EP1330505B1 - Method for producing diesel fuel by moderate pressure hydrocracking - Google Patents

Method for producing diesel fuel by moderate pressure hydrocracking Download PDF

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Publication number
EP1330505B1
EP1330505B1 EP01974410A EP01974410A EP1330505B1 EP 1330505 B1 EP1330505 B1 EP 1330505B1 EP 01974410 A EP01974410 A EP 01974410A EP 01974410 A EP01974410 A EP 01974410A EP 1330505 B1 EP1330505 B1 EP 1330505B1
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EP
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Prior art keywords
hydrocracking
fraction
residue
diesel
vacuum
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German (de)
French (fr)
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EP1330505A1 (en
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Pierre Marion
Eric Benazzi
Didier Duee
Christophe Gueret
Alain Billon
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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
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
    • 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
    • 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
    • C10G69/04—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 step of catalytic cracking in the absence of hydrogen
    • 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
    • C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °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
    • C10G2300/10—Feedstock materials
    • C10G2300/1074—Vacuum distillates
    • 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
    • C10G2300/1077—Vacuum residues
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/307—Cetane number, cetane index
    • 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

Definitions

  • the invention relates to a process with moderate pressure hydrocracking, for the production of very high quality diesel with high yields.
  • the invention also relates to a process including said hydrocracking process and a catalytic cracking process, as well as the installation that can be used for carrying out said method.
  • the refining industry must now find refining schemes to adapt to the stringent fuel quality standards that will be in effect in Europe in 2005.
  • the maximum sulfur content of diesel fuel must be at most 50 ppm.
  • the 95% distillation point (ASTM D-86) of diesel, currently 360 ° C, will probably be reduced, for example 10 ° C, which would currently represent for a refinery a decrease of 5% in volume of diesel produced. It is also envisaged to divide by at least the current polyaromatic contents which are about 11% by mass at present. The cetane number required would, at the same time, be increased beyond 51, for example from the current value of 51 to 52.
  • the distillation of the crude is not sufficient to cover the production of diesel, diesel is currently produced by high pressure hydrocracking processes (generally at least 120 bar hydrogen partial pressure) dealing with heavy loads which are fillers having a temperature T 95 most often of the order of at least 500 ° C, T 95 being the temperature of the 95% volume point obtained by simulated distillation (ASTM-D28 87). Heavy compounds are cracked into lighter compounds, some of which is found in the middle distillate cut (diesel and kerosene) of hydrocracking distillation. Such high pressure methods are conventional.
  • the process described in the present application is a hydrocracking process operating at moderate pressures (above 70 bar and at most 100 bar hydrogen partial pressure) which makes it possible to directly obtain a diesel that meets the 2005 specifications. from relatively light loads under more economical conditions than high pressure hydrocracking.
  • the distillation residue is recycled to the process after purging.
  • Point T 5 represents the temperature point 5% volume obtained by simulated distillation (ASTM D28 87).
  • the charges have a point T 5 between 320-400 ° C or between 320-370 ° C.
  • a fraction of diesel for example heavy diesel from the atmospheric distillation of the crude, which most often has a T 5 point of the order of at least 280 ° C. This heavy diesel fraction can just as easily be obtained directly in the atmospheric residue.
  • diesel addition is particularly advantageous. Indeed, it allows to treat with a hydrotreatment followed by hydrocracking at a moderate pressure a heavy part of the diesel fraction which is loaded with nitrogen compounds and sulfur most difficult to hydrotreat. Therefore, conventional hydrotreating can be used to treat the remaining diesel fraction, and there is no need for expensive investment.
  • the hydrodesulfurization of the heavy fraction is carried out with an improvement in its qualities (cetane number higher than that which would have been obtained by severe hydrotreatment alone).
  • the usable fillers also have a temperature T 95 of at most 470 ° C, more preferably at most 450 ° C, or better still in the range 390-430 ° C, T 95 representing the temperature of the 95% point obtained by simulated distillation (ASTM-D28 87).
  • VGO vacuum gas oil
  • HGO heavy atmospheric gas oils
  • mixtures of the said fillers or mixtures thereof can be mentioned as fillers.
  • said feeds with at least one diesel fraction for example from the distillation of crude or a unit of FCC (catalytic cracking).
  • the hydrocarbon feedstocks treated generally have sulfur contents of 0.2 to 4% by mass and nitrogen of 100 to 3500 ppm by weight. They are therefore generally previously hydrotreated before being hydrocracked so as to lower the contents of organic nitrogen (that is to say of nitrogen forming part of organic molecules) below 80 ppm, or better still 50 ppm and preferably below 10 ppm, and organic sulfur contents (i.e., sulfur containing organic molecules) below 200 ppm and preferably below 50 ppm. These hydrotreated loads (called clean) can then be subjected to hydrocracking.
  • the conversion carried out in the hydrotreatment is generally at least 10% by volume and less than 40% by product boiling below 350 ° C.
  • the hydrotreatment can be carried out either in the hydrocracking reactor and in at least one bed preceding the first bed of the hydrocracking catalyst, in the direction of flow of the feedstock, or in an independent reactor preceding the reactor. hydrocracking. There is or there is no intermediate separation of the regenerated gases by the hydrotreatment. The first mode (same reactor) without intermediate separation is preferred. Also included in the process is an embodiment in which the hydrotreatment is carried out in the refinery very upstream of the hydrocracking, intermediate treatments may also be performed.
  • the process can operate with or without recycling the distillation residue of the hydrocracking effluent (unconverted fraction).
  • recycling is carried out, it is carried out to the hydrocracking reactor if it is separated from that of hydrotreatment, for example, or to the feedstock entering the reactor where hydrotreatment and hydrocracking are carried out.
  • the conversion to products boiling below 350 ° C. is at least 80% by volume, and more generally at least 90% by volume, or at least 90% by volume. 95% volume.
  • catalysts which contain at least one amorphous support and at least one hydro-dehydrogenating element (generally at least one element of groups VIB and VIII non-noble, and most often at least one element of group VIB and at least one a non-noble group VIII element).
  • hydro-dehydrogenating element generally at least one element of groups VIB and VIII non-noble, and most often at least one element of group VIB and at least one a non-noble group VIII element.
  • a hydrotreating catalyst comprises at least one matrix, at least one hydro-dehydrogenating element chosen from the group formed by the elements of group VIB and group VIII of the periodic table, optionally at least one promoter element deposited on the catalyst and selected from the group consisting of phosphorus, boron and silicon, optionally at least one group VIIA element (chlorine, fluorine preferred), and optionally at least one element of group VIIB (preferred manganese), optionally at least minus one element of the VB (preferred niobium) group.
  • this catalyst contains boron and / or silicon as a promoter element, optionally with addition of phosphorus as another promoter element.
  • the contents of boron, silicon and phosphorus are then from 0.1 to 20%, preferably from 0.1 to 15%, and still more preferably from 0.1 to 10%.
  • the matrices that can be used alone or as a mixture are, by way of nonlimiting example, alumina, halogenated alumina, silica, silica-alumina, clays (for example, natural clays such as kaolin or bentonite), magnesia, titanium oxide, boron oxide, zirconia, aluminum phosphates, titanium phosphates, zirconium phosphates, coal, aluminates. It is preferred to use matrices containing alumina, in all these known forms those skilled in the art, and even more preferably the aluminas, for example gamma alumina.
  • hydro-dehydrogenating function is preferably filled by at least one metal or metal compound of non-noble groups VIII and VI preferably selected from molybdenum, tungsten, nickel and cobalt.
  • this role is provided by the combination of at least one Group VIII element (Ni, Co) with at least one Group VIB element (Mo, W).
  • This catalyst may advantageously contain phosphorus; in fact, it is known in the prior art that this compound provides two advantages to hydrotreatment catalysts: an ease of preparation, especially when impregnating solutions of nickel and molybdenum, and a better hydrogenation activity.
  • the total concentration of Group VI and VIII metal oxides is between 5 and 40% by weight and preferably between 7 and 30% and the weight ratio expressed as metal oxide between metal (or metals) of the group VIB metal (or metals) from group VIII is preferably between 20 and 1.25 and even more preferred between 10 and 2.
  • the concentration of phosphorus oxide P 2 O 5 is less than 15% by weight and preferably 10 % weight
  • Such a catalyst has a higher activity in hydrogenation of aromatic hydrocarbons and in hydrodenitrogenation and hydrodesulphurization than the catalyst formulas without boron and / or silicon, and also has a greater hydrocracking activity and selectivity than the catalytic formulas known in the art. prior art.
  • the catalyst with boron and silicon is particularly interesting.
  • this particularly high activity of the catalysts with boron and silicon is due to the strengthening of the acidity of the catalyst by the joint presence of boron and silicon on the matrix which induces on the one hand an improvement of the hydrogenating, hydrodesulphurizing and hydrodenitrogenating properties and, on the other hand, an improvement of the hydrocracking activity with respect to the catalysts usually used in the hydroconversion hydrorefining reactions.
  • the preferred catalysts are the NiMo and / or NiW catalysts on alumina, also the NiMo and / or NiW catalysts on alumina doped with at least one element included in the group of atoms formed by phosphorus, boron, silicon and fluorine, or alternatively NiMo and / or NiW catalysts on silica-alumina, or on silica-alumina-oxide titanium doped or not by at least one element included in the group of atoms formed by phosphorus, boron, fluorine and silicon.
  • Another type of catalyst of particular interest (especially in improved activity) in hydrotreating, contains a partially amorphous Y zeolite which will be described later in the hydrocracking catalysts.
  • the catalysts used in the process according to the present invention are preferably subjected beforehand to a sulphurization treatment making it possible, at least in part, to convert the metal species into sulphide before they come into contact with the feedstock. load to be processed.
  • This activation treatment by sulfurization is well known to those skilled in the art and can be performed by any method already described in the literature either in-situ, that is to say in the reactor, or ex-situ.
  • a conventional sulphurization method well known to those skilled in the art consists of heating in the presence of hydrogen sulphide (pure or for example under a stream of a hydrogen / hydrogen sulphide mixture) at a temperature of between 150 and 800 ° C. preferably between 250 and 600 ° C, generally in a crossed-bed reaction zone.
  • a preferred catalyst comprises at least one zeolite Y, at least one matrix and a hydro-dehydrogenating function.
  • it may also contain at least one element chosen from boron, phosphorus and silicon, at least one element of G VIIA (chlorine, fluorine for example), at least one element of group VIIB (manganese for example), with least one element of the group VB (niobium for example).
  • the catalyst contains at least one porous or poorly crystallized oxide type mineral matrix.
  • aluminas silicas, silica-aluminas, aluminates, alumina-boron oxide, magnesia, silica-magnesia, zirconia, titanium oxide, silica, clay, alone or in mixture.
  • the hydro-dehydrogenating function is generally provided by at least one group VI B element (for example molybdenum and / or tungsten) and / or at least one non-noble group VIII element (for example cobalt and / or nickel) of the classification. periodic elements.
  • a preferred catalyst essentially contains at least one Group VI metal, and / or at least one non-noble Group VIII metal, zeolite Y, and alumina.
  • An even more preferred catalyst essentially contains nickel, molybdenum, zeolite Y and alumina.
  • the catalyst optionally contains at least one element selected from the group formed by boron, silicon and phosphorus.
  • the catalyst optionally contains at least one element of group VIIA, preferably chlorine and fluorine, optionally at least one element of group VIIB (manganese for example), optionally at least one element of group VB (niobium for example) ).
  • Boron, silicon and / or phosphorus may be in the matrix, the zeolite or are preferably deposited on the catalyst and then mainly located on the matrix.
  • a preferred catalyst contains B and / or Si as a promoter element preferably deposited in addition to the promoter phosphorus. The quantities introduced are 0.1-20% by weight of catalyst calculated as oxide.
  • the element introduced, and in particular silicon, mainly located on the matrix of the support can be characterized by techniques such as the Castaing microprobe (distribution profile of the various elements), transmission electron microscopy coupled with an X analysis of the components of the catalysts, or even by establishing a distribution map of the elements present in the catalyst by electron microprobe.
  • silicon in the range 0-20% it is counted only the added silicon and not that of the zeolite.
  • the zeolite may optionally be doped with metal elements such as, for example, rare earth metals, especially lanthanum and cerium, or noble or non-noble metals of group VIII, such as platinum, palladium or ruthenium, rhodium, iridium, iron and other metals such as manganese, zinc, magnesium.
  • metal elements such as, for example, rare earth metals, especially lanthanum and cerium, or noble or non-noble metals of group VIII, such as platinum, palladium or ruthenium, rhodium, iridium, iron and other metals such as manganese, zinc, magnesium.
  • zeolites Y can be used.
  • a particularly advantageous acidic zeolite HY is characterized by various specifications: an overall molar ratio SiO 2 / Al 2 O 3 of between approximately 6 and 70 and preferably between approximately 12 and 50: a sodium content of less than 0.15% by weight determined on zeolite calcined at 1100 ° C .; a crystalline parameter has elementary mesh of between 24.58 x 10 -10 m and 24.24 x 10 -10 m, and preferably between 24.38 x 10 -10 m and 24.26 x 10 -10 m; a sodium recovery CNa capacity, expressed in grams of Na per 100 grams of modified zeolite, neutralized and then calcined, greater than about 0.85; a specific surface area determined by the BET method of greater than about 400 m 2 / g and preferably greater than 550 m 2 / g, a water vapor adsorption capacity at 25 ° C.
  • the zeolite has a porous distribution, determined by nitrogen physisorption, comprising between 5 and 45% and preferably between 5 and 40% of the total pore volume of the zeolite contained in pores with a diameter of between 20 ⁇ 10 -10 m and 80 ⁇ 10 -10 m, and between 5 and 45% and preferably between 5 and 40% of the total pore volume of the zeolite contained in pores of diameter greater than 80 x 10 -10 m and generally less than 1000 x 10 -10 m, the remainder of the pore volume being contained in pores with a diameter of less than 20 x 10 -10 m.
  • a preferred catalyst using this type of zeolite contains a matrix, at least one dealuminated zeolite Y having a crystalline parameter of between 2.424 nm and 2.455 nm, preferably between 2.426 and 2.388 nm, a higher overall SiO 2 / Al 2 O 3 molar ratio.
  • a catalyst comprising a partially amorphous Y zeolite is used for hydrocracking.
  • Peak levels and crystalline fractions are determined by X-ray diffraction, using a procedure derived from ASTM Method D3906-97 "Determination of Relative X-ray Diffraction Intensities of Faujasite-Type-Containing Materials". This method may be referred to for the general conditions of application of the procedure and, in particular, for the preparation of samples and references.
  • a diffractogram is composed of the characteristic lines of the crystallized fraction of the sample and of a background, caused mainly by the diffusion of the amorphous fraction or microcrystalline of the sample (a weak diffusion signal is linked to the apparatus, air , sample holder, etc.)
  • the peak level of the sample will be compared to that of a reference considered as 100% crystalline (NaY for example).
  • the peak level of a perfectly crystalline NaY zeolite is of the order of 0.55 to 0.60.
  • the peak level of a conventional USY zeolite is 0.45 to 0.55, its crystalline fraction relative to a perfectly crystalline NaY is from 80 to 95%.
  • the peak level of the solid which is the subject of the present invention is less than 0.4 and preferably less than 0.35. Its crystalline fraction is therefore less than 70%, preferably less than 60%.
  • the partially amorphous zeolites are prepared according to the techniques generally used for dealumination, from commercially available Y zeolites, that is to say which generally have high crystallinities (at least 80%). More generally, zeolites having a crystalline fraction of at least 60%, or at least 70%, may be used.
  • the Y zeolites generally used in hydrocracking catalysts are manufactured by modifying commercially available Na-Y zeolite. This modification leads to zeolites said stabilized, ultra-stabilized or dealuminated. This modification is carried out by at least one of the dealumination techniques, and for example the hydrothermal treatment, the acid attack. Preferably, this modification is carried out by combining three types of operations known to those skilled in the art: hydrothermal treatment, ion exchange and acid attack.
  • Another particularly interesting zeolite is a zeolite not dealuminated globally and very acidic.
  • zeolite not dealuminated overall is meant a zeolite Y (structural type FAU, faujasite) according to the nomenclature developed in "Atlas of zeolites structure types", WM Meier, DH Olson and Ch. Baerlocher, 4 th revised Edition 1996, Elsevier.
  • the crystalline parameter of this zeolite may have decreased by extraction of aluminum from the structure or framework during the preparation but the ratio Global SiO 2 / Al 2 O 3 has not changed since the aluminum has not been chemically extracted.
  • Such a non-dealuminated zeolite globally has a composition of silicon and aluminum expressed by the overall SiO 2 / Al 2 O 3 ratio equivalent to the non-dealuminated Y zeolite of departure.
  • This zeolite Y not dealuminated globally can be in the hydrogen form or be at least partially exchanged with metal cations, for example using alkaline earth metal cations and / or atomic number rare earth metal cations. to 71 included.
  • a zeolite devoid of rare earths and alkaline earths is preferable, as is the catalyst.
  • Y zeolite not globally dealuminated generally has a crystalline parameter greater than 2.438 nm, an overall SiO 2 / Al 2 O 3 ratio of less than 8, an SiO 2 / Al 2 O 3 framework ratio of less than 21 and greater than the SiO 2 ratio. 2 / Al 2 O 3 overall.
  • the zeolite globally not dealuminated can be obtained by any treatment which does not extract the aluminum sample, such as for example the steam treatment, treatment with SiCl 4 ...
  • Another type of catalyst that is advantageous for hydrocracking contains an amorphous acid oxide matrix of phosphorus doped alumina type, a non-dealuminated Y zeolite which is globally and highly acidic, and optionally at least one group VIIA element and in particular fluorine.
  • the invention is not limited to the cited and preferred Y zeolites, but other types of Y zeolites may be used in this process.
  • the catalyst Prior to the injection of the feedstock, the catalyst is subjected to a sulfurization treatment making it possible, at least in part, to transform the metal species into sulfide before they come into contact with the feedstock to be treated.
  • This activation treatment by sulfurization is well known to those skilled in the art and can be performed by any method already described in the literature either in-situ, that is to say in the reactor, or ex-situ.
  • a conventional sulphurization method well known to those skilled in the art consists of heating in the presence of hydrogen sulphide (pure or for example under a stream of a hydrogen / hydrogen sulphide mixture) at a temperature of between 150 and 800 ° C. preferably between 250 and 600 ° C, generally in a crossed-bed reaction zone.
  • hydrotreatment and hydrocracking catalysts are in the same reactor or in two reactors without intermediate separation, they are sulphurized at the same time.
  • the liquid effluent from the hydrocracking is then distilled to separate a naphtha cut, a diesel cut, possibly a kerosene cut (which may sometimes be included at least partly in the diesel cut), LPG light gases. There remains a liquid residue which can be advantageously recycled in the process after purging generally.
  • the process makes it possible to directly produce a diesel having a 95% volume distillation point below 360 ° C., and generally this point is at most 350 ° C. or even at most 340 ° C., having a sulfur content. at most 50 ppm, and generally at most 10 ppm, having a cetane number of at least 52 and most generally at least 54 and preferably having a polyaromatic content of at most 6% wt. and generally at most 1%, and preferably a pour point of less than -10 ° C, and preferably an aromatic content of less than 15 wt%.
  • Kerosene may possibly be at least partly sent to the diesel pool, depending on the needs of the operator.
  • middle distillate kerosene + diesel
  • LPG light gases represent at most 10% by weight and more generally at most 5% by weight
  • naphtha generally at least 20% by volume
  • the figure 1 represents an embodiment of the moderate pressure hydrocracking process.
  • the Figures 2B , 2C , 3 , 4 illustrate an integration of this process into a catalytic cracking plant, the Figure 2A showing the prior art.
  • the hydrocracking process at moderate pressure is schematized figure 1 .
  • the charge to be treated enters the pipe 1, it is in this figure, added the recycling of the hydrocracking residue through the pipe 2 and hydrogen through the pipe 3. It passes through a heat exchanger 4 in mixture with the recycled hydrogen fed via the pipe 5, then through a heater 6 before being introduced into the reactor (or zone) 7 hydrocracking at moderate pressure optionally containing the upstream or hydrotreating zones.
  • the reactor 7 contains at least one catalytic bed 8 of at least one hydrocracking catalyst. Preferably, it may contain upstream of the first bed 8 at least one hydrotreatment catalyst.
  • the liquid effluent from the reactor and exiting through line 9 passes through exchanger 4 and then into a gas-liquid separator 10 separating hydrogen which is recycled via line 5 to the hydrocracking reactor 7.
  • the separated liquid effluent leaving the line 11 is preferably sent to a stripper 12 which separates naphtha and light gases through line 13 and a resulting effluent exiting through line 14 is distilled in the column 15 of atmospheric distillation.
  • This arrangement schematically illustrates an embodiment of the distillation. Any other provision known to those skilled in the art resulting in separating the same products is also suitable.
  • the product separation zone separates a hydrocracking residue having a boiling point greater than at least 535 ° C., and comprises a purge pipe for said residue and optionally a pipe for recycling said purged residue towards the zone or the reactor. hydrocracking.
  • the hydrocracking process described here can very advantageously be integrated into the refinery at the level of a catalytic cracking process (generally FCC: fluidized catalytic cracking).
  • FCC fluidized catalytic cracking
  • the Figure 2A represents a current installation.
  • the crude hydrocarbon feedstock (or crude oil) that arrives via the pipe 20 is distilled in the atmospheric column 21. It is separated from (this naphtha fraction will also be understood by this term generally (line 22), a jet fuel fraction ( pipe 23), a diesel fraction (line 24).
  • Said vacuum distillate is sent to a catalytic cracking unit 28 (generally in a fluidized bed) which, by this process, produces, among others, naphtha discharged via line 29, a strongly aromatic diesel type fraction (light cycle oil LCO). discharged through line 30, and a "slurry" or residue exiting through line 31.
  • a catalytic cracking unit 28 generally in a fluidized bed
  • LCO strongly aromatic diesel type fraction
  • the vacuum residue is processed in a visbreaking unit 39, which produces, among others, naphtha (line 40) and diesel (line 41) which are of poor quality.
  • the visbreaking residue (line 42) is only usable as fuel and slurry, a portion of the LCO can be used to flow this fuel.
  • the Figure 2B shows the process and the installation according to the invention, associating a hydrocracking at moderate pressure and a catalytic cracking.
  • the installation according to the invention ( Figure 2B ) comprises in addition to that of the prior art ( Figure 2A ), the moderate pressure hydrocracking unit 32 which receives a light fraction resulting from the vacuum distillation fed into line 33.
  • the unit 32 comprises the reactor (s) or hydrocracking zone (s) at moderate pressure and the associated separations making it possible, among other things, to leave a high-grade diesel via a line 34, via the pipe 35 a naphtha and by a line 36 purging the hydrocracking residue.
  • the unit 32 also comprises a hydrotreatment zone before hydrocracking.
  • the hydrocracking residue can at least partly be sent to catalytic cracking (unit 28) but not required.
  • the purge of the hydrocracking process is advantageously sent to the unit 28.
  • the atmospheric residue which therefore contains at least a portion of the heavy atmospheric gas oil, is distilled under vacuum in at least a light fraction (distillate) and at least a heavy fraction (distillate), and a residue remains under vacuum.
  • Said light fraction to be treated by hydrocracking has a temperature T 5 which is between 250 and 400 ° C and a temperature T 95 which is at most 470 ° C. It is a light vacuum diesel fuel (LVGO). The final boiling point is chosen by the operator according to the column at his disposal and according to the valuation required by the products. Said light fraction has the other characteristics of the hydrocarbon feeds treated by the process according to the invention and previously described.
  • this light pressure hydrocracking vacuum distillate treatment can be implemented when the production and / or the quality of the diesel need to be increased, regardless of the type of treatment reserved for the distillate (s). heavy (s) and residue of vacuum distillation.
  • the vacuum distillation residue (line 38) which generally has a temperature T 5 of at least 535 ° C, at least 550 ° C preferably, or even at least 565 ° C or 570 ° C, can be submitted for example to visbreaking (shown figure 1 ) or a residue hydroconversion or coking.
  • At least one so-called heavy vacuum distillate fraction located between the light fraction having a T 95 temperature of at most 470 ° C, and the residue under vacuum, is subjected to catalytic cracking.
  • the figure 3 represents an installation and a process in which the heavy fraction resulting from distillation under vacuum and which is subjected to catalytic cracking, is, before said cracking, subjected to hydrotreatment in a zone 43.
  • the references of the previous figures are repeated here.
  • All conventional hydrotreating catalysts are usable.
  • Catalysts containing at least one non-noble group VIII element (Co, Ni for example) and at least one group VIB element (Mo, W for example) deposited on a support preferably based on alumina or silica are mentioned.
  • -alumina alumina.
  • the particularity of this step lies in its operating conditions: a hydrogen partial pressure between 25 and 90 bar, preferably less than 85 bar, or even lower than 80 bar, or even lower than 70 bar, and a temperature of 350.degree. 450 ° C, preferably 370-430 ° C adjusted so as to maintain a conversion of at least 10% and preferably less than 40% in products boiling below 350 ° C and preferably 15-30%.
  • the hydrotreated effluent then passes into the catalytic cracking unit 28.
  • FIG 4 it is schematically represented a contribution of heavy diesel fraction in the unit 32 which is carried out hydrocracking at moderate pressure.
  • it is obtained in atmospheric distillation, in addition to the naphtha cuts (line 22), kerosene (line 23), a light diesel fraction LGO (line 46) and a heavy diesel fraction HGO (line 47).
  • This heavy diesel fraction is sent to unit 32 where it will undergo hydrotreatment and then hydrocracking at moderate pressure.
  • the present application describes a process for the production of diesel and naphtha, the production of diesel being carried out by a moderate pressure hydrocracking process as explained above, and the production of naphtha being obtained essentially by catalytic cracking.
  • the hydrocracking purge is sent by catalytic cracking.
  • the diesel has a cetane number of 49 and a sulfur content of 2100 ppm. To be in specification (51 cetane and 350 ppm sulfur), it must undergo a conventional desulfurization.
  • the diesel has a cetane number of only 48 and must therefore undergo extremely severe hydrodesulfurization and hydrogenation that can not be achieved in the current units.
  • the naphtha pool would have a sulfur content of 270 ppm, which would require severe subsequent treatments to reduce it to 10-50 ppm. Also, to avoid expensive investments, the naphtha fraction from the FCC will be treated separately in severe hydrodesulfurization, with the disadvantage of lowering the octane number.
  • the other naphtha fractions (for example from the visbreductor, from the crude distillation, etc.) will be sent to reforming and possibly an isomerization unit after hydrotreatment.
  • the cetane of the diesel remains at about 48.
  • the FCC naphtha has a content of 15 ppm sulfur, and in the naphtha pool the sulfur content can be lowered as low as about 5.5 ppm, without loss of sulfur. sensitive octane.
  • the vacuum distillation separates, a light fraction 350-410 ° C, a heavy fraction 410-565 ° C and a residue 565 ° C +.
  • the diesel / naphtha balance could be adjusted to more high-quality diesel, while reducing the production of 40cst fuel (-6.3%) somewhat, adapting the refinery to market needs.
  • the FCC unit does not work at full capacity, the operator can very advantageously introduce a charge supplement able to be treated in FCC (such as an atmospheric residue). This addition will preferably be carried out in the feed entering the vacuum distillation column (dashed lines on the figure 3 ).

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Abstract

The invention concerns a process for moderate pressure hydrocracking (i.e., at a hydrogen partial pressure of more than 70 bars and at most 100 bars) with a conversion of at least 80% by volume, of a feed with a T5 temperature in the range 250° C. to 400° C. and a T95 temperature of at most 470° C. (T5 and T95 measured in accordance with ASTM-D2887), to produce a diesel with a 95% distillation point of less than 360° C., a sulphur content of at most 50 ppm and a cetane number of more than 51. The process operates with or without a recycle of the liquid effluent. Highly advantageously, it can be integrated into a refinery layout comprising catalytic cracking. The invention also concerns a unit for carrying out said process.

Description

L'invention concerne un procédé avec hydrocraquage à pression modérée, pour la production de diesel de très haute qualité avec des rendements élevés.The invention relates to a process with moderate pressure hydrocracking, for the production of very high quality diesel with high yields.

L'invention concerne également un procédé incluant ledit procédé d'hydrocraquage et un procédé de craquage catalytique, ainsi que l'installation utilisable pour la mise en oeuvre dudit procédé.The invention also relates to a process including said hydrocracking process and a catalytic cracking process, as well as the installation that can be used for carrying out said method.

L'industrie du raffinage doit dès maintenant trouver des schémas de raffinage pour s'adapter à la sévérisation des normes concernant la qualité des carburants et qui seront en vigueur en Europe en 2005. La teneur maximale en soufre du diesel devra être d'au plus 50 ppm. Le point de distillation 95% (ASTM D-86) du diesel, actuellement de 360°C, sera probablement réduit, par exemple de 10°C, ce qui représenterait actuellement pour une raffinerie une diminution de 5% en volume de diesel produit. Il est également envisagé de diviser au moins par deux les teneurs en polyaromatiques actuelles qui sont d'environ 11 % massique actuellement. L'indice de cétane exigé serait parallèlement augmenté au-delà de 51, passant par exemple de la valeur actuelle de 51 à 52.The refining industry must now find refining schemes to adapt to the stringent fuel quality standards that will be in effect in Europe in 2005. The maximum sulfur content of diesel fuel must be at most 50 ppm. The 95% distillation point (ASTM D-86) of diesel, currently 360 ° C, will probably be reduced, for example 10 ° C, which would currently represent for a refinery a decrease of 5% in volume of diesel produced. It is also envisaged to divide by at least the current polyaromatic contents which are about 11% by mass at present. The cetane number required would, at the same time, be increased beyond 51, for example from the current value of 51 to 52.

Dans le même temps, la demande en diesel ne cesse de croître et on s'attend à des accroissements de demande de près de 20% dans la décennie.At the same time, diesel demand is steadily growing and demand increases are expected to be around 20% in the decade.

La distillation du brut ne suffisant pas à couvrir la production de diesel, on produit actuellement du diesel par des procédés d'hydrocraquage à haute pression (en général d'au moins 120 bars en pression partielle d'hydrogène) traitant des charges lourdes qui sont des charges présentant une température T95 le plus souvent de l'ordre de 500°C au moins, T95 étant la température du point 95% volume obtenu par distillation simulée (ASTM-D28 87). Les composés lourds sont craqués en composés plus légers, dont une partie se retrouve dans la coupe distillat moyen, (diesel et kérosène) de la distillation de l'hydrocraquage. De tels procédés à haute pression sont classiques.The distillation of the crude is not sufficient to cover the production of diesel, diesel is currently produced by high pressure hydrocracking processes (generally at least 120 bar hydrogen partial pressure) dealing with heavy loads which are fillers having a temperature T 95 most often of the order of at least 500 ° C, T 95 being the temperature of the 95% volume point obtained by simulated distillation (ASTM-D28 87). Heavy compounds are cracked into lighter compounds, some of which is found in the middle distillate cut (diesel and kerosene) of hydrocracking distillation. Such high pressure methods are conventional.

Pour parvenir aux nouvelles normes, le diesel de distillation du brut devra subir une hydrodésulfuration profonde. Par ailleurs, l'hydrocraquage haute pression est une solution qui peut s'avérer onéreuse. On a donc recherché une solution plus avantageuse qui de plus, pourrait s'intégrer dans les unités actuelles pour utiliser au mieux les ressources existantes de la raffinerie.To reach the new standards, crude distillation diesel will have to undergo deep hydrodesulfurization. In addition, high pressure hydrocracking is a solution that can be expensive. A more advantageous solution has therefore been sought which, moreover, could be integrated into the current units in order to make the best use of the existing resources of the refinery.

Le procédé exposé dans la présente demande est un procédé d'hydrocraquage fonctionnant à des pressions modérées (au-delà de 70 bars et d'au plus 100 bars en pression partielle hydrogène) qui permet d'obtenir directement un diesel répondant au spécifications 2005 à partir de charges relativement légères dans des conditions plus économiques que l'hydrocraquage haute pression.The process described in the present application is a hydrocracking process operating at moderate pressures (above 70 bar and at most 100 bar hydrogen partial pressure) which makes it possible to directly obtain a diesel that meets the 2005 specifications. from relatively light loads under more economical conditions than high pressure hydrocracking.

Plus précisément, l'invention concerne un procédé de traitement de charge hydrocarbonée brute comprenant les étapes suivantes :

  • distillation atmosphérique de la charge hydrocarbonée brute, produisant au moins une fraction naphta, au moins une fraction carburéacteur, au moins une fraction diesel et un résidu atmosphérique,
  • distillation sous vide du résidu atmosphérique pour séparer au moins une fraction distillat légère, au moins une fraction distillat lourde et un résidu sous vide à point d'ébullition d'au moins 535°C,
  • craquage catalytique d'au moins une fraction distillat lourde, éventuellement additionnée d'une partie au moins du résidu d'hydrocraquage,
  • traitement de ladite fraction légère pour produire un diesel ayant un point de distillation 95% inférieur à 360°C, une teneur en soufre d'au plus 50 ppm et un indice de cétane supérieur à 51, ledit procédé traitant des charges hydrocarbonées ayant une température T5 comprise entre 250 et 400°C et une température T95 d'au plus 470°C, ledit procédé comprenant un hydrotraitement produisant un effluent ayant une teneur en azote organique en-dessous de 10ppm puis un hydrocraquage à pression modérée avec un catalyseur d'hydrocraquage comprenant au moins une zéolite Y, au moins une matrice et une fonction hydro-déshydrogénante, ledit hydrocraquage opérant sous une pression partielle d'hydrogène supérieure à 70 bars et d'au plus 100 bars, à une température d'au moins 320°C, avec un rapport volumique H2/charge d'au moins 200 NI/NI, une vitesse volumique horaire de 0,15-7h-1, le procédé réalisant une conversion d'au moins 80% volume et l'effluent liquide obtenu par hydrocraquage étant distillé pour séparer le diesel.
More specifically, the invention relates to a crude hydrocarbon feedstock treatment process comprising the following steps:
  • atmospheric distillation of the crude hydrocarbon feedstock, producing at least one naphtha fraction, at least one jet fuel fraction, at least one diesel fraction and one atmospheric residue,
  • vacuum distillation of the atmospheric residue to separate at least one light distillate fraction, at least one heavy distillate fraction and a vacuum residue having a boiling point of at least 535 ° C,
  • catalytic cracking of at least one heavy distillate fraction, optionally with at least a portion of the hydrocracking residue added thereto,
  • treating said light fraction to produce a diesel having a distillation point 95% below 360 ° C, a sulfur content of at most 50 ppm and a cetane number greater than 51, said process treating hydrocarbon feeds having a temperature T 5 between 250 and 400 ° C and a temperature T 95 of at most 470 ° C, said process comprising a hydrotreatment producing an effluent having an organic nitrogen content below 10 ppm and then hydrocracking at moderate pressure with a catalyst hydrocracking composition comprising at least one zeolite Y, at least one matrix and a hydro-dehydrogenating function, said hydrocracking operating under a hydrogen partial pressure of greater than 70 bar and at most 100 bar, at a temperature of at least 320 ° C, with a volume ratio H 2 / load of at least 200 NI / NI, an hourly space velocity of 0.15-7h -1 , the process achieving a conversion of at least 80% volume and the effluent ob liquid held by hydrocracking being distilled to separate the diesel.

De préférence, le résidu de distillation est recyclé dans le procédé après purge.Preferably, the distillation residue is recycled to the process after purging.

Les charges, l'hydrotraitement, l'hydrocraquageLoads, hydrotreatment, hydrocracking

Les charges traitées dans le procédé présentent un point T5 compris entre 250 et 400°C et de préférence entre 280 et 370°C. Le point T5 représente la température du point 5% volume obtenu par distillation simulée (ASTM-D28 87).The feeds treated in the present process a point T5 between 250 and 400 ° C and preferably between 280 and 370 ° C. Point T 5 represents the temperature point 5% volume obtained by simulated distillation (ASTM D28 87).

Généralement, les charges ont un point T5 compris entre 320-400°C ou encore entre 320-370°C. Très avantageusement on peut ajouter à ces charges une fraction du diesel, par exemple du diesel lourd issu de la distillation atmosphérique du brut, qui présente le plus souvent un point T5 de l'ordre d'au moins 280°C. Cette fraction diesel lourd peut tout aussi bien être obtenue directement dans le résidu atmosphérique.Generally, the charges have a point T 5 between 320-400 ° C or between 320-370 ° C. Very advantageously can be added to these loads a fraction of diesel, for example heavy diesel from the atmospheric distillation of the crude, which most often has a T 5 point of the order of at least 280 ° C. This heavy diesel fraction can just as easily be obtained directly in the atmospheric residue.

Cette disposition (ajout de diesel) est particulièrement avantageuse. En effet, elle permet de traiter par un hydrotraitement suivi d'un hydrocraquage à pression modérée une partie lourde de la fraction diesel qui est chargée en composés azotés et soufrés les plus difficiles à hydrotraiter. Dès lors, un hydrotraitement conventionnel est utilisable pour traiter la fraction diesel restante, et il n'est pas besoin d'investissement coûteux.This provision (diesel addition) is particularly advantageous. Indeed, it allows to treat with a hydrotreatment followed by hydrocracking at a moderate pressure a heavy part of the diesel fraction which is loaded with nitrogen compounds and sulfur most difficult to hydrotreat. Therefore, conventional hydrotreating can be used to treat the remaining diesel fraction, and there is no need for expensive investment.

De plus, en traitant cette partie lourde du diesel dans le procédé selon l'invention, l'hydrodésulfuration de la fraction lourde est réalisée avec parallèlement une amélioration de ses qualités (indice de cétane supérieur à celui qui aurait été obtenu par hydrotraitement sévère seul).Moreover, by treating this heavy part of the diesel in the process according to the invention, the hydrodesulfurization of the heavy fraction is carried out with an improvement in its qualities (cetane number higher than that which would have been obtained by severe hydrotreatment alone). .

Les charges utilisables présentent également une température T95 d'au plus 470°C, ou mieux d'au plus 450°C, ou mieux compris dans l'intervalle 390-430°C, T95 représentant la température du point 95% obtenu par distillation simulée (ASTM-D28 87).The usable fillers also have a temperature T 95 of at most 470 ° C, more preferably at most 450 ° C, or better still in the range 390-430 ° C, T 95 representing the temperature of the 95% point obtained by simulated distillation (ASTM-D28 87).

On peut citer comme charges des distillats sous vide légers, une fraction légère d'un gazole sous vide (VGO) conventionnel (par exemple la moitié la plus légère), les gazoles atmosphériques lourds (HGO), les mélanges desdites charges ou encore des mélanges desdites charges avec au moins une fraction diesel par exemple provenant de la distillation du brut ou d'une unité de FCC (craquage catalytique).Light vacuum distillates, a light fraction of a conventional vacuum gas oil (VGO) (for example the lightest half), heavy atmospheric gas oils (HGO), mixtures of the said fillers or mixtures thereof can be mentioned as fillers. said feeds with at least one diesel fraction for example from the distillation of crude or a unit of FCC (catalytic cracking).

Les charges hydrocarbonées traitées présentent généralement des teneurs en soufre de 0,2 à 4% massiques et en azote de 100-3500 ppm massiques. Elles sont donc généralement préalablement hydrotraitées avant d'être hydrocraquées de façon à abaisser les teneurs en azote organique (c'est-à-dire d'azote faisant partie de molécules organiques) en-dessous de 80 ppm, ou mieux de 50 ppm et de préférence en-dessous de 10 ppm, et les teneurs en soufre organique, (c'est-à-dire des soufres faisant partie de molécules organiques) en-dessous de 200 ppm et de préférence en-dessous de 50 ppm. Ces charges hydrotraitées (dites propres) peuvent ensuite être soumises à l'hydrocraquage.The hydrocarbon feedstocks treated generally have sulfur contents of 0.2 to 4% by mass and nitrogen of 100 to 3500 ppm by weight. They are therefore generally previously hydrotreated before being hydrocracked so as to lower the contents of organic nitrogen (that is to say of nitrogen forming part of organic molecules) below 80 ppm, or better still 50 ppm and preferably below 10 ppm, and organic sulfur contents (i.e., sulfur containing organic molecules) below 200 ppm and preferably below 50 ppm. These hydrotreated loads (called clean) can then be subjected to hydrocracking.

Les conditions de l'hydrotraitement sont généralement :

  • pression de 5-25MPa, avec de préférence une pression partielle d'hydrogène supérieure à 70 bars et d'au plus 100 bars, de préférence d'au moins 80 bars ou encore d'au moins 85 bars,
  • température d'au moins 320°C, en général d'au moins 350°C et d'au plus 450°C le plus souvent, voire même d'au plus 430°C,
  • rapport volumique H2/charge d'au moins 100 NI/I, et le plus souvent entre 100-2000 NI/I ou encore 300-2000 NI/I,
  • vitesse volumique horaire de 0,1-10h-1, de préférence 0,15-7h-1, et avantageusement 0,05-4h-1.
The conditions of hydrotreatment are generally:
  • a pressure of 5-25 MPa, with a hydrogen partial pressure of greater than 70 bar and a maximum of 100 bar, preferably of at least 80 bar or at least 85 bar,
  • temperature of not less than 320 ° C, generally not less than 350 ° C and not more than 450 ° C, and often not more than 430 ° C,
  • H 2 / load ratio of at least 100 N / I, and most often between 100-2000 N / I or 300-2000 N / I,
  • hourly space velocity of 0.1-10 h -1, preferably 0,15-7h -1 and advantageously 0,05-4h -1.

La conversion réalisée dans l'hydrotraitement est généralement d'au moins 10% volume et inférieure à 40% en produit bouillant au-dessous de 350°C.The conversion carried out in the hydrotreatment is generally at least 10% by volume and less than 40% by product boiling below 350 ° C.

L'hydrotraitement peut être réalisé soit dans le réacteur d'hydrocraquage et dans au moins un lit précédant le premier lit du catalyseur d'hydrocraquage, dans le sens de l'écoulement de la charge, soit dans un réacteur indépendant précédant le réacteur d'hydrocraquage. Il y a ou il n'y a pas de séparation intermédiaire des gaz régénérés par l'hydrotraitement. Le premier mode (même réacteur) sans séparation intermédiaire est préféré. Est comprise également dans le procédé une réalisation dans laquelle l'hydrotraitement est réalisé dans la raffinerie très en amont de l'hydrocraquage, des traitements intermédiaires pourront être également effectués.The hydrotreatment can be carried out either in the hydrocracking reactor and in at least one bed preceding the first bed of the hydrocracking catalyst, in the direction of flow of the feedstock, or in an independent reactor preceding the reactor. hydrocracking. There is or there is no intermediate separation of the regenerated gases by the hydrotreatment. The first mode (same reactor) without intermediate separation is preferred. Also included in the process is an embodiment in which the hydrotreatment is carried out in the refinery very upstream of the hydrocracking, intermediate treatments may also be performed.

La charge propre est, au moins en partie, en présence d'hydrogène mise au contact d'au moins un catalyseur d'hydrocraquage dans les conditions opératoires suivantes :

  • pression partielle d'hydrogène supérieure à 70 bars et d'au plus 100 bars, de référence d'au moins 80 bars ou encore d'au moins 85 bars,
  • température d'au moins 320°C, en général d'au moins 350°C et d'au plus 450°C le plus souvent, voire même d'au plus 430°C,
  • rapport volumique H2/charge d'au moins 200NI/NI et le plus souvent entre 300-2000NI/NI.
  • Vitesse volumique horaire 0,15-7h-1, de préférence 0,05-4h-1.
The intrinsic charge is, at least in part, in the presence of hydrogen brought into contact with at least one hydrocracking catalyst under the following operating conditions:
  • hydrogen partial pressure greater than 70 bar and at most 100 bar, with a reference of at least 80 bar or at least 85 bar,
  • temperature of not less than 320 ° C, generally not less than 350 ° C and not more than 450 ° C, and often not more than 430 ° C,
  • volume ratio H2 / load of at least 200NI / NI and most often between 300-2000NI / NI.
  • Hourly volume velocity 0.15-7h -1 , preferably 0.05-4h -1 .

Le procédé peut fonctionner avec ou sans recyclage du résidu de distillation de l'effluent d'hydrocraquage (fraction non convertie). Lorsqu'il y a recyclage, il est effectué vers le réacteur d'hydrocraquage s'il est séparé de celui d'hydrotraitement par exemple ou encore dans la charge entrant dans le réacteur où sont effectués l'hydrotraitement et l'hydrocraquage.The process can operate with or without recycling the distillation residue of the hydrocracking effluent (unconverted fraction). When recycling is carried out, it is carried out to the hydrocracking reactor if it is separated from that of hydrotreatment, for example, or to the feedstock entering the reactor where hydrotreatment and hydrocracking are carried out.

Dans ces conditions, au niveau du procédé dans sa globalité, la conversion en produits bouillant au-dessous de 350°C est d'au moins 80% volume, et plus généralement d'au moins 90% volume, ou encore d'au moins 95% volume.Under these conditions, at the level of the process as a whole, the conversion to products boiling below 350 ° C. is at least 80% by volume, and more generally at least 90% by volume, or at least 90% by volume. 95% volume.

Les catalyseurs d'hydrotraitementHydrotreating catalysts

Des catalyseurs classiques peuvent être utilisés, qui contiennent au moins un support amorphe et au moins un élément hydro-déshydrogénant (généralement au moins un élément des groupes VIB et VIII non noble, et le plus souvent au moins un élément du groupe VIB et au moins un élément du groupe VIII non noble).Conventional catalysts may be used, which contain at least one amorphous support and at least one hydro-dehydrogenating element (generally at least one element of groups VIB and VIII non-noble, and most often at least one element of group VIB and at least one a non-noble group VIII element).

De façon très avantageuse, un catalyseur d'hydrotraitement comprend au moins une matrice, au moins un élément hydro-déshydrogénant choisi dans le groupe formé par les éléments du groupe VIB et du groupe VIII de la classification périodique, éventuellement au moins un élément promoteur déposé sur le catalyseur et choisi dans le groupe formé par le phosphore, le bore et le silicium, éventuellement au moins un élément du groupe VIIA (chlore, fluor préférés), et éventuellement au moins un élément du groupe VIIB (manganèse préféré), éventuellement au moins un élément du groupe VB (niobium préféré).Very advantageously, a hydrotreating catalyst comprises at least one matrix, at least one hydro-dehydrogenating element chosen from the group formed by the elements of group VIB and group VIII of the periodic table, optionally at least one promoter element deposited on the catalyst and selected from the group consisting of phosphorus, boron and silicon, optionally at least one group VIIA element (chlorine, fluorine preferred), and optionally at least one element of group VIIB (preferred manganese), optionally at least minus one element of the VB (preferred niobium) group.

De façon générale, le catalyseur d'hydrotraitement contient :

  • 5-40% poids d'au moins un élément des groupes VIB et VIII non noble (%oxyde)
  • 0-20% d'au moins un élément promoteur choisi parmi le phosphore, le bore, le silicium (% oxyde), de préférence 0,1-20% ; avantageusement le bore et/ou le silicium sont présents, et éventuellement le phosphore.
  • 0-20% d'au moins un élément du groupe VIIB (manganèse par exemple)
  • 0-20% d'au moins un élément du groupe VIIA (fluor, chlore par exemple)
  • 0-60% d'au moins un élément du groupe VB (niobium par exemple)
  • 0,1-95% d'au moins une matrice, et de préférence l'alumine
In general, the hydrotreatment catalyst contains:
  • 5-40% by weight of at least one element of groups VIB and VIII non-noble (% oxide)
  • 0-20% of at least one promoter element selected from phosphorus, boron, silicon (% oxide), preferably 0.1-20%; advantageously boron and / or silicon are present, and possibly phosphorus.
  • 0-20% of at least one element of group VIIB (manganese for example)
  • 0-20% of at least one VIIA group element (fluorine, chlorine, for example)
  • 0-60% of at least one element of group VB (niobium for example)
  • 0.1-95% of at least one matrix, and preferably alumina

De préférence, ce catalyseur contient du bore et/ou du silicium comme élément promoteur, avec éventuellement en plus du phosphore comme autre élément promoteur. Les teneurs en bore, silicium, phosphore sont alors de 0,1-20%, de préférence 0,1-15%, encore plus avantageusement 0,1-10%.Preferably, this catalyst contains boron and / or silicon as a promoter element, optionally with addition of phosphorus as another promoter element. The contents of boron, silicon and phosphorus are then from 0.1 to 20%, preferably from 0.1 to 15%, and still more preferably from 0.1 to 10%.

Les matrices qui peuvent être utilisés seuls ou en mélange sont à titre d'exemple non limitatif l'alumine, l'alumine halogénée, la silice, la silice-alumine, les argiles (par exemple parmi les argiles naturelles telles que le kaolin ou la bentonite), la magnésie, l'oxyde de titane, l'oxyde de bore, la zircone, les phosphates d'aluminium, les phosphates de titane, les phosphates de zirconium, le charbon, les aluminates. On préfère utiliser des matrices contentant de l'alumine, sous toutes ces formes connues de l'Homme du métier, et de manière encore plus préférée les alumines, par exemple l'alumine gamma.The matrices that can be used alone or as a mixture are, by way of nonlimiting example, alumina, halogenated alumina, silica, silica-alumina, clays (for example, natural clays such as kaolin or bentonite), magnesia, titanium oxide, boron oxide, zirconia, aluminum phosphates, titanium phosphates, zirconium phosphates, coal, aluminates. It is preferred to use matrices containing alumina, in all these known forms those skilled in the art, and even more preferably the aluminas, for example gamma alumina.

Le rôle de fonction hydro-déshydrogénante est remplie de préférence par au moins un métal ou composé de métal des groupes VIII non noble et VI de préférence choisi(s) parmi le molybdène, tungstène, nickel et cobalt. De préférence, ce rôle est assuré par la combinaison d'au moins un élément du Groupe VIII (Ni, Co) avec au moins un élément du groupe VIB (Mo, W).The role of hydro-dehydrogenating function is preferably filled by at least one metal or metal compound of non-noble groups VIII and VI preferably selected from molybdenum, tungsten, nickel and cobalt. Preferably, this role is provided by the combination of at least one Group VIII element (Ni, Co) with at least one Group VIB element (Mo, W).

Ce catalyseur pourra contenir avantageusement du phosphore ; en effet il est connu dans l'art antérieur que ce composé apporte deux avantages aux catalyseurs d'hydrotraitement : une facilité de préparation lors notamment de l'imprégnation des solutions de nickel et de molybdène, et une meilleure activité d'hydrogénation.
Dans un catalyseur préféré, la concentration totale en oxydes de métaux des groupes VI et VIII est comprise entre 5 et 40 % en poids et de préférence entre 7 et 30 % et le rapport pondéral exprimé en oxyde métallique entre métal (ou métaux) du groupe VIB sur métal (ou métaux) du groupe VIII est de préférence compris entre 20 et 1,25 et encore plus préféré entre 10 et 2. La concentration en oxyde de phosphore P2O5 sera inférieure à 15 % poids et de préférence à 10 % poids.This catalyst may advantageously contain phosphorus; in fact, it is known in the prior art that this compound provides two advantages to hydrotreatment catalysts: an ease of preparation, especially when impregnating solutions of nickel and molybdenum, and a better hydrogenation activity.
In a preferred catalyst, the total concentration of Group VI and VIII metal oxides is between 5 and 40% by weight and preferably between 7 and 30% and the weight ratio expressed as metal oxide between metal (or metals) of the group VIB metal (or metals) from group VIII is preferably between 20 and 1.25 and even more preferred between 10 and 2. the concentration of phosphorus oxide P 2 O 5 is less than 15% by weight and preferably 10 % weight

Un autre catalyseur d'hydrotraitement préféré qui contient du bore et/ou silicium (et de préférence du bore et du silicium), renferme généralement en % poids par rapport à la masse totale du catalyseur au moins un métal choisi dans les groupes suivants et avec les teneurs suivantes :

  • 3 à 60%, de préférence de 3 à 45% et de manière encore plus préférée de 3 à 30% d'au moins un métal du groupe VIB
et éventuellement,
  • 0 à 30%, de préférence de 0 à 25% et de manière encore plus préférée de 0 à 20% d'au moins un métal du groupe VIII,
le catalyseur renfermant en outre au moins un support choisi dans les groupes suivants avec les teneurs suivantes :
  • 0 à 99%, avantageusement 0,1 à 99%, de préférence de 10 à 98% et de manière encore plus préférée de 15 à 95% d'au moins une matrice amorphe ou mal cristallisée,
le dit catalyseur étant caractérisé en ce qu'il renferme en outre,
  • 0,1 à 20%, de préférence de 0,1 à 15% et de manière encore plus préférée de 0,1 à 10% de bore et/ou 0,1 à 20%, de préférence de 0,1 à 15% et de manière encore plus préférée de 0,1 à 10% de silicium.
et éventuellement,
  • 0 à 20%, de préférence de 0,1 à 15% et de manière encore plus préférée de 0,1 à 10% de phosphore,
et éventuellement encore,
  • 0 à 20%, de préférence de 0,1 à 15% et de manière encore plus préférée de 0,1 à 10% d'au moins un élément choisi dans le groupe VIIA, de préférence le fluor.
D'une façon générale, on préfère les formules ayant les rapports atomiques suivants:
  • un rapport atomique métal du groupe VIII/métaux du groupe VIB compris entre 0 et 1,
  • un rapport atomique B/métaux du groupe VIB compris entre 0,01 et 3,
  • un rapport atomique Si/métaux du groupe VIB compris entre 0,01 et 1,5,
  • un rapport atomique P/métaux du groupe VIB compris entre 0,01 et 1,
  • un rapport atomique élément du groupe VIIA/métaux du groupe VIB compris entre 0,01 et 2.
Another preferred hydrotreatment catalyst which contains boron and / or silicon (and preferably boron and silicon) generally contains, in% by weight with respect to the total mass of the catalyst, at least one metal selected from the following groups and with the following contents:
  • 3 to 60%, preferably 3 to 45% and even more preferably 3 to 30% of at least one Group VIB metal
and eventually,
  • 0 to 30%, preferably 0 to 25% and even more preferably 0 to 20% of at least one Group VIII metal,
the catalyst additionally containing at least one support selected from the following groups with the following contents:
  • 0 to 99%, advantageously 0.1 to 99%, preferably 10 to 98% and even more preferably 15 to 95% of at least one amorphous or poorly crystallized matrix,
said catalyst being characterized in that it further contains
  • 0.1 to 20%, preferably 0.1 to 15% and even more preferably 0.1 to 10% boron and / or 0.1 to 20%, preferably 0.1 to 15% and even more preferably from 0.1 to 10% of silicon.
and eventually,
  • 0 to 20%, preferably 0.1 to 15% and even more preferably 0.1 to 10% phosphorus,
and possibly again,
  • 0 to 20%, preferably 0.1 to 15% and even more preferably 0.1 to 10% of at least one member selected from group VIIA, preferably fluorine.
In general, formulas having the following atomic ratios are preferred:
  • a group VIII metal / Group VIB metal atomic ratio of between 0 and 1,
  • an atomic ratio B / metals of group VIB of between 0.01 and 3,
  • a Si / Group VIB atomic ratio of between 0.01 and 1.5,
  • an atomic ratio P / metals of group VIB of between 0.01 and 1,
  • an atomic ratio of element VIIA / Group VIB metals between 0.01 and 2.

Un tel catalyseur présente une activité en hydrogénation des hydrocarbures aromatiques et en hydrodéazotation et en hydrodésulfuration plus importante que les formules catalytiques sans bore et/ou silicium, et présente également une activité et une sélectivité en hydrocraquage plus importante que les formules catalytiques connues dans l'art antérieur. Le catalyseur avec bore et silicium est particulièrement intéressant. Sans vouloir être lié par une quelconque théorie, il semble que cette activité particulièrement élevée des catalyseurs avec du bore et du silicium est due aux renforcement de l'acidité du catalyseur par la présence conjointe du bore et du silicium sur la matrice ce qui induit d'une part une amélioration des propriétés hydrogénante, hydrodésulfurante, hydrodéazotante et d'autre part une amélioration de l'activité en hydrocraquage par rapport aux catalyseurs utilisés habituellement dans les réactions d'hydroraffinage d'hydroconversion.Such a catalyst has a higher activity in hydrogenation of aromatic hydrocarbons and in hydrodenitrogenation and hydrodesulphurization than the catalyst formulas without boron and / or silicon, and also has a greater hydrocracking activity and selectivity than the catalytic formulas known in the art. prior art. The catalyst with boron and silicon is particularly interesting. Without wishing to be bound by any theory, it seems that this particularly high activity of the catalysts with boron and silicon is due to the strengthening of the acidity of the catalyst by the joint presence of boron and silicon on the matrix which induces on the one hand an improvement of the hydrogenating, hydrodesulphurizing and hydrodenitrogenating properties and, on the other hand, an improvement of the hydrocracking activity with respect to the catalysts usually used in the hydroconversion hydrorefining reactions.

Les catalyseurs préférés sont les catalyseurs NiMo et/ou NiW sur alumine, également les catalyseurs NiMo et/ou NiW sur alumine dopée avec au moins un élément compris dans le groupe des atomes formé par le phosphore, le bore, le silicium et le fluor, ou encore les catalyseurs NiMo et/ou NiW sur silice-alumine, ou sur silice-alumine-oxyde de titane dopée ou non par au moins un élément compris dans le groupe des atomes formés par le phosphore, le bore, le fluor et le silicium.The preferred catalysts are the NiMo and / or NiW catalysts on alumina, also the NiMo and / or NiW catalysts on alumina doped with at least one element included in the group of atoms formed by phosphorus, boron, silicon and fluorine, or alternatively NiMo and / or NiW catalysts on silica-alumina, or on silica-alumina-oxide titanium doped or not by at least one element included in the group of atoms formed by phosphorus, boron, fluorine and silicon.

Un autre type de catalyseur particulièrement intéressant (notamment en activité améliorée) en hydrotraitemement, renferme une zéolithe Y partiellement amorphe qui sera décrit ultérieurement dans les catalyseurs d'hydrocraquage.Another type of catalyst of particular interest (especially in improved activity) in hydrotreating, contains a partially amorphous Y zeolite which will be described later in the hydrocracking catalysts.

Préalablement à l'injection de la charge, les catalyseurs utilisés dans le procédé selon la présente invention sont de préférence soumis préalablement à un traitement de sulfuration permettant de transformer, au moins en partie, les espèces métalliques en sulfure avant leur mise en contact avec la charge à traiter. Ce traitement d'activation par sulfuration est bien connu de l'Homme du métier et peut être effectué par toute méthode déjà décrite dans la littérature soit in-situ, c'est-à-dire dans le réacteur, soit ex-situ.Prior to the injection of the feedstock, the catalysts used in the process according to the present invention are preferably subjected beforehand to a sulphurization treatment making it possible, at least in part, to convert the metal species into sulphide before they come into contact with the feedstock. load to be processed. This activation treatment by sulfurization is well known to those skilled in the art and can be performed by any method already described in the literature either in-situ, that is to say in the reactor, or ex-situ.

Une méthode de sulfuration classique bien connue de l'homme du métier consiste à chauffer en présence d'hydrogène sulfuré (pur ou par exemple sous flux d'un mélange hydrogène/hydrogène sulfuré) à une température comprise entre 150 et 800°C, de préférence entre 250 et 600°C, généralement dans une zone réactionnelle à lit traversé.A conventional sulphurization method well known to those skilled in the art consists of heating in the presence of hydrogen sulphide (pure or for example under a stream of a hydrogen / hydrogen sulphide mixture) at a temperature of between 150 and 800 ° C. preferably between 250 and 600 ° C, generally in a crossed-bed reaction zone.

Les catalyseurs d'hydrocraquageHydrocracking catalysts

Un catalyseur préféré comprend au moins une zéolithe Y, au moins une matrice et une fonction hydro-déshydrogénante. Eventuellement, il peut également contenir au moins un élément choisi parmi le bore, le phosphore et le silicium, au moins un élément du G VIIA (chlore, fluor par exemple), au moins un élément du groupe VIIB (manganèse par exemple), au moins un élément du groupe VB (niobium par exemple).A preferred catalyst comprises at least one zeolite Y, at least one matrix and a hydro-dehydrogenating function. Optionally, it may also contain at least one element chosen from boron, phosphorus and silicon, at least one element of G VIIA (chlorine, fluorine for example), at least one element of group VIIB (manganese for example), with least one element of the group VB (niobium for example).

Le catalyseur renferme au moins une matrice minérale poreuse ou mal cristallisée de type oxyde. On peut citer à titre d'exemple non limitatif les alumines, les silices, les silice-alumines, les aluminates, l'alumine-oxyde de bore, la magnésie, le silice-magnésie, le zircone, l'oxyde de titane, l'argile, seuls ou en mélange.The catalyst contains at least one porous or poorly crystallized oxide type mineral matrix. By way of nonlimiting example, mention may be made of aluminas, silicas, silica-aluminas, aluminates, alumina-boron oxide, magnesia, silica-magnesia, zirconia, titanium oxide, silica, clay, alone or in mixture.

La fonction hydro-déshydrogénante est généralement assurée par au moins un élément du groupe VI B (par exemple molybdène et/ou tungstène) et/ou au moins un élément du groupe VIII non noble (par exemple cobalt et/ou nickel) de la classification périodique des éléments. Un catalyseur préféré contient essentiellement au moins un métal du groupe VI, et/ou au moins un métal du groupe VIII non noble, la zéolithe Y et de l'alumine. Un catalyseur encore plus préféré contient essentiellement du nickel, du molybdène, une zéolithe Y et de l'alumine.The hydro-dehydrogenating function is generally provided by at least one group VI B element (for example molybdenum and / or tungsten) and / or at least one non-noble group VIII element (for example cobalt and / or nickel) of the classification. periodic elements. A preferred catalyst essentially contains at least one Group VI metal, and / or at least one non-noble Group VIII metal, zeolite Y, and alumina. An even more preferred catalyst essentially contains nickel, molybdenum, zeolite Y and alumina.

Le catalyseur renferme éventuellement au moins un élément choisi dans le groupe formé par le bore, le silicium et le phosphore. De façon avantageuse, le catalyseur renferme éventuellement au moins un élément du groupe VIIA, de préférence le chlore et le fluor, éventuellement au moins un élément du groupe VIIB (manganèse par exemple), éventuellement au moins un élément du groupe VB (niobium par exemple).The catalyst optionally contains at least one element selected from the group formed by boron, silicon and phosphorus. Advantageously, the catalyst optionally contains at least one element of group VIIA, preferably chlorine and fluorine, optionally at least one element of group VIIB (manganese for example), optionally at least one element of group VB (niobium for example) ).

Le bore, le silicium et/ou le phosphore peuvent être dans la matrice, la zéolithe ou sont de préférence déposés sur le catalyseur et alors principalement localisés sur la matrice. Un catalyseur préféré contient du B et/ou Si comme élément promoteur déposé avec de préférence en plus du phosphore promoteur. Les quantités introduites sont de 0,1-20% poids de catalyseur calculé en oxyde.Boron, silicon and / or phosphorus may be in the matrix, the zeolite or are preferably deposited on the catalyst and then mainly located on the matrix. A preferred catalyst contains B and / or Si as a promoter element preferably deposited in addition to the promoter phosphorus. The quantities introduced are 0.1-20% by weight of catalyst calculated as oxide.

L'élément introduit, et en particulier le silicium, principalement localisé sur la matrice du support peut être caractérisé par des techniques telles que la microsonde de Castaing (profil de répartition des divers éléments), la microscopie électronique par transmission couplée à une analyse X des composants du catalyseurs, ou bien encore par l'établissement d'une cartographie de répartition des éléments présents dans le catalyseur par microsonde électronique.The element introduced, and in particular silicon, mainly located on the matrix of the support can be characterized by techniques such as the Castaing microprobe (distribution profile of the various elements), transmission electron microscopy coupled with an X analysis of the components of the catalysts, or even by establishing a distribution map of the elements present in the catalyst by electron microprobe.

D'une façon générale, un catalyseur préféré d'hydrocraquage renferme avantageusement :

  • 0,1-80% poids de zéolite Y
  • 0,1-40% poids d'au moins un élément des groupes VIB et VIII (% oxyde)
  • 0,1-99,8% poids de matrice (% oxyde)
  • 0-20% poids d'au moins un élément choisi dans le groupe formé par P, B, Si (% oxyde), de préférence 0,1-20%
  • 0-20% poids d'au moins un élément du groupe VIIA, de préférence 0,1-20%
  • 0-20% poids d'au moins un élément du groupe VIIB, de préférence 0,1-20%
  • 0-60% poids d'au moins un élément du groupe VB, de préférence 0,1-60%
In general, a preferred hydrocracking catalyst advantageously contains:
  • 0.1-80% by weight of zeolite Y
  • 0.1-40% by weight of at least one group VIB and VIII element (% oxide)
  • 0.1-99.8% weight of matrix (% oxide)
  • 0-20% by weight of at least one element selected from the group consisting of P, B, Si (% oxide), preferably 0.1-20%
  • 0-20% weight of at least one element of group VIIA, preferably 0.1-20%
  • 0-20% weight of at least one group VIIB element, preferably 0.1-20%
  • 0-60% by weight of at least one element of group VB, preferably 0.1-60%

En ce qui concerne le silicium, dans la fourchette 0-20% il n'est compté que le silicium ajouté et non celui de la zéolite.For silicon, in the range 0-20% it is counted only the added silicon and not that of the zeolite.

La zéolite peut être éventuellement dopée par des éléments métalliques comme par exemple les métaux de la famille des terres rares, notamment le lanthane et le cérium, ou des métaux nobles ou non nobles du groupe VIII, comme le platine, le palladium, le ruthénium, le rhodium, l'iridium, le fer et d'autres métaux comme le manganèse, le zinc, le magnésium.The zeolite may optionally be doped with metal elements such as, for example, rare earth metals, especially lanthanum and cerium, or noble or non-noble metals of group VIII, such as platinum, palladium or ruthenium, rhodium, iridium, iron and other metals such as manganese, zinc, magnesium.

Différents zéolites Y peuvent être utilisées.Different zeolites Y can be used.

Une zéolithe acide H-Y particulièrement avantageuse est caractérisée par différentes spécifications : un rapport molaire global SiO2/Al2O3 compris entre environ 6 et 70 et de manière préférée entre environ 12 et 50 : une teneur en sodium inférieure à 0,15 % poids déterminée sur la zéolithe calcinée à 1 100 °C ; un paramètre cristallin a de la maille élémentaire compris entre 24,58 x 10-10 m et 24,24 x 10-10 m et de manière préférée entre 24,38 x 10-10 m et 24,26 x 10 -10m ; une capacité CNa de reprise en ions sodium, exprimée en gramme de Na par 100 grammes de zéolithe modifiée, neutralisée puis calcinée, supérieure à environ 0,85 ; une surface spécifique déterminée par la méthode B.E.T. supérieure à environ 400 m2/g et de préférence supérieure à 550 m2/g, une capacité d'adsorption de vapeur d'eau à 25°C pour une pression partielle de 2,6 torrs (soit 34,6 MPa), supérieure à environ 6 %, et avantageusement, la zéolite présente une répartition poreuse, déterminée par physisorption d'azote, comprenant entre 5 et 45 % et de préférence entre 5 et 40 % du volume poreux total de la zéolithe contenu dans des pores de diamètre situé entre 20 x 10-10m et 80 x 10-10m, et entre 5 et 45 % et de préférence entre 5 et 40 % du volume poreux total de la zéolithe contenu dans des pores de diamètre supérieur à 80 x 10-10m et généralement inférieur à 1000 x 10-10m, le reste du volume poreux étant contenu dans les pores de diamètre inférieur à 20 x 10-10 m.A particularly advantageous acidic zeolite HY is characterized by various specifications: an overall molar ratio SiO 2 / Al 2 O 3 of between approximately 6 and 70 and preferably between approximately 12 and 50: a sodium content of less than 0.15% by weight determined on zeolite calcined at 1100 ° C .; a crystalline parameter has elementary mesh of between 24.58 x 10 -10 m and 24.24 x 10 -10 m, and preferably between 24.38 x 10 -10 m and 24.26 x 10 -10 m; a sodium recovery CNa capacity, expressed in grams of Na per 100 grams of modified zeolite, neutralized and then calcined, greater than about 0.85; a specific surface area determined by the BET method of greater than about 400 m 2 / g and preferably greater than 550 m 2 / g, a water vapor adsorption capacity at 25 ° C. for a partial pressure of 2.6 torr (ie 34.6 MPa), greater than about 6%, and advantageously, the zeolite has a porous distribution, determined by nitrogen physisorption, comprising between 5 and 45% and preferably between 5 and 40% of the total pore volume of the zeolite contained in pores with a diameter of between 20 × 10 -10 m and 80 × 10 -10 m, and between 5 and 45% and preferably between 5 and 40% of the total pore volume of the zeolite contained in pores of diameter greater than 80 x 10 -10 m and generally less than 1000 x 10 -10 m, the remainder of the pore volume being contained in pores with a diameter of less than 20 x 10 -10 m.

Un catalyseur préféré utilisant ce type de zéolite renferme une matrice, au moins une zéolithe Y désaluminée et possédant un paramètre cristallin compris entre 2,424 nm et 2,455 nm de préférence entre 2,426 et 2,438 nm, un rapport molaire SiO2/Al2O3 global supérieur à 8, une teneur en cations des métaux alcalino-terreux ou alcalins et/ou des cations des terres rares telle que le rapport atomique (n x M n+)/Al est inférieur à 0,8 de préférence inférieur à 0,5 ou encore à 0,1, une surface spécifique déterminée par la méthode B.E.T supérieure à 400 m2/g de préférence supérieure à 550m2/g, et une capacité d'adsorption d'eau à 25°C pour une valeur P/Po de 0,2, supérieure à 6% poids, ledit catalyseur comprenant également au moins un métal hydro-déshydrogénant, et du silicium déposé sur le catalyseur.A preferred catalyst using this type of zeolite contains a matrix, at least one dealuminated zeolite Y having a crystalline parameter of between 2.424 nm and 2.455 nm, preferably between 2.426 and 2.388 nm, a higher overall SiO 2 / Al 2 O 3 molar ratio. at 8, a cation content of the alkaline earth or alkaline metals and / or rare earth cations such that the atomic ratio ( n × M n + ) / Al is less than 0.8, preferably less than 0.5, or 0.1, a specific surface area determined by the BET method of 400 m 2 / g, preferably greater than 550m 2 / g, and a water adsorption capacity at 25 ° C for a P / Po value of 0, 2 greater than 6% by weight, said catalyst also comprising at least one hydro-dehydrogenating metal, and silicon deposited on the catalyst.

Dans un mode de réalisation avantageux selon l'invention, il est utilisé pour l'hydrocraquage un catalyseur comprenant une zéolithe Y partiellement amorphe.In an advantageous embodiment according to the invention, a catalyst comprising a partially amorphous Y zeolite is used for hydrocracking.

On entend par zéolithe Y partiellement amorphe, un solide présentant :

  • i/ un taux de pic qui est inférieur à 0,40 de préférence inférieur à environ 0,30
  • ii/ une fraction cristalline exprimée par rapport à une zéolithe Y de référence sous forme sodique (Na) qui est inférieure à environ 60%, de préférence inférieur à environ 50%, et déterminée par diffraction des rayons X.
The term "partially amorphous Y zeolite" means a solid having:
  • i / a peak rate which is less than 0.40, preferably less than about 0.30
  • ii / a crystalline fraction expressed relative to a reference zeolite Y in sodium form (Na) which is less than about 60%, preferably less than about 50%, and determined by X-ray diffraction.

De préférence, les zéolithes Y partiellement amorphes, solides entrant dans la composition du catalyseur selon l'invention présentent l'une au moins (et de préférence toutes) des autres caractéristiques suivantes :

  • iii/ un rapport Si/Al global supérieur à 15, de préférence supérieur à 20 et inférieur à 150,
  • iv/ un rapport Si/Al IV de charpente supérieur ou égal au rapport Si/Al global,
  • v/ un volume poreux au moins égal à 0,20 ml/g de solide dont une fraction, comprise entre 8% et 50%, est constituée de pores ayant une diamètre d'au moins 5 nm (nanomètre) soit 50 Å.
  • vi/ une surface spécifique de 210-800 m2/g , de préférence 250-750 m2/g et avantagement 300-600 m2/g
Preferably, the partially amorphous, solid Y zeolites used in the composition of the catalyst according to the invention have at least one (and preferably all) of the following other characteristics:
  • iii / an overall Si / Al ratio greater than 15, preferably greater than 20 and less than 150,
  • iv / an Si / Al IV ratio of framework greater than or equal to the overall Si / Al ratio,
  • v / a pore volume at least equal to 0.20 ml / g of solid, of which a fraction, comprised between 8% and 50%, consists of pores having a diameter of at least 5 nm (nm) or 50 Å.
  • vi / a specific surface area of 210-800 m 2 / g, preferably 250-750 m 2 / g and advantageously 300-600 m 2 / g

Les taux de pics et les fractions cristallines sont déterminés par diffraction des rayons X, en utilisant une procédure dérivée de la méthode ASTM D3906-97 « Détermination of Relative X-ray Diffraction Intensities of Faujasite-Type-Containing Materials ». On pourra se référer à cette méthode pour les conditions générales d'application de la procédure et, en particulier, pour la préparation des échantillons et des références.Peak levels and crystalline fractions are determined by X-ray diffraction, using a procedure derived from ASTM Method D3906-97 "Determination of Relative X-ray Diffraction Intensities of Faujasite-Type-Containing Materials". This method may be referred to for the general conditions of application of the procedure and, in particular, for the preparation of samples and references.

Un diffractogramme est composé des raies caractéristiques de la fraction cristallisée de l'échantillon et d'un fond, provoqué essentiellement par la diffusion de la fraction amorphe ou microcristailine de l'échantillon (un faible signal de diffusion est lié à l'appareillage, air, porte-échantillon, etc.) Le taux de pics d'une zéolithe est le rapport, dans une zone angulaire prédéfinie (typiquement 8 à 40° 2θ lorsqu'on utilise le rayonnement Kα du cuivre, 1 = 0,154 nm), de l'aire des raies de la zéolithe (pics) sur l'aire globale du diffractogramme (pics+fond). Ce rapport pics/(pics+fond) est proportionnel à la quantité de zéolithe cristallisée dans le matériau. Pour estimer la fraction cristalline d'un échantillon de zéolithe Y, on comparera le taux de pics de l'échantillon à celui d'une référence considérée comme 100% cristallisée (NaY par exemple). Le taux de pics d'une zéolithe NaY parfaitement cristallisée est de l'ordre de 0,55 à 0,60.A diffractogram is composed of the characteristic lines of the crystallized fraction of the sample and of a background, caused mainly by the diffusion of the amorphous fraction or microcrystalline of the sample (a weak diffusion signal is linked to the apparatus, air , sample holder, etc.) The peak rate of a zeolite is the ratio, in a predefined angular zone (typically 8 to 40 ° 2θ when copper Kα radiation is used, 1 = 0.154 nm), the zeolite line area (peaks) on the overall area of the diffractogram (peaks + background). This peak / peak ratio is proportional to the amount of crystallized zeolite in the material. To estimate the crystalline fraction of a sample of zeolite Y, the peak level of the sample will be compared to that of a reference considered as 100% crystalline (NaY for example). The peak level of a perfectly crystalline NaY zeolite is of the order of 0.55 to 0.60.

Le taux de pics d'une zéolithe USY classique est de 0,45 à 0,55, sa fraction cristalline par rapport à une NaY parfaitement cristallisée est de 80 à 95 %. Le taux de pics du solide faisant l'objet de la présente invention est inférieur à 0,4 et de préférence inférieur à 0,35. Sa fraction cristalline est donc inférieure à 70 %, de préférence inférieure à 60 %.The peak level of a conventional USY zeolite is 0.45 to 0.55, its crystalline fraction relative to a perfectly crystalline NaY is from 80 to 95%. The peak level of the solid which is the subject of the present invention is less than 0.4 and preferably less than 0.35. Its crystalline fraction is therefore less than 70%, preferably less than 60%.

Les zéolites partiellement amorphes sont préparées selon les techniques généralement utilisées pour la désalumination, à partir de zéolites Y disponibles commercialement, c'est-à-dire qui présentent généralement des cristallinités élevées (au moins 80%). Plus généralement on pourra partir de zéolites ayant une fraction cristalline d'au moins 60%, ou d'au moins 70%.The partially amorphous zeolites are prepared according to the techniques generally used for dealumination, from commercially available Y zeolites, that is to say which generally have high crystallinities (at least 80%). More generally, zeolites having a crystalline fraction of at least 60%, or at least 70%, may be used.

Les zéolithes Y utilisées généralement dans les catalyseurs d'hydrocraquage sont fabriquées par modification de zéolithe Na-Y disponible commercialement. Cette modification permet d'aboutir à des zéolithes dites stabilisées, ultra-stabilisées ou encore désaluminées. Cette modification est réalisée par l'une au moins des techniques de désalumination, et par exemple le traitement hydrothermique, l'attaque acide. De préférence, cette modification est réalisée par combinaison de trois types d'opérations connues de l'homme de l'art : le traitement hydrothermique, l'échange ionique et l'attaque acide.The Y zeolites generally used in hydrocracking catalysts are manufactured by modifying commercially available Na-Y zeolite. This modification leads to zeolites said stabilized, ultra-stabilized or dealuminated. This modification is carried out by at least one of the dealumination techniques, and for example the hydrothermal treatment, the acid attack. Preferably, this modification is carried out by combining three types of operations known to those skilled in the art: hydrothermal treatment, ion exchange and acid attack.

Une autre zéolite particulièrement intéressante est une zéolite non désaluminée globalement et très acide.Another particularly interesting zeolite is a zeolite not dealuminated globally and very acidic.

Par zéolithe non désaluminée globalement on entend une zéolithe Y (type structural FAU, faujasite) selon la nomenclature développée dans "Atlas of zeolites structure types", W.M. Meier, D.H. Olson et Ch. Baerlocher, 4th revised Edition 1996, Elsevier. Le paramètre cristallin de cette zéolithe peut avoir diminué par extraction des aluminiums de la structure ou charpente lors de la préparation mais le rapport SiO2/Al2O3 global n'a pas changé car les aluminiums n'ont pas été extraits chimiquement. Une telle zéolithe non désaluminée globalement a donc une composition en silicium et aluminium exprimée par le rapport SiO2/Al2O3 global équivalent à la zéolithe Y non désaluminée de départ. Les valeurs des paramètres (rapport SiO2/Al2O3 et paramètre cristallin sont données plus loin.). Cette zéolithe Y non désaluminée globalement peut être sous la forme hydrogène soit être au moins partiellement échangée avec des cations métalliques, par exemple à l'aide de cations des métaux alcalino-terreux et/ou des cations de métaux de terres rares de numéro atomiques 57 à 71 inclus. On préférera une zéolithe dépourvue de terres rares et d'alcalino-terreux, de même pour le catalyseur.By zeolite not dealuminated overall is meant a zeolite Y (structural type FAU, faujasite) according to the nomenclature developed in "Atlas of zeolites structure types", WM Meier, DH Olson and Ch. Baerlocher, 4 th revised Edition 1996, Elsevier. The crystalline parameter of this zeolite may have decreased by extraction of aluminum from the structure or framework during the preparation but the ratio Global SiO 2 / Al 2 O 3 has not changed since the aluminum has not been chemically extracted. Such a non-dealuminated zeolite globally therefore has a composition of silicon and aluminum expressed by the overall SiO 2 / Al 2 O 3 ratio equivalent to the non-dealuminated Y zeolite of departure. The values of the parameters (SiO 2 / Al 2 O 3 ratio and crystalline parameter are given below). This zeolite Y not dealuminated globally can be in the hydrogen form or be at least partially exchanged with metal cations, for example using alkaline earth metal cations and / or atomic number rare earth metal cations. to 71 included. A zeolite devoid of rare earths and alkaline earths is preferable, as is the catalyst.

La zéolite Y non globalement désaluminée présente généralement un paramètre cristallin supérieur à 2,438 nm, un rapport SiO2 / Al2O3 global inférieur à 8, un rapport molaire SiO2 / Al2O3 de charpente inférieur à 21 et supérieur au rapport SiO2 / Al2O3 global. La zéolithe globalement non désaluminée peut être obtenue par tout traitement qui n'extrait pas les aluminium de l'échantillon, tel que par exemple le traitement à la vapeur d'eau, le traitement par SiCl4...Y zeolite not globally dealuminated generally has a crystalline parameter greater than 2.438 nm, an overall SiO 2 / Al 2 O 3 ratio of less than 8, an SiO 2 / Al 2 O 3 framework ratio of less than 21 and greater than the SiO 2 ratio. 2 / Al 2 O 3 overall. The zeolite globally not dealuminated can be obtained by any treatment which does not extract the aluminum sample, such as for example the steam treatment, treatment with SiCl 4 ...

Un autre type de catalyseur avantageux pour l'hydrocraquage contient une matrice oxyde amorphe acide de type alumine dopée par le phosphore, une zéolithe Y non désaluminée globalement et très acide et éventuellement au moins un élément du groupe VIIA et notamment le fluor.Another type of catalyst that is advantageous for hydrocracking contains an amorphous acid oxide matrix of phosphorus doped alumina type, a non-dealuminated Y zeolite which is globally and highly acidic, and optionally at least one group VIIA element and in particular fluorine.

L'invention n'est pas limitée aux zéolites Y citées et préférées, mais d'autres types de zéolites Y peuvent être utilisés dans ce procédé.The invention is not limited to the cited and preferred Y zeolites, but other types of Y zeolites may be used in this process.

Préalablement à l'injection de la charge, le catalyseur est soumis à un traitement de sulfuration permettant de transformer, au moins en partie, les espèces métalliques en sulfure avant leur mise en contact avec la charge à traiter. Ce traitement d'activation par sulfuration est bien connu de l'Homme du métier et peut être effectué par toute méthode déjà décrite dans la littérature soit in-situ, c'est-à-dire dans le réacteur, soit ex-situ.Prior to the injection of the feedstock, the catalyst is subjected to a sulfurization treatment making it possible, at least in part, to transform the metal species into sulfide before they come into contact with the feedstock to be treated. This activation treatment by sulfurization is well known to those skilled in the art and can be performed by any method already described in the literature either in-situ, that is to say in the reactor, or ex-situ.

Une méthode de sulfuration classique bien connue de l'homme du métier consiste à chauffer en présence d'hydrogène sulfuré (pur ou par exemple sous flux d'un mélange hydrogène/hydrogène sulfuré) à une température comprise entre 150 et 800°C, de préférence entre 250 et 600°C, généralement dans une zone réactionnelle à lit traversé.A conventional sulphurization method well known to those skilled in the art consists of heating in the presence of hydrogen sulphide (pure or for example under a stream of a hydrogen / hydrogen sulphide mixture) at a temperature of between 150 and 800 ° C. preferably between 250 and 600 ° C, generally in a crossed-bed reaction zone.

Lorsque les catalyseurs d'hydrotraitement et d'hydrocraquage sont dans le même réacteur ou dans deux réacteurs sans séparation intermédiaire, ils sont sulfurés dans le même temps.When the hydrotreatment and hydrocracking catalysts are in the same reactor or in two reactors without intermediate separation, they are sulphurized at the same time.

La séparation et les produitsSeparation and products

L'effluent liquide issu de l'hydrocraquage est ensuite distillé de façon à séparer une coupe naphta, une coupe diesel, éventuellement une coupe kérosène (qui peut être parfois incluse au moins en partie dans la coupe diesel), les gaz légers LPG. Il reste un résidu liquide qui peut-être avantageusement recyclé dans le procédé après purge généralement.The liquid effluent from the hydrocracking is then distilled to separate a naphtha cut, a diesel cut, possibly a kerosene cut (which may sometimes be included at least partly in the diesel cut), LPG light gases. There remains a liquid residue which can be advantageously recycled in the process after purging generally.

Il est bien évident que l'hydrogène a été également préalablement séparé de l'effluent liquide, qui a pu être ultérieurement strippé avant d'être distillé.It is obvious that the hydrogen has also been previously separated from the liquid effluent, which could subsequently be stripped before being distilled.

De façon inattendue, on a constaté qu'avec le procédé selon l'invention, on obtient directement des diesels de très bonnes qualités répondant aux spécifications et sans qu'aucun traitement supplémentaire (hydrodésulfuration sévère, hydrogénations...) ne soit nécessaire pour améliorer ses qualités.Unexpectedly, it has been found that with the process according to the invention, diesels of very good quality are obtained directly which meet the specifications and without any additional treatment (severe hydrodesulphurisation, hydrogenations, etc.) being necessary to improve his qualities.

Ainsi, le procédé permet de produire directement un diesel ayant un point de distillation 95% volume inférieur à 360°C, et généralement ce point est d'au plus 350°C voire d'au plus 340°C, ayant une teneur en soufre d'au plus 50 ppm, et généralement d'au plus 10 ppm, ayant un indice de cétane d'au moins 52 et le plus généralement d'au moins 54 et ayant de préférence une teneur en polyaromatiques d'au plus 6% pds et généralement d'au plus 1%, et de préférence un point d'écoulement inférieur à -10°C, et de préférence une teneur en aromatiques inférieure à 15% pds.Thus, the process makes it possible to directly produce a diesel having a 95% volume distillation point below 360 ° C., and generally this point is at most 350 ° C. or even at most 340 ° C., having a sulfur content. at most 50 ppm, and generally at most 10 ppm, having a cetane number of at least 52 and most generally at least 54 and preferably having a polyaromatic content of at most 6% wt. and generally at most 1%, and preferably a pour point of less than -10 ° C, and preferably an aromatic content of less than 15 wt%.

Il est également produit dans ce procédé un kérosène de bonne qualité ayant un point de fumée supérieur à 20 mm, de préférence supérieur à 22 mm, et ayant une teneur en soufre inférieure à 50 ppm, de préférence inférieure à 10 ppm. Le kérosène peut-être éventuellement au moins en partie envoyé dans le pool diesel, selon les besoins de l'exploitant.It is also produced in this process a good quality kerosene having a smoke point greater than 20 mm, preferably greater than 22 mm, and having a sulfur content of less than 50 ppm, preferably less than 10 ppm. Kerosene may possibly be at least partly sent to the diesel pool, depending on the needs of the operator.

Il est tout à fait remarquable d'obtenir de telles qualités de diesel sans traitement ultérieur et pour un investissement bien moindre qu'un hydrocraquage à haute pression, tout en permettant la valorisation de charges "légères" de la raffinerie telles que les gazoles actuels qui, du fait de la sévérisation des spécifications, se retrouveront soit en excès soit devoir subir des traitements ultérieurs sévères.It is quite remarkable to obtain such qualities of diesel without further treatment and for a much lower investment than a hydrocracking at high pressure, while allowing the valuation of "light" loads of the refinery such as current gas oils which, because of the severity of the specifications, will find themselves either in excess or have to undergo subsequent severe treatments.

En ce qui concerne les rendements en distillat moyen(kérosène + diesel) produit, ils se situent à au moins 60% volume, le plus souvent à au moins 65% volume. Les autres produits formés sont des gaz légers LPG (représentent au plus 10% pds et plus généralement au plus 5% pds) et du naphta (généralement au moins 20% volume).As for the yields of middle distillate (kerosene + diesel) produced, they are at least 60% volume, most often at least 65% volume. The other products formed are LPG light gases (represent at most 10% by weight and more generally at most 5% by weight) and naphtha (generally at least 20% by volume).

Les figuresThe figures

On décrira ci-après brièvement le procédé en se reportant aux figures. La figure 1 représente un mode de réalisation du procédé d'hydrocraquage à pression modérée. Les figures 2B, 2C, 3, 4 illustrent une intégration de ce procédé dans une installation de craquage catalytique, la figure 2A montrant l'art antérieur.The method will be briefly described below with reference to the figures. The figure 1 represents an embodiment of the moderate pressure hydrocracking process. The Figures 2B , 2C , 3 , 4 illustrate an integration of this process into a catalytic cracking plant, the Figure 2A showing the prior art.

Le procédé d'hydrocraquage à pression modérée est schématisée figure 1. La charge à traiter entre par la conduite 1, elle est sur cette figure, additionnée du recyclage du résidu d'hydrocraquage par la conduite 2 et d'hydrogène par la conduite 3. Elle passe à travers un échangeur de chaleur 4 en mélange avec l'hydrogène recyclé amené par la conduite 5, puis à travers un réchauffeur 6 avant d'être introduite dans le réacteur (ou la zone) 7 d'hydrocraquage à pression modérée contenant éventuellement en amont la ou les zones d'hydrotraitement.The hydrocracking process at moderate pressure is schematized figure 1 . The charge to be treated enters the pipe 1, it is in this figure, added the recycling of the hydrocracking residue through the pipe 2 and hydrogen through the pipe 3. It passes through a heat exchanger 4 in mixture with the recycled hydrogen fed via the pipe 5, then through a heater 6 before being introduced into the reactor (or zone) 7 hydrocracking at moderate pressure optionally containing the upstream or hydrotreating zones.

Le réacteur 7 contient au moins un lit catalytique 8 d'au moins un catalyseur d'hydrocraquage. De préférence, il peut contenir en amont du premier lit 8 au moins un catalyseur d'hydrotraitement. L'effluent liquide issu du réacteur et sortant par la conduite 9 passe par l'échangeur 4 puis dans un séparateur gaz-liquide 10 séparant l'hydrogène qui est recyclé par la conduite 5 vers le réacteur 7 d'hydrocraquage.The reactor 7 contains at least one catalytic bed 8 of at least one hydrocracking catalyst. Preferably, it may contain upstream of the first bed 8 at least one hydrotreatment catalyst. The liquid effluent from the reactor and exiting through line 9 passes through exchanger 4 and then into a gas-liquid separator 10 separating hydrogen which is recycled via line 5 to the hydrocracking reactor 7.

L'effluent liquide séparé sortant par la conduite 11 est envoyé de préférence dans un strippeur 12 qui sépare du naphta et des gaz légers par la conduite 13 et un effluent résultant sortant par la conduite 14 est distillé dans la colonne 15 de distillation atmosphérique. Cet agencement illustre schématiquement un mode de réalisation de la distillation. Toute autre disposition connue de l'homme du métier aboutissant à séparer les mêmes produits convient aussi.The separated liquid effluent leaving the line 11 is preferably sent to a stripper 12 which separates naphtha and light gases through line 13 and a resulting effluent exiting through line 14 is distilled in the column 15 of atmospheric distillation. This arrangement schematically illustrates an embodiment of the distillation. Any other provision known to those skilled in the art resulting in separating the same products is also suitable.

Il est ainsi obtenu un diesel évacué par la conduite 16 et un résidu recyclé par la conduite 2 au réacteur d'hydrocraquage, hormis la purge par la conduite 17. Eventuellement, un kérosène est obtenu.There is thus obtained a diesel exhausted by line 16 and a residue recycled via line 2 to the hydrocracking reactor, except for the purge via line 17. Optionally, a kerosene is obtained.

Ainsi, la zone de séparation des produits sépare un résidu d'hydrocraquage à point d'ébullition supérieur à au moins 535°C, et comporte une conduite de purge dudit résidu et éventuellement une conduite de recyclage dudit résidu purgé vers la zone ou le réacteur d'hydrocraquage.Thus, the product separation zone separates a hydrocracking residue having a boiling point greater than at least 535 ° C., and comprises a purge pipe for said residue and optionally a pipe for recycling said purged residue towards the zone or the reactor. hydrocracking.

Pour faciliter la lecture de la figure, on n'a pas représenté les compresseurs et utilités qui sont connus de l'homme du métier.To facilitate the reading of the figure, it has not shown the compressors and utilities that are known to those skilled in the art.

Le procédé d'hydrocraquage ici décrit peut très avantageusement être intégré dans la raffinerie au niveau d'un procédé de craquage catalytique (en général FCC : craquage catalytique en lit fluidisé).The hydrocracking process described here can very advantageously be integrated into the refinery at the level of a catalytic cracking process (generally FCC: fluidized catalytic cracking).

Il en résulte un procédé combiné produisant à la fois du diesel de bonne qualité et du naphta (en vue de la production d'essence).The result is a combined process producing both good quality diesel and naphtha (for gasoline production).

L'invention concerne également une installation pour la mise en oeuvre du procédé ci-dessus décrit. Cette installation comporte :

  • une colonne de distillation d'une charge hydrocarbonée permettant de séparer au moins une fraction ayant une température T5 comprise entre 250°C et 400°C et une température T95 d'au plus 470°C,
  • au moins une zone d'hydrotraitement de ladite charge ou de ladite fraction ,
  • au moins une zone d'hydrocraquage à pression modérée de ladite fraction, ladite pression étant supérieure à 70 bars et d'au plus 100 bars,
  • au moins une zone de séparation des produits permettant d'obtenir un diesel ayant un point de distillation 95% inférieur à 360°C, une teneur en soufre d'au plus 50 ppm et un indice de cétane supérieur à 51.
The invention also relates to an installation for carrying out the method described above. This installation comprises:
  • a distillation column of a hydrocarbon feedstock for separating at least one fraction having a temperature T 5 of between 250 ° C and 400 ° C and a temperature T 95 of at most 470 ° C,
  • at least one hydrotreatment zone of said charge or fraction,
  • at least one hydrocracking zone at moderate pressure of said fraction, said pressure being greater than 70 bar and at most 100 bar,
  • at least one product separation zone for obtaining a diesel having a distillation point 95% below 360 ° C, a sulfur content of at most 50 ppm and a cetane number greater than 51.

Dans une réalisation plus particulière montrée ci-après, l'installation comporte :

  • une colonne de distillation atmosphérique de ladite charge brute pour séparer au moins du naphta, du diesel et un résidu atmosphérique,
  • une colonne de distillation sous vide pour traiter ledit résidu atmosphérique, et pour séparer au moins une fraction distillat sous vide et un résidu sous vide,
  • installation dans laquelle la colonne de distillation atmosphérique ou la colonne de distillation sous vide comporte au moins une conduite récupérant une fraction ayant une température T5 comprise entre 250°C et 400°C et une température T95 d'au plus 470°C,
  • l'installation comporte également au moins une zone d'hydrotraitement de ladite fraction suivie d'au moins une zone d'hydrocraquage à pression modérée et d'au moins une zone de séparation des produits et permettant d'obtenir un diesel ayant un point de distillation 95% inférieur à 360°C, une teneur en soufre d'au plus 50 ppm et un indice de cétane supérieur à 51.
In a more particular embodiment shown below, the installation comprises:
  • an atmospheric distillation column of said raw feedstock for separating at least naphtha, diesel and an atmospheric residue,
  • a vacuum distillation column for treating said atmospheric residue, and for separating at least one vacuum distillate fraction and a vacuum residue,
  • in which the atmospheric distillation column or the vacuum distillation column comprises at least one pipe recovering a fraction having a temperature T 5 between 250 ° C and 400 ° C and a temperature T 95 of at most 470 ° C,
  • the installation also comprises at least one hydrotreatment zone of said fraction followed by at least one moderate pressure hydrocracking zone and at least one separation zone of the products and making it possible to obtain a diesel having a point of distillation 95% below 360 ° C, a sulfur content of not more than 50 ppm and a cetane number greater than 51.

Pour mieux comprendre l'invention et son intérêt, il a été schématisé figure 2A l'art antérieur et figure 2B l'invention, et on décrira le procédé de l'invention à l'aide de ces figures.To better understand the invention and its interest, it has been schematized Figure 2A the prior art and Figure 2B the invention, and the method of the invention will be described by means of these figures.

La figure 2A représente une installation actuelle. La charge hydrocarbonée brute (ou pétrole brut) qui arrive par la conduite 20 est distillée dans la colonne atmosphérique 21. Il est séparé une (on comprendra par ce terme généralement aussi au moins une) fraction naphta (conduite 22), une fraction carburéacteur (conduite 23), une fraction diesel (conduite 24).The Figure 2A represents a current installation. The crude hydrocarbon feedstock (or crude oil) that arrives via the pipe 20 is distilled in the atmospheric column 21. It is separated from (this naphtha fraction will also be understood by this term generally (line 22), a jet fuel fraction ( pipe 23), a diesel fraction (line 24).

Le résidu atmosphérique sortant par la conduite 25 est distillé sous vide dans la colonne 26 de distillation sous vide. Il est séparé une fraction distillat sous vide (conduite 27) et il reste un résidu sous vide (conduite 38).The atmospheric residue exiting through line 25 is distilled under vacuum in column 26 of vacuum distillation. A vacuum distillate fraction is separated (line 27) and a vacuum residue remains (line 38).

Ledit distillat sous vide est envoyé dans une unité de craquage catalytique 28 (en général en lit fluidisé) qui par ce procédé produit, entre autres, du naphta évacué par la conduite 29, une fraction de type diesel fortement aromatique (light cycle oil LCO) évacuée par la conduite 30, et un "slurry" ou résidu sortant par la conduite 31.Said vacuum distillate is sent to a catalytic cracking unit 28 (generally in a fluidized bed) which, by this process, produces, among others, naphtha discharged via line 29, a strongly aromatic diesel type fraction (light cycle oil LCO). discharged through line 30, and a "slurry" or residue exiting through line 31.

Le plus souvent, le résidu sous vide est traité dans une unité de viscoréduction 39, qui produit, entre autres, du naphta (conduite 40) et du diesel (conduite 41) qui sont de faible qualité. Le résidu de viscoréduction (conduite 42) n'est utilisable que comme fuel ainsi que le slurry, une partie du LCO pouvant servir à fluxer ce fuel.Most often, the vacuum residue is processed in a visbreaking unit 39, which produces, among others, naphtha (line 40) and diesel (line 41) which are of poor quality. The visbreaking residue (line 42) is only usable as fuel and slurry, a portion of the LCO can be used to flow this fuel.

La figure 2B montre le procédé et l'installation selon l'invention, associant un hydrocraquage à pression modérée et un craquage catalytique.The Figure 2B shows the process and the installation according to the invention, associating a hydrocracking at moderate pressure and a catalytic cracking.

On reconnaît les repères de la figure 2A, et pour ne pas alourdir le schéma on n'a pas représenté le viscoréducteur, mais il est généralement présent dans l'installation.We recognize the benchmarks of the Figure 2A , and not to weigh down the diagram, the visor reducer was not shown, but it is generally present in the installation.

L'installation selon l'invention (figure 2B) comprend en plus de celle de l'art antérieur (figure 2A), l'unité d'hydrocraquage 32 à pression modérée qui reçoit une fraction légère issue de la distillation sous vide amenée dans la conduite 33.The installation according to the invention ( Figure 2B ) comprises in addition to that of the prior art ( Figure 2A ), the moderate pressure hydrocracking unit 32 which receives a light fraction resulting from the vacuum distillation fed into line 33.

L'unité 32 comprend le(s) réacteur(s) ou zone (s) d'hydrocraquage à pression modérée et les séparations associées permettant de sortir entre autres, par une conduite 34 un diesel de haute qualité, par la conduite 35 un naphta et par une conduite 36 la purge du résidu d'hydrocraquage. Habituellement, l'unité 32 comprend également une zone d'hydrotraitement avant hydrocraquage.The unit 32 comprises the reactor (s) or hydrocracking zone (s) at moderate pressure and the associated separations making it possible, among other things, to leave a high-grade diesel via a line 34, via the pipe 35 a naphtha and by a line 36 purging the hydrocracking residue. Usually, the unit 32 also comprises a hydrotreatment zone before hydrocracking.

Le résidu d'hydrocraquage peut au moins en partie être envoyée au craquage catalytique (unité 28) mais sans que ce soit obligatoire. La purge du procédé d'hydrocraquage est avantageusement envoyée à l'unité 28.The hydrocracking residue can at least partly be sent to catalytic cracking (unit 28) but not required. The purge of the hydrocracking process is advantageously sent to the unit 28.

On n'a pas représenté ici le recyclage du résidu purgé vers la zone d'hydrocraquage, ou vers le réacteur d'hydrocraquage comportant également la zone d'hydrotraitement. Recyclage et passage de la purge en FCC peuvent se faire séparément ou ensemble.The recycling of the purged residue to the hydrocracking zone, or to the hydrocracking reactor also comprising the hydrotreatment zone is not shown here. Recycling and venting in FCC can be done separately or together.

Dans le cadre du procédé selon l'invention, tel qu'illustré par exemple figure 2B avec un FCC, lors de la distillation atmosphérique le point de coupe pour la coupe diesel distillée (conduite 24) est choisi par l'exploitant.In the context of the process according to the invention, as illustrated for example Figure 2B with an FCC, during atmospheric distillation the cutting point for the distilled diesel cut (line 24) is chosen by the operator.

Le résidu atmosphérique, qui contient donc au moins une partie du gazole atmosphérique lourd, est distillé sous vide en au moins une fraction (distillat) légère et au moins une fraction (distillat) lourde, et il reste un résidu sous vide.The atmospheric residue, which therefore contains at least a portion of the heavy atmospheric gas oil, is distilled under vacuum in at least a light fraction (distillate) and at least a heavy fraction (distillate), and a residue remains under vacuum.

Ladite fraction légère à traiter par hydrocraquage présente une température T5 qui est comprise entre 250 et 400°C et une température T95 qui est d'au plus 470°C. C'est un gazole sous vide léger (LVGO). Le point d'ébullition final est choisi par l'exploitant selon la colonne à sa disposition et selon la valorisation souhaitée par les produits. Ladite fraction légère présente les autres caractéristiques des charges hydrocarbonées traitées par le procédé selon l'invention et précédemment décrits.Said light fraction to be treated by hydrocracking has a temperature T 5 which is between 250 and 400 ° C and a temperature T 95 which is at most 470 ° C. It is a light vacuum diesel fuel (LVGO). The final boiling point is chosen by the operator according to the column at his disposal and according to the valuation required by the products. Said light fraction has the other characteristics of the hydrocarbon feeds treated by the process according to the invention and previously described.

D'une façon générale, ce traitement de distillat sous vide léger par hydrocraquage à pression modérée peut-être mis en oeuvre lorsque la production et/ou la qualité du diesel veulent être augmentées, peu importe le type de traitement réservé aux distillat(s) lourd(s) et résidu de la distillation sous vide.In general, this light pressure hydrocracking vacuum distillate treatment can be implemented when the production and / or the quality of the diesel need to be increased, regardless of the type of treatment reserved for the distillate (s). heavy (s) and residue of vacuum distillation.

Dans un autre mode de réalisation, au lieu de fractionner le résidu atmosphérique en fraction(s) légères(s) et lourde(s) par distillation sous vide, et d'envoyer la (les) fraction(s) légère(s) en hydrocraquage, on prend (si le type de colonne le permet) la coupe gazole lourd ayant sensiblement les mêmes températures T5 et T95 au niveau de la distillation atmosphérique. Ce mode est illustré figure 2C où on reconnaît les repères des figures précédents et où la charge à l'unité 32 est un gazole atmosphérique amené par la conduite 37. Dans cette figure, la conduite 33 n'existe plus. Dans ce cas, le résidu atmosphérique bouillant au-dessus du gazole lourd est distillé sous vide, la distillation sous vide produit également un résidu et au moins une fraction distillat sous vide appelée ici lourde.In another embodiment, instead of fractioning the atmospheric residue into light (s) and heavy (s) fraction (s) by vacuum distillation, and sending the light fraction (s) into the hydrocracking, it takes (if the type of column allows) the heavy gas oil cut having substantially the same temperatures T 5 and T 95 at the atmospheric distillation. This mode is illustrated Figure 2C where the markings of the preceding figures are recognized and where the charge to the unit 32 is an atmospheric gas oil brought by the pipe 37. In this figure, the pipe 33 no longer exists. In this case, the atmospheric residue boiling over the heavy gas oil is distilled under vacuum, the vacuum distillation also produces a residue and at least a vacuum distillate fraction here called heavy.

Le résidu de distillation sous vide (conduite 38) qui présente généralement une température T5 d'au moins 535°C, d'au moins 550°C de préférence, voire d'au moins 565°C ou 570°C, peut être soumis par exemple à une viscoréduction (montré figure 1) ou à une hydroconversion de résidu ou un cokage.The vacuum distillation residue (line 38) which generally has a temperature T 5 of at least 535 ° C, at least 550 ° C preferably, or even at least 565 ° C or 570 ° C, can be submitted for example to visbreaking (shown figure 1 ) or a residue hydroconversion or coking.

Dans tous les cas, au moins une fraction distillat sous vide dite lourde, située entre la fraction légère ayant une température T95 d'au plus 470°C, et le résidu sous vide, est soumise au craquage catalytique.In all cases, at least one so-called heavy vacuum distillate fraction, located between the light fraction having a T 95 temperature of at most 470 ° C, and the residue under vacuum, is subjected to catalytic cracking.

La figure 3 représente une installation et un procédé dans lesquels la fraction lourde issue de la distillation sous vide et qui est soumise au craquage catalytique, est, avant ledit craquage, soumise à un hydrotraitement dans une zone 43. Les références des précédentes figures sont reprises ici.The figure 3 represents an installation and a process in which the heavy fraction resulting from distillation under vacuum and which is subjected to catalytic cracking, is, before said cracking, subjected to hydrotreatment in a zone 43. The references of the previous figures are repeated here.

Cet hydrotraitement avant le FCC se déroule en présence d'au moins un catalyseur amorphe. Tous les catalyseurs conventionnels d'hydrotraitement sont utilisables. On citera les catalyseurs contenant au moins un élément du groupe VIII non noble (Co, Ni par exemple) et au moins un élément du groupe VIB (Mo, W par exemple) déposés sur un support à base de préférence d'alumine ou de silice-alumine. La particularité de cette étape réside dans ses conditions opératoires : une pression partielle d'hydrogène entre 25 et 90 bars, de préférence inférieure à 85 bars, ou encore inférieure à 80 bars, ou encore inférieure à 70 bars, et une température de 350-450°C, de préférence 370-430°C ajustées de façon à maintenir une conversion d'au moins 10% et de préférence inférieure à 40% en produits bouillant au-dessous de 350°C et de préférence 15-30%.This hydrotreatment before the FCC takes place in the presence of at least one amorphous catalyst. All conventional hydrotreating catalysts are usable. Catalysts containing at least one non-noble group VIII element (Co, Ni for example) and at least one group VIB element (Mo, W for example) deposited on a support preferably based on alumina or silica are mentioned. -alumina. The particularity of this step lies in its operating conditions: a hydrogen partial pressure between 25 and 90 bar, preferably less than 85 bar, or even lower than 80 bar, or even lower than 70 bar, and a temperature of 350.degree. 450 ° C, preferably 370-430 ° C adjusted so as to maintain a conversion of at least 10% and preferably less than 40% in products boiling below 350 ° C and preferably 15-30%.

Il est ainsi produit un naphta (conduite 44) et un diesel (conduite 45) mais de qualité moyenne et destiné soit à un usage de fuel domestique soit au pool diesel.It is thus produced a naphtha (pipe 44) and a diesel (pipe 45) but of average quality and intended either for use of domestic fuel oil or diesel pool.

L'effluent hydrotraité passe ensuite dans l'unité de craquage catalytique 28.The hydrotreated effluent then passes into the catalytic cracking unit 28.

Sur la figure 4, on a schématiquement représenté un apport de fraction diesel lourd dans l'unité 32 où est réalisé l'hydrocraquage à pression modérée. Dans cette réalisation, il est obtenu à la distillation atmosphérique, en plus des coupes naphta (conduite 22), kérosène (conduite 23), une fraction diesel léger LGO (conduite 46) et une fraction diesel lourd HGO (conduite 47). Cette fraction diesel lourd est envoyée dans l'unité 32 où elle subira un hydrotraitement puis un hydrocraquage à pression modérée.On the figure 4 , it is schematically represented a contribution of heavy diesel fraction in the unit 32 which is carried out hydrocracking at moderate pressure. In this embodiment, it is obtained in atmospheric distillation, in addition to the naphtha cuts (line 22), kerosene (line 23), a light diesel fraction LGO (line 46) and a heavy diesel fraction HGO (line 47). This heavy diesel fraction is sent to unit 32 where it will undergo hydrotreatment and then hydrocracking at moderate pressure.

Ainsi, la présente demande décrit un procédé de production de diesel et de naphta, la production de diesel étant effectuée par un procédé d'hydrocraquage à pression modérée tel qu'exposé ci-dessus, et la production de naphta étant obtenue essentiellement par craquage catalytique. De préférence, la purge d'hydrocraquage est envoyée en craquage catalytique.Thus, the present application describes a process for the production of diesel and naphtha, the production of diesel being carried out by a moderate pressure hydrocracking process as explained above, and the production of naphtha being obtained essentially by catalytic cracking. . Preferably, the hydrocracking purge is sent by catalytic cracking.

On a exposé une réalisation préférée de ce type de procédé, mais d'autres réalisations, autres agencements des procédés pour atteindre le même but sont possibles.A preferred embodiment of this type of process has been disclosed, but other embodiments, other arrangements of the methods for achieving the same purpose are possible.

Pour illustrer l'intérêt de l'invention, il est ci-après chiffré la production d'un schéma de raffinage actuel, d'un schéma actuel pour une production de diesel aux spécifications 2005 et d'un schéma selon l'invention. Dans le schéma de la figure 2A (schéma actuel spécifications 2000) pour un traitement de 10 Mt/an de brut de mer du Nord, on a (schéma 1) :

  • naphta    3,17 Mt/an
  • carburateur    0,73 Mt/an
  • Diesel    2,32 Mt/an
  • Fuel domestique    1,5 Mt/an
  • Fuel à partir d'un résidu 565°C+ soumis à une viscoréduction : 1,42 Mt/an de fuel 40 cst (dilué par LCO et incluant slurry)
To illustrate the interest of the invention, it is hereinafter quantified the production of a current refining scheme, a current scheme for a production of diesel specifications 2005 and a scheme according to the invention. In the diagram of the Figure 2A (current scheme specifications 2000) for a treatment of 10 Mt / year of North Sea crude, we have (scheme 1):
  • naphtha 3.17 Mt / yr
  • carburetor 0.73 Mt / yr
  • Diesel 2.32 Mt / yr
  • Domestic fuel 1.5 Mt / year
  • Fuel from a viscosity-reduced 565 ° C + residue: 1.42 Mt / yr of 40 cst fuel oil (diluted by LCO and including slurry)

Le diesel a un indice de cétane de 49 et une teneur en soufre de 2100 ppm. Pour être aux spécifications (cétane 51 et soufre 350 ppm), il doit subir une désulfuration classique.The diesel has a cetane number of 49 and a sulfur content of 2100 ppm. To be in specification (51 cetane and 350 ppm sulfur), it must undergo a conventional desulfurization.

Sans changement dans le schéma de raffinerie, mais avec des qualités diesel aux spécifications 2005 (point 95% pris à 340°C), on a (schéma 2) :

  • naphta    3,32 Mt/an
  • coupe carburéacteur    0,82 Mt/an
  • diesel    2,13 Mt/an
  • Fuel domestique    1,36 Mt/an
  • Fuel 40cst à partir du résidu 565°C+    1,43 Mt/an
No change in the refinery scheme, but with diesel qualities at 2005 specifications (95% point taken at 340 ° C), we have (Figure 2):
  • naphtha 3.32 Mt / yr
  • cutting carburettor 0.82 Mt / year
  • diesel 2.13 Mt / yr
  • Domestic fuel 1.36 Mt / yr
  • Fuel 40cst from residue 565 ° C + 1.43 Mt / year

Le diesel a un indice de cétane de seulement 48 et doit donc subir une hydrodésulfuration et une hydrogénation extrêmement sévères qu'il n'est pas possible de réaliser dans les unités actuelles.The diesel has a cetane number of only 48 and must therefore undergo extremely severe hydrodesulfurization and hydrogenation that can not be achieved in the current units.

Le pool naphta aurait une teneur en soufre de 270 ppm massiques, ce qui nécessiterait des traitements ultérieurs sévères pour la réduire à 10-50 ppm massiques. Aussi, pour éviter des investissements coûteux, la fraction naphta issue du FCC sera traitée séparément en hydrodésulfuration sévère, avec pour inconvénient d'abaisser l'indice d'octane. Les autres fractions naphta (par exemple issues du viscoréducteur, de la distillation du brut...) seront envoyées au reforming et éventuellement une unité d'isomérisation après hydrotraitement.The naphtha pool would have a sulfur content of 270 ppm, which would require severe subsequent treatments to reduce it to 10-50 ppm. Also, to avoid expensive investments, the naphtha fraction from the FCC will be treated separately in severe hydrodesulfurization, with the disadvantage of lowering the octane number. The other naphtha fractions (for example from the visbreductor, from the crude distillation, etc.) will be sent to reforming and possibly an isomerization unit after hydrotreatment.

L'addition au schéma 2 précédant d'un hydrotraitement avant le craquage catalytique (tel que montré figure 3 mais sous hydrocraquage) a pour conséquence (schéma 3) :

  • naphta    3,06 Mt/an
  • carburéacteur    0,84 Mt/an
  • diesel    2,57 Mt/an
  • fuel domestique    1,40 Mt/an
  • fuel 40 cst à partir du résidu 565°C+    1,36 Mt/an
The addition to scheme 2 preceding a hydrotreatment before catalytic cracking (as shown figure 3 but under hydrocracking) has the consequence (scheme 3):
  • naphtha 3.06 Mt / yr
  • 0.84 Mt / a
  • 2.57 Mt / y diesel
  • domestic fuel 1,40 Mt / year
  • fuel 40 cst from the residue 565 ° C + 1,36 Mt / an

Le cétane du diesel reste à environ 48. Le naphta de FCC a une teneur de 15 ppm en soufre, et dans le pool naphta la teneur en soufre peut alors être abaissée aussi bas que 5,5 ppm environ, et ce sans perte d'octane sensible.The cetane of the diesel remains at about 48. The FCC naphtha has a content of 15 ppm sulfur, and in the naphtha pool the sulfur content can be lowered as low as about 5.5 ppm, without loss of sulfur. sensitive octane.

Avec un schéma 4 préféré selon l'invention (figure 3) incluant l'hydrocraquage à pression modérée, on obtient (schéma 4) :

  • naphta    2,90 Mt/an
  • carburateur   0,86 Mt/an
  • diesel    2,82 Mt/an
  • fuel domestique    1,44 Mt/an
  • fuel 40 cst    1,34 Mt/an
With a preferred scheme 4 according to the invention ( figure 3 ) including hydrocracking at moderate pressure, we obtain (scheme 4):
  • naphtha 2.90 Mt / yr
  • carburetor 0.86 Mt / yr
  • diesel 2.82 Mt / yr
  • domestic fuel 1,44 Mt / year
  • fuel 40 cst 1.34 Mt / year

Dans ce cas, la distillation sous vide sépare, une fraction légère 350-410°C, une fraction lourde 410-565°C et un résidu 565°C+.In this case, the vacuum distillation separates, a light fraction 350-410 ° C, a heavy fraction 410-565 ° C and a residue 565 ° C +.

En hydrocraquage, la conversion est quasi-complète (≥ 98%), la consommation en H2 de 1,85%pds, la pression est de 90 bars ppH2.
Le diesel obtenu : point 95% 340°C point d'éclair >60°C cétane 56 soufre <10 ppm polyaromatiques <1%pds In hydrocracking, the conversion is almost complete (≥ 98%), the H2 consumption of 1.85% wt, the pressure is 90 bar ppH 2 .
The diesel obtained: 95% point 340 ° C flash point > 60 ° C cetane 56 sulfur <10 ppm polyaromatic <1 wt%

La comparaison de ces chiffres montre l'excellente qualité du diesel obtenu par un schéma selon l'invention, qualité jamais atteinte directement auparavant.The comparison of these figures shows the excellent quality of the diesel obtained by a scheme according to the invention, quality never reached directly before.

Par rapport à un hydrocraquage classique, pour des mêmes qualités de produit, on a pu réaliser une économie de 50 bars en pression d'hydrogène, ce qui abaisse considérablement les coûts.Compared to conventional hydrocracking, for the same product qualities, it has been possible to achieve a saving of 50 bars in hydrogen pressure, which considerably lowers the costs.

En termes de productivité, les quantités des produits sont similaires à celles du schéma 3, mais par contre la comparaison avec le schéma 2 (raffinerie actuelle mise aux spécifications 2005) montre des gains importants, pour la même quantité de pétrole brut en : diesel +32,4% kérosène 4,9% In terms of productivity, the quantities of the products are similar to those of scheme 3, but on the other hand the comparison with scheme 2 (current refinery set to 2005 specifications) shows significant gains, for the same quantity of crude oil in: diesel + 32.4% kerosene 4.9%

On a ainsi pu ajuster la balance diesel/naphta vers plus de diesel de haute qualité, tout en réduisant quelque peu la production de fuel 40cst (-6,3%) adaptant ainsi la raffinerie aux besoins du marché. De plus, l'unité de FCC ne travaillant pas à pleine capacité, l'exploitant pourra très avantageusement introduire un supplément de charge apte à être traité en FCC (tel qu'un résidu atmosphérique). Cette addition sera réalisée de préférence dans la charge entrant dans la colonne de distillation sous vide (traits pointillés sur la figure 3).As a result, the diesel / naphtha balance could be adjusted to more high-quality diesel, while reducing the production of 40cst fuel (-6.3%) somewhat, adapting the refinery to market needs. In addition, the FCC unit does not work at full capacity, the operator can very advantageously introduce a charge supplement able to be treated in FCC (such as an atmospheric residue). This addition will preferably be carried out in the feed entering the vacuum distillation column (dashed lines on the figure 3 ).

Claims (12)

  1. A process for treatment of crude hydrocarbonated feed comprising the following steps :
    - atmospheric distillation of the crude hydrocarbonated feed, producing at least one naphta fraction, at least one kerosene fraction, at least one diesel fraction and an atmospheric residue,
    - vacuum distillation of the atmospheric residue to separate at least one light distillate fraction, at least one heavy distillate fraction and a vacuum residue with a boiling point of more than at least 535°C ,
    - catalytic cracking of at least one heavy distillate fraction, optionally added with at least a part of the hydrocracking residue,
    - treatment of said light fraction for producing a diesel having a 95% distillation point of less than 360°C, a sulphur content of at most 50 ppm and a cetane number of more than 51, said process treating hydrocarbon feeds with a T5 temperature in the range 250°C to 400°C and a T95 temperature of at most 470°C, said process comprising hydrotreatment which produces an effluent having an organic nitrogen content below 10ppm followed by moderate pressure hydrocracking with a hydrocracking catalyst comprising at least one Y zeolite, at least one matrix and at least one hydro-dehydrogenating function, said hydrocracking being carried out at a hydrogen partial pressure of more than 70 bars and at most 100 bars, at a temperature of at least 320°C, with a H2/feed volume ratio of at least 200 NI/NI, and at an hourly space velocity of 0.15-7 h-1, the process being carried out with a conversion of at least 80% by volume and the liquid effluent obtained by hydrocracking being distilled to separate the diesel.
  2. A process according to claim 1, in which the hydrocracking residue is recycled to the process after purging.
  3. A process according to any one of the preceding claims, in which the moderate pressure hydrocracking purge undergoes catalytic cracking.
  4. A process according to any one of the preceding claims, in which the conversion is at least 95% by volume.
  5. A process according to any one of the preceding claims in which, before undergoing catalytic cracking, the heavy vacuum distillate is hydrotreated under a hydrogen partial pressure of 25-90 bars, at a temperature of 350-430°C, with a conversion of at least 10% and less than 40% by volume, to products boiling below 350°C.
  6. A process according to any one of the preceding claims, in which the vacuum residue undergoes a treatment by a process selected from the group formed by visbreaking, residue hydroconversion, and coking processes.
  7. A process according to any one of the preceding claims, in which the diesel obtained has a 95% point of at most 340°C, a sulphur content of at least 10 ppm and a cetane number of at least 54.
  8. A process according to any one of the preceding claims, in which atmospheric distillation also produces a heavy atmospheric gasoil cut, said cut being also treated with the said light fraction by the process according to any one of the preceding claims.
  9. A unit for producing diesel from a crude hydrocarbon feed, comprising:
    - a column for atmospheric distillation of said crude feed to separate at least naphtha, diesel and an atmospheric residue;
    - a vacuum distillation column to treat said atmospheric residue, and to separate at least one vacuum distillate and a vacuum residue;
    - in which unit the atmospheric distillation column or vacuum distillation column comprises at least one line recovering a fraction with a T5 temperature in the range 250°C to 400°C and a T95 temperature of at most 470°C;
    - the unit also comprising at least one zone for hydrotreating said fraction followed by at least one moderate pressure hydrocracking zone and at least one zone for separating products to obtain a diesel with a 95% distillation point of less than 360°C, a sulphur content of at most 50 ppm and a cetane number of more than 51
    - and a catalytic cracking zone for treating at least one vacuum distillate fraction located between the fraction with a T95 temperature of at most 470°C and the vacuum residue.
  10. A unit according to claim 9, in which the product separation zone separates a hydrocracking residue with a boiling point of more than at least 535°C and comprises a purge line for said residue and optionally a line for recycling said purged residue towards the hydrocracking zone or reactor.
  11. A unit according to any one of claims 9 to 10, comprising a line supplying the purge to the catalytic cracking zone.
  12. A unit according to any one of claims 9 to 11, comprising a hydrotreatment zone prior to the catalytic cracking zone.
EP01974410A 2000-10-05 2001-09-28 Method for producing diesel fuel by moderate pressure hydrocracking Expired - Lifetime EP1330505B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0012736 2000-10-05
FR0012736A FR2815041B1 (en) 2000-10-05 2000-10-05 PROCESS FOR THE PRODUCTION OF DIESEL BY MODERATE PRESSURE HYDROCRACKING
PCT/FR2001/003016 WO2002028989A1 (en) 2000-10-05 2001-09-28 Method for producing diesel fuel by moderate pressure hydrocracking

Publications (2)

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EP1330505A1 EP1330505A1 (en) 2003-07-30
EP1330505B1 true EP1330505B1 (en) 2010-08-18

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US (1) US20040050753A1 (en)
EP (1) EP1330505B1 (en)
JP (1) JP4939724B2 (en)
KR (1) KR100738294B1 (en)
AT (1) ATE478127T1 (en)
BR (1) BR0114280B1 (en)
DE (1) DE60142843D1 (en)
ES (1) ES2351112T3 (en)
FR (1) FR2815041B1 (en)
TW (1) TWI225889B (en)
WO (1) WO2002028989A1 (en)

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JP4576334B2 (en) * 2003-03-07 2010-11-04 Ｊｘ日鉱日石エネルギー株式会社 Hydrotreating process for diesel oil fraction
RU2378050C2 (en) * 2004-12-23 2010-01-10 Энститю Франсэ Дю Петроль Zeolite catalysts with controlled content of promoter element and improved method of processing hydrocarbon fractions
FR2886941B1 (en) * 2005-06-09 2010-02-12 Inst Francais Du Petrole SOFT HYDROCRACKING PROCESS INCLUDING DILUTION OF THE LOAD
BR112012024722B8 (en) * 2010-03-31 2018-09-11 Exxonmobil Res & Eng Co hydroprocessing of feeds in the boiling range of diesel.
US8557106B2 (en) 2010-09-30 2013-10-15 Exxonmobil Research And Engineering Company Hydrocracking process selective for improved distillate and improved lube yield and properties
WO2014098820A1 (en) 2012-12-19 2014-06-26 Exxonmobil Research And Engineering Company Mesoporous zeolite -y hydrocracking catalyst and associated hydrocracking processes
FR3000097B1 (en) * 2012-12-20 2014-12-26 Ifp Energies Now INTEGRATED PROCESS FOR THE TREATMENT OF PETROLEUM LOADS FOR THE PRODUCTION OF LOW SULFUR CONTENT FIELDS
RU2544237C1 (en) * 2013-08-13 2015-03-20 Светлана Изаковна Сельская Processing method of hydrocarbon raw material
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US11517887B2 (en) 2018-08-17 2022-12-06 China Petroleum & Chemical Corporation Modified Y-type molecular sieve, catalytic cracking catalyst comprising the same, their preparation and application thereof

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FR2815041B1 (en) 2018-07-06
WO2002028989A1 (en) 2002-04-11
FR2815041A1 (en) 2002-04-12
US20040050753A1 (en) 2004-03-18
ATE478127T1 (en) 2010-09-15
JP2004510875A (en) 2004-04-08
KR100738294B1 (en) 2007-07-12
BR0114280B1 (en) 2012-02-22
KR20030036889A (en) 2003-05-09
EP1330505A1 (en) 2003-07-30
BR0114280A (en) 2003-07-29
JP4939724B2 (en) 2012-05-30
DE60142843D1 (en) 2010-09-30
ES2351112T3 (en) 2011-01-31
TWI225889B (en) 2005-01-01

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