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EP2333031B1 - Verfahren zur Herstellung von Kerosin- und Dieselkraftstoffen sowie zur gleichzeitigen Herstellung von Wasserstoff aus gesättigten leichten Fraktionen - Google Patents

Verfahren zur Herstellung von Kerosin- und Dieselkraftstoffen sowie zur gleichzeitigen Herstellung von Wasserstoff aus gesättigten leichten Fraktionen 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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Prior art keywords
stage
unit
effluent
oligomerization
kerosene
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English (en)
French (fr)
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EP2333031A1 (de
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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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
    • C10G69/126—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step polymerisation, e.g. oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
    • C10G35/09—Bimetallic catalysts in which at least one of the metals is a platinum group metal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1022—Fischer-Tropsch products
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/301—Boiling range
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4012—Pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/08—Jet fuel

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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Claims (10)

  1. Verfahren zur Herstellung von Kerosin- und Dieselkraftstoffen und zur gleichzeitigen Erzeugung von Wasserstoff ausgehend von einer leichten gesättigten Charge (F1) mit einer Kohlenstoffzahl im Bereich von C3 bis C7, bestehend:
    a) aus einer Leichtnaphtha-Fraktion (NL) mit einer Kohlenstoffatomzahl von 5 bis 7, die von Primärdestillations- oder Hydrocracking-Anlagen oder einer Fischer-Tropsch-Anlage stammt, mit einem Destillationsintervall zwischen 30 °C und 120°C, wobei diese Leichtnaphtha-Fraktion zuvor hydrobehandelt wird, so dass sie von den sauerstoffhaltigen, stickstoffhaltigen und schwefelhaltigen Verbindungen befreit ist,
    b) aus einer C3/C4-Fraktion (LPG) mit einem beliebigen Verhältnis von C3 und C4, die von den sauerstoffhaltigen und schwefelhaltigen Verbindungen befreit ist,
    wobei das Verfahren die Abfolge von folgenden Schritten umfasst:
    - einen Schritt der Trennung (1) der Normal- und Iso-Paraffine unter Verwendung eines Molekularsiebes auf der Basis von alkalischen Zeolithen mit kleinen Poren von der Art der mit 5A bezeichneten Molekularsiebe, der es ermöglicht, einen ersten Abstrom (F1)-, der im Wesentlichen aus Normal-Paraffinen besteht und zum Schritt der Dehydrierung (2) geleitet wird, und einen zweiten Abstrom (F8), der im Wesentlichen aus Iso-Paraffinen besteht und zu dem Benzinpool geleitet oder in Form von petrochemischem Naphtha verwertet wird, zu gewinnen,
    - einen Schritt der Dehydrierung (2) der Normal-Paraffine aus dem Schritt der Trennung, der bei einem Druck zwischen 1,3 und 5 bar (absolut) und bei einer Temperatur zwischen 400 °C und 700 °C durchgeführt wird, unter Verwendung eines Dehydrierungskatalysators, der aus einem Edelmetall der Gruppe VIII, das aus Platin, Iridium und Rhodium ausgewählt ist, und aus mindestens einem Promotor, der aus der aus Zinn, Germanium, Blei, Gallium, Indium und Thallium bestehenden Gruppe ausgewählt ist, besteht, wobei das Edelmetall und der Promotor auf einen inerten Träger aufgebracht sind, der aus der Gruppe ausgewählt ist, die von Siliciumdioxid, Aluminiumoxid, Titanoxid, Siliciumdioxid-Magnesiumoxid oder einer beliebigen Mischung dieser Stoffe gebildet wird, und wobei der Schritt der Dehydrierung (2) ermöglicht, einen Abstrom (F2) zu gewinnen, der im Wesentlichen aus Olefinen mit einer Kohlenstoffzahl im Bereich von 3 bis 7 besteht und als olefinischer Abstrom (F2) bezeichnet wird,
    - einen Schritt der Oligomerisierung (3) des gesamten in Schritt (2) erhaltenen olefinischen Abstroms (F2) oder eines Teils desselben in einer Oligomerisierungsanlage (3) unter Verwendung eines Oligomerisierungskatalysators, der aus der Gruppe ausgewählt ist, die von fester Phosphorsäure, den lonenaustauschharzen, den Siliciumdioxid-Aluminiumoxiden oder den Silicoaluminaten wie etwa den reinen Zeolithen oder Zeolithen auf einem Aluminiumoxid-Träger gebildet wird, wobei der Schritt der Oligomerisierung (3) ermöglicht, einen Abstrom (F3), der hauptsächlich aus Olefinen von C10 bis C25 besteht, und einen "Benzin"-Abstrom (F4), der hauptsächlich aus Paraffinen von C5 bis C10 besteht und der von dem Abstrom (F3) durch Destillation getrennt und zum Eingang der Oligomerisierungsanlage (3) zurückgeführt wird, zu gewinnen,
    - einen Schritt der Hydrierung (4) des gesamten olefinischen Abstroms (F3) aus dem Schritt der Oligomerisierung (3) oder eines Teils desselben, der in flüssiger Phase in einem oder mehreren Festbettreaktoren bei Temperaturen zwischen 50 °C und 350 °C und unter Drücken von 5 bis 50 bar durchgeführt wird, unter Verwendung eines Hydrierungskatalysators auf der Basis eines Metalls, das aus der Gruppe ausgewählt ist, die von Platin, Palladium und Nickel gebildet wird, und auf einen inerten Träger wie Siliciumdioxid oder Aluminiumoxid oder eine beliebige Mischung dieser beiden Bestandteile aufgebracht ist, wobei der Schritt der Hydrierung (4) ermöglicht, einen Abstrom (F6) zu gewinnen, welcher eine zum größten Teil paraffinische Diesel- oder Kerosinkraftstoff-Fraktion ist.
  2. Verfahren zur Herstellung von Kerosin- und Dieselkraftstoffen und zur gleichzeitigen Erzeugung von Wasserstoff nach Anspruch 1, wobei der im Schritt der Dehydrierung (2) verwendete Katalysator aus Platin und Zinn besteht, die auf ein durch ein Alkali neutralisiertes Aluminiumoxid aufgebracht sind.
  3. Verfahren zur Herstellung von Kerosin- und Dieselkraftstoffen und zur gleichzeitigen Erzeugung von Wasserstoff nach einem der Ansprüche 1 bis 2, wobei der im Schritt (4) der Hydrierung verwendete Wasserstoff wenigstens teilweise von dem Wasserstoff stammt, der in Schritt (2) erzeugt wird.
  4. Verfahren zur Herstellung von Kerosinkraftstoffen gemäß der Spezifikation JET A1 und zur gleichzeitigen Erzeugung von Wasserstoff nach Anspruch 1, wobei der Schritt der Oligomerisierung (3) mit Harzen bei Temperaturen zwischen 20 °C und 200 °C und vorzugsweise zwischen 70 °C und 180 °C und unter Drücken von 10 bar bis 100 bar und vorzugsweise von 30 bar bis 65 bar durchgeführt wird.
  5. Verfahren zur Herstellung von Kerosinkraftstoffen gemäß der Spezifikation JET A1 und zur gleichzeitigen Erzeugung von Wasserstoff nach Anspruch 1, wobei der Schritt der Oligomerisierung (3) mit Siliciumdioxid-Aluminiumoxid bei Temperaturen zwischen 120 °C und 250 °C und unter Drücken von 20 bar bis 65 bar durchgeführt wird.
  6. Verfahren zur Herstellung von Kerosin- und Dieselkraftstoffen und zur gleichzeitigen Erzeugung von Wasserstoff nach Anspruch 1, wobei im Schritt der Oligomerisierung (3) eine Benzinfraktion (ES) zugeführt wird, die von einer katalytischen Crackanlage (FCC), einer Verkokungsanlage, einer Visbreaking-Anlage oder einer Fischer-Tropsch-Anlage oder von einer Dampfcrackanlage stammt und die in einer Mischung mit dem Abstrom (F2) von Schritt 2 behandelt wird.
  7. Verfahren zur Herstellung von Kerosin- und Dieselkraftstoffen und zur gleichzeitigen Erzeugung von Wasserstoff nach Anspruch 1, wobei im Schritt der Oligomerisierung (3) eine C3 und C4 enthaltende Fraktion zugeführt wird, die von einer katalytischen Crackanlage (FCC), einer Verkokungsanlage, einer Visbreaking-Anlage oder einer Fischer-Tropsch-Anlage oder von einer Dampfcrackanlage stammt und die in einer Mischung mit dem Abstrom (F2) von Schritt 2 behandelt wird.
  8. Verfahren zur Herstellung von Kerosin- und Dieselkraftstoffen und zur gleichzeitigen Erzeugung von Wasserstoff nach Anspruch 1, wobei im Schritt der Hydrierung (4) eine Fraktion (F7) mit einem Siedepunkt, der höher als 150 °C ist, zugeführt wird, die Schwefelanteile von weniger als 5 ppm enthält, zum Beispiel Fraktionen, die direkt von der Anlage zur atmosphärischen Destillation des Rohöls stammen oder von der katalytischen Crackanlage (FCC) stammen oder von einer Hydrocracking-Anlage oder Anlage zur katalytischen Reformierung stammen.
  9. Verfahren zur Herstellung von Kerosin- und Dieselkraftstoffen und zur gleichzeitigen Erzeugung von Wasserstoff nach einem der Ansprüche 1 bis 8, wobei der Schritt der Dehydrierung (2) in einer regenerativen oder semi-regenerativen Betriebsweise durchgeführt wird.
  10. Verfahren zur Herstellung von Kerosin- und Dieselkraftstoffen und zur gleichzeitigen Erzeugung von Wasserstoff nach einem der Ansprüche 1 bis 9, wobei der Schritt der Oligomerisierung (3) in einer regenerativen oder semi-regenerativen Betriebsweise durchgeführt wird.
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