EP2158303B1 - Verfahren zur herstellung von mitteldestillaten durch hydroisomerisierung und hydrocracking eines schweren teils aus einer fischer-tropsch-effluenz - Google Patents

Verfahren zur herstellung von mitteldestillaten durch hydroisomerisierung und hydrocracking eines schweren teils aus einer fischer-tropsch-effluenz Download PDF

Info

Publication number
EP2158303B1
EP2158303B1 EP08805641.1A EP08805641A EP2158303B1 EP 2158303 B1 EP2158303 B1 EP 2158303B1 EP 08805641 A EP08805641 A EP 08805641A EP 2158303 B1 EP2158303 B1 EP 2158303B1
Authority
EP
European Patent Office
Prior art keywords
range
measured
process according
weight
pore volume
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP08805641.1A
Other languages
English (en)
French (fr)
Other versions
EP2158303A2 (de
Inventor
Nathalie Marchal-George
Jean Cosyns
Vincent Coupard
Eric Caprani
Damien Douziech
Aurélie DANDEU
Stéphane FEDOU
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
IFP Energies Nouvelles IFPEN
Eni SpA
Original Assignee
IFP Energies Nouvelles IFPEN
Eni SpA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by IFP Energies Nouvelles IFPEN, Eni SpA filed Critical IFP Energies Nouvelles IFPEN
Publication of EP2158303A2 publication Critical patent/EP2158303A2/de
Application granted granted Critical
Publication of EP2158303B1 publication Critical patent/EP2158303B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • 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
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/043—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton
    • 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
    • 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

Definitions

  • the present invention describes a process for the hydrocracking and hydroisomerization treatment of feedstocks from the Fischer-Tropsch process, making it possible to obtain middle distillates (gas oil, kerosene), ie initial boiling point cuts. at least 150 ° C and final at most 340 ° C and optionally oil bases.
  • the synthesis gas (CO + H 2 ) is catalytically converted into oxygenates and substantially linear hydrocarbons in gaseous, liquid or solid form.
  • these products mainly made of normal paraffins, can not be used as such, in particular because of their cold-holding properties that are not very compatible with the usual uses of petroleum fractions.
  • the pour point of a linear hydrocarbon containing 20 carbon atoms per molecule (boiling point equal to about 340 ° C., ie often included in the middle distillate cut) is + 37 ° C. about which makes its use impossible, the specification being -15 ° C for diesel.
  • the hydrocarbons from the Fischer-Tropsch process comprising mainly n-paraffins must be converted into more valuable products such as, for example, gas oil, kerosene, which are obtained, for example, after catalytic hydrocracking / hydroisomerization reactions.
  • These products are generally free of heteroatomic impurities such as sulfur, nitrogen or metals. They contain practically no aromatics, naphthenes and more generally cycles, in particular in the case of cobalt catalysts.
  • oxygenated compounds may have a significant content of unsaturated compounds of olefinic type and oxygenated products (such as alcohols, carboxylic acids, ketones, aldehydes and esters). These oxygenated and unsaturated compounds are more concentrated in the light fractions. Thus in the C5 + fraction corresponding to the products boiling at an initial boiling point of between 20 ° C. and 40 ° C., these compounds represent between 10-20% by weight of olefinic type unsaturated compounds and between 5-10% by weight. of oxygenated compounds.
  • One of the objectives of the invention is to eliminate, during a hydrotreatment step, upstream of a hydrocracking step, the olefinic type unsaturated compounds, said hydrotreatment step being carried out under less severe conditions. than those of the hydrocracking step. Unsaturated olefinic compounds present in the hydrocracking feeds reduce the service life of a hydrocracking catalyst.
  • the transformation of the unsaturated compounds can have a negative impact on the hydroisomerization / hydrocracking step and cause, for example, a thermal runaway of the reaction, a large coking of the catalyst or the formation of gum by oligomerization.
  • One of the advantages of the invention is to provide a method for producing middle distillates from a paraffinic feedstock produced by Fischer Tropsch synthesis in which the hydrocracking step is preceded by a hydrogenation step allowing elimination previously and under less severe conditions than those used in the hydrocracking step, the most reactive elements and in particular unsaturated compounds of olefinic type.
  • the Shell patent application discloses a process for the production of middle distillates from a filler obtained by Fischer-Tropsch synthesis.
  • the feedstock resulting from the Fischer-Tropsch synthesis can be treated in its entirety, but preferably the C4- fraction is withdrawn from the feedstock so that only the C5 + fraction boiling at a temperature above 20 ° C. be introduced in the subsequent step.
  • Said feedstock is subjected to a hydrotreatment to hydrogenate the olefins and alcohols in the presence of a large excess of hydrogen, so that the conversion of products boiling above 370 ° C into products with a lower boiling point is less than 20%.
  • the hydrotreated effluent consisting of high molecular weight paraffinic hydrocarbons is preferably separated from the hydrocarbon compounds having a low molecular weight and in particular the C4- fraction before the second hydroconversion stage. At least a portion of the remaining C5 + fraction is then subjected to a hydrocracking / hydroisomerization step with a conversion of products boiling above 370 ° C into products having a boiling point of at least 40% by weight.
  • the patent application US 2002/0169219 discloses a process for producing a C5-C20 cut from a paraffinic feedstock produced by Fischer Tropsch synthesis, however the feedstock undergoing the hydrotreatment and hydrocracking steps described in D1 results from a mixture of a fraction C5-C20 from the Fischer Tropsch process and a C5 + fraction containing sulfur from the fractionation of a natural gas source.
  • the step of hydrotreating said feedstock is carried out at a temperature of between 204 and 482 ° C. and at a hydrogen flow rate corresponding to a hydrogen / hydrocarbon volume ratio of between 53.4 and 356 Nl / l / h. .
  • the patent GB 1,430,973 discloses a two-stage hydrocracking process of an aromatic charge comprising 20 to 70% by volume of aromatics and a boiling point between 221 and 537 ° C, in order to obtain a rich naphtha fraction in aromatic and a kerosene fraction with a low aromatic content.
  • the hydrotreatment stage upstream of the hydrocracking stages operates at a temperature of between 287 and 454 ° C.
  • Step a) according to the invention is a step of separation of at least one C4- fraction, called light, with a final boiling point of less than 20 ° C, preferably less than 10 ° C and very preferably less than 0 ° C, of the effluent resulting from the Fischer Tropsch synthesis so as to obtain a single C5 + fraction, so-called heavy, with an initial boiling point of between 20 and 40 ° C and preferably having a boiling point greater than or equal to 30 ° C , constituting at least a part of the charge of the hydrogenation step b) according to the invention.
  • the effluent from the Fischer-Tropsch synthesis unit is, at the outlet of the Fischer-Tropsch synthesis unit advantageously divided into two fractions, a light fraction, called cold condensate, (line (1)) and a fraction heavy, called waxes, (pipe (3)).
  • the two fractions thus defined comprise water, carbon dioxide (CO 2 ), carbon monoxide (CO) and unreacted hydrogen (H 2 ).
  • the light fraction, cold condensate contains light hydrocarbon compounds C1 to C4, called C4- fraction, in the form of gas.
  • the light fraction, called cold condensate (1), and the heavy fraction, called waxes (3) are separately treated in separate fractionation means and then recombined in line (5), so as to obtain a single C5 + fraction.
  • said heavy, initial boiling point between 20 and 40 ° C and preferably having a boiling temperature greater than or equal to 30 ° C.
  • the heavy fraction, called waxes enters a fractionation means (4) via line (3).
  • the fractionation means (4) may for example consist of methods well known to those skilled in the art such as rapid expansion (or flash, according to the English terminology), distillation or stripping.
  • a flash or flash tank or a stripper is sufficient to remove most of the water, carbon dioxide (CO 2 ) and carbon monoxide (CO) through the line (4 ') of the heavy fraction, called waxes.
  • the light fraction enters a fractionation means (2) via the pipe (1).
  • the fractionation means (2) may for example consist of methods well known to those skilled in the art such as a flash or flash tank, distillation or stripping.
  • the fractionation means (2) is a distillation column allowing the elimination of the light and gaseous hydrocarbon compounds C1 to C4, called gas fraction C4-, corresponding to products boiling at a temperature below 20 ° C, preferably below at 10 ° C and very preferably, below 0 ° C, through the pipe (2 ').
  • a stabilized C5 + liquid fraction corresponding to products boiling at an initial boiling point of between 20 and 40 ° C. and preferably having a boiling point greater than or equal to 30 ° C., is thus recovered in the pipe (5) and constitutes the charge of the hydrogenation step b) of the process according to the invention.
  • the light fraction, called cold condensate, leaving the Fischer-Tropsch synthesis unit via line (1) and the heavy fraction, called waxes, leaving the Fischer-Tropsch synthesis unit via line (3) are recombined in the pipe (18) and treated in the same fractionation means (4).
  • the fractionation means (4) may for example consist of methods well known to those skilled in the art such as flash, distillation or stripping.
  • the fractionation means (4) is a distillation column allowing the removal of the gas fraction C4-, water, carbon dioxide (CO 2 ) and carbon monoxide (CO) through the pipe (4 ').
  • a stabilized C5 + liquid fraction corresponding to the products boiling at a boiling point of between 20 and 40 ° C. and preferably having a boiling point greater than or equal to 30 ° C., is thus recovered at the outlet of the fractionation means (4). ) in the pipe (5) and constitutes the charge of the hydrogenation step b) of the process according to the invention.
  • Step b) of the process according to the invention is a step of hydrogenation of the olefinic type unsaturated compounds of at least a part and preferably of the whole of the C5 + heavy liquid fraction resulting from step a) of the process according to the invention, in the presence of hydrogen and a hydrogenation catalyst.
  • Said C5 + liquid heavy fraction is admitted in the presence of hydrogen (line 6) in a hydrogenation zone (7) containing a hydrogenation catalyst which aims to saturate the unsaturated olefinic compounds present in the C5 + heavy liquid fraction. described above.
  • the catalyst used in step (b) according to the invention is a non-crunchy or slightly cracking hydrogenation catalyst comprising at least one metal of group VIII of the periodic table of the elements and comprising at least one carrier with refractory oxide base.
  • said catalyst comprises at least one group VIII metal chosen from nickel, molybdenum, tungsten, cobalt, ruthenium, indium, palladium and platinum and comprising at least one oxide-based support refractory selected from alumina and silica alumina.
  • group VIII metal chosen from nickel, molybdenum, tungsten, cobalt, ruthenium, indium, palladium and platinum and comprising at least one oxide-based support refractory selected from alumina and silica alumina.
  • the Group VIII metal is chosen from nickel, palladium and platinum.
  • the group VIII metal is chosen from palladium and / or platinum and the content of this metal is advantageously between 0.1% and 5%. % by weight, and preferably between 0.2% and 0.6% by weight relative to the total weight of the catalyst.
  • the Group VIII metal is palladium.
  • the metal of group VIII is nickel and the content of this metal is advantageously between 5% and 25% by weight, preferably between 7%. and 20% by weight based on the total weight of the catalyst.
  • the catalyst support used in step (b) of the process according to the invention is a refractory oxide-based support, preferably chosen from alumina and silica-alumina.
  • the support When the support is an alumina, it has a BET specific surface to limit the polymerization reactions on the surface of the hydrogenation catalyst, said surface being between 5 and 140 m 2 / g.
  • the support When the support is a silica-alumina, the support contains a percentage of silica of between 5 and 95% by weight, preferably between 10 and 80%, more preferably between 20 and 60% and very preferably between 30 and 50%. a BET specific surface area of between 100 and 550 m 2 / g, preferably between 150 and 500 m 2 / g, preferably less than 350 m 2 / g and even more preferably less than 250 m 2 / g ,
  • the hydrogenation stage b) of the process according to the invention is preferably carried out in one or more fixed bed reactor (s).
  • the feedstock is brought into contact with the hydrogenation catalyst in the presence of hydrogen and at operating temperatures and pressures allowing the hydrogenation of the olefinic unsaturated compounds present in the feedstock.
  • the oxygenated compounds are not converted, the liquid hydrogen effluent from step b) of the process according to the invention therefore does not contain water resulting from the conversion of said oxygenated compounds.
  • the operating conditions of the hydrogenation stage b) are chosen so that the effluent leaving said hydrogenation zone (7) is in the liquid state: indeed, the amount of hydrogen introduced into the hydrogenation zone (7) corresponds to a quantity of hydrogen in slight excess with respect to the quantity of hydrogen strictly necessary to carry out the hydrogenation reaction of the unsaturated compounds of the type olefin.
  • the liquid hydrogenated effluent does not contain hydrocarbon compounds boiling at a temperature below 20 ° C., preferably below 10 ° C. and very preferred, lower than 0 ° C, corresponding to the gaseous fraction C4-.
  • the operating conditions of the hydrogenation step b) of the process according to the invention are the following: the temperature within said hydrogenation zone (7) is between 100 and 180 ° C. and preferably between 120 and 180 ° C. and 165 ° C, the total pressure is between 0.5 and 6 MPa, preferably between 1 and 5 MPa and even more preferably between 2 and 5 MPa.
  • the feedstock flow rate is such that the hourly space velocity (ratio of the hourly flow rate at 15 ° C of liquid fresh feed over the catalyst volume loaded) is between 1 and 10 h -1, preferably between 1 and 5 h -1 and even more preferably between 1 and 4 h -1 .
  • the hydrogen that feeds the hydrotreating zone is introduced at a rate such that the volume ratio hydrogen / hydrocarbons is between 10 and 50 Nl / l / h, and preferably between 15 and 35 Nl / l / h.
  • the olefinic type unsaturated compounds are hydrogenated more than 50%, preferably more than 75% and preferably more than 85%.
  • the hydrogenation step b) of the process according to the invention is preferably carried out under conditions such as conversion to products having boiling points greater than or equal to 370 ° C in products having lower boiling points. at 370 ° C is zero.
  • the hydrogenated effluent from step b) of the process according to the invention therefore does not contain compounds boiling at a temperature below 20 ° C, preferably below 10 ° C and very preferably below 0 ° C C, corresponding to the gas fraction C4-.
  • step b) of the process according to the invention use is made of a guard bed (not shown in the figures) containing at least one guard bed catalyst upstream of the hydrogenation zone ( 7) to reduce the content of solid mineral particles and possibly reduce the content of harmful metal compounds for hydrogenation catalysts.
  • the guard bed may advantageously be either integrated in the hydrogenation zone (7) upstream of the hydrogenation catalyst bed or be placed in a separate zone upstream of the hydrogenation zone (7).
  • the treated fractions may optionally contain solid particles such as inorganic solids. They may optionally contain metals contained in hydrocarbon structures such as more or less soluble organometallic compounds.
  • fines fines resulting from a physical or chemical attrition of the catalyst. They can be micron or sub-micron. These mineral particles then contain the active components of these catalysts without the following list being limiting: alumina, silica, titanium, zirconia, cobalt oxide, iron oxide, tungsten, rhuthenium oxide, etc.
  • These solid minerals may be present under the calcined mixed oxide form: for example, alumina-cobalt, alumina-iron, alumina-silica, alumina-zirconia, alumina-titanium, alumina-silica-cobalt, alumina-zirconia-cobalt, ....
  • the catalyst fines described above may have a higher silica content than the catalyst formulation resulting from the intimate interaction between the catalyst fines and anti-foaming agents described above.
  • the guard bed catalysts used may advantageously be in the form of spheres or extrudates. It is however advantageous that the catalyst is in the form of extrudates with a diameter of between 0.5 and 5 mm and more particularly between 0.7 and 2.5 mm.
  • the shapes are cylindrical (which can be hollow or not), cylindrical twisted, multilobed (2, 3, 4 or 5 lobes for example), rings.
  • the cylindrical shape is preferably used, but any other shape may be used.
  • the bed bed catalysts may, in another preferred embodiment, have more specific geometric shapes in order to increase their void fraction.
  • the void fraction of these catalysts is between 0.2 and 0.75.
  • Their outer diameter can vary between 1 and 35 mm.
  • guard bed catalysts used are not impregnated with an active phase.
  • Guard beds can be marketed by Norton- Saint-Gobain, for example example MacroTrap® guard beds.
  • Guard beds can be marketed by Axens in the ACT family: ACT077, ACT935, ACT961 or HMC841, HMC845, HMC941 or HMC945. It may be particularly advantageous to superpose these catalysts in at least two different beds of varying heights.
  • the catalysts having the highest void content are preferably used in the first catalytic bed or first catalytic reactor inlet. It may also be advantageous to use at least two different reactors for these catalysts.
  • These guard bed catalysts used may advantageously have macroporosity.
  • the macroporous volume for a mean diameter at 50 nm is greater than 0.1 cm 3 / g and a total volume greater than 0.60 cm 3 / g.
  • the mercury volume for a pore diameter greater than 1 micron is greater than 0.5 cm 3 / g and the mercury volume for a pore diameter greater than 10 microns is greater than 0.25 cm 3 /boy Wut.
  • the solids content is advantageously less than 20 ppm, preferably less than 10 ppm and even more preferably less than 5 ppm.
  • the soluble silicon content is advantageously less than 5 ppm, preferably less than 2 ppm and even more preferably less than 1 ppm.
  • step b) of the process according to the invention all the liquid hydrogenated effluent is directly sent to a hydrocracking / hydroisomerization zone (10).
  • step c) of the process according to the invention the totality of the liquid hydrogenated effluent resulting from step b) of the process according to the invention is directly sent, without prior separation step, to the zone of hydroisomerization / hydrocracking (10) containing the hydroisomerization / hydrocracking catalyst and preferably at the same time as a hydrogen stream (line 9).
  • the temperature used in this step is generally between 200 and 450 ° C. and preferably from 250 ° C. to 450 ° C., advantageously from 300 to 450 ° C., and even more advantageously above 320 ° C. or for example between 320 ° -420 ° C. vs.
  • the hydroisomerization and hydrocracking step c) of the process according to the invention is advantageously carried out under conditions such that the pass conversion into products with boiling points greater than or equal to 370 ° C. into products having points. boiling point below 370 ° C. is greater than 80% by weight, and even more preferably at least 85%, preferably greater than 88%, so as to obtain middle distillates (gas oil and kerosene) having sufficiently good cold (pour point, freezing point) to meet the specifications in force for this type of fuel.
  • the majority of catalysts currently used in hydroisomerization / hydrocracking are of the bifunctional type associating an acid function with a hydrogenating function.
  • the acid function is generally provided by supports with large surface areas (150 to 800 m2.g-1 generally) having a surface acidity, such as halogenated aluminas (chlorinated or fluorinated in particular), phosphorus aluminas, combinations of oxides of boron and aluminum, silica aluminas.
  • the hydrogenating function is generally provided either by one or more metals of group VIII of the periodic table of the elements, such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, or by an association of at least a Group VI metal such as chromium, molybdenum and tungsten and at least one Group VIII metal.
  • the equilibrium between the two acid and hydrogenating functions is the fundamental parameter which governs the activity and the selectivity of the catalyst.
  • a weak acidic function and a strong hydrogenating function give catalysts which are not very active and selective towards isomerization whereas a strong acid function and a low hydrogenating function give very active and cracking-selective catalysts.
  • a third possibility is to use a strong acid function and a strong hydrogenating function to obtain a very active catalyst but also very selective towards isomerization. It is therefore possible, judiciously choosing each of the functions to adjust the activity / selectivity of the catalyst.
  • the hydroisomerization-hydrocracking catalysts are bifunctional catalysts comprising an amorphous acid support (preferably a silica-alumina) and a hydro-dehydrogenating metal function preferably provided by at least one noble metal.
  • the support is said to be amorphous, that is to say devoid of molecular sieves, and in particular of zeolite, as well as the catalyst.
  • the amorphous acidic support is advantageously a silica-alumina but other supports are usable.
  • the catalyst preferably does not contain added halogen, other than that which could be introduced for the impregnation of the noble metal, for example.
  • the catalyst does not contain added halogen, for example fluorine.
  • the support has not been impregnated with a silicon compound.
  • the two stages b) and c) of the process according to the invention, hydrogenation and hydroisomerization-hydrocracking, can advantageously be carried out on the two types of catalysts in two or more different reactors, and / or in the same reactor.
  • the characteristics associated with the corresponding catalyst are identical to those of the silica alumina described above.
  • step c) of the process according to the invention said catalyst is sulphurized.
  • a palladium-containing catalyst is used in the hydrogenation step b) and in the hydroisomerization / hydrocracking step c), a platinum-containing catalyst.
  • a palladium-containing catalyst is used in the hydrogenation step b) and in the hydroisomerization / hydrocracking step c), a sulphurized catalyst containing at least one hydro-dehydrogenating element selected from Group VIII non-noble metals and Group VIB metals.
  • a catalyst containing at least one non-noble hydro-dehydrogenating element of group VIII and in step c) of hydroisomerization is used.
  • hydrocracking a sulphurized catalyst containing at least one hydro-dehydrogenating element chosen from Group VIII non-noble metals and Group VIB metals.
  • the effluent (so-called hydrocracked / hydroisomerized fraction) leaving the hydroisomerization / hydrocracking zone (10), resulting from step (c) of the process according to the invention, is sent, in accordance with step d) of process according to the invention, in a distillation train (11), which incorporates an atmospheric distillation and optionally a vacuum distillation, which aims to separate the conversion products of boiling point below 340 ° C and preferably less than 370 ° C and including in particular those formed during step (c) in the hydroisomerization / hydrocracking reactor (10), and to separate the residual fraction whose initial boiling point is generally greater than at least 340 ° C and preferably greater than or equal to at least 370 ° C.
  • the conversion products and hydroisomerized is separated in addition to the light gases C1-C4 (line 12) at least one gasoline fraction (or naphtha) (line 13), and at least one middle distillate fraction kerosene (line 14) and diesel (line 15).
  • the residual fraction whose initial boiling point is generally greater than at least 340 ° C and preferably greater than or equal to at least 370 ° C is recycled (line 16) in step c) of the process according to the invention at the head of the zone (10) for hydroisomerization and hydrocracking.
  • said residual fraction can provide excellent bases for the oils.
  • step (c) zone 10
  • step (c) zone 10
  • the gas oil and kerosene cuts are preferably recovered separately or mixed, but the cutting points are adjusted by the operator according to his needs. It has been found that it is advantageous to recycle a portion of the kerosene to improve its cold properties.
  • the gas oil (s) obtained has a pour point of at most 0 ° C, generally below -10 ° C and often below -15 ° C.
  • the cetane number is greater than 60, generally greater than 65, often greater than 70.
  • the resulting kerosene (s) has a freezing point of not more than -35 ° C, generally less than -40 ° C.
  • the smoke point is greater than 25 mm, usually greater than 30 mm.
  • the yield of gasoline is always less than 50% by weight, preferably less than 40% by weight, advantageously less than 30% by weight or 20% by weight or even 15% by weight.

Landscapes

  • 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)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (14)

  1. Verfahren zur Herstellung von Mitteldestillaten aus einer paraffinischen Beschickung, die durch Fischer-Tropsch-Synthese hergestellt wird, umfassend die folgenden aufeinanderfolgenden Schritte:
    a) Trennen von mindestens einer gasförmigen Fraktion C4-, der sogenannten leichten Fraktion, mit einem Endsiedepunkt von weniger als 20 °C von dem Abstrom aus der Fischer-Tropsch-Syntheseeinheit, derart, um eine einzige flüssige Fraktion C5+, die sogenannte schwere Fraktion, mit einem Anfangssiedepunkt, der zwischen 20 und 40 °C liegt, zu erhalten,
    b) Hydrierung ungesättigter Verbindungen des olefinischen Typs von mindestens einem Teil der schweren Fraktion C5+ in Anwesenheit von Wasserstoff und von einem Hydrierkatalysator bei einer Temperatur zwischen 100 °C und 180 °C, bei einem Gesamtdruck zwischen 0,5 und 6 MPa, mit einer stündlichen Volumengeschwindigkeit zwischen 1 und 10 h-1 und mit einem Wasserstoffdurchsatz, der einem Volumenverhältnis Wasserstoff/Kohlenwasserstoffen entspricht, das zwischen 10 und 50 NI/I/h beträgt,
    c) Hydroisomerisieren/Hydrocracken des gesamten hydrierten flüssigen Abstroms aus Schritt b) ohne vorherigen Trennungsschritt in Anwesenheit von Wasserstoff und von einem Hydroisomerierungs-/Hydrocrackkatalysator,
    d) Destillation des hydrogecrackten/hydroisomerisierten Abstroms.
  2. Verfahren nach Anspruch 1, wobei der Abstrom aus der Fischer-Tropsch-Syntheseeinheit am Ausgang der Fischer-Tropsch-Syntheseeinheit in zwei Fraktionen, eine leichte Fraktion, die Kalt- Kondensat genannt wird, und eine schwere Fraktion, die Wachse genannt wird, geteilt wird.
  3. Verfahren nach Anspruch 2, wobei die leichte Fraktion, die Kalt- Kondensat genannt wird, und die schwere Fraktion, die Wachse genannt wird, in getrennten Fraktioniermitteln getrennt behandelt und dann derart rekombiniert werden, um eine einzige Fraktion C5+, die sogenannte schwere Fraktion, mit einem Anfangssiedepunkt, der zwischen 20 und 40 °C liegt, zu erhalten.
  4. Verfahren nach Anspruch 2, wobei die leichte Fraktion, die Kalt- Kondensat genannt wird, und die schwere Fraktion, die Wachse genannt wird, in einem gleichen Fraktioniermittel rekombiniert und behandelt werden.
  5. Verfahren nach einem der Ansprüche 1 bis 4, wobei der Hydrierkatalysator mindestens ein Metall der Gruppe VIII des Periodensystems der Elemente umfasst und mindestens einen hitzebeständigen Oxidträger umfasst.
  6. Verfahren nach einem der Ansprüche 1 bis 5, wobei das Metall der Gruppe VIII Palladium ist.
  7. Verfahren nach Anspruch 6, wobei die Hydrierung ungesättigter Verbindungen des olefinischen Typs von mindestens einem Teil der schweren Fraktion bei einem Volumenverhältnis Wasserstoff/Kohlenwasserstoffen betrieben wird, das zwischen 15 und 35 NI/I/h beträgt.
  8. Verfahren nach einem der Ansprüche, 1 bis 7, wobei ein Schutzbett verwendet wird, das mindestens einen Schutzbettkatalysator vorgelagert vor der Hydrierzone umfasst, wobei das Schutzbett entweder in die Hydrierzone vorgelagert vor dem Hydrierungskatalysatorbett integriert wird oder in einem separaten Bereich vorgelagert vor der Hydrierzone angeordnet wird.
  9. Verfahren nach einem der Ansprüche 1 bis 8, wobei der Schritt (c) des Hydroisomerisierens/Hydrocrackens unter einem Druck zwischen 0,2 und 15 MPa, bei einer Raumgeschwindigkeit zwischen 0,1 h-1 und 10 h-1, mit einer Wasserstoffrate zwischen 100 und 2000 Normalliter Wasserstoff pro Liter Beschickung und pro Stunde und bei einer Temperatur zwischen 200 und 450 °C durchgeführt wird.
  10. Verfahren nach einem der Ansprüche 1 bis 9, wobei der Hydroisomerierungs-/Hydrocrackkatalysator bis zu 3 Gew.% Metall von mindestens einem hydrierend-dehydrierenden Element, das aus den Edelmetallen der Gruppe VIII ausgewählt wird, und einen Träger, der mindestens ein Siliciumdioxid-Aluminiumoxid umfasst (oder vorzugsweise daraus gebildet ist), wobei das Siliciumdioxid-Aluminiumoxid die folgenden Eigenschaften aufweist:
    - einen Gewichtsgehalt an Siliziumdioxid SiO2, der zwischen 5 und 95 % beträgt
    - einen Gehalt an Na von weniger als 300 Gewichts-ppm,
    - ein Gesamtporenvolumen, das zwischen 0,45 und 1,2 ml/g beträgt, das durch Quecksilberporosimetrie gemessen wird,
    - wobei die Porosität von Siliciumdioxid-Aluminiumoxid die Folgende ist:
    i/ das Volumen der Mesoporen, deren Durchmesser zwischen 40 A bis 150 Å beträgt und deren mittlerer Durchmesser zwischen 80 und 140 Å variiert, stellt zwischen 20 und 80 % des Gesamtporenvolumens dar, das durch Quecksilberporosimetrie gemessen wird,
    ii/ das Volumen der Makroporen, deren Durchmesser über 500 Å beträgt und vorzugsweise zwischen 1.000 und 10.000 Å beträgt, stellt zwischen 20 und 80 % des Gesamtporenvolumens dar, das durch Quecksilberporosimetrie gemessen wird,
    - eine spezifische Oberfläche, die zwischen 100 und 550 m2/g beträgt.
  11. Verfahren nach einem der Ansprüche 1 bis 9, wobei der Hydroisomerierungs-/Hydrocrackkatalysator bis zu 3 Gew.% Metall von mindestens einem hydrierend-dehydrierenden Element, das aus den Edelmetallen der Gruppe VIII des Periodensystems ausgewählt wird, von 0,01 bis 5,5 Gew.% Oxid eines Dotierungselements, das aus Phosphor, Bor und Silizium ausgewählt wird, und einen nicht-zeolithischen Träger auf der Basis von Siliciumdioxid-Aluminiumoxid umfasst, der eine Menge von über 15 Gew.% und von weniger als oder gleich 95 Gew.% Siliciumdioxid (SiO2) enthält, wobei das Siliciumdioxid-Aluminiumoxid die folgenden Eigenschaften aufweist:
    - einen mittleren Porendurchmesser, der durch Quecksilberporosimetrie gemessen wird, der zwischen 20 und 140 Å beträgt,
    - ein Gesamtporenvolumen, das durch Quecksilberporosimetrie gemessen wird, das zwischen 0,1 ml/g und 0,5 ml/g beträgt,
    - ein Gesamtporenvolumen, das durch Stickstoffporosimetrie gemessen wird, das zwischen 0,1 ml/g und 0,6 ml/g beträgt,
    - eine spezifische BET-Oberfläche, die zwischen 100 und 550 m2/g beträgt,
    - ein Porenvolumen, das durch Quecksilberporosimetrie gemessen wird, das im Bereich der Poren mit einem Durchmesser von über 140 Å unter 0,1 ml/g beträgt,
    - ein Porenvolumen, das durch Quecksilberporosimetrie gemessen wird, das im Bereich der Poren mit einem Durchmesser von über 160 Å unter 0,1 ml/g beträgt,
    - ein Porenvolumen, das durch Quecksilberporosimetrie gemessen wird, das im Bereich der Poren mit einem Durchmesser von über 200 Å unter 0,1 ml/g beträgt,
    - ein Porenvolumen, das durch Quecksilberporosimetrie gemessen wird, das im Bereich der Poren mit einem Durchmesser von über 500 Å unter 0,1ml/g beträgt,
    - ein Röntgendiffraktogramm, das mindestens die wichtigsten Strahlen enthält, die für mindestens eines der Übergangsaluminiumoxide charakteristisch sind, die zu der Gruppe gehören, die aus den alpha-, rho-, chi-, eta-, gamma-, kappa-, theta- und delta-Aluminiumoxiden gebildet ist,
    - eine Stampfdichte der Katalysatoren von über 0,55 g/cm3.
  12. Verfahren nach einem der Ansprüche 1 bis 9, wobei der Hydroisomerierungs-/Hydrocrackkatalysator zwischen 2,5 und 5 Gew.% Oxid eines Elements der Gruppe VIII und zwischen 20 und 35 Gew.% Oxid eines Elements der Gruppe VIBbezogen auf das Gewicht des Endkatalysators, eventuell von 0,01 bis 5,5 Gew.% Oxid eines Dotierungselements, das aus Phosphor, Bor und Silizium ausgewählt wird, und einen nicht-zeolithischen Träger auf der Basis von Siliciumdioxid-Aluminiumoxid umfasst, der eine Menge von über 15 Gew.% und weniger als oder gleich 95 Gew.% Siliciumdioxid (SiO2) enthält, wobei das Siliciumdioxid-Aluminiumoxid die folgenden Eigenschaften aufweist:
    - einen mittleren Porendurchmesser, der durch Quecksilberporosimetrie gemessen wird, der zwischen 20 und 140 Å beträgt,
    - ein Gesamtporenvolumen, das durch Quecksilberporosimetrie gemessen wird, das zwischen 0,1 ml/g und 0,5 ml/g beträgt,
    - ein Gesamtporenvolumen, das durch Stickstoffporosimetrie gemessen wird, das zwischen 0,1 ml/g und 0,6 ml/g beträgt,
    - eine spezifische BET-Oberfläche, die zwischen 100 und 550 m2/g beträgt,
    - ein Porenvolumen, das durch Quecksilberporosimetrie gemessen wird, das im Bereich der Poren mit einem Durchmesser von über 140 Å unter 0,1 ml/g beträgt,
    - ein Porenvolumen, das durch Quecksilberporosimetrie gemessen wird, das im Bereich der Poren mit einem Durchmesser von über 160 Å unter 0,1 ml/g beträgt,
    - ein Porenvolumen, das durch Quecksilberporosimetrie gemessen wird, das im Bereich der Poren mit einem Durchmesser von über 200 Å unter 0,1 ml/g beträgt,
    - ein Porenvolumen, das durch Quecksilberporosimetrie gemessen wird, das im Bereich der Poren mit einem Durchmesser von über 500 Å unter 0,1 ml/g beträgt,
    - ein Röntgendiffraktogramm, das mindestens die wichtigsten Strahlen enthält, die für mindestens eines der Übergangsaluminiumoxide charakteristisch sind, die zu der Gruppe gehören, die aus den alpha-, rho-, chi-, eta-, gamma-, kappa-, theta- und delta-Aluminiumoxiden gebildet ist,
    - eine Stampfdichte der Katalysatoren von über 0,55 g/cm3.
  13. Verfahren nach Anspruch 12, wobei der Katalysator sulfidiert ist.
  14. Verfahren nach einem der Ansprüche 1 bis 13, wobei mindestens einer der Kerosin- oder Dieselschnitte, der aus dem Schritt d) hervorgegangen ist, mindestens teilweise in den Schritt c) zurückgeführt wird.
EP08805641.1A 2007-06-12 2008-06-03 Verfahren zur herstellung von mitteldestillaten durch hydroisomerisierung und hydrocracking eines schweren teils aus einer fischer-tropsch-effluenz Active EP2158303B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0704224A FR2917419B1 (fr) 2007-06-12 2007-06-12 Procede de production de distillats moyens par hydroisomerisation et hydrocraquage d'une fraction lourde issue d'un effluent fischer-tropsch
PCT/FR2008/000753 WO2009004179A2 (fr) 2007-06-12 2008-06-03 Procede de production de distillats moyens par hydroisomerisation et hydrocraquage d'une fraction lourde issue d'un effluent fischer-tropsch

Publications (2)

Publication Number Publication Date
EP2158303A2 EP2158303A2 (de) 2010-03-03
EP2158303B1 true EP2158303B1 (de) 2017-01-04

Family

ID=38944565

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08805641.1A Active EP2158303B1 (de) 2007-06-12 2008-06-03 Verfahren zur herstellung von mitteldestillaten durch hydroisomerisierung und hydrocracking eines schweren teils aus einer fischer-tropsch-effluenz

Country Status (10)

Country Link
US (1) US8709234B2 (de)
EP (1) EP2158303B1 (de)
CN (1) CN101730732B (de)
BR (1) BRPI0813815A8 (de)
CA (1) CA2689932C (de)
FR (1) FR2917419B1 (de)
MY (1) MY157735A (de)
RU (1) RU2469069C2 (de)
WO (1) WO2009004179A2 (de)
ZA (1) ZA200908037B (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2944028B1 (fr) * 2009-04-03 2011-05-06 Inst Francais Du Petrole Procede de production de distillats moyens par hydroisomerisation et hydrocraquage d'une fraction lourde issue d'un effluent fischer-tropsch mettant en oeuvre une resine
FR2944027B1 (fr) * 2009-04-03 2011-05-06 Inst Francais Du Petrole Procede de production de distillats moyens par hydroisomerisation et hydrocraquage d'une fraction lourde issue d'un effluent fischer-tropsch
FR2963015B1 (fr) 2010-07-22 2012-09-07 Centre Nat Rech Scient Procede de photocommutation thermique de materiaux a transition de spin et applications
RU2623088C1 (ru) * 2016-06-16 2017-06-22 Акционерное общество "Всероссийский научно-исследовательский институт по переработке нефти" (АО "ВНИИ НП") Способ получения моторных топлив
CN109722291B (zh) * 2017-10-27 2020-11-13 中国石油化工股份有限公司 降低高干点航煤冰点的方法
US11685869B2 (en) 2021-10-01 2023-06-27 Emerging Fuels Technology, Inc. Method for the production of synthetic jet fuel

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3726788A (en) * 1970-10-15 1973-04-10 Exxon Research Engineering Co Two-stage hydrocracking with intermediate fractionation
US5057635A (en) * 1990-02-08 1991-10-15 Uop Process for isomerizing olefins in gasoline streams
ES2110051T5 (es) * 1992-08-18 2002-10-01 Shell Int Research Procedimiento de preparacion de combustibles hidrocarbonados.
US20040112792A1 (en) * 1998-02-13 2004-06-17 Murphy William J. Method for making lube basestocks
TW511030B (en) * 2000-12-04 2002-11-21 Ren-Huang Weng A method and system providing on-line web page reading record
US6515033B2 (en) * 2001-05-11 2003-02-04 Chevron U.S.A. Inc. Methods for optimizing fischer-tropsch synthesis hydrocarbons in the distillate fuel range
FR2826973B1 (fr) * 2001-07-06 2005-09-09 Inst Francais Du Petrole Procede de production de distillats moyens par hydroisomerisation et hydrocraquage de 2 fractions issues de charges provenant du procede fischer-tropsch
FR2850393B1 (fr) * 2003-01-27 2005-03-04 Inst Francais Du Petrole Procede de production de distillats moyens par hydroisomerisation et hydrocraquage de charges issues du procede fischer-tropsch
US7332073B2 (en) * 2004-03-31 2008-02-19 Chevron U.S.A. Inc. Process for removing contaminants from Fischer-Tropsch feed streams

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
ZA200908037B (en) 2012-04-25
US8709234B2 (en) 2014-04-29
FR2917419A1 (fr) 2008-12-19
WO2009004179A2 (fr) 2009-01-08
RU2469069C2 (ru) 2012-12-10
RU2010100634A (ru) 2011-07-20
CN101730732B (zh) 2014-05-28
BRPI0813815A8 (pt) 2017-03-14
CN101730732A (zh) 2010-06-09
CA2689932C (fr) 2016-05-03
MY157735A (en) 2016-07-15
US20100298451A1 (en) 2010-11-25
EP2158303A2 (de) 2010-03-03
BRPI0813815A2 (pt) 2014-12-30
WO2009004179A3 (fr) 2009-02-19
FR2917419B1 (fr) 2014-10-24
AU2008270132A1 (en) 2009-01-08
CA2689932A1 (fr) 2009-01-08

Similar Documents

Publication Publication Date Title
CA2239827C (fr) Procede de conversion de fractions lourdes petrolieres comprenant une etape de conversion en lit bouillonnant et une etape d'hydrocraquage
WO2017186484A1 (fr) Procédé de conversion comprenant des lits de garde permutables d'hydrodemetallation, une etape d'hydrotraitement en lit fixe et une etape d'hydrocraquage en reacteurs permutables
EP2158303B1 (de) Verfahren zur herstellung von mitteldestillaten durch hydroisomerisierung und hydrocracking eines schweren teils aus einer fischer-tropsch-effluenz
FR2776297A1 (fr) Procede de conversion de fractions lourdes petrolieres comprenant une etape d'hydrotraitement en lit fixe, une etape de conversion en lit bouillonnant et une etape de craquage catalytique
FR2718145A1 (fr) Procédé de traitement avec hydroisomérisation de charges issues du procédé fischer-tropsch.
FR2797883A1 (fr) Procede de production d'huiles ayant un indice de viscosite eleve
FR2926087A1 (fr) Procede multietapes de production de distillats moyens par hydroisomerisation et hydrocraquage d'un effluent produit par le procede fischer-tropsch
WO2010112691A1 (fr) Procede de production de distillats moyens par hydroisomerisation et hydrocraquage d'une fraction lourde issue d'un effluent fischer-tropsch mettant en oeuvre une resine
WO2008017742A1 (fr) Procede et installation de traitement de petrole brut avec conversion de résidu asphalténique
WO2009106704A2 (fr) Procede de production de distillats moyens par hydroisomerisation et hydrocraquage sequences d'un effluent produit par le procede fischer-tropsch
FR2989381A1 (fr) Production de distillats moyens a partir d'un effluent issu de la synthese fischer-tropsch comprenant une etape de reduction de la teneur en composes oxygenes
FR3091533A1 (fr) Procede d’ hydrocraquage en deux etapes pour la production de naphta comprenant une etape d’hydrogenation mise en œuvre en amont de la deuxieme etape d’hydrocraquage
WO2010112690A1 (fr) Procédé de production de distillats moyens par hydroisomerisation et hydrocraquage d'une fraction lourde issue d'un effluent fischer-tropsch
WO2020144095A1 (fr) Procede d' hydrocraquage en deux etapes pour la production de naphta comprenant une etape d'hydrogenation mise en œuvre en aval de la deuxieme etape d'hydrocraquage
EP3476917B1 (de) Verfahren zum starten eines produktionsverfahrens von kerosin und dieselkraftstoff mithilfe von kohlenwasserstoffverbindungen, die durch fischer-tropsch-synthese erzeugt werden
WO2020144096A1 (fr) Procede d'hydrocraquage en deux etapes comprenant une etape d'hydrogenation en amont de la deuxieme etape d'hydrocraquage pour la production de distillats moyens
WO2020144097A1 (fr) Procede d'hydrocraquage en deux etapes comprenant une etape d'hydrogenation en aval de la deuxieme etape d'hydrocraquage pour la production de distillats moyens
WO2008065284A2 (fr) Procede de conversion de gaz en liquides a logistique simplifiee
EP2586851A1 (de) Herstellungsverfahren von Mitteldestillaten, bei dem die aus dem Fischer-Tropsch-Verfahren hervorgegangene Charge und der Wasserstofffluss eine begrenzte Menge von Sauerstoff enthalten
FR3089518A1 (fr) Procede ameliore de conversion d’une charge lourde en distillats moyens faisant appel a un enchainement d’unites d’hydrocraquage, de vapocraquage et d’oligomerisation
FR2970478A1 (fr) Procede d'hydroconversion en lit fixe d'un petrole brut, etete ou non, un fractionnement, puis un desasphaltage de la fraction lourde pour la production d'un brut synthetique preraffine
WO2005012460A1 (fr) Procede d'amelioration du point d'ecoulement de charges hydrocarbonees issues du procede fischer-tropsch, utilisant un catalyseur a base de zeolithe zbm-30
FR2989380A1 (fr) Procede optimise de production de distillats moyens a partir d'une charge issue du procede fischer-tropsch contenant une quantite limitee de composes oxygenes
FR3084084A1 (fr) Procede de production d'olefines et de distillats moyens a partir d'un effluent hydrocarbone issu de la synhtese fischer-tropsch
FR3091537A1 (fr) Procede d’hydrocraquage en une etape comprenant une etape d'hydrogenation en amont ou en aval de l’etape d’hydrocraquage pour la production de distillats moyens

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20100112

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA MK RS

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: ENI S.P.A.

Owner name: IFP ENERGIES NOUVELLES

17Q First examination report despatched

Effective date: 20101228

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20160824

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 859246

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170115

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602008048261

Country of ref document: DE

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

Ref country code: NL

Ref legal event code: MP

Effective date: 20170104

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 859246

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170104

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170104

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170405

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170104

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170104

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170104

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170404

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170504

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170104

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170104

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170104

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170104

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170404

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170104

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170504

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602008048261

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170104

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170104

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170104

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170104

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170104

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: IFP ENERGIES NOUVELLES

Owner name: ENI S.P.A.

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170104

26N No opposition filed

Effective date: 20171005

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602008048261

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170104

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20170603

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170104

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170630

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170603

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170603

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170603

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180103

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170630

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20170630

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170104

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20080603

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170104

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170104

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230622

Year of fee payment: 16

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230808