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EP2333031B1 - Process to produce high quality kerosine and diesel fuels and hydrogen coproduction from light saturated fractions - Google Patents

Process to produce high quality kerosine and diesel fuels and hydrogen coproduction from light saturated fractions Download PDF

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Publication number
EP2333031B1
EP2333031B1 EP10290586A EP10290586A EP2333031B1 EP 2333031 B1 EP2333031 B1 EP 2333031B1 EP 10290586 A EP10290586 A EP 10290586A EP 10290586 A EP10290586 A EP 10290586A EP 2333031 B1 EP2333031 B1 EP 2333031B1
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EP
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Prior art keywords
stage
unit
effluent
oligomerization
kerosene
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German (de)
French (fr)
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EP2333031A1 (en
Inventor
Jean Cosyns
Annick Pucci
Quentin Debuisschert
Fabienne Le Peltier
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/12Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
    • C10G69/126Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step polymerisation, e.g. oligomerisation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G35/00Reforming naphtha
    • C10G35/04Catalytic reforming
    • C10G35/06Catalytic reforming characterised by the catalyst used
    • C10G35/085Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
    • C10G35/09Bimetallic catalysts in which at least one of the metals is a platinum group metal
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1022Fischer-Tropsch products
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1037Hydrocarbon fractions
    • C10G2300/1044Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/201Impurities
    • C10G2300/202Heteroatoms content, i.e. S, N, O, P
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/30Physical properties of feedstocks or products
    • C10G2300/301Boiling range
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006Temperature
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40Characteristics of the process deviating from typical ways of processing
    • C10G2300/4012Pressure
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04Diesel oil
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/08Jet fuel

Definitions

  • the present invention provides an attractive solution allowing from light naphtha (including any proportion of cut C3 and C4 called "LPG") to meet an increased demand for diesel fuel and kerosene, without involving new and expensive units of hydrocracking.
  • light naphtha including any proportion of cut C3 and C4 called "LPG”
  • the solution described in the present invention is particularly suitable for remodeling of existing refining schemes.
  • refiners face excess gasoline whose exports in deficit geographic areas are uncertain at short term with increased refining capacity and / or lower consumption in the areas concerned.
  • This hydrogen production unit is generally a steam reforming unit for methane or petroleum gas (LPG), more rarely an oxy-fuel combustion unit of various petroleum fractions.
  • the present solution can be defined as an alternative to the "hydrocracking" solution involving only smaller investment units and moreover generating hydrogen.
  • the present invention makes it possible to produce mainly a kerosene or diesel fuel of high quality by using a sequence of processes also allowing the production of hydrogen.
  • This last aspect is very important because, in general, the needs of the hydrogen refinery are increasing due to the development of different hydrotreatment units required to reach the ultimate sulfur specifications (10 ppm weight).
  • the charge consists of a so-called light naphtha section to which can be added any proportion of C3 or C4 cut called "LPG" cut.
  • the "light naphtha” cut noted (NL) in the process diagram) corresponds to a number of carbon atoms ranging from 5 to 7, and correspondingly to a boiling point ranging from 50 ° C. to 120 ° C.
  • a charge of the present process is called a hydrocarbon feedstock ranging from C3 to C7.
  • C3-C7 is sent to a separation unit of normal and iso-paraffins (1).
  • paraffins are called linear paraffins and paraffins are paraffins with at least one branch.
  • This separation unit of normal and iso paraffins (1) is installed when higher octane diesels higher than 45 are targeted with the use of zeolites in the oligomerization unit (3).
  • This arrangement also offers the advantage of producing gasoline with a much improved octane number compared to the starting naphtha, corresponding to the flow of iso paraffins (F8).
  • paraffins thus obtained (F1) are then sent to a dehydrogenation unit (2) which makes it possible to produce hydrogen (H2), and an effluent (F2) containing predominantly olefins and unconverted paraffins.
  • the olefin-rich fraction (F2) obtained at the end of step 2 is then sent to an oligomerization unit (3), which produces, for the most part, a carbon atom-containing olefin (F3) fraction ranging from typically from C10 to C24, boiling in the distillate range, ie in a temperature range between 150 ° C and 380 ° C.
  • F3 carbon atom-containing olefin
  • the effluent section of the oligomerization unit (3) is hereinafter referred to as the diesel cut text. It can optionally be restricted by fractionation or by varying the severity of the oligomerization unit (3) to a distillation range cut of between 150 ° C and 310 ° C, called kerosene.
  • a gasoline fraction having a boiling point of less than 150 ° C. is produced in a smaller quantity than the light naphtha starting, and having, in addition, an improved octane number, or even a much improved one. when using the optional separation unit normal / isoparaffins (1).
  • any olefinic cut from the refinery from C3 to C10 (denoted by ES), for example olefinic cuts from a catalytic cracking unit (abbreviated as FCC). ), or a unit of steam cracking, or a unit of coquéfaction or visbreduction or from a Fischer Tropsch unit.
  • FCC catalytic cracking unit
  • a unit of steam cracking or a unit of coquéfaction or visbreduction or from a Fischer Tropsch unit.
  • the diesel or kerosene fraction (F3) derived from the oligomerization unit (3) is sent to a hydrogenation stage (4), which makes it possible to obtain, depending on the catalytic system used, an excellent kerosene fuel or a diesel fuel cut.
  • Part of the hydrogen produced in step (2) can serve as a booster to the hydrogenation step (4).
  • the present invention makes it possible to simultaneously treat in the hydrogenation unit (4) any section with a boiling point greater than 150 ° C., and preferably between 150 ° and 380 °, coming from the refinery (denoted F7), by examples of the cuts directly from the atmospheric distillation unit of the crude, or from a catalytic cracking unit (abbreviated FCC), or from hydrocracking unit or from a catalytic reforming unit gasolines (in addition to olefins) with a beneficial effect on the quality of the resulting kerosene (improvement of the smoke point) or the resulting diesel (improvement of the cetane number).
  • FCC catalytic cracking unit
  • hydrocracking unit or from a catalytic reforming unit gasolines (in addition to olefins)
  • a beneficial effect on the quality of the resulting kerosene improvement of the smoke point
  • the resulting diesel improvement of the cetane number
  • the hydrogenation unit (4) preferably uses a low-temperature technology, mainly in the liquid phase, which allows a saving in investment and an improvement of the cetane performance of the diesel fraction compared to conventional methods of hydrotreatment operating in the gas phase. Nevertheless, if such a conventional hydrotreating unit is available on the site, it can be used to carry out the hydrogenation step (4).
  • the sulfur content of the feedstock to the hydrogenation unit will be less than 5 ppm by weight, and preferably lower at 1 ppm weight.
  • the catalyst used in the dehydrogenation step (2) consists of platinum and tin deposited on an alumina neutralized with an alkali.
  • the hydrogen used during the hydrogenation step (4) comes at least in part from the hydrogen generated in step (2).
  • the method according to the invention may be more particularly oriented towards the production of kerosene fuel with JET A1 specifications.
  • the oligomerization step (3) is carried out on resins at temperatures of between 20 ° C. and 200 ° C., and preferably between 70 ° C. and 180 ° C., and under pressures of 10 bar to 100 ° C. bars, and preferably from 30 bars to 65 bars.
  • the oligomerization step (3) can be carried out on silica-alumina at temperatures between 20 ° C and 300 ° C, and preferably between 120 ° C and 250 ° C, and at pressures of 10 bar to 100 bar, and preferably 20 bar to 65 bar.
  • the process according to the invention can be further characterized by introducing into the oligomerization step (3) at least one gasoline cut (ES) and / or at least one cut containing C3 and C4 from a catalytic cracking unit (FCC), a coker, a visbreaking unit, a Fischer Tropsch synthesis unit or a steam cracking unit which is treated in admixture with the effluent (F2) of the dehydrogenation stage (2).
  • FCC catalytic cracking unit
  • FCC catalytic cracking unit
  • coker a coker
  • visbreaking unit a visbreaking unit
  • Fischer Tropsch synthesis unit or a steam cracking unit which is treated in admixture with the effluent (F2) of the dehydrogenation stage (2).
  • F2 catalytic cracking unit
  • the process according to the invention can also be characterized by the introduction in the hydrogenation step (4) of a section (F7) 150 ° C + containing sulfur contents of less than 5 ppm (preferably less than 1 ppm). , for example cuts directly from the atmospheric distillation unit of the crude, or from the catalytic cracking unit (FCC), or from hydrocracking unit or catalytic reforming.
  • a section (F7) 150 ° C + containing sulfur contents of less than 5 ppm (preferably less than 1 ppm). for example cuts directly from the atmospheric distillation unit of the crude, or from the catalytic cracking unit (FCC), or from hydrocracking unit or catalytic reforming.
  • the dehydrogenation step (2) and / or the oligomerization step (3) can operate in regenerative or semi-regenerative mode.
  • the notation and / or means that one or the other of the steps (2) or (3), or the two steps (2) and (3) are concerned by the implementation in regenerative or semi-regenerative mode.
  • the hydrogen produced by the dehydrogenation step (2) may be sent, at least in part, to the unit operations that consume the refinery, possibly after passage in purification unit using a membrane or sieve (PSA).
  • PSA membrane or sieve
  • the process according to the present invention uses as feedstock a light naphtha (NL) having a distillation range generally between 30 ° C and 120 ° C, to which can be added any proportion of C3 and / or C4 cut called "LPG" cut. .
  • NL light naphtha
  • light naphtha is understood to mean a petroleum cut having generally from 3 to 10 carbon atoms, preferably from 4 to 7 carbon atoms, and composed of various chemical families, mainly paraffins and a certain proportion of aromatics and dicarboxylic acids. olefins.
  • LPG is understood to mean a section having a distillation range of -40 ° C. to + 10 ° C., predominantly consisting of propane and butane and a certain proportion of olefins.
  • a desulfurization and denitrogenation step is carried out in a hydrotreatment unit (HDT) according to a technology known to those skilled in the art, so as to avoid the poisoning of the catalysts involved in the downstream units.
  • HDT hydrotreatment unit
  • the light naphtha section with the LPG cut, noted (F1) is then sent to a separation unit of the normal and iso paraffins (1) using a molecular sieve.
  • This technology well known to those skilled in the art, preferably uses small-pore alkaline zeolites such as those referred to as 5A which make it possible to obtain a mixture composed mainly of normal paraffins (F1) ".
  • any method for producing a paraffin enriched cut such as those using membranes or molecular sieves or combinations thereof, may be contemplated within the context of the present process.
  • the branched paraffin stream (F8) which has an improved octane number relative to the incoming light naphtha (NL), is used to supply the gasoline pool.
  • the hydrogen / hydrocarbon molar ratio is generally between 0.1 and 20, preferably between 0.5 and 10.
  • the mass flow rate of feed (F1) treated per unit mass of catalyst is generally between 0.5 and 200 kg / (kg.hour).
  • the catalysts used in the dehydrogenation unit (2) generally consist of a Group VIII noble metal M selected from the group consisting of platinum, palladium, iridium, and rhodium, and at least one selected promoter in the group consisting of tin, germanium, lead, gallium, indium, thallium.
  • the catalysts of the dehydrogenation unit (2) may also contain an alkaline or alkaline earth compound.
  • the noble metal M and the promoter are deposited on an inert support chosen from the group formed by silica, alumina, titanium oxide, silica magnesia, or any mixture of said elements.
  • the catalyst according to the invention preferably contains from 0.01% to 10% by weight, more preferably from 0.02% to 2% by weight, and very preferably from 0.05% to 0.7% by weight.
  • at least one noble metal M selected from the group consisting of platinum, palladium, rhodium and iridium.
  • the metal M is platinum or palladium, and very preferably platinum.
  • the promoter content is preferably between 0.01% and 10% by weight, more preferably between 0.05% and 5% by weight, and very preferably between 0.1% and 2% by weight.
  • the catalyst of the dehydrogenation unit (2) can advantageously contain both platinum and tin.
  • the alkaline compound is selected from the group consisting of lithium, sodium, potassium, rubidium and cesium. Lithium, sodium or potassium are the preferred alkalis, and lithium or potassium are even more preferred alkalis.
  • the content of alkaline compound is preferably between 0.05% and 10% by weight, more preferably between 0.1% and 5% by weight, and even more preferably between 0.15% and 2% by weight. .
  • the alkaline earth compound is selected from the group consisting of magnesium, calcium, strontium or barium. Magnesium or calcium are the preferred alkaline earths and magnesium is the most preferred alkaline earth metal.
  • the content of alkaline earth compound is preferably between 0.05% and 10% by weight, more preferably between 0.1% and 5% by weight, and even more preferably between 0.15% and 2%. % weight
  • the catalyst of the dehydrogenation unit (2) may further optionally contain at least one halogen or halogenated compound in proportions of the order of 0.1% to 3% by weight.
  • a metalloid such as sulfur in proportions of the order of 0.1% to 2% by weight of the catalyst.
  • the sulfur in the form of hydrogen sulphide is then recovered at the top of the stabilization column with the cracked gases.
  • the catalyst of the dehydrogenation unit (2) is deactivated by deposition of carbon on the surface of said catalyst, generally called “coke” deposit, it is necessary to regenerate it by burning this coke. To ensure continuous operation of the dehydrogenation unit (2), it is then necessary to have at least two reactors, one of the reactors being in the reaction phase, the other reactor in the regeneration phase.
  • this technology well known to those skilled in the art, can be very expensive, and one can also use a semi-regenerative or continuous regeneration technology such as that well known in catalytic reforming which consists in transferring in a "batch” manner. or continuously the catalyst of the reactor operating in another capacity in which is carried out the regeneration of the catalyst by coke roping.
  • An important advantage of the continuous regeneration technology is that it greatly reduces the catalyst inventory, and thus reduces the initial investment.
  • a second advantage is that it keeps the catalyst constantly in its state of maximum activity.
  • the olefinic effluent (F2) from the dehydrogenation unit (2) is then sent to an oligomerization unit (3) for converting the C5 to C7 olefins into heavier olefins, namely C10 to C24.
  • any olefinic cut (ES) of the refinery ranging from C3 to C10, for example a gasoline cut after catalytic cracking (FCC). , a petrol cut from a steam-cracking unit, a gasoline of co-filtration or visbreaking, or a Fischer Tropsch gasoline.
  • FCC catalytic cracking
  • the effluent (F3) of the oligomerization unit (3) is composed of a mixture of olefinic oligomers of C 10 to C 24 and a light fraction preferably of C 5 to C 10 containing unconverted C 5 to C 7 olefins, a fraction of the initial C 5 to C 7 paraffins of the feed, and products resulting from cracking and recombination reactions which are easy to separate by simple distillation.
  • reaction effluent or the gasoline fraction preferentially C5 to C10 with the residual LPG, (noted F4) is recycled at the same time. entry of the oligomerization unit (3).
  • a lighter fraction (F5) ranging from C5 to C7 with the residual LPG, in order to totally or almost totally convert the normal paraffins into olefins, and thus maximize the diesel fuel efficiency relative to the starting load.
  • the semi-continuous or continuous regeneration sections of the dehydrogenation unit (2) and the oligomerization unit (3) can be integrated, that is to say use common equipment.
  • the mixture of heavy olefins (F3) from the oligomerization unit (3) is then sent to a hydrogenation unit (4).
  • a hydrogenation unit (4) To do this, one part of the hydrogen (H2) produced by the dehydrogenation unit (2) is used, the other part, the largest part, being able to be exported to the various hydrotreatment units of the refinery.
  • the hydrogenation (4) can be carried out in a manner known to those skilled in the art in a hydrotreatment pathway over NiMo, CoMo or NiCoMo catalyst.
  • the hydrogenation (4) is carried out on catalysts based on Group VIII metals deposited on an inert support, such as, for example, silica or alumina.
  • Group VIII metals that can be used as hydrogenation catalysts include nickel, palladium or platinum.
  • the hydrogenation (4) generally takes place in the liquid phase in a fixed bed reactor at temperatures between 50 ° C and 300 ° C, and preferably between 100 ° C and 200 ° C, and under pressures of 5 to 50 bar, and preferably 10 to 30 bar.
  • the cetane number of the resulting diesel cut is generally between 45 and 55 with the use of zeolites in the oligomerization unit (3).
  • KT / yr light naphtha
  • LN light naphtha
  • RON engine octane
  • the light C4-C5-C6 mixture is directed to a dehydrogenation unit (2) operating at a pressure of 1.3 bar and at an average temperature of 550 ° C. on a platinum and tin catalyst deposited on alumina, with a H 2 / HC molar recycle rate of 0.5.
  • the effluent of the dehydrogenation unit (2) with a recycle at 1/1 rate relative to the fresh feed of the normal C4 -C6 paraffins from the oligomerization unit (3) has the following general composition: Effluent of the dehydrogenation unit KT / year olefins NC4 " 70.1 olefins NC5 "+ NC6" 176.4 Paraffin NC4 40.8 paraffins N C5 + NC6 51 Total 338.3
  • the effluent from the dehydrogenation unit (2) containing the olefins and paraffins is then directed to an oligomerization plant for olefins (3) operating at about 300 ° C. over a zeolite catalyst based on ZSM5.
  • the total amount of C5-C10 gasoline produced containing the starting C5-C6 paraffins amounts to 88 KT / year with an RON motor octane measured at 78.
  • the saturated C4-C5-C6 cut can be sent as a naphtha to a petrochemical site reducing the amount of gasoline produced to 61.3 KT / year.
  • the effluent of the oligomerization (3) is sent to the hydrogenation unit (4).
  • the hydrogenation unit (4) operates on a nickel-based catalyst at temperatures between 150 ° and 200 ° C.
  • the effluent from the hydrogenation unit (4) has a cetane number of 41, ie a cetane number of 46.
  • the hydrogen consumed in the hydrogenation (4) is equal to 2.0 KT / year.
  • the net quantity of hydrogen produced by the process according to the invention is therefore 5.1 KT / year.
  • the gasoline amount was reduced by 62% relative to the incoming light naphtha (NL) with a simultaneous 10 octane gain point (RON) relative to the incoming light naphtha (NL).
  • the process described in the present invention thus makes it possible not only to produce a good quality diesel fuel, but also to produce hydrogen, contrary to conventional processes, and to reduce the quantities of gasolines and butane currently in excess, in particular on the European market.
  • the light starting naphtha has an engine octane (RON) of 68.
  • This light naphtha is directed to a normal / iso paraffin separation unit (1) operating on a 5A molecular sieve. This gives 83.5 KT / year of nC5 + nC6 paraffins, the isofparaffin rich fraction (F8) being sent to the gasoline pool.
  • the mixture of nC4 + nC5 + nC6 is sent to a dehydrogenation unit (2) operating at a pressure of 1.3 bar and at an average temperature of 550 ° C on a platinum-tin catalyst on alumina, with a rate of H2 / HC molar recycle of 0.5.
  • the effluent from the dehydrogenation unit (2) with a 1/1 recycle of normal C4 -C6 paraffins from the oligomerization unit (3) has the following general composition; Effluent of the dehydrogenation unit (2) KT / year olefins N C4 " 70.1 olefins N C5 "+ NC6" 63.7 paraffins NC4 40.8 paraffins N C5 + NC6 18.5 Total 193.1
  • the effluent from the dehydrogenation unit (2) containing the olefins and paraffins is then directed to an oligomerization plant for olefins (3) operating at about 300 ° C. over a zeolite catalyst based on ZSM5.
  • the total amount of C5-C10 gasoline produced containing the starting C5-C6 paraffins amounts to 38.6 KT / year with an RON motor octane measured at 80.
  • the saturated C4-C5-C6 cut can be sent as a naphtha to a petrochemical site reducing the amount of gasoline produced at the oligomerization (3) to 33.4 KT / year.
  • the effluent of the oligomerization (3) is sent to the hydrogenation unit (4).
  • the hydrogenation unit (4) operates on a nickel-based catalyst at temperatures between 150 ° and 200 ° C.
  • the effluent of the hydrogenation unit (4) has a cetane number of 46, ie a cetane number of 51.
  • the hydrogen consumed in the hydrogenation (4) is equal to 1.1 KT / year.
  • the net quantity of hydrogen produced by the process according to the invention is therefore 2.7 KT / year.
  • the method described in the present invention not only makes it possible to produce a good quality diesel fuel, but also to produce hydrogen contrary to conventional processes, and to reduce the quantities of gasoline and butane currently in surplus especially in the European market.
  • the 187.1 KT / year of gasoline produced comprises the C5-C6 iso paraffins and the C5-C10 fraction produced during oligomerization.
  • the amount of gasoline produced is 20% lower than the amount of light incoming naphtha (NL) with simultaneously an improved octane number of 20 points relative to the incoming light naphtha (NL).
  • Example 3 load C4 / C5 / C6 "maxi kerosene" (not according to the invention)
  • KT / yr light naphtha
  • NL light naphtha
  • RON engine octane
  • the light C4-C5-C6 mixture is directed to a dehydrogenation unit (2) operating at a pressure of 1.3 bar and at an average temperature of 550 ° C, with an H2 / HC molar recycle ratio of 0.5.
  • the dehydrogenation (2) is carried out on a catalyst based on platinum and tin deposited on alumina.
  • the effluent of the dehydrogenation unit (2) with a recycle at a rate of 1/1 relative to the fresh feedstock of the C4-C6 n paraffins from the oligomerization unit (3) has the following general composition: Effluent of the dehydrogenation unit KT / year olefins N C4 " 70.1 olefins N C5 "+ NC6" 176.4 paraffins NC4 40.8 paraffins N C5 + NC6 51 Total 338.3
  • the total amount of C5-C10 gasoline produced containing the starting C5-C6 paraffins and unconverted olefins amounts to 139.2 Kt / yr.
  • the effluent of the oligomerization (3) boiling in the range of kerosene and diesel is highly olefinic is sent to the hydrogenation unit (4).
  • the hydrogenation unit (4) operates on a nickel-based catalyst at temperatures between 150 ° and 200 ° C.
  • the kerosene produced at the hydrogenation unit (4) has a smoke point of 35 mm, a vanishing point of the crystals below -60 ° C, and an ASTM D86 end point of less than 300 ° C, in line with the specifications required for kerosene meeting the JET A1 standard.
  • the hydrogen consumed in the hydrogenation (4) is equal to 1.6 KT / year.
  • the small amount of diesel produced is generally injected into the diesel pool without any significant impact on the pool cetane despite its low cetane number of 30.
  • the net quantity of hydrogen produced by the process according to the invention is therefore 5.5 KT / year.
  • the amount of gasoline produced was reduced by 40% relative to the incoming light naphtha (NL) feed simultaneously with a 20 octane (RON) gain still relative to the incoming light naphtha ( NL).
  • the method described in the present invention therefore makes it possible not only to produce a good quality kerosene fuel, but also to produce hydrogen in contrast to conventional processes, and to reduce the quantities of gasolines and butane currently in excess, particularly on the European market.

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Description

INTRODUCTIONINTRODUCTION

L'évolution des moteurs automobiles entraîne actuellement une augmentation de la demande en carburant diesel au dépend de celle de l'essence.The evolution of automotive engines is currently driving an increase in the demand for diesel fuel at the expense of that of gasoline.

Les prévisions concernant l'évolution du marché des carburants automobiles indiquent une diminution quasi généralisée dans le monde de la demande en essence. Ainsi, alors qu'en 2000 le rapport de consommation d'essence par rapport au diesel était de 2, on prévoit qu'il sera proche de 1,5 en 2015. Pour l'union européenne, cette diminution est extrêmement forte, puisque ce rapport qui était de 1 en 2000 devrait passer à 0,5 en 2012.Forecasts for the evolution of the automotive fuel market point to an almost universal decline in the world of gasoline demand. Thus, while in 2000 the ratio of gasoline consumption to diesel was 2, it is expected that it will be close to 1.5 in 2015. For the European Union, this reduction is extremely strong, since The ratio, which was 1 in 2000, is expected to increase to 0.5 in 2012.

Par ailleurs, la demande en kérosène devrait également significativement augmenter dans les prochaines années en liaison avec l'évolution du marché du transport aérien.In addition, the demand for kerosene is also expected to increase significantly in the coming years in connection with the evolution of the air transport market.

Cette évolution inéluctable vers une demande accrue en distillats moyens, et la diminution de la demande en essence pose à l'industrie du raffinage un grave problème d'adaptation de l'offre à la demande, et ceci dans un délai très court peu compatible avec la construction de nouvelles installations coûteuses et longues à mettre en oeuvre, telles que les hydrocraquages de gasoil sous vide.This unavoidable evolution towards an increased demand for middle distillates, and the decrease in the demand for petrol, poses a serious problem for the refining industry in adapting supply to demand, and this in a very short time that is not very compatible with the construction of new installations that are costly and time consuming to implement, such as the hydrocrackings of vacuum gas oil.

La présente invention propose une solution attractive permettant à partir de naphta léger (incluant une proportion quelconque de coupe C3 et C4 dite "LPG") de répondre à une demande accrue en carburant diesel et kérosène, sans impliquer d'unités neuves et couteuses d'hydrocraquage.The present invention provides an attractive solution allowing from light naphtha (including any proportion of cut C3 and C4 called "LPG") to meet an increased demand for diesel fuel and kerosene, without involving new and expensive units of hydrocracking.

La solution décrite dans la présente invention est particulièrement adaptée à des remodelages de schémas de raffinage existants.The solution described in the present invention is particularly suitable for remodeling of existing refining schemes.

Elle permet en plus de générer de l'hydrogène, dont la demande s'accroît dans les raffineries pour répondre à l'accroissement des capacités des unités d'hydrotraitement pour produire des carburants reformulés (spécifications Euro 3, 4, 5 ou CARB I, II).It also generates hydrogen, which is growing in refineries to meet the increased capacity of hydrotreating units to produce reformulated fuels (Euro 3, 4, 5 or CARB I specifications). II).

ART ANTERIEURPRIOR ART

Dans un marché dominé par la consommation d'essence, comme c'est le cas par exemple aux États-Unis, la production de carburant diesel est assurée essentiellement à partir des distillats moyens dit "straight run", c'est à dire provenant de la distillation directe du pétrole brut.In a market dominated by the consumption of gasoline, as is the case for example in the United States, the production of diesel fuel is ensured essentially from the so-called "straight run" middle distillates, that is to say from direct distillation of crude oil.

Ces distillats moyens doivent être hydrotraités pour répondre aux spécifications maintenant très sévères de teneur en soufre (10 ppm max) et de teneurs en aromatiques. Actuellement cette production est notoirement insuffisante et oblige les raffineurs dans certaines zones géographiques, et notamment en Europe, à importer du carburant diesel pour satisfaire à la demande intérieure.These middle distillates must be hydrotreated to meet the now very strict specifications of sulfur content (10 ppm max) and aromatics contents. Currently this production is notoriously insufficient and requires refiners in certain geographical areas, especially in Europe, to import diesel fuel to meet domestic demand.

Inversement, et particulièrement en Europe, les raffineurs font face à des excédents d'essence dont les exportations dans les zones géographiques déficitaires sont incertaines à court terme avec l'augmentation des capacités de raffinage et/ou la baisse de consommation dans les zones concernées.Conversely, and particularly in Europe, refiners face excess gasoline whose exports in deficit geographic areas are uncertain at short term with increased refining capacity and / or lower consumption in the areas concerned.

Pour toutes ces raisons, un certain nombre de raffineurs ont construit des installations d'hydrocraquage qui permettent de transformer des coupes lourdes telles que le gasoil sous-vide en carburant diesel de très bonne qualité. Néanmoins, ce procédé est très coûteux en investissement et utilités car il fonctionne à très haute pression (supérieures à 100 bars), et entraîne une très forte consommation d'hydrogène (de l'ordre de 10 kg à 30 kg d'hydrogène par tonne de charge), nécessitant d'implanter une installation spécifique de production d'hydrogène.For all these reasons, a number of refiners have built hydrocracking plants that convert heavy cuts such as vacuum gas oil into high quality diesel fuel. However, this process is very costly in investment and utilities because it operates at very high pressure (above 100 bar), and causes a very high hydrogen consumption (of the order of 10 kg to 30 kg of hydrogen per tonne load), requiring the installation of a specific hydrogen production facility.

Cette unité de production d'hydrogène est généralement une unité de vaporéformage de méthane ou de gaz de pétrole (LPG), plus rarement une unité d'oxycombustion de diverses coupes pétrolières.This hydrogen production unit is generally a steam reforming unit for methane or petroleum gas (LPG), more rarely an oxy-fuel combustion unit of various petroleum fractions.

Quelle que soit l'unité de production d'hydrogène retenue, cette installation représente un investissement très lourd et nécessite l'importation de matières premières coûteuses.Whatever the hydrogen production unit selected, this installation represents a very heavy investment and requires the importation of expensive raw materials.

La présente solution peut se définir comme une alternative à la solution "hydrocraquage" ne faisant appel qu'à des unités d'investissement moindre et de surcroit générant de l'hydrogène.The present solution can be defined as an alternative to the "hydrocracking" solution involving only smaller investment units and moreover generating hydrogen.

Parmi l'art antérieur concernant la production d'essence à partir de coupes contenues dans la gamme C3- C7, on peut citer:

  • le brevet GB 2 186 287 qui divulgue un procédé de production d'une coupe essence et d'une coupe kérosène à partir d'une charge comprenant 4 atomes de carbone, telle qu'une fraction butane issue d'un craquage catalytique, le dit procédé comprenant une déshydrogénation de la charge, suivie d'une oligomérisation de l'effluent de déshydrogénation et d'une séparation de l'effluent d'oligomérisation en hydrogène.
  • le brevet US 2003/073875 A1 qui décrit un procédé de production d'essence comprenant la séparation des iso alcanes et normales alcanes avant la déshydrogénation des normales alcanes en oléfines et comprenant une réaction d'alkylation des oléfines sur les iso alcanes.
  • le document " Dealing with dieselisation " de Stockle Mike et Knight Tina, issu du 14 ième congrès ERTC de Berlin du 11 novembre 2009 qui divulgue un procédé de production de kérosène par déshydrogénation d'une coupe naphta légère et d'une coupe LPG saturée, oligomérisation du produit et recyclage de la fraction C5-C8 de l'effluent oligomérisé.
Among the prior art concerning the production of gasoline from sections contained in the C3-C7 range, mention may be made of:
  • the patent GB 2,186,287 which discloses a process for producing a gasoline cut and a kerosene cut from a feed comprising 4 carbon atoms, such as a butane fraction from a catalytic cracking, the said process comprising a dehydrogenation of the charge, followed by oligomerization of the dehydrogenation effluent and a separation of the oligomerization effluent into hydrogen.
  • the patent US 2003/073875 A1 which describes a process for producing gasoline comprising separating the iso alkanes and normal alkanes prior to the dehydrogenation of normal alkanes to olefins and comprising an alkylation reaction of the olefins on the isoalkanes.
  • the document " Dealing with Dieselisation "by Stockle Mike and Knight Tina, from the 14th ERTC Berlin Congress, November 11, 2009 which discloses a process for producing kerosene by dehydrogenation of a light naphtha cut and a saturated LPG cut, oligomerization of the product and recycling of the C5-C8 fraction of the oligomerized effluent.

DESCRIPTION SOMMAIRE DE L'INVENTIONSUMMARY DESCRIPTION OF THE INVENTION

La présente invention permet de produire majoritairement un carburant kérosène ou diesel de haute qualité en utilisant un enchaînement de procédés permettant également la production d'hydrogène. Ce dernier aspect est très important car, de manière générale, les besoins de la raffinerie en hydrogène vont en croissant en raison du développement des différentes unités d'hydrotraitement requises pour atteindre les spécifications ultimes en soufre (10 ppm poids).The present invention makes it possible to produce mainly a kerosene or diesel fuel of high quality by using a sequence of processes also allowing the production of hydrogen. This last aspect is very important because, in general, the needs of the hydrogen refinery are increasing due to the development of different hydrotreatment units required to reach the ultimate sulfur specifications (10 ppm weight).

Dans la présente invention, la charge est constituée d'une coupe dite naphta léger auquel on peut ajouter une proportion quelconque de coupe C3 ou C4 dite coupe "LPG". La coupe "naphta léger" notée (NL) sur le schéma du procédé) correspond à un nombre d'atomes de carbone allant de 5 à 7, et corrélativement à un point d'ébullition allant de 50°C à 120°C. Dans la suite du texte, on appelle charge du présent procédé une charge hydrocarbure allant de C3 à C7.In the present invention, the charge consists of a so-called light naphtha section to which can be added any proportion of C3 or C4 cut called "LPG" cut. The "light naphtha" cut noted (NL) in the process diagram) corresponds to a number of carbon atoms ranging from 5 to 7, and correspondingly to a boiling point ranging from 50 ° C. to 120 ° C. In the remainder of the text, a charge of the present process is called a hydrocarbon feedstock ranging from C3 to C7.

On fait l'hypothèse que la coupe naphta léger (NL) est préalablement hydrotraitée de manière à la libérer de toutes les impuretés azotés et soufrés qu'elle peut contenir.It is assumed that the light naphtha (NL) section is hydrotreated beforehand so as to free it from any nitrogen and sulfur impurities it may contain.

La charge C3-C7 est envoyée dans une unité de séparation des normales et iso paraffines (1). Pour éviter toute ambiguïté, on appelle normale paraffines les paraffines linéaires, et iso paraffines les paraffines présentant au moins un branchement.Charge C3-C7 is sent to a separation unit of normal and iso-paraffins (1). For the avoidance of doubt, paraffins are called linear paraffins and paraffins are paraffins with at least one branch.

Cette unité de séparation des normales et iso paraffines (1) est installée quand on vise des diesels à haut indice d'octane supérieur à 45 avec utilisation de zéolithes dans l'unité d'oligomérisation (3). Cet arrangement offre aussi l'avantage de produire de l'essence avec un indice d'octane très amélioré par rapport au naphta de départ, correspondant au flux d'iso paraffines (F8).This separation unit of normal and iso paraffins (1) is installed when higher octane diesels higher than 45 are targeted with the use of zeolites in the oligomerization unit (3). This arrangement also offers the advantage of producing gasoline with a much improved octane number compared to the starting naphtha, corresponding to the flow of iso paraffins (F8).

Les normales paraffines ainsi obtenues (F1)" sont ensuite envoyées dans une unité de déshydrogénation (2) qui permet de produire de l'hydrogène (H2), et un effluent (F2) contenant majoritairement des oléfines ainsi que des paraffines non transformées.The paraffins thus obtained (F1) are then sent to a dehydrogenation unit (2) which makes it possible to produce hydrogen (H2), and an effluent (F2) containing predominantly olefins and unconverted paraffins.

La coupe (F2) riche en oléfines obtenue à l'issue de l'étape 2, est ensuite envoyée dans une unité d'oligomérisation (3) qui produit majoritairement une coupe d'oléfines (F3) à nombre d'atome de carbone allant typiquement de C10 à C24, bouillant dans la gamme des distillats, c'est à dire dans un intervalle de température compris entre 150°C et 380°C.The olefin-rich fraction (F2) obtained at the end of step 2 is then sent to an oligomerization unit (3), which produces, for the most part, a carbon atom-containing olefin (F3) fraction ranging from typically from C10 to C24, boiling in the distillate range, ie in a temperature range between 150 ° C and 380 ° C.

La coupe effluent de l'unité d'oligomérisation (3), est appelé dans la suite du texte coupe diesel. Elle peut éventuellement être restreinte par fractionnement ou en jouant sur la sévérité de l'unité d'oligomérisation (3) à une coupe d'intervalle de distillation compris entre 150°C et 310°C, appelé kérosène.The effluent section of the oligomerization unit (3) is hereinafter referred to as the diesel cut text. It can optionally be restricted by fractionation or by varying the severity of the oligomerization unit (3) to a distillation range cut of between 150 ° C and 310 ° C, called kerosene.

On produit par ailleurs en sortie de l'oligomérisation (3) une fraction essence de point d'ébullition inférieur à 150°C en quantité moindre que le naphta léger de départ, et ayant de surcroît un indice d'octane amélioré, voir très amélioré quand on utilise l'unité optionnelle de séparation normales/isoparaffines (1).Furthermore, at the output of the oligomerization (3), a gasoline fraction having a boiling point of less than 150 ° C. is produced in a smaller quantity than the light naphtha starting, and having, in addition, an improved octane number, or even a much improved one. when using the optional separation unit normal / isoparaffins (1).

Il est possible de traiter simultanément dans l'unité d'oligomérisation (3) toute coupe oléfinique de la raffinerie allant de C3 à C10 (notée ES), par exemple les coupes oléfiniques issues d'une unité de craquage catalytique (notée en abrégé FCC), ou d'une unité de vapocraquage, ou encore d'une unité de coquéfaction ou de viscoréduction ou encore issue d'une unité Fischer Tropsch.It is possible to simultaneously treat in the oligomerization unit (3) any olefinic cut from the refinery from C3 to C10 (denoted by ES), for example olefinic cuts from a catalytic cracking unit (abbreviated as FCC). ), or a unit of steam cracking, or a unit of coquéfaction or visbreduction or from a Fischer Tropsch unit.

La coupe diesel ou kérosène (F3) issue de l'unité d'oligomérisation (3) est envoyée dans une étape d'hydrogénation (4), qui permet d'obtenir selon le système catalytique utilisé un excellent carburant kérosène ou une coupe diesel de nombre de cétane supérieur à 45 ne contenant ni soufre, ni poly aromatiques, et ayant une teneur en aromatiques inférieure à 10 %.The diesel or kerosene fraction (F3) derived from the oligomerization unit (3) is sent to a hydrogenation stage (4), which makes it possible to obtain, depending on the catalytic system used, an excellent kerosene fuel or a diesel fuel cut. cetane number greater than 45 containing neither sulfur nor aromatic poly, and having an aromatic content of less than 10%.

Une partie de l'hydrogène produit à l'étape (2) peut servir d'appoint à l'étape (4) d'hydrogénation.Part of the hydrogen produced in step (2) can serve as a booster to the hydrogenation step (4).

La présente invention permet de traiter simultanément dans l'unité d'hydrogénation (4) toute coupe de point d'ébullition supérieur à 150 °C, et préférentiellement compris entre 150° et 380°, provenant de la raffinerie (notée F7), par exemple des coupes directement issues de l'unité de distillation atmosphérique du brut, ou issues d'une unité de craquage catalytique (notée en abrégé FCC), ou encore issues d'unité d'hydrocraquage ou issues d'une unité de réformage catalytique des essences, de manière à en hydrogéner les aromatiques (en plus des oléfines) avec une incidence bénéfique sur la qualité du kérosène résultant (amélioration du point de fumée) ou du diesel résultant (amélioration de l'indice de cétane).The present invention makes it possible to simultaneously treat in the hydrogenation unit (4) any section with a boiling point greater than 150 ° C., and preferably between 150 ° and 380 °, coming from the refinery (denoted F7), by examples of the cuts directly from the atmospheric distillation unit of the crude, or from a catalytic cracking unit (abbreviated FCC), or from hydrocracking unit or from a catalytic reforming unit gasolines (in addition to olefins) with a beneficial effect on the quality of the resulting kerosene (improvement of the smoke point) or the resulting diesel (improvement of the cetane number).

L'unité d'hydrogénation (4) utilise de préférence une technologie travaillant à basse température, principalement en phase liquide, permettant une économie d'investissement et une amélioration des performances en terme de cétane de la coupe diesel par rapport à des procédés conventionnels d'hydrotraitement opérant en phase gazeuse. Néanmoins si une telle unité d'hydrotraitement conventionnelle est disponible sur le site, elle peut être utilisée pour réaliser l'étape (4) d'hydrogénation.The hydrogenation unit (4) preferably uses a low-temperature technology, mainly in the liquid phase, which allows a saving in investment and an improvement of the cetane performance of the diesel fraction compared to conventional methods of hydrotreatment operating in the gas phase. Nevertheless, if such a conventional hydrotreating unit is available on the site, it can be used to carry out the hydrogenation step (4).

Dans le cas d'une unité d'hydrogénation (4) faisant appel à la technologie basse température et phase liquide, la teneur en soufre de la charge à l'unité d'hydrogénation sera inférieure à 5 ppm poids, et de manière préférée inférieure à 1 ppm poids.In the case of a hydrogenation unit (4) using low temperature and liquid phase technology, the sulfur content of the feedstock to the hydrogenation unit will be less than 5 ppm by weight, and preferably lower at 1 ppm weight.

Les caractéristiques de la coupe diesel améliorée et débarrassée de soufre produite en utilisant des zéolithes dans l'unité d'oligomérisation (3) sont les suivantes:

  • point 95% vol ASTM D86 inférieur à 360°C
  • nombre de cétane supérieur à 45
  • point d'éclair supérieur à 55°C
  • teneur en polyaromatiques inférieure à 5% volume.
The characteristics of the improved and sulfur-free diesel cut produced using zeolites in the oligomerization unit (3) are as follows:
  • point 95% vol ASTM D86 less than 360 ° C
  • cetane number greater than 45
  • flash point above 55 ° C
  • polyaromatic content less than 5% volume.

Les caractéristiques de la coupe kérosène améliorée et débarrassée de soufre produite en utilisant des catalyseurs acides non zéolithiques tels que décrits précédemment dans l'unité d'oligomérisation (3), sont les suivantes :

  • point final ASTM D86 inférieure à 300°C
  • point de fumée supérieur à 30 mm
  • point de disparition des cristaux inférieure à -60°C
  • point d'éclair supérieur à 38°C.
The characteristics of the improved and sulfur-free kerosene cut produced using non-zeolitic acid catalysts as previously described in the oligomerization unit (3) are as follows:
  • end point ASTM D86 less than 300 ° C
  • smoke point greater than 30 mm
  • point of disappearance of crystals less than -60 ° C
  • flash point above 38 ° C.

De manière plus précise, la présente invention peut se définir comme un procédé de production de carburants kérosène et diesel et de coproduction d'hydrogène à partir d'une charge insaturée légère (F1) de nombre d'atomes de carbone compris entre C3 et C7 et constituée :

  1. a) d'une coupe naphta léger (NL) à nombre d'atome de carbone allant de 5 à 7 provenant d'unités de distillation primaire, d'hydrocracking ou d'unité Fischer Tropsch, d'intervalle de distillation compris entre 30°C et 120°C, ladite coupe naphta léger étant préalablement hydrotraitée ou débarrassée des composées oxygénés, azotés, et soufrés et
  2. b) d'une coupe en C3 /C4 (dite "LPG") présente en proportion quelconque, ledit procédé comprenant la suite d'étapes suivantes :
    • une étape de séparation (1) des normales et iso paraffines, faisant appel à un tamis moléculaire à base de zéolithes alcalines à petits pores tels que celles dénommées 5A. permettant de récupérer un premier effluent (F1)" essentiellement constitué de normales paraffines envoyé à l'étape de déshydrogénation (2) et un second effluent (F8) essentiellement constitué d'iso paraffines qui est envoyé au pool essence ou valorisé sous forme de naphta pétrochimique,
    • une étape de déshydrogénation (2) des normales paraffines issues de l'étape de séparation précédente opérant à pression comprise entre 1,3 et 5 bars absolus, et à une température comprise entre 400°C et 700 °C, de préférence comprise entre 500°C et 600°C, et faisant appel à un catalyseur de déshydrogénation constitué d'un métal noble du groupe VIII choisi parmi le platine, l'iridium, le rhodium, et d'au moins un promoteur sélectionné dans le groupe constitué par l'étain, le germanium, le plomb, le gallium, l'indium, le thallium, ledit métal noble et ledit promoteur étant déposés sur un support inerte choisi dans le groupe formé par la silice, l'alumine, l'oxyde de titane, la silice magnésie, ou un mélange quelconque desdits éléments, ladite étape de déshydrogénation (2) permettant de récupérer un effluent (F2) essentiellement constitué d'oléfines à nombre d'atomes de carbone compris entre 3 et 7, dit effluent oléfinique (F2),
    • une étape d'oligomérisation (3) de tout ou partie de l'effluent oléfinique (F2) obtenu à l'étape (2) dans une unité d'oligomérisation (3) faisant appel à un catalyseur d'oligomérisation choisi dans le groupe formé par l'acide phosphorique solide, les résines échangeuses d'ions, les silices alumines ou les silico aluminates tels que les zéolithes pures ou supportées sur alumine, la dite étape d'oligomérisation (3) permettant de récupérer un effluent (F3) majoritairement constitué d'oléfines allant de
    • C10 à C25, et un effluent "essence" (F4) constitué majoritairement de paraffines allant de C5 à C10 qui est séparé de l'effluent (F3) par distillation et recyclé à l'entrée de l'unité d'oligomérisation (3),
une étape d'hydrogénation (4) de l'effluent oléfinique (F3) issu de l'étape d'oligomérisation (3) réalisée en phase liquide dans un ou plusieurs réacteurs à lit fixe, à des températures comprises entre 50°C et 300 °C, et de préférence entre 100°C et 200°C, et sous des pressions de 5 à 50 bars, et de préférence de 10 à 30 bars (1 bar = 105 Pascals), et faisant appel à un catalyseur d'hydrogénation à base d'un métal choisi dans le groupe formé par le platine, le palladium ou le nickel déposés sur un support inerte tel que la silice ou l'alumine, ou tout mélange de ces deux composants, ladite étape d'hydrogénation permettant de récupérer un effluent (F6) qui est une coupe carburant diesel ou kérosène majoritairement paraffinique.More precisely, the present invention can be defined as a process for producing kerosene and diesel fuels and for co-producing hydrogen from a light unsaturated filler (F1) having a number of carbon atoms between C3 and C7. and constituted:
  1. (a) a 5 to 7 carbon numbered light naphtha (NL) cut from primary distillation units, hydrocracking units or Fischer Tropsch units, distillation range of 30 ° C and 120 ° C, said light naphtha cut being previously hydrotreated or freed of oxygenated compounds, nitrogen, and sulfur and
  2. b) a C3 / C4 ("LPG") cut in any proportion, said process comprising the following sequence of steps:
    • a separation step (1) of the normal and iso paraffins, using a molecular sieve based on small pore alkaline zeolites such as those referred to as 5A. for recovering a first effluent (F1) "essentially consisting of normal paraffins sent to the dehydrogenation step (2) and a second effluent (F8) consisting essentially of iso paraffins which is sent to the gasoline pool or recovered in the form of naphtha petrochemical,
    • a dehydrogenation step (2) of normal paraffins resulting from the preceding separation step operating at a pressure of between 1.3 and 5 bars absolute, and at a temperature of between 400 ° C. and 700 ° C., preferably between 500 ° C. and 500 ° C .; ° C and 600 ° C, and using a dehydrogenation catalyst consisting of a noble metal group VIII selected from platinum, iridium, rhodium, and at least one promoter selected from the group consisting of tin, germanium, lead, gallium, indium, thallium, said noble metal and said promoter being deposited on an inert support selected from the group consisting of silica, alumina, titanium oxide, silica magnesia, or any mixture of said elements, said dehydrogenation step (2) making it possible to recover an effluent (F2) consisting essentially of olefins with a number of carbon atoms of between 3 and 7, referred to as olefinic effluent (F2) ,
    • an oligomerization step (3) of all or part of the olefinic effluent (F2) obtained in step (2) in an oligomerization unit (3) using an oligomerization catalyst chosen from the group formed by solid phosphoric acid, ion exchange resins, silica aluminas or silico aluminates such as pure or supported zeolites on alumina, said oligomerization step (3) for recovering an effluent (F3) consisting mainly of olefins from
    • C10 to C25, and a "gasoline" effluent (F4) consisting mainly of paraffins from C5 to C10 which is separated from the effluent (F3) by distillation and recycled to the input of the oligomerization unit (3) ,
a step of hydrogenation (4) of the olefinic effluent (F3) resulting from the oligomerization step (3) carried out in the liquid phase in one or more fixed-bed reactors, at temperatures of between 50 ° C. and 300 ° C. ° C, and preferably between 100 ° C and 200 ° C, and at pressures of 5 to 50 bar, and preferably 10 to 30 bar (1 bar = 10 5 Pascals), and using a catalyst of hydrogenation based on a metal selected from the group consisting of platinum, palladium or nickel deposited on an inert support such as silica or alumina, or any mixture of these two components, said hydrogenation step for recovering an effluent (F6) which is a diesel fuel cut or kerosene predominantly paraffinic.

Dans une première variante du procédé selon l'invention, le catalyseur utilisé dans l'étape de déshydrogénation (2) est constitué de platine et d'étain déposé sur une alumine neutralisée par un alcalin.In a first variant of the process according to the invention, the catalyst used in the dehydrogenation step (2) consists of platinum and tin deposited on an alumina neutralized with an alkali.

Dans une autre variante du procédé selon l'invention, l'hydrogène utilisé lors de l'étape (4) d'hydrogénation provient au moins en partie de l'hydrogène généré à l'étape (2).In another variant of the process according to the invention, the hydrogen used during the hydrogenation step (4) comes at least in part from the hydrogen generated in step (2).

Le procédé selon l'invention peut être plus particulièrement orienté vers la production de carburant diesel à haut indice de cétane. Dans ce cas, la charge (F1) est introduite en amont de l'unité de déshydrogénation (2) dans une unité de séparation des normales et iso paraffines (1), faisant appel à un tamis moléculaire à base de zéolithes alcalines à petits pores tels que celles dénommées 5A, permettant de récupérer un premier effluent (F1)" essentiellement constitué de normales paraffines envoyé à l'étape de déshydrogénation (2) et un second effluent (F8) essentiellement constitué d'iso paraffines qui est envoyé au pool essence ou valorisé sous forme de naphta pétrochimique,

  • l'étape de déshydrogénation (2) étant réalisée à pression comprise entre 1,3 et 5 bars absolus, et à une température comprise entre 400°C et 700°C, et de préférence comprise entre 500°C et 600 °C, et faisant appel à un catalyseur de déshydrogénation constitué d'un métal noble du groupe VIII choisi parmi le platine, l'iridium, le rhodium, et d'un promoteur sélectionné dans le groupe constitué par l'étain, le germanium, le plomb, le gallium, l'indium, le thallium, ledit métal noble et ledit promoteur étant déposés sur un support inerte choisi dans le groupe formé par la silice, l'alumine, l'oxyde de titane, la silice magnésie, ou un mélange quelconque desdits éléments,
  • l'étape d'oligomérisation (3) étant réalisée sur catalyseur zéolithique à des températures comprises entre 150°C et 500°C et préférentiellement entre 200°C et 350°C, et sous des pressions de 10 à 100 bars, et préférentiellement de 20 à 65 bars,
  • l'étape d'hydrogénation (4) étant réalisée en phase liquide, à des températures comprises entre 50°C et 300 °C, et de préférence entre 100°C et 200°C, et sous des pressions de 5 bars à 50 bars, et de préférence de 10 bars à 30 bars, et faisant appel à un catalyseur d'hydrogénation à base d'un métal choisi dans le groupe formé par le platine, le palladium ou le nickel déposés sur un support inerte tel que la silice ou l'alumine, ou tout mélange de ces deux composants.
The process according to the invention can be more particularly oriented towards the production of diesel fuel with a high cetane number. In this case, the charge (F1) is introduced upstream of the dehydrogenation unit (2) into a separation unit of normal and iso-paraffins (1), using a molecular sieve based on small pore alkaline zeolites. such as those designated 5A, for recovering a first effluent (F1) "essentially consisting of normal paraffins sent to the dehydrogenation stage (2) and a second effluent (F8) consisting essentially of iso paraffins which is sent to the gasoline pool or recovered as petrochemical naphtha,
  • the dehydrogenation step (2) being carried out at a pressure of between 1.3 and 5 bars absolute, and at a temperature of between 400 ° C. and 700 ° C., and preferably between 500 ° C. and 600 ° C., and using a dehydrogenation catalyst consisting of a noble metal of group VIII selected from platinum, iridium, rhodium, and a promoter selected from the group consisting of tin, germanium, lead, gallium, indium, thallium, said noble metal and said promoter being deposited on an inert support selected from the group formed by silica, alumina, titanium oxide, silica magnesia, or any mixture of said elements ,
  • the oligomerization step (3) being carried out on a zeolitic catalyst at temperatures of between 150 ° C. and 500 ° C. and preferably between 200 ° C. and 350 ° C., and under pressures of 10 to 100 bar, and preferably of 20 to 65 bars,
  • the hydrogenation step (4) being carried out in the liquid phase, at temperatures of between 50 ° C. and 300 ° C., and preferably between 100 ° C. and 200 ° C., and at pressures of 5 bars at 50 bars. , and preferably from 10 bar to 30 bar, and using a hydrogenation catalyst based on a metal selected from the group formed by platinum, palladium or nickel deposited on an inert support such as silica or alumina, or any mixture of these two components.

Dans une autre variante de la présente invention, le procédé selon l'invention peut être plus particulièrement orienté vers la production de carburant kérosène aux spécifications JET A1. Dans ce cas, l'étape d'oligomérisation (3) est réalisée sur résines à des températures comprises entre 20°C et 200°C, et préférentiellement entre 70°C et 180°C, et sous des pressions de 10 bars à 100 bars, et préférentiellement de 30 bars à 65 bars.In another variant of the present invention, the method according to the invention may be more particularly oriented towards the production of kerosene fuel with JET A1 specifications. In this case, the oligomerization step (3) is carried out on resins at temperatures of between 20 ° C. and 200 ° C., and preferably between 70 ° C. and 180 ° C., and under pressures of 10 bar to 100 ° C. bars, and preferably from 30 bars to 65 bars.

Toujours dans le cas d'un procédé orienté vers la production de kérosène aux spécifications JET A1, l'étape d'oligomérisation (3) peut être réalisée sur silice alumine à des températures comprises entre 20°C et 300°C, et préférentiellement entre 120°C et 250°C, et sous des pressions de 10 bars à 100 bars, et préférentiellement de 20 bars à 65 bars.Still in the case of a process oriented towards the production of kerosene to JET A1 specifications, the oligomerization step (3) can be carried out on silica-alumina at temperatures between 20 ° C and 300 ° C, and preferably between 120 ° C and 250 ° C, and at pressures of 10 bar to 100 bar, and preferably 20 bar to 65 bar.

Le procédé selon l'invention peut encore se particulariser par l'introduction à l'étape d'oligomérisation (3) d'au moins une coupe essence (ES) et/ou d'au moins une coupe contenant des C3 et des C4 provenant d'une unité de craquage catalytique (FCC), de cokéfaction, de viscoréduction, d'une unité de synthèse Fischer Tropsch ou d'une unité de vapocraquage qui est traitée en mélange avec l'effluent (F2) de l'étape de déshydrogénation (2).The process according to the invention can be further characterized by introducing into the oligomerization step (3) at least one gasoline cut (ES) and / or at least one cut containing C3 and C4 from a catalytic cracking unit (FCC), a coker, a visbreaking unit, a Fischer Tropsch synthesis unit or a steam cracking unit which is treated in admixture with the effluent (F2) of the dehydrogenation stage (2).

Le procédé selon l'invention peut également se particulariser par l'introduction à l'étape d'hydrogénation (4) d'une coupe (F7) 150 °C+ contenant des teneurs en soufre inférieures à 5 ppm (préférentiellement inférieur à 1 ppm), par exemple des coupes directement issues de l'unité de distillation atmosphérique du brut, ou issues de l'unité de craquage catalytique (FCC), ou encore issues d'unité d'hydrocraquage ou du reformage catalytique.The process according to the invention can also be characterized by the introduction in the hydrogenation step (4) of a section (F7) 150 ° C + containing sulfur contents of less than 5 ppm (preferably less than 1 ppm). , for example cuts directly from the atmospheric distillation unit of the crude, or from the catalytic cracking unit (FCC), or from hydrocracking unit or catalytic reforming.

Dans une autre variante du procédé selon l'invention, l'étape de déshydrogénation (2) et/ou l'étape d'oligomérisation (3) peuvent fonctionner en mode régénératif ou semi régénératif. La notation et/ou signifie que l'une ou l'autre des étapes (2) ou (3), ou les deux étapes (2) et (3) sont concernées par la mise en oeuvre en mode régénératif ou semi régénératif.In another variant of the process according to the invention, the dehydrogenation step (2) and / or the oligomerization step (3) can operate in regenerative or semi-regenerative mode. The notation and / or means that one or the other of the steps (2) or (3), or the two steps (2) and (3) are concerned by the implementation in regenerative or semi-regenerative mode.

Enfin dans une variante du procédé de production de carburants kérosène et diesel selon la présente invention, l'hydrogène produit par l'étape de déshydrogénation (2) peut être envoyé, au moins en partie, vers les opérations unitaires consommatrices de la raffinerie éventuellement après passage dans unité de purification utilisant une membrane ou un tamis (PSA).Finally, in a variant of the process for producing kerosene and diesel fuels according to the present invention, the hydrogen produced by the dehydrogenation step (2) may be sent, at least in part, to the unit operations that consume the refinery, possibly after passage in purification unit using a membrane or sieve (PSA).

DESCRIPTION DETAILLEE DE L'INVENTIONDETAILED DESCRIPTION OF THE INVENTION

La présente description fait référence à la figure 1 qui représente le schéma du procédé dans laquelle les unités et flux marqués en pointillé sont optionnelles.This description refers to the figure 1 which represents the scheme of the process in which the units and flows marked in dashed lines are optional.

Le procédé selon la présente invention utilise comme charge un naphta léger (NL) ayant un intervalle de distillation généralement compris entre 30°C et 120°C, auquel on peut rajouter une proportion quelconque de coupe C3 et/ou C4 dite coupe "LPG".The process according to the present invention uses as feedstock a light naphtha (NL) having a distillation range generally between 30 ° C and 120 ° C, to which can be added any proportion of C3 and / or C4 cut called "LPG" cut. .

On entend par naphta léger une coupe pétrolière ayant généralement de 3 à 10 atomes de carbone, de manière préférée de 4 à 7 atomes de carbone, et composée de diverses familles chimiques, principalement des paraffines ainsi qu'une certaine proportion d'aromatiques et d'oléfines.The term light naphtha is understood to mean a petroleum cut having generally from 3 to 10 carbon atoms, preferably from 4 to 7 carbon atoms, and composed of various chemical families, mainly paraffins and a certain proportion of aromatics and dicarboxylic acids. olefins.

On entend par coupe "LPG" une coupe ayant un intervalle de distillation de -40°C à +10°C, majoritairement constituée de propane et de butane ainsi qu'une certaine proportion d'oléfines.The term "LPG" is understood to mean a section having a distillation range of -40 ° C. to + 10 ° C., predominantly consisting of propane and butane and a certain proportion of olefins.

Le plus souvent la coupe "naphta léger" notée en abrégé (NL), provient de la distillation d'un naphta long (30°C - 200°C), préalablement désulfurée en vue de la production d'essence par reformage catalytique. Si nécessaire, on peut également utiliser directement un naphta léger provenant de la distillation directe du brut.Most often the cut "light naphtha" abbreviated (NL), comes from the distillation of a long naphtha (30 ° C - 200 ° C), previously desulfurized for the production of gasoline by catalytic reforming. If necessary, it is also possible to directly use a light naphtha coming from the direct distillation of the crude.

Dans ce cas, on procède à une étape de désulfuration et de déazotation dans une unité d'hydrotraitement (HDT) selon une technologie connue de l'homme du métier, de manière à éviter l'empoisonnement des catalyseurs intervenant dans les unités en aval.In this case, a desulfurization and denitrogenation step is carried out in a hydrotreatment unit (HDT) according to a technology known to those skilled in the art, so as to avoid the poisoning of the catalysts involved in the downstream units.

La coupe naphta léger additionnée de la coupe LPG, notée (F1), est alors envoyée dans une unité de séparation des normales et iso paraffines (1) faisant appel à un tamis moléculaire. Cette technologie bien connue de l'homme de l'art, utilise préférentiellement des zéolithes alcalines à petits pores tels que celles dénommées 5A qui permettent d'obtenir un mélange composé majoritairement de normales paraffines (F1)".The light naphtha section with the LPG cut, noted (F1), is then sent to a separation unit of the normal and iso paraffins (1) using a molecular sieve. This technology, well known to those skilled in the art, preferably uses small-pore alkaline zeolites such as those referred to as 5A which make it possible to obtain a mixture composed mainly of normal paraffins (F1) ".

Plus généralement, tout procédé permettant de produire une coupe enrichie en normales paraffines, tel que ceux utilisant des membranes ou des tamis moléculaires ou leurs combinaisons, peut être envisagé dans le cadre du présent procédé.More generally, any method for producing a paraffin enriched cut, such as those using membranes or molecular sieves or combinations thereof, may be contemplated within the context of the present process.

Le flux de paraffines ramifiées (F8) qui possède un indice d'octane amélioré par rapport au naphta léger entrant (NL), permet d'alimenter le pool essence.The branched paraffin stream (F8), which has an improved octane number relative to the incoming light naphtha (NL), is used to supply the gasoline pool.

La partie contenant majoritairement des molécules linéaires (F1)' est ensuite envoyée dans une unité de déshydrogénation (2) opérant à une pression comprise entre 2 bars et 20 bars absolus, de préférence comprise entre 1 bar et 5 bars (1 bar= 105 Pascals) absolus, et de manière encore plus préférée à la pression atmosphérique (à plus ou moins 0,5 bar près), et à une température comprise entre 400°C et 700 °C, de préférence comprise entre 500°C et 600°C.The part containing predominantly linear molecules (F1) 'is then sent to a dehydrogenation unit (2) operating at a pressure of between 2 bar and 20 bar absolute, preferably between 1 bar and 5 bar (1 bar = 10 5 Pascals) absolute, and even more preferably at atmospheric pressure (within plus or minus 0.5 bar), and at a temperature between 400 ° C and 700 ° C, preferably between 500 ° C and 600 ° vs.

Dans l'unité de déshydrogénation (2), Il peut être avantageux d'utiliser l'hydrogène comme diluant. Le rapport molaire hydrogène/ hydrocarbure est généralement compris entre 0,1 et 20, de préférence entre 0,5 et 10.In the dehydrogenation unit (2), it may be advantageous to use hydrogen as a diluent. The hydrogen / hydrocarbon molar ratio is generally between 0.1 and 20, preferably between 0.5 and 10.

Le débit massique de charge (F1) traitée par unité de masse de catalyseur est généralement compris entre 0,5 et 200 kg/(kg.heure).The mass flow rate of feed (F1) treated per unit mass of catalyst is generally between 0.5 and 200 kg / (kg.hour).

Les catalyseurs utilisés dans l'unité de déshydrogénation (2) sont généralement constitués d'un métal noble M du groupe VIII choisi dans le groupe formé par le platine, le palladium, l'iridium, et le rhodium, et au moins un promoteur sélectionné dans le groupe constitué par l'étain, le germanium, le plomb, le gallium, l'indium, le thallium.The catalysts used in the dehydrogenation unit (2) generally consist of a Group VIII noble metal M selected from the group consisting of platinum, palladium, iridium, and rhodium, and at least one selected promoter in the group consisting of tin, germanium, lead, gallium, indium, thallium.

Les catalyseurs de l'unité de déshydrogénation (2) peuvent contenir également un composé alcalin ou alcalino-terreux.The catalysts of the dehydrogenation unit (2) may also contain an alkaline or alkaline earth compound.

Le métal noble M et le promoteur sont déposés sur un support inerte choisi dans le groupe formé par la silice, l'alumine, l'oxyde de titane, la silice magnésie, ou un mélange quelconque desdits éléments.The noble metal M and the promoter are deposited on an inert support chosen from the group formed by silica, alumina, titanium oxide, silica magnesia, or any mixture of said elements.

Le catalyseur selon l'invention contient préférentiellement de 0,01% à 10 % poids, de manière plus préférée de 0,02% à 2 % poids, et de manière très préférée de 0,05% à 0,7 % poids d'au moins un métal noble M sélectionné dans le groupe constitué par le platine, le palladium, le rhodium et l'iridium. De préférence le métal M est du platine ou de palladium, et de manière très préférée du platine.The catalyst according to the invention preferably contains from 0.01% to 10% by weight, more preferably from 0.02% to 2% by weight, and very preferably from 0.05% to 0.7% by weight. at least one noble metal M selected from the group consisting of platinum, palladium, rhodium and iridium. Preferably the metal M is platinum or palladium, and very preferably platinum.

La teneur en promoteur est de préférence comprise entre 0,01% et 10% poids, de manière plus préférée entre 0,05% et 5% poids, et de manière très préférée entre 0,1% et 2% poids. Selon une variante préférée du procédé selon l'invention, le catalyseur de l'unité de déshydrogénation (2) peut avantageusement contenir à la fois du platine et de l'étain.The promoter content is preferably between 0.01% and 10% by weight, more preferably between 0.05% and 5% by weight, and very preferably between 0.1% and 2% by weight. According to a preferred variant of the process according to the invention, the catalyst of the dehydrogenation unit (2) can advantageously contain both platinum and tin.

Le composé alcalin est sélectionné dans le groupe constitué par le lithium, le sodium, le potassium, le rubidium et le césium. Le lithium, le sodium ou le potassium sont les alcalins préférés, et le lithium ou le potassium sont les alcalins encore plus préférés.The alkaline compound is selected from the group consisting of lithium, sodium, potassium, rubidium and cesium. Lithium, sodium or potassium are the preferred alkalis, and lithium or potassium are even more preferred alkalis.

La teneur en composé alcalin est de préférence comprise entre 0,05% et 10 % poids, de manière plus préférée comprise entre 0,1% et 5% poids, et de manière encore plus préférée comprise entre 0,15% et 2% poids.The content of alkaline compound is preferably between 0.05% and 10% by weight, more preferably between 0.1% and 5% by weight, and even more preferably between 0.15% and 2% by weight. .

Le composé alcalino-terreux est sélectionné dans le groupe constitué par le magnésium, le calcium, le strontium ou le baryum. Le magnésium ou le calcium sont les alcalino-terreux préférés et le magnésium est l'alcalino-terreux le plus préféré.The alkaline earth compound is selected from the group consisting of magnesium, calcium, strontium or barium. Magnesium or calcium are the preferred alkaline earths and magnesium is the most preferred alkaline earth metal.

La teneur en composé alcalino-terreux est de préférence comprise entre 0,05% et 10% poids, de manière plus préférée comprise entre 0,1% et 5 % poids, et de manière encore plus préférée comprise entre 0,15% et 2 % poids.The content of alkaline earth compound is preferably between 0.05% and 10% by weight, more preferably between 0.1% and 5% by weight, and even more preferably between 0.15% and 2%. % weight

Le catalyseur de l'unité de déshydrogénation (2) peut en outre contenir éventuellement, au moins un halogène ou composé halogéné dans des proportions de l'ordre de 0,1% à 3% poids.The catalyst of the dehydrogenation unit (2) may further optionally contain at least one halogen or halogenated compound in proportions of the order of 0.1% to 3% by weight.

Il peut aussi éventuellement contenir un métalloïde tel que le soufre dans des proportions de l'ordre de 0,1% à 2 % pds du catalyseur.It may also optionally contain a metalloid such as sulfur in proportions of the order of 0.1% to 2% by weight of the catalyst.

Selon les coupes envoyées à l'unité de déshydrogénation (2), on peut obtenir des productions d'hydrogène (H2) comprises entre 1 et 3 tonnes pour 100 tonnes de charge.According to the cuts sent to the dehydrogenation unit (2), it is possible to obtain hydrogen (H2) productions of between 1 and 3 tons per 100 tons of charge.

Il est possible dans le cadre de la présente invention de traiter simultanément dans l'unité de déshydrogénation (2) toute coupe majoritairement paraffinique plus légère que les C5, et de manière préférée, des coupes butane et propane.It is possible in the context of the present invention to simultaneously treat in the dehydrogenation unit (2) any predominantly paraffinic fraction lighter than the C5, and preferably, butane and propane cuts.

Quand on travaille à forte proportion de propane et butane, on peut être amené à injecter quelques dizaines de ppm de soufre, préférentiellement sous forme DMDS.When working with a high proportion of propane and butane, it may be necessary to inject a few tens of ppm of sulfur, preferably in DMDS form.

On récupère alors le soufre sous forme d'hydrogène sulfuré en tête de la colonne de stabilisation avec les gaz craqués.The sulfur in the form of hydrogen sulphide is then recovered at the top of the stabilization column with the cracked gases.

Le catalyseur de l'unité de déshydrogénation (2) se désactivant par dépôt de carbone à la surface dudit catalyseur, dépôt généralement appelé "coke", il est nécessaire de le régénérer par brûlage de ce coke. Pour assurer un fonctionnement continu de l'unité de déshydrogénation (2), il est alors nécessaire de disposer d'au moins deux réacteurs, un des réacteurs étant en phase de réaction, l'autre réacteur en phase de régénération. Cependant cette technologie, bien connue de l'homme du métier, peut être très coûteuse, et l'on peut aussi utiliser une technologie semi régénérative ou à régénération continue comme celle bien connue dans le reformage catalytique qui consiste à transférer de manière "batch" ou continu le catalyseur du réacteur en opération dans une autre capacité dans laquelle est réalisée la régénération du catalyseur par rulage du coke.The catalyst of the dehydrogenation unit (2) is deactivated by deposition of carbon on the surface of said catalyst, generally called "coke" deposit, it is necessary to regenerate it by burning this coke. To ensure continuous operation of the dehydrogenation unit (2), it is then necessary to have at least two reactors, one of the reactors being in the reaction phase, the other reactor in the regeneration phase. However, this technology, well known to those skilled in the art, can be very expensive, and one can also use a semi-regenerative or continuous regeneration technology such as that well known in catalytic reforming which consists in transferring in a "batch" manner. or continuously the catalyst of the reactor operating in another capacity in which is carried out the regeneration of the catalyst by coke roping.

Un avantage important de la technologie de régénération continue est qu'elle permet de réduire fortement l'inventaire de catalyseur, et donc de réduire l'investissement initial. Un deuxième avantage est qu'elle permet de maintenir constamment le catalyseur dans son état d'activité maximale.An important advantage of the continuous regeneration technology is that it greatly reduces the catalyst inventory, and thus reduces the initial investment. A second advantage is that it keeps the catalyst constantly in its state of maximum activity.

Dans le cas de la déshydrogénation des paraffines, on peut ainsi maintenir leur conversion en oléfines à un niveau très proche ou égal à la limite permise par la thermodynamique. Ainsi pour les paraffines de C5 à C7 une conversion moyenne en oléfines de 45% à 80 % est accessible.In the case of the dehydrogenation of paraffins, it is thus possible to maintain their conversion to olefins at a level very close to or equal to the limit allowed by thermodynamics. Thus for paraffins C 5 to C 7 an average conversion to olefins of 45% to 80% is accessible.

L'effluent oléfinique (F2) de l'unité de déshydrogénation (2) est ensuite envoyé vers une unité d'oligomérisation (3) permettant de transformer les oléfines de C5 à C7 en oléfines plus lourdes à savoir de C10 à C24 environ.The olefinic effluent (F2) from the dehydrogenation unit (2) is then sent to an oligomerization unit (3) for converting the C5 to C7 olefins into heavier olefins, namely C10 to C24.

Il est possible dans le cadre de la présente invention de traiter simultanément dans l'unité d'oligomérisation (3) toute coupe oléfinique (ES) de la raffinerie allant de C3 à C10, par exemple une coupe essence issue du craquage catalytique (FCC), une coupe essence issue d'une unité de vapocraquage, une essence de coquéfaction ou de viscoréduction, ou encore une essence de Fischer Tropsch.It is possible in the context of the present invention to simultaneously treat in the oligomerization unit (3) any olefinic cut (ES) of the refinery ranging from C3 to C10, for example a gasoline cut after catalytic cracking (FCC). , a petrol cut from a steam-cracking unit, a gasoline of co-filtration or visbreaking, or a Fischer Tropsch gasoline.

Tout type de catalyseur acide choisi dans le groupe formé par l'acide phosphorique imprégné sur silice de type SPA (acide phosphorique supporté), les résines échangeuses d'ions, les silices alumines ou les silico aluminates telles que les zéolithes pures ou supportées sur support alumine, peut être envisagé pour l'étape d'oligomérisation (3).

  1. a) Les catalyseurs de type SPA produisent majoritairement des essences et sont de fait mal adaptés à la production massive de distillats. Ils opèrent dans des gammes de températures comprises entre 100°C et 300 °C, et de préférence entre 160°C et 250 °C à des pressions comprises entre 20 et 100 bars et de préférence entre 30 et 65 bars.
  2. b) Quand on veut maximiser les oligomères à nombre d'atomes de carbone supérieur à 10, on utilise préférentiellement des résines échangeuses d'ion ou des silices alumines ou des zéolithes.
    Seules les zéolithes qui permettent grâce à leur porosité particulière d'obtenir des oléfines lourdes linéaires ou peu branchées sont adaptées à la production de diesel de haute qualité, c'est à dire, après hydrogénation, ayant un nombre de cétane supérieur à 45.
    Avec l'utilisation d'un catalyseur zéolithique, l'unité d'oligomérisation (3) est opérée à des températures comprises entre 150°C et 500 °C, et de préférence entre 200°C et 350°C, et à des pressions comprises entre 20 et 100 bars, et de préférence entre 30 et 65 bars.
  3. c) Il est aussi possible d'obtenir des productions importantes de distillats en opérant sur des catalyseurs de type résine ou silice alumine. Dans ce cas, le cétane de la fraction diesel reste faible, inférieur à 35. On vise alors à valoriser la coupe distillat moyen essentiellement sous forme de kérosène qui présente alors d'excellentes propriétés compatibles avec la norme JET A1, aussi bien en termes de propriétés à froid que de point de fumée.
    Les catalyseurs de types résines sont choisis pour leur bonne tenue mécanique dans des gammes de température de 20°C à 250°C, et de préférence entre 70°C et 180°C, à des pressions comprises entre 20 bars et 100 bars, de préférence entre 30 bars et 65 bars.
    Ces catalyseurs de type résines, peu coûteux et non régénérables, présentent l'avantage d'avoir des durées de cycles acceptables dans une opération en lit fixe car ils sont moins sensibles aux contaminants que les zéolithes et les silices alumines.
    Par rapport aux résines, les catalyseurs de type silice alumine présentent l'avantage d'être régénérables de sorte que, malgré leur coûts supérieurs aux résines, des économies substantielles sont réalisés en terme de consommation de catalyseur.
    On minimise les opérations de chargement et déchargement en utilisant une régénération in situ.
  4. d) Avec l'utilisation d'un catalyseur silice alumine, l'unité d'oligomérisation (3) est opérée à des températures comprises entre 20°C et 300°C, et préférentiellement entre 120°C et 250°C, et sous des pressions de 10 bars à 100 bars, et préférentiellement de 20 bars à 65 bars.
Any type of acid catalyst chosen from the group formed by phosphoric acid impregnated on silica of the SPA type (phosphoric acid supported), the exchange resins of ions, silica aluminas or silico aluminates such as pure zeolites or supported on alumina support, can be envisaged for the oligomerization step (3).
  1. a) SPA type catalysts mainly produce gasoline and are therefore poorly suited to the production of distillates. They operate in temperature ranges between 100 ° C and 300 ° C, and preferably between 160 ° C and 250 ° C at pressures between 20 and 100 bar and preferably between 30 and 65 bar.
  2. b) When it is desired to maximize the oligomers with a number of carbon atoms greater than 10, ion exchange resins or silica aluminas or zeolites are preferably used.
    Only zeolites which, thanks to their particular porosity, make it possible to obtain linear or slightly branched heavy olefins, are suitable for the production of high quality diesel, that is to say, after hydrogenation, having a cetane number greater than 45.
    With the use of a zeolite catalyst, the oligomerization unit (3) is operated at temperatures between 150 ° C and 500 ° C, and preferably between 200 ° C and 350 ° C, and at pressures between 20 and 100 bar, and preferably between 30 and 65 bar.
  3. c) It is also possible to obtain significant production of distillates by operating on catalysts of the resin or silica alumina type. In this case, the cetane of the diesel fraction remains low, less than 35. It is then aimed at upgrading the middle distillate cut essentially in the form of kerosene, which then has excellent properties compatible with the JET A1 standard, both in terms of cold properties than smoke point.
    The resins type catalysts are chosen for their good mechanical strength in temperature ranges of 20 ° C. to 250 ° C., and preferably between 70 ° C. and 180 ° C., at pressures of between 20 bars and 100 bars, preferably between 30 bars and 65 bars.
    These resins catalysts, inexpensive and non-regenerable, have the advantage of having acceptable cycle times in a fixed bed operation because they are less sensitive to contaminants than zeolites and silica aluminas.
    Compared with the resins, the silica-alumina type catalysts have the advantage of being regenerable so that, despite their higher costs than the resins, substantial savings are made in terms of catalyst consumption.
    Loading and unloading operations are minimized by using in situ regeneration.
  4. d) With the use of a silica-alumina catalyst, the oligomerization unit (3) is operated at temperatures between 20 ° C and 300 ° C, and preferably between 120 ° C and 250 ° C, and under pressures from 10 bar to 100 bar, and preferably from 20 bar to 65 bar.

L'effluent (F3) de l'unité d'oligomérisation (3) est composé d'un mélange d'oligomères oléfiniques de C10 à C24 et d'une fraction légère préférentiellement de C5 à C10 contenant les oléfines C5 à C7 non converties, d'une fraction des paraffines initiales C5 à C7 de la charge, et des produits résultant de réactions de craquage et recombinaison qu'il est facile de séparer par simple distillation.The effluent (F3) of the oligomerization unit (3) is composed of a mixture of olefinic oligomers of C 10 to C 24 and a light fraction preferably of C 5 to C 10 containing unconverted C 5 to C 7 olefins, a fraction of the initial C 5 to C 7 paraffins of the feed, and products resulting from cracking and recombination reactions which are easy to separate by simple distillation.

Pour contrôler l'exothermicité de la réaction d'oligomérisation (3), et favoriser la production de fraction lourde, l'effluent de réaction ou la fraction essence préférentiellement de C5 à C10 avec les LPG résiduel, (noté F4) est recyclée à l'entrée de l'unité d'oligomérisation (3).To control the exothermicity of the oligomerization reaction (3), and to promote the production of heavy fraction, the reaction effluent or the gasoline fraction preferentially C5 to C10 with the residual LPG, (noted F4) is recycled at the same time. entry of the oligomerization unit (3).

De façon préférée, on pourra recycler à l'unité de déshydrogénation (2) une fraction (F5) plus légère allant de C5 à C7 avec les LPG résiduels, afin de convertir totalement ou quasi totalement les normales paraffines en oléfines, et ainsi maximiser le rendement en carburant diesel par rapport à la charge de départ.Preferably, it will be possible to recycle to the dehydrogenation unit (2) a lighter fraction (F5) ranging from C5 to C7 with the residual LPG, in order to totally or almost totally convert the normal paraffins into olefins, and thus maximize the diesel fuel efficiency relative to the starting load.

Pour assurer un fonctionnement continu de l'unité de d'oligomérisation, il est alors nécessaire de disposer d'au moins deux réacteurs ou train de réacteurs, un des réacteurs (ou un des train de réacteurs) étant en phase de réaction, l'autre réacteur (ou un des train de réacteurs) étant en phase de régénération.To ensure continuous operation of the oligomerization unit, it is then necessary to have at least two reactors or reactor train, one of the reactors (or one of the reactor train) being in the reaction phase, the another reactor (or one of the reactor train) being in the regeneration phase.

Avec l'utilisation de zéolithes pures ou sur support alumine, on peut aussi mettre en oeuvre une technologie semi régénérative ou à régénération continue comme celle bien connue dans le reformage catalytique des essences qui consiste à transférer de manière "batch" ou continu le catalyseur contenu dans un ou plusieurs réacteurs en opération dans une autre capacité dans laquelle est réalisée la régénération du catalyseur par combustion du coke déposé.With the use of pure zeolites or alumina support, it is also possible to implement a semi-regenerative or continuously regenerative technology such as is well known in the catalytic reforming of gasolines which consists of transferring "batch" or continuous the catalyst contained in one or more reactors in operation in another capacity in which the regeneration of the catalyst is carried out by combustion of the deposited coke.

De manière optionnelle, les sections de régénération semi continue ou continue de l'unité de déshydrogénation (2) et de l'unité d'oligomérisation (3) pourront être intégrées, c'est à dire utiliser des équipements communs.Optionally, the semi-continuous or continuous regeneration sections of the dehydrogenation unit (2) and the oligomerization unit (3) can be integrated, that is to say use common equipment.

Le mélange d'oléfines lourdes (F3) issues de l'unité d'oligomérisation (3) est ensuite envoyé dans une unité d'hydrogénation (4). Pour ce faire, on utilise une partie de l'hydrogène (H2) produit par l'unité de déshydrogénation (2), l'autre partie, la plus importante, pouvant être exportée vers les diverses unités d'hydrotraitement de la raffinerie.The mixture of heavy olefins (F3) from the oligomerization unit (3) is then sent to a hydrogenation unit (4). To do this, one part of the hydrogen (H2) produced by the dehydrogenation unit (2) is used, the other part, the largest part, being able to be exported to the various hydrotreatment units of the refinery.

L'hydrogénation (4) peut être réalisée de manière connue de l'homme de l'art selon une voie hydrotraitement sur catalyseur NiMo, CoMo ou NiCoMo.The hydrogenation (4) can be carried out in a manner known to those skilled in the art in a hydrotreatment pathway over NiMo, CoMo or NiCoMo catalyst.

De préférence dans le cadre de la présente invention, l'hydrogénation (4) est réalisée sur des catalyseurs à base de métaux du groupe VIII déposés sur un support inerte, tel que par exemple la silice ou l'alumine.Preferably in the context of the present invention, the hydrogenation (4) is carried out on catalysts based on Group VIII metals deposited on an inert support, such as, for example, silica or alumina.

Les métaux du groupe VIII utilisable comme catalyseur d'hydrogénation sont notamment le nickel, le palladium ou le platine.Group VIII metals that can be used as hydrogenation catalysts include nickel, palladium or platinum.

L'hydrogénation (4) se déroule généralement en phase liquide dans un réacteur à lit fixe à des températures comprises entre 50°C et 300 °C, et de préférence entre 100°C et 200°C, et sous des pressions de 5 à 50 bars, et de préférence de 10 à 30 bars.The hydrogenation (4) generally takes place in the liquid phase in a fixed bed reactor at temperatures between 50 ° C and 300 ° C, and preferably between 100 ° C and 200 ° C, and under pressures of 5 to 50 bar, and preferably 10 to 30 bar.

On réalise un taux d'hydrogénation d'au moins 25 %, de manière préférée égal ou supérieur à 75 %, et de manière très préférée égal ou supérieur à 95 %.A hydrogenation rate of at least 25%, preferably 75% or more, and most preferably 95% or more, is achieved.

Le nombre de cétane de la coupe diesel résultante est généralement compris entre 45 et 55 avec l'utilisation de zéolithes dans l'unité d'oligomérisation (3).The cetane number of the resulting diesel cut is generally between 45 and 55 with the use of zeolites in the oligomerization unit (3).

EXEMPLEEXAMPLE Exemple 1 (non conforme à l'invention)Example 1 (not according to the invention)

On dispose dans une raffinerie de 232 Kilotonnes par an (KT/an) de naphta léger (LN) contenant 36 % de n paraffines à 5 et 6 atomes de carbone ainsi que 113,4 KT/an de n-butane. Le naphta léger de départ possède un octane moteur (RON) de 68.In a refinery there is 232 kilotons per year (KT / yr) of light naphtha (LN) containing 36% n paraffins with 5 and 6 carbon atoms and 113.4 KT / yr with n-butane. The light starting naphtha has an engine octane (RON) of 68.

Le mélange léger C4-C5-C6 est dirigé vers une unité de déshydrogénation (2) opérant à pression de 1,3 bar et à une température moyenne de 550 °C sur un catalyseur à base de platine et étain déposé sur alumine, avec un taux de recycle molaire H2/HC de 0.5. L'effluent de l'unité de déshydrogénation (2) avec un recycle à taux 1/1 par rapport à la charge fraîche des normales paraffines C4 -C6 provenant de l'unité d'oligomérisation (3) a la composition générale suivante : Effluent de l'unité de déshydrogénation KT/an Oléfines
NC4"
70,1
Oléfines
NC5"+NC6"
176,4
Paraffine
NC4
40,8
Paraffines
N C5 + NC6
51
Total 338,3
The light C4-C5-C6 mixture is directed to a dehydrogenation unit (2) operating at a pressure of 1.3 bar and at an average temperature of 550 ° C. on a platinum and tin catalyst deposited on alumina, with a H 2 / HC molar recycle rate of 0.5. The effluent of the dehydrogenation unit (2) with a recycle at 1/1 rate relative to the fresh feed of the normal C4 -C6 paraffins from the oligomerization unit (3) has the following general composition: Effluent of the dehydrogenation unit KT / year olefins
NC4 "
70.1
olefins
NC5 "+ NC6"
176.4
Paraffin
NC4
40.8
paraffins
N C5 + NC6
51
Total 338.3

On produit également 7,1 KT/an d'hydrogène.7.1 KT / year of hydrogen is also produced.

L'effluent de l'unité de déshydrogénation (2) contenant les oléfines et paraffines est alors dirigé vers une installation d'oligomérisation des oléfines (3) opérant vers 300°C environ sur un catalyseur zéolithique à base de ZSM5.The effluent from the dehydrogenation unit (2) containing the olefins and paraffins is then directed to an oligomerization plant for olefins (3) operating at about 300 ° C. over a zeolite catalyst based on ZSM5.

La quasi-totalité des oléfines est transformée en oligomères

  • 85 % est transformé en oligomères bouillant dans la gamme diesel à savoir de C10 à C24, ce qui correspond à 209,5 KT/an produites
  • 15 % est transformé en essence (C5 à C10) bouillant dans la gamme essence, à savoir 37 KT/an produites
Almost all olefins are transformed into oligomers
  • 85% is converted into oligomers boiling in the diesel range ie C10 to C24, which corresponds to 209.5 KT / year produced
  • 15% is converted into gasoline (C5 to C10) boiling in the gasoline range, namely 37 KT / year produced

La quantité totale d'essence C5-C10 produite contenant les paraffines C5-C6 de départ se monte à 88 KT/an avec un octane moteur RON mesurée à 78.The total amount of C5-C10 gasoline produced containing the starting C5-C6 paraffins amounts to 88 KT / year with an RON motor octane measured at 78.

On produit aussi 40,8 KT/an de butane résiduel.40.8 KT / year of residual butane is also produced.

Optionnellement la coupe saturée C4-C5-C6 peut être envoyée comme naphta à un site pétrochimique réduisant la quantité d'essence produite à 61,3 KT/an.Optionally the saturated C4-C5-C6 cut can be sent as a naphtha to a petrochemical site reducing the amount of gasoline produced to 61.3 KT / year.

L'effluent de l'oligomérisation (3) est envoyé dans l'unité d'hydrogénation (4).The effluent of the oligomerization (3) is sent to the hydrogenation unit (4).

L'unité d'hydrogénation (4) fonctionne sur un catalyseur à base de nickel à des températures comprises entre 150° et 200°C.The hydrogenation unit (4) operates on a nickel-based catalyst at temperatures between 150 ° and 200 ° C.

L'effluent de l'unité d'hydrogénation (4) a un indice de cétane de 41, soit un indice de cétane moteur de 46.The effluent from the hydrogenation unit (4) has a cetane number of 41, ie a cetane number of 46.

L'hydrogène consommé dans l'hydrogénation (4) est égal à 2,0 KT/an.The hydrogen consumed in the hydrogenation (4) is equal to 2.0 KT / year.

La quantité nette d'hydrogène produite par le procédé selon l'invention est donc de 5,1 KT/an.The net quantity of hydrogen produced by the process according to the invention is therefore 5.1 KT / year.

Dans l'exemple traité, on a réduit de 62% la quantité d'essence par rapport au naphta léger entrant (NL) avec simultanément 10 point de gain d'octane (RON) par rapport au naphta léger entrant (NL).In the example discussed, the gasoline amount was reduced by 62% relative to the incoming light naphtha (NL) with a simultaneous 10 octane gain point (RON) relative to the incoming light naphtha (NL).

Le procédé décrit dans la présente invention permet donc non seulement de produire un carburant diesel de bonne qualité, mais également de produire de l'hydrogène, contrairement aux procédés conventionnels, et de diminuer les quantités d'essences et de butane actuellement excédentaires, en particulier sur le marché européen.The process described in the present invention thus makes it possible not only to produce a good quality diesel fuel, but also to produce hydrogen, contrary to conventional processes, and to reduce the quantities of gasolines and butane currently in excess, in particular on the European market.

Exemple 2 " marche diesel maxi indice de cétane" (conforme à l'invention)Example 2 "diesel step maxi cetane number" (in accordance with the invention)

On dispose dans une raffinerie de 232 Kilotonnes par an (KT/an) de naphta léger (LN) contenant 36 % de normales paraffines à 5 et 6 atomes de carbone.In a refinery there is 232 kilotons per year (KT / yr) of light naphtha (LN) containing 36% of normal paraffins with 5 and 6 carbon atoms.

Le naphta léger de départ possède un octane moteur (RON) de 68.The light starting naphtha has an engine octane (RON) of 68.

Ce naphta léger est dirigé vers une unité de séparation normales/iso paraffines (1) opérant sur un tamis moléculaire de type 5A. On obtient ainsi 83,5 KT/ an de nC5 + nC6 paraffines, la fraction riche en iso paraffine (F8) étant envoyée au pool essence.This light naphtha is directed to a normal / iso paraffin separation unit (1) operating on a 5A molecular sieve. This gives 83.5 KT / year of nC5 + nC6 paraffins, the isofparaffin rich fraction (F8) being sent to the gasoline pool.

On dispose également de 113,4 KT/an de n butane.There is also 113.4 KT / year of n butane.

Le mélange de nC4 + nC5 + nC6 est envoyé dans une unité de déshydrogénation (2) opérant à pression de 1,3 bars et à une température moyenne de 550 °C sur un catalyseur à base de platine et étain sur alumine, avec un taux de recycle molaire H2/HC de 0,5. L'effluent de l'unité de déshydrogénation (2) avec un recycle à taux 1/1 des normales paraffines C4 -C6 provenant de l'unité d'oligomérisation (3) a la composition générale suivante ; Effluent de l'unité de déshydrogénation (2) KT/an Oléfines
N C4"
70,1
Oléfines
N C5" + NC6 "
63,7
Paraffines
NC4
40,8
Paraffines
N C5 + NC6
18,5
Total 193,1
The mixture of nC4 + nC5 + nC6 is sent to a dehydrogenation unit (2) operating at a pressure of 1.3 bar and at an average temperature of 550 ° C on a platinum-tin catalyst on alumina, with a rate of H2 / HC molar recycle of 0.5. The effluent from the dehydrogenation unit (2) with a 1/1 recycle of normal C4 -C6 paraffins from the oligomerization unit (3) has the following general composition; Effluent of the dehydrogenation unit (2) KT / year olefins
N C4 "
70.1
olefins
N C5 "+ NC6"
63.7
paraffins
NC4
40.8
paraffins
N C5 + NC6
18.5
Total 193.1

On produit également 3,8 KT/an d'hydrogène.3.8 KT / year of hydrogen is also produced.

L'effluent de l'unité de déshydrogénation (2) contenant les oléfines et paraffines est alors dirigé vers une installation d'oligomérisation des oléfines (3) opérant à 300 °C environ sur un catalyseur zéolithique à base de ZSM5.The effluent from the dehydrogenation unit (2) containing the olefins and paraffins is then directed to an oligomerization plant for olefins (3) operating at about 300 ° C. over a zeolite catalyst based on ZSM5.

La quasi-totalité des oléfines est transformée en oligomères.

  • 85 % est transformé en oligomères bouillant dans la gamme diesel à savoir de C10 à C24, ce qui correspond à 113,7 KT/an produites
  • 15 % est transformé en essence (C5 à C10) bouillant dans la gamme essence, à savoir 20,1 KT/an produites.
Almost all olefins are converted to oligomers.
  • 85% is converted into oligomers boiling in the diesel range ie C10 to C24, which corresponds to 113.7 KT / year produced
  • 15% is converted into gasoline (C5 to C10) boiling in the gasoline range, namely 20.1 KT / year produced.

La quantité totale d'essence C5-C10 produite contenant les paraffines C5-C6 de départ se monte à 38,6 KT/an avec un octane moteur RON mesurée à 80.The total amount of C5-C10 gasoline produced containing the starting C5-C6 paraffins amounts to 38.6 KT / year with an RON motor octane measured at 80.

On produit aussi 40,8 tonnes/an de butane résiduel.40.8 tons / year of residual butane is also produced.

Optionnellement, la coupe saturée C4-C5-C6 peut être envoyée comme naphta à un site pétrochimique réduisant la quantité d'essence produite à l'oligomérisation (3) à 33,4 KT/an. L'effluent de l'oligomérisation (3) est envoyé à l'unité d'hydrogénation (4).Optionally, the saturated C4-C5-C6 cut can be sent as a naphtha to a petrochemical site reducing the amount of gasoline produced at the oligomerization (3) to 33.4 KT / year. The effluent of the oligomerization (3) is sent to the hydrogenation unit (4).

l'unité d'hydrogénation (4) fonctionne sur un catalyseur à base de nickel à des températures comprises entre 150° et 200°C. L'effluent de l'unité d'hydrogénation (4) a un indice de cétane de 46, soit un indice de cétane moteur de 51.the hydrogenation unit (4) operates on a nickel-based catalyst at temperatures between 150 ° and 200 ° C. The effluent of the hydrogenation unit (4) has a cetane number of 46, ie a cetane number of 51.

L'hydrogène consommé dans l'hydrogénation (4) est égal à 1,1 KT/an.The hydrogen consumed in the hydrogenation (4) is equal to 1.1 KT / year.

La quantité nette d'hydrogène produite par le procédé selon l'invention est donc de 2,7 KT/an.The net quantity of hydrogen produced by the process according to the invention is therefore 2.7 KT / year.

Le procédé décrit dans la présente invention permet non seulement de produire un carburant diesel de bonne qualité, mais également de produire de l'hydrogène contrairement aux procédés conventionnels, et de diminuer les quantités d'essences et de butane actuellement excédentaires en particulier sur le marché européen.The method described in the present invention not only makes it possible to produce a good quality diesel fuel, but also to produce hydrogen contrary to conventional processes, and to reduce the quantities of gasoline and butane currently in surplus especially in the European market.

Selon le procédé décrit dans la présente invention les 187,1 KT/an d'essence produite comprend les iso paraffines C5-C6 et la fraction C5-C10 produite à l'oligomérisation.According to the process described in the present invention, the 187.1 KT / year of gasoline produced comprises the C5-C6 iso paraffins and the C5-C10 fraction produced during oligomerization.

La quantité d'essence produite est de 20% inférieur à la quantité de naphta léger entrant (NL) avec simultanément un indice d'octane amélioré de 20 point par rapport au naphta léger entrant (NL).The amount of gasoline produced is 20% lower than the amount of light incoming naphtha (NL) with simultaneously an improved octane number of 20 points relative to the incoming light naphtha (NL).

Exemple 3 charge C4/C5/C6 "maxi kérosène" ( non conforme à l'invention)Example 3 load C4 / C5 / C6 "maxi kerosene" (not according to the invention)

On dispose dans une raffinerie de 232 Kilotonnes par an (KT/an) de naphta léger (NL) contenant 36 % de n paraffines à 5 et 6 atomes de carbone ainsi que 113,4 KT/an de n-butane. Le naphta léger de départ possède un octane moteur (RON) de 68.In a refinery, there are 232 kilotonnes per year (KT / yr) of light naphtha (NL) containing 36% of n paraffins with 5 and 6 carbon atoms and 113.4 KT / year of n-butane. The light starting naphtha has an engine octane (RON) of 68.

Le mélange léger C4-C5-C6 est dirigé vers une unité de déshydrogénation (2) opérant à pression de 1,3 bars et à une température moyenne de 550 °C, avec un taux de recycle molaire H2/HC de 0,5.The light C4-C5-C6 mixture is directed to a dehydrogenation unit (2) operating at a pressure of 1.3 bar and at an average temperature of 550 ° C, with an H2 / HC molar recycle ratio of 0.5.

La déshydrogénation (2) est réalisée sur un catalyseur à base de platine et étain déposé sur alumine.The dehydrogenation (2) is carried out on a catalyst based on platinum and tin deposited on alumina.

L'effluent de l'unité de déshydrogénation (2) avec un recycle à taux 1/1 par rapport à la charge fraîche des n paraffines C4 -C6 provenant de l'unité d'oligomérisation (3) a la composition générale suivante : Effluent de l'unité de déshydrogénation KT/an Oléfines
N C4"
70,1
Oléfines
N C5" + NC6"
176,4
Paraffines
NC4
40,8
Paraffines
N C5 + NC6
51
Total 338,3
The effluent of the dehydrogenation unit (2) with a recycle at a rate of 1/1 relative to the fresh feedstock of the C4-C6 n paraffins from the oligomerization unit (3) has the following general composition: Effluent of the dehydrogenation unit KT / year olefins
N C4 "
70.1
olefins
N C5 "+ NC6"
176.4
paraffins
NC4
40.8
paraffins
N C5 + NC6
51
Total 338.3

On produit également 7,1 KT/an d'hydrogène.7.1 KT / year of hydrogen is also produced.

L'effluent de l'unité de déshydrogénation (2) contenant les oléfines et paraffines est alors dirigé vers une installation d'oligomérisation des oléfines (3) opérant à 180°C environ sur catalyseur silice alumine, et avec un recyclage des coupes C4 à C6.

  • 63 % de la charge d'oligomérisation (F2) est transformé en oligomères bouillant dans la gamme du kérosène à savoir de C10 à C20, ce qui correspond à 140 KT/an produites
  • 7% de la charge d'oligomérisation (F2) est transformé en oligomères bouillant dans la gamme du diesel à savoir de C20 à C24, ce qui correspond à 15,1 KT/an produites
  • 30 % de la charge d'oligomérisation est transformé en essence (C5 à C10) bouillant dans la gamme essence, à savoir 66,7 KT/an produites.
The effluent from the dehydrogenation unit (2) containing the olefins and paraffins is then directed to an oligomerization plant for olefins (3) operating at about 180 ° C. over silica-alumina catalyst, and with recycling of the C4 cuts to C6.
  • 63% of the oligomerization charge (F2) is converted into oligomers boiling in the range of kerosene ie C10 to C20, which corresponds to 140 KT / year produced
  • 7% of the oligomerization charge (F2) is converted into oligomers boiling in the range of diesel ie C20 to C24, which corresponds to 15.1 KT / year produced
  • 30% of the oligomerization charge is converted into gasoline (C5 to C10) boiling in the gasoline range, namely 66.7 KT / year produced.

On produit aussi 44 Kt/an de butane résiduel contenant les oléfines C4 non converties.44 Kt / yr of residual butane containing unconverted C4 olefins are also produced.

La quantité totale d'essence C5-C10 produite contenant les paraffines C5-C6 de départ et les oléfines non converties se monte à 139,2 Kt/an.The total amount of C5-C10 gasoline produced containing the starting C5-C6 paraffins and unconverted olefins amounts to 139.2 Kt / yr.

L'effluent de l'oligomérisation (3) bouillant dans la gamme du kérosène et du diesel est très oléfinique est envoyée sur l'unité d'hydrogénation (4).The effluent of the oligomerization (3) boiling in the range of kerosene and diesel is highly olefinic is sent to the hydrogenation unit (4).

L'unité d'hydrogénation (4) fonctionne sur un catalyseur à base de nickel à des températures comprises entre 150° et 200°C.The hydrogenation unit (4) operates on a nickel-based catalyst at temperatures between 150 ° and 200 ° C.

Après fractionnement, le kérosène produit à l'unité d'hydrogénation (4) a un point de fumée de 35 mm, un point de disparition des cristaux inférieur à -60°C, et un point final ASTM D86 inférieur à 300°C, en ligne avec les spécifications requises pour un kérosène respectant la norme JET A1.After fractionation, the kerosene produced at the hydrogenation unit (4) has a smoke point of 35 mm, a vanishing point of the crystals below -60 ° C, and an ASTM D86 end point of less than 300 ° C, in line with the specifications required for kerosene meeting the JET A1 standard.

L'hydrogène consommé dans l'hydrogénation (4) est égal à 1,6 KT/an.The hydrogen consumed in the hydrogenation (4) is equal to 1.6 KT / year.

La faible quantité de diesel produite est généralement injectée dans le pool diesel sans incidence importante sur le cétane du pool malgré son faible cétane de 30.The small amount of diesel produced is generally injected into the diesel pool without any significant impact on the pool cetane despite its low cetane number of 30.

La quantité nette d'hydrogène produite par le procédé selon l'invention est donc de 5,5 KT/an.The net quantity of hydrogen produced by the process according to the invention is therefore 5.5 KT / year.

Dans l'exemple traité, on a réduit de 40% la quantité d'essence produite par rapport à la charge naphta léger entrante (NL) avec simultanément un gain de 20 points d'octane (RON) toujours par rapport au naphta léger entrant (NL).In the example discussed, the amount of gasoline produced was reduced by 40% relative to the incoming light naphtha (NL) feed simultaneously with a 20 octane (RON) gain still relative to the incoming light naphtha ( NL).

Le procédé décrit dans la présente invention permet donc non seulement de produire un carburant kérosène de bonne qualité, mais également de produire de l'hydrogène contrairement aux procédés conventionnels, et de diminuer les quantités d'essences et de butane actuellement excédentaires, en particulier sur le marché européen.The method described in the present invention therefore makes it possible not only to produce a good quality kerosene fuel, but also to produce hydrogen in contrast to conventional processes, and to reduce the quantities of gasolines and butane currently in excess, particularly on the European market.

Claims (10)

  1. Process for the production of kerosene and diesel fuels and the coproduction of hydrogen from a saturated light feed (F1) with a number of carbons between C3 and C7 constituted by:
    a) a light naphtha cut (NL) with a number of carbon atoms in the range from 5 to 7 originating from units for primary distillation, for hydrocracking or a Fischer Tropsch unit, with a distillation range between 30°C and 120°C, said light naphtha cut being previously hydrotreated to remove oxygen-containing, nitrogen-containing and sulphur-containing compounds and,
    b) a C3/C4 cut (LPG) present in any proportion, from which oxygen-containing and sulphur-containing compounds have been removed, said process comprising the following successive stages:
    - a stage of separation (1) of the normal and iso-paraffins, employing a molecular sieve based on small-pore alkaline zeolites such as those designated 5A, making it possible to recover a first effluent (F1)" essentially constituted by normal paraffins which is sent to the dehydrogenation stage (2) and a second effluent (F8) essentially constituted by iso-paraffins which is sent to the gasoline pool or is upgraded to petrochemical naphtha,
    - a stage of dehydrogenation (2) of the normal paraffins originating from the separation stage operating at a pressure between 1.3 and 5 bar absolute, and at a temperature between 400°C and 700°C, and employing a dehydrogenation catalyst constituted by a group VIII precious metal selected from platinum, iridium, rhodium, and at least one promoter selected from the group constituted by tin, germanium, lead, gallium, indium, thallium, said precious metal and said promoter being deposited on an inert support selected from the group formed by silica, alumina, titanium oxide, silica-magnesia, or any mixture of said components, and said stage of dehydrogenation (2) making it possible to recover an effluent (F2) essentially constituted by olefins with a number of carbon atoms between 3 and 7, called olefinic effluent (F2),
    - a stage of oligomerization (3) of some or all of the olefinic effluent (F2) obtained in stage (2) in an oligomerization unit (3) employing an oligomerization catalyst selected from the group formed by solid phosphoric acid, ion exchange resins, silica-aluminas or aluminosilicates such as zeolites, pure or supported on alumina, said stage of oligomerization (3) making it possible to recover an effluent (F3) in the majority constituted by olefins in the range from C10 to C25, and a "gasoline" effluent (F4) in the majority constituted by paraffins in the range from C5 to C10 which is separated from effluent (F3) by distillation and is recycled to the inlet of the oligomerization unit (3),
    - a stage of hydrogenation (4) of some or all of the olefinic effluent (F3) originating from the oligomerization stage (3) carried out in the liquid phase in one or more fixed-bed reactors, at temperatures between 50°C and 350°C, and at pressures from 5 to 50 bar, and employing a hydrogenation catalyst based on a metal selected from the group formed by platinum, palladium or nickel deposited on an inert support such as silica or alumina or any mixture of these two components, said stage of hydrogenation (4) making it possible to recover an effluent (F6) which is a diesel or kerosene fuel cut that is in the majority paraffinic.
  2. Process for the production of kerosene and diesel fuels, and the coproduction of hydrogen according to claim 1, characterized in that the catalyst used in the dehydrogenation stage (2) is constituted by platinum and tin deposited on an alumina neutralized with an alkali.
  3. Process for the production of kerosene and diesel fuels, and the coproduction of hydrogen according to any one of claims 1 and 2, characterized in that the hydrogen used during stage (4) of hydrogenation comes at least partly from the hydrogen generated in stage (2).
  4. Process for the production of kerosene fuels to JET A1 specifications and for the coproduction of hydrogen according to claim 1, characterized in that the oligomerization stage (3) is carried out on resins at temperatures between 20°C and 200°C, and preferably between 70°C and 180°C, and at pressures from 10 bar to 100 bar, and preferably from 30 bar to 65 bar.
  5. Process for the production of kerosene fuels to JET A1 specifications and for the coproduction of hydrogen according to claim 1, characterized in that the oligomerization stage (3) is carried out on silica-alumina at temperatures between 120°C and 250°C, and at pressures from 20 bar to 65 bar.
  6. Process for the production of kerosene and diesel fuels and for the coproduction of hydrogen according to claim 1, characterized in that the oligomerization stage (3) is supplied with a gasoline cut (ES) or at least one cut containing C3 and C4 fractions originating from a catalytic cracking unit (FCC), coking unit, visbreaker, or a Fischer-Tropsch unit, or from a steam cracking unit, which is treated in a mixture with the effluent (F2) from stage 2.
  7. Process for the production of kerosene and diesel fuels and for the coproduction of hydrogen according to claim 1, characterized in that the oligomerization stage (3) is supplied with a cut containing C3 and C4 fractions originating from a catalytic cracking unit (FCC), coking unit, visbreaker, or a Fischer-Tropsch unit, or from a steam cracking unit, which is treated in a mixture with the effluent (F2) from stage 2.
  8. Process for the production of kerosene and diesel fuels and for the coproduction of hydrogen according to claim 1, characterized in that the hydrogenation stage (4) is supplied with a cut (F7) of boiling point above 150°C, with a sulphur content below 5 ppm, for example cuts originating directly from the unit for atmospheric distillation of crude, or from the catalytic cracking unit (FCC), or from a unit for hydrocracking or catalytic reforming.
  9. Process for the production of kerosene and diesel fuels and for the coproduction of hydrogen according to any one of claims 1 to 8, characterized in that the dehydrogenation stage (2) operates in regenerative or semi-regenerative mode.
  10. Process for the production of kerosene and diesel fuels and for the coproduction of hydrogen according to any one of claims 1 to 9, characterized in that the oligomerization stage (3) operates in regenerative or semi-regenerative mode.
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