-48 , ZBM-30, I ⁇ ZM-1, COK-7.
• the acidic solid is silica alumina.
• a binder can advantageously also be used during the support shaping step. A binder is preferably used when zeolite is used.
• Said binder is advantageously chosen from silica (S1O 2 ), alumina (Al 2 O 3 ), clays, titanium oxide (T1O 2 ), boron oxide (B 2 O 3 ) and zirconia (ZrC>2) taken alone or in a mixture.
• said binder is chosen from silica and alumina and even more preferably, said binder is alumina in all its forms known to those skilled in the art, such as for example gamma alumina.
• a preferred catalyst used in the process according to the invention comprises a silica-alumina and at least tungsten and/or molybdenum and at least nickel and/or cobalt, said catalyst being sulfurized.
• the tungsten and/or molybdenum content is advantageously comprised, in oxide equivalent, between 5 and 50% by weight relative to the finished catalyst, preferably between 10 and 40% by weight and very preferably between 15 and 35% by weight.
• weight and the nickel and/or cobalt content of said catalyst is advantageously comprised, in oxide equivalent, between 0.5 and 10% by weight relative to the finished catalyst, preferably between 1 and 8% by weight and very preferably between 1.5 and 6% by weight.
• the element content is perfectly measured using X-ray fluorescence.
• a preferred catalyst used in the process according to the invention comprises a particular silica-alumina, said silica-alumina having:
• silica content is advantageously between 10 and 50% by weight
• an average diameter of the mesopores measured by mercury porosimetry between 3 and 12 nm, preferably between 3 nm and 11 nm and very preferably between 4 nm and 10.5 nm,
• a total pore volume measured by mercury porosimetry of between 0.4 and 1.2 ml/g, preferably between 0.4 and 1.0 ml/g and very preferably between 0.4 and 0.8 ml /g,
• the mean diameter of the mesopores is defined as being the diameter corresponding to the cancellation of the curve derived from the mercury intrusion volume obtained from the mercury porosity curve for pore diameters between 2 and 50 ⁇ m.
• the metal distribution coefficient of said preferred catalyst is greater than 0.1, preferably greater than 0.2 and very preferably greater than 0.4.
• the distribution coefficient represents the distribution of the metal inside the catalyst grain.
• the partition coefficient of metals can be measured by Castaing microprobe.
• step e) of the process according to the invention the effluent from step d) undergoes a fractionation step, preferably in a distillation train which integrates atmospheric distillation and optionally vacuum distillation, to obtain at least a middle distillate fraction.
• step e) is to separate the gases from the liquid, and in particular to recover the hydrogen-rich gases which may also contain light substances such as the Ci - C4 cut and at least one diesel cut, at least one kerosene cut and at least one minus a naphtha cup. Upgrading the naphtha cut is not the subject of the present invention, but this cut can advantageously be sent to a steam cracking or catalytic reforming unit.
• Figure 1 represents the evolution of the cloud point of the liquid effluent as a function of time during the hydroconversion in Example 4.
• Figure 2 represents the evolution of the cloud point of the liquid effluent as a function of time during the hydroconversion in example 7.
• Figure 3 represents the evolution of the cloud point of the liquid effluent as a function of time during the hydroconversion in example 8.
• Figure 4 represents the evolution of the cloud point of the liquid effluent as a function of time during the hydroconversion in Example 9.
• Example 1 preparation of a hydrotreating catalyst (C1)
• the catalyst is an industrial catalyst based on nickel, molybdenum and phosphorus on alumina with contents of molybdenum oxide M0O3 of 22% by weight, nickel oxide NiO of 4% by weight and phosphorus oxide P2O5 of 5% by weight relative to to the total weight of the finished catalyst, supplied by the company AXENS.
• Example 2 Preparation of a hydroconversion catalyst in accordance with the invention (C2)
• the silica-alumina powder is prepared according to the synthesis protocol described in patent EP1 415 712A.
• the amounts of orthosilicic acid and aluminum hydrate are chosen so as to have a composition of 70% by weight of alumina Al 2 O 3 and 30% by weight of silica S1O 2 in the final solid.
• This mixture is rapidly homogenized in a commercial colloid mill in the presence of nitric acid so that the nitric acid content of the suspension leaving the mill is 8% relative to the mixed silica-alumina solid. Then the suspension is conventionally dried in an atomizer in a conventional manner at 300°C to 60°C. The powder thus prepared is shaped in a Z arm in the presence of 8% nitric acid relative to the anhydrous product. Extrusion is carried out by passing the paste through a die fitted with 1.4 mm diameter holes. The extrudates thus obtained are dried in an oven at 140°C then calcined under a flow of dry air at 550°C then calcined at 850°C in the presence of steam.
• the silica-alumina extrudates are then subjected to a dry impregnation step with an aqueous solution of ammonium metatungstate and nickel nitrate, left to mature in a water soaker for 24 hours at room temperature and then calcined for two hours under dry air in bed traversed at 450°C (temperature rise ramp of 5°C/min).
• the content by weight of tungsten oxide WO 3 of the finished catalyst after calcination is 27%, the content of nickel oxide NiO is 3.5%.
• the metal distribution coefficient measured by Castaing microprobe is equal to 0.93.
• Example 3 hydrotreatment of a feed from a renewable source according to a process in accordance with the invention
• Table 1 Characteristics of the rapeseed oil used as a feedstock for the hydrotreatment
• the catalyst is sulfurized in-situ in the unit, with a distillation gas oil containing 2% by weight of dimethyldisulphide , under a total pressure of 5.1 MPa, a hydrogen/gas oil ratio with additives of 700 Nm 3 per m 3 .
• the volume of diesel fuel added per volume of catalyst and per hour is set at 1 h 1 .
• the sulfurization is carried out for 12 hours at 350° C., with a temperature rise ramp of 10° C. per hour.
• the operating conditions of the unit are adjusted in order to carry out the hydrotreatment of the charge:
• the hydrogen used is supplied by Air Product and has a purity greater than 99.999% by volume.
• a gas/liquid separator so as to recover a light fraction containing mainly hydrogen, propane, water in vapor form, carbon oxides (CO and CO2) and ammonia and a liquid hydrocarbon effluent mainly consisting of linear hydrocarbons.
• the water present in the liquid hydrocarbon effluent is removed by settling.
• the liquid hydrocarbon effluent thus obtained contains an atomic oxygen content of less than 80 ppm by weight, said atomic oxygen content being measured by the infrared adsorption technique described in patent application US2009/0018374, and a sulfur content of 2 ppm by weight and a nitrogen content of less than 1 ppm by weight, said nitrogen and sulfur contents being measured respectively by chemiluminescence and by UV fluorescence.
• Said liquid hydrocarbon effluent has a density of 791 kg/m 3 .
• the liquid hydrocarbon effluent is composed of paraffins; its composition, measured by gas chromatography, is provided in Table 2.
• Table 2 composition of the liquid hydrocarbon effluent used as feedstock for hydroconversion
• Example 4 Hydroconversion of the liquid hydrocarbon effluent from Example 3 according to a process not in accordance with the invention
• Catalyst C2 undergoes an in-situ sulfurization step in the unit, with isane to which 2% by weight of dimethyldisulfide has been added, under a total pressure of 5.1 MPa, a hydrogen ratio / isane with additive of 350 Nm 3 per m 3 .
• the volume of isane added per volume of catalyst and per hour is set at 1 h 1 .
• the sulfurization is carried out for 12 hours at 350° C., with a temperature rise ramp of 10° C. per hour.
• the operating conditions of the unit are adjusted in order to carry out the hydroconversion of the liquid hydrocarbon effluent containing 500 ppm by weight of sulfur:
• the hydrogen stream used and entering the hydroconversion stage is provided by Air Product, it has a purity greater than 99.999%, it is free of hydrogen sulphide.
• the ratio between the partial pressure of hydrogen sulphide and the partial pressure of hydrogen is then equal to 4.10 -4 .
• Temperature stages at 333 and 343°C are carried out in order to vary the severity of the hydroconversion.
• the measurement (typically daily) of the cloud point (by the ASTM D5773 method) of the liquid effluent makes it possible to follow the evolution of the performance of the catalyst at each temperature level. For each temperature, the test duration is extended until a stable cloud point is obtained. Once cloud point stability is achieved, the liquid effluent is accumulated for 24 hours. Under the chosen operating conditions, no deactivation of the catalyst is observed (see Figure 1).
• the average distillate yield is calculated as follows:
• the cloud point and the motor cetane number of the middle distillate cut are respectively determined by the ASTM D5773 method, and by the CFR method by ASTM D613.
• the main characteristics of the effluents produced and the associated operating conditions are shown in Table 3.
• Example 5 Hydroconversion of the liquid hydrocarbon effluent from Example 3 according to a process in accordance with the invention
• Catalyst C2 undergoes a sulfurization step identical to that reported in Example 4.
• the operating conditions of the unit are adjusted in order to carry out the hydroconversion of the liquid hydrocarbon effluent containing 50 ppm by weight of sulfur:
• the hydrogen stream used and entering the hydroconversion stage is supplied by Air Product, it has a purity greater than 99.999% by volume, it is free of hydrogen sulphide.
• the ratio between the partial pressure of hydrogen sulphide and the partial pressure of hydrogen is then equal to 4.10 -5 .
• the temperature stages are adjusted in order to obtain cloud points of the middle distillate comparable to those obtained in example 4.
• the measurement (typically daily) of the cloud point of the liquid effluent makes it possible to follow the evolution of the performances catalyst at each temperature level. For each temperature, the test duration is extended until a stable cloud point is obtained. Once cloud point stability is achieved, the liquid effluent is accumulated for 24 hours. Under the chosen operating conditions, no deactivation of the catalyst is observed.
• Example 4 Said liquid effluent is then weighed and then fractionated by distillation in order to determine the average distillate yield in the manner reported in Example 4.
• the main characteristics of the effluents produced and the associated operating conditions are shown in Table 3. It can be seen that compared to non-compliant Example 4, the reduction in the P(H2S)/P(H2) ratio makes it possible to improve the activity of the catalyst. Indeed, the temperature required to reach a comparable cloud point value is 2 to 3 degrees lower. In addition, the reduction in the P(H2S)/P(H2) ratio also makes it possible to improve the selectivity of the catalyst since for a comparable cloud point value, the yield of middle distillate increases by 5 points.
• Example 6 Hydroconversion of the liquid hydrocarbon effluent resulting from example 3 according to a method in accordance with the invention
• Catalyst C2 undergoes a sulfurization step identical to that reported in Example 4.
• the operating conditions of the unit are adjusted in order to carry out the hydroconversion of the liquid hydrocarbon effluent containing 50 ppm by weight of sulfur:
• the hydrogen stream used and entering the hydroconversion stage is supplied by Air Product, it has a purity greater than 99.999% by volume, it is free of hydrogen sulphide.
• the ratio between the partial pressure of hydrogen sulphide and the partial pressure of hydrogen is then equal to 1.2.10 -5 .
• the temperature stages are adjusted in order to obtain cloud points of the middle distillate comparable to those obtained in example 4.
• the measurement (typically daily) of the cloud point of the liquid effluent makes it possible to follow the evolution of the performances catalyst at each temperature level. For each temperature, the test duration is extended until a stable cloud point is obtained. Once the stability of the cloud point is reached, we accumulates liquid effluent for 24 hours. Under the operating conditions chosen, no deactivation of the catalyst is observed.
• Example 4 Said liquid effluent is then weighed and then fractionated by distillation in order to determine the average distillate yield in the manner reported in Example 4.
• the main characteristics of the effluents produced and the associated operating conditions are reported in Table 3. It is noted that compared to Example 4 not conforming, the reduction of the P(H 2 S)/P(H2) ratio makes it possible to improve the activity of the catalyst. Indeed, the temperature required to reach a comparable cloud point value is 5 to 6 degrees lower. In addition, the reduction in the P(H 2 S)/P(H2) ratio also makes it possible to improve the selectivity of the catalyst since for a comparable cloud point value, the yield of middle distillate increases by 6 points.
• Table 3 Main characteristics of the effluents produced by hydroconversion and associated operating conditions
• Example 7 Hydroconversion of the liquid hydrocarbon effluent from Example 3 according to a process not in accordance with the invention
• Catalyst C2 undergoes an in-situ sulphidation step in the unit, with isane to which 2% by weight of dimethyl disulphide has been added, under a total pressure of 5.1 MPa, a hydrogen/gasoil ratio with additive of 700 Nm 3 per m 3 .
• the volume of isane added per volume of catalyst and per hour is set at 1 h 1 .
• the sulfurization is carried out for 12 hours at 350° C., with a temperature rise ramp of 10° C. per hour.
• the operating conditions of the unit are adjusted in order to carry out the hydroconversion of the liquid hydrocarbon effluent containing 50 ppm by weight of sulfur:
• the hydrogen stream used in the hydroconversion step is supplied by Air Product, it has a purity greater than 99.999% by volume, it is free of hydrogen sulphide.
• the ratio between the partial pressure of hydrogen sulphide and the partial pressure of hydrogen is then equal to 6.10 -5 .
• Temperature stages at 326 then 336°C are carried out in order to vary the severity of the hydroconversion, and a return point is carried out at 326°C to evaluate the deactivation of the catalyst.
• the regular measurement (typically daily) of the cloud point of the liquid effluent makes it possible to follow the evolution of the performance of the catalyst at each temperature level. For each temperature, the test duration is extended until a stable cloud point is obtained. Once cloud point stability is achieved, the liquid effluent is accumulated for 24 hours. Said liquid effluent is then weighed and then fractionated by distillation in order to determine the average distillate yield in the manner reported in Example 4.
• Figure 2 represents the evolution of the daily measurement of the liquid effluent during the test.
• the catalyst undergoes deactivation at each temperature of the test as evidenced by the increase in the value of the cloud point between the start and the end of each temperature level.
• the cloud point increases from -19°C (after 36 hours) to -10°C at 252 hours, at which point catalyst activity stabilizes.
• a deactivation is also observed at the second point (temperature plateau at 336° C.).
• the return point carried out at 326°C confirms the deactivation of the catalyst: the cloud point stabilizes at 1°C, against -10°C as a stabilized value at the end of the first point.
• the increase in cloud point between the first measured value and the last measured value is used to assess catalyst deactivation:
• Catalyst deactivation final cloud point (°C) - initial cloud point (°C)
• Example 8 Hydroconversion of the liquid hydrocarbon effluent resulting from example 3 according to a method in accordance with the invention
• Catalyst C2 undergoes a sulfurization step identical to that reported in Example 6.
• the hydrogen stream used in the hydroconversion step is supplied by Air Product, it has a purity greater than 99.999% by volume, it is free of hydrogen sulphide.
• the ratio between the partial pressure of hydrogen sulphide and the partial pressure of hydrogen is then equal to 1.2 10 5 .
• Temperature stages at 326 then 336° C. are carried out in order to vary the severity of the hydroconversion, and a return point is carried out at 326° C. to evaluate the deactivation of the catalyst.
• the regular measurement (typically daily) of the cloud point of the liquid effluent makes it possible to follow the evolution of the performance of the catalyst at each temperature level. For each temperature, the test duration is extended until a stable cloud point is obtained. Once cloud point stability has been achieved, the liquid effluent is accumulated for 24 hours. Said liquid effluent is then weighed and then fractionated by distillation in order to determine the average distillate yield in the manner reported in Example 4.
• Figure 3 represents the evolution of the daily measurement of the liquid effluent during the test.
• the catalyst undergoes deactivation at each temperature of the test, just as is observed in Example 7, which is non-compliant.
• the deactivation is less pronounced than in example 7.
• the cloud point increases from -20° C. (after 24 hours) to -15° C. at 288 hours, value at which the activity of the catalyst stabilizes.
• a deactivation is also observed at the second point (temperature plateau at 336° C.).
• Table 4 Main characteristics of effluents produced by hydroconversion and associated operating conditions
• Example 9 Hydroconversion of the liquid hydrocarbon effluent resulting from example 3 according to a method in accordance with the invention
• the P(H 2 S)/P(H2) ratio is not in accordance with the invention during certain periods. For example due to occasional malfunctioning of any tools for purifying the hydrogen sent to the unit and/or the liquid hydrocarbon effluent from step c).
• the readjustment of the P(H 2 S)/P(H2) ratio in a range in accordance with the invention, after operation under non-compliant conditions, also makes it possible to improve the performance of the catalyst as illustrated below.
• Catalyst C2 undergoes a sulfurization step identical to that reported in Example 6.
• the step of hydroconversion of the liquid hydrocarbon effluent from Example 3 is carried out under different operating conditions, some of which simulate temporary operation of the unit not in accordance with the invention during certain periods.
• the Table 5 shows the different operating conditions implemented. Throughout the test, the temperature, the total pressure, the hydrogen/charge ratio and the WH are kept constant. Points 1 and 4 are not in accordance with the invention because of their too high P(H2S)/P(H2) ratio (additivation of dimethyldisulphide in the charge), whereas points 2 and 3 are in conformity. For points 2 and 4 oxygenated impurities are also present in the hydrogen flow. This is done by using a standard mixture containing hydrogen, carbon monoxide and carbon dioxide supplied by Air Product.
• the atomic O content contained in the hydrogen flow is then 4200 ppm by volume.
• the regular measurement (typically daily) of the cloud point of the liquid effluent makes it possible to follow the evolution of the performance of the catalyst at each temperature level. For each temperature, the test duration is extended until a stable cloud point is obtained. Once cloud point stability has been achieved, the liquid effluent is accumulated for 24 hours. Said liquid effluent is then weighed and then fractionated by distillation in order to determine the average distillate yield in the manner reported in Example 4.
• Figure 4 represents the evolution of the daily measurement of the liquid effluent during the test. Under the operating conditions chosen, the catalyst undergoes deactivation at the first point of the test (non-compliant), just as is observed in examples 7 and 8. It is observed that the cloud point stabilizes at a value of -6° vs. All other things being equal, adjusting the P(H2S)/P(H2) ratio to a value in accordance with the invention, at point 2, allows the catalyst to regain activity. At point 2 the cloud point stabilizes at -8°C. At point 3, the addition of oxygenated compounds in the hydrogen induces a loss of activity of the catalyst, the cloud point then stabilizing at -5°C.
• Table 5 shows the main characteristics of the effluents produced at each operating point, when the unit is stabilized.
• the mode of operation according to the invention is advantageous. All other things being equal, adjusting the P(H 2 S)/P(H2) ratio to values in accordance with the invention makes it possible both to gain in middle distillate yield but also to improve the cold properties of said middle distillate (comparison point 1 and point 2 and comparison point 3 and point 4).

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• General Chemical & Material Sciences (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Crystallography & Structural Chemistry (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Catalysts (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=76920900

Family Applications (1)

Country Status (7)

Family Cites Families (12)

• 2021
  • 2021-05-04 FR FR2104684A patent/FR3122661B1/fr active Active
• 2022
  • 2022-04-15 EP EP22723126.3A patent/EP4334412A1/de active Pending
  • 2022-04-15 BR BR112023021919A patent/BR112023021919A2/pt unknown
  • 2022-04-15 WO PCT/EP2022/060159 patent/WO2022233561A1/fr active Application Filing
  • 2022-04-15 CN CN202280032957.7A patent/CN117280014A/zh active Pending
  • 2022-04-15 US US18/558,622 patent/US20240240108A1/en active Pending
  • 2022-05-02 AR ARP220101151A patent/AR125744A1/es unknown

Also Published As

Similar Documents

Legal Events