EP1336649B1 - Procédé d'amélioration de coupes gazoles aromatiques et naphteno-aromatiques - Google Patents

Procédé d'amélioration de coupes gazoles aromatiques et naphteno-aromatiques Download PDF

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EP1336649B1
EP1336649B1 EP03290340A EP03290340A EP1336649B1 EP 1336649 B1 EP1336649 B1 EP 1336649B1 EP 03290340 A EP03290340 A EP 03290340A EP 03290340 A EP03290340 A EP 03290340A EP 1336649 B1 EP1336649 B1 EP 1336649B1
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Prior art keywords
hydrorefining
weight
group
zeolite
catalyst
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German (de)
English (en)
French (fr)
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EP1336649A1 (fr
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Eric Benazzi
Patrick Bourges
Christophe Gueret
Pierre Marion
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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

Definitions

  • the present invention relates to the field of fuels for internal combustion engines. It relates more particularly to the conversion of a diesel fuel cup and in particular the manufacture of a fuel for compression ignition engine. It also relates to the fuel thus obtained.
  • diesel fuel cuts whether from the direct distillation of a crude oil or from a conversion process such as catalytic cracking, still contain significant amounts of aromatic, nitrogenous and sulfur compounds. .
  • a fuel must have a cetane number greater than 51, a sulfur content of less than 350 ppm (parts per million by mass), a density, d15 / 4, at 15 ° C lower than 0.845 g / cm 3 , a content of polyaromatic compounds of less than 11% by weight and a temperature, T95, of 95% boiling of its components lower than 360 ° C.
  • Diesel fuel cuts generally come either from direct distillation of crude oil or from catalytic cracking: that is to say, light distillate (LCO initials for Light Cycle Oil) cuts, heavy fraction cuts (English initials). HCO for Heavy Cycle Oil), or another conversion process (coking, visbreaking, hydroconversion of residue, etc.) or gas oils from distillation of aromatic crude oil or naphthenoaromatic type Cerro-Negro, Zuata, El Pao. It is particularly important to produce an effluent that can be directly and fully recovered as a fuel cut of very high quality.
  • LCO initials Light Cycle Oil
  • HCO Heavy Cycle Oil
  • gas oils from distillation of aromatic crude oil or naphthenoaromatic type Cerro-Negro, Zuata, El Pao. It is particularly important to produce an effluent that can be directly and fully recovered as a fuel cut of very high quality.
  • the FR 2,777,290 proposes a process combining a hydrocracking with a hydrogenation in order to reduce the sulfur content and to increase the cetane number of the fuels thus produced. This process, which is already performing well, must however be improved to meet the increasingly stringent requirements that will be required in most industrialized countries.
  • EP-A-0 093 552 describes a hydrocracking process.
  • An improved process has been found which combines hydrocracking with hydrogenation to produce fuels with even higher specifications, not only with a maximum sulfur content of 350 ppm, preferably 50 ppm, and a minimum cetane number. of 51, preferably 53, in particular 58, but also a maximum T95 temperature of 360 ° C, preferably 340 ° C, a maximum content of polyaromatic compounds of 11% by weight, preferably 6% by weight in particular 1% by weight and a maximum d15 / 4 density of 0.845 g / cm 3 , preferably 0.825 g / cm 3 .
  • the fuels obtained by this improved process thus have a high cetane number, a reduced sulfur content meeting current and future specifications.
  • they have a boiling temperature T95, a density d15 / 4 and polyaromatic compound contents sufficiently reduced to meet not only the current specifications, and preferably the forecasts of future European specifications of 2005.
  • An object of the present invention is also to provide a process that can be operated under simple and economically viable conditions, and in particular does not involve high pressures and leading to good diesel yields.
  • the operating conditions of the process of the invention have, surprisingly, led to fuels having not only a reduced sulfur content and a higher cetane number, but also a 95% boiling temperature, T95. components with an aromatic content and density d15 / 4 at 15 ° C having lower values.
  • the gas oils to be treated are generally light gas oils, such as, for example, straight-run gas oils, liquid catalytic crackers (FCC) or (LCO). They generally have an initial boiling point of at least 180 ° C and a final boiling point of at most 370 ° C.
  • the weight composition of these feeds by hydrocarbon families varies according to the intervals. Depending on the compositions usually encountered, the paraffin contents are between 5.0 and 30.0% by weight and naphthenes between 5.0 and 60% by weight.
  • the diesel feeds preferably have an aromatic content (including the polyaromatic and naphthenoaromatic compounds) between 20% and 90%, in particular between 40% and 80% by weight.
  • the process according to the invention makes it possible, during the first hydrorefining step, to reduce the sulfur content, the nitrogen content, the content of aromatic and polyaromatic compounds, as well as to increase the cetane number.
  • the conversion to products having a boiling point below 150 ° C is limited to the hydrorefining step.
  • the conversion to products having a boiling point below 150 ° C is, for the hydrorefining step, between 1 and 15%, preferably 5 and 15% by weight.
  • the operating conditions to be applied to respect these conversion rates favor the reduction of the content of aromatic compounds by hydrogenating them and increasing the cetane number.
  • the conversion to products having a boiling point of less than 150 ° C. is also, over the two hydrorefining and hydrocracking stages, maintained below a certain limit, beyond It has been found that the cetane number may be reduced by the presence of aromatic compounds.
  • the conversion to products having a boiling point below 150 ° C. is, on both hydrorefining and hydrocracking stages, less than 40%, preferably less than 35%, in particular less than 30%, for example less than 25% by weight.
  • a zeolite catalyst is used during the hydrocracking step at a temperature lower than that of the hydrorefining step. It was surprisingly found that this made it possible to complete the hydrogenation of aromatic compounds and polyaromatics while still allowing moderate cracking of the feedstock, since said cracking is carried out at relatively low temperatures.
  • the difference between the temperature TR1 of the hydrorefining step and the hydrocracking temperature TR2 of the step is between 5 ° C. and 70 ° C., especially between 10 ° C. and 60 ° C., in particular between 15 ° C and 50 ° C.
  • this difference can be between 11 ° C and 70 ° C, preferably between 13 ° C and 60 ° C, in particular between 15 ° C and 50 ° C.
  • the process of the invention thus makes it possible to increase, during the hydrocracking step, the cetane number while decreasing the density, d15 / 4, and the temperature, T95, of the diesel fraction.
  • the fuel produced thus meets the most stringent future specifications.
  • the catalyst used during the hydrorefining stage of the process of the present invention also called hydrorefining catalyst, comprises on an amorphous mineral support, at least one metal of group VIB of the periodic table of the elements. at least one non-noble metal of group VIII of this classification and at least one promoter element.
  • the metals of groups VIB and VIII constitute the hydro-dehydrogenating element of the hydrorefining catalyst.
  • the feedstock is brought into contact with a hydrorefining catalyst comprising at least one support, at least one element of group VIB of the periodic table, at least one group VIII element. this same classification, at least one promoter element, the latter being deposited on said catalyst, optionally at least one element of group VIIB such as manganese, and optionally at least one element of the group VB such as niobium.
  • the promoter element is chosen from the group consisting of phosphorus, boron, silicon and fluorine.
  • the hydrorefining catalyst comprises as promoting elements boron and / or silicon, as well as optionally and, preferably, phosphorus.
  • the boron, silicon and phosphorus contents are then generally understood, for each of these elements, between 0.1 and 20% by weight, preferably between 0.1 and 15% by weight, in particular between 0.1 and 10%. in weight.
  • the presence of phosphorus provides at least two advantages to the hydrorefining catalyst. Phosphorus facilitates the impregnation of nickel and molybdenum solutions, and it also improves the hydrogenation activity.
  • the amorphous inorganic supports of the hydrorefining catalyst can be used alone or as a mixture.
  • These supports for the hydrorefining catalyst may be chosen from alumina, halogenated alumina, silica, silica-alumina, clays, magnesia, titanium oxide, boron oxide, zirconia, aluminum phosphates, titanium phosphates, zirconium phosphates, coal, aluminates.
  • the clays it is possible to choose natural clays, such as kaolin or bentonite.
  • the supports used contain alumina, in all these forms known to those skilled in the art, and even more preferably are aluminas, for example gamma-alumina.
  • the hydro-dehydrogenating function of the hydrorefining catalyst is generally fulfilled by at least one Group VIB metal of the periodic table of elements and at least one non-noble metal of group VIII of this classification, these metals preferably being chosen among molybdenum, tungsten, nickel and cobalt.
  • this function can be provided by the combination of at least one element of group VIII (Ni, Co) with at least one element of group VIB (Mo, W).
  • the hydrorefining catalyst comprising phosphorus is such that the total concentration of Group VIB and VIII metal oxides is between 5 and 40% by weight, preferably between 7 and 30% by weight. weight.
  • the weight ratio expressed as metal oxide between metal (or metals) of group VIB on metal (or metals) of group VIII is, for its part, preferably between 20 and 1.25, even more preferably between 10 and 2.
  • the concentration of phosphorus oxide P 2 O 5 in this catalyst is preferably less than 15% by weight, in particular less than 10% by weight.
  • Such a hydrorefining catalyst has an activity in hydrogenation of aromatic hydrocarbons, hydrodenitrogenation and hydrodesulphurization greater than the catalyst formulas without boron and / or silicon.
  • This type of catalyst also has a greater hydrocracking activity and selectivity than the catalytic formulas known in the prior art.
  • a catalyst comprising boron and silicon is particularly active, which induces, on the one hand, an improvement of the hydrogenating, hydrodesulphurizing and hydrodenitrogenous properties and, on the other hand, an improvement in the hydrocracking activity with respect to the catalysts used. usually in hydroconversion hydrotreatment reactions.
  • the preferred hydrorefining 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 constituted by by phosphorus, boron, silicon and fluorine.
  • Other preferred catalysts are NiMo and / or NiW catalysts on silica-alumina or on silica-alumina-titanium oxide, doped or not, by at least one element included in the group of atoms consisting of phosphorus, boron, fluorine and silicon.
  • the hydrorefining step is advantageously carried out at a pressure ranging from 5 to 15 MPa, preferably from 6 to 13 MPa, even more preferably from 7 to 11 MPa and at a temperature ranging from 310 ° C. to 420 ° C. preferably 320 to 400 ° C, more preferably 340 to 400 ° C.
  • the recycling of pure hydrogen by volume of charge may advantageously be between 200 and 2500 Nm 3 / m 3 of charge, preferably between 300 and 2000 Nm 3 / m 3 .
  • the space velocity may be, for its part, between 0.1 and 5, preferably between 0.1 and 3, expressed in volume of liquid charge per volume of catalyst and per hour.
  • the organic nitrogen content targeted is generally less than 50 mass ppm, preferably less than 20 ppm, in particular less than 10 mass ppm.
  • all the products resulting from the hydrorefining step is engaged in the hydrocracking step of the process of the invention.
  • the hydrorefining step and the hydrocracking step generally take place in at least two distinct reaction zones. These reaction zones may be contained in one or more reactors.
  • the catalyst used during the hydrocracking step of the process of the invention also called hydrocracking catalyst, comprises at least one zeolite which may preferably be chosen from the group consisting of zeolite Y (of structural type). FAU), zeolite NU-86 and zeolite Beta (structural type BEA).
  • This hydrocracking catalyst further comprises at least one inorganic binder (or matrix) and a hydro-dehydrogenating element.
  • This catalyst may optionally comprise at least one element selected from the group consisting of boron, phosphorus, silicon, at least one element of group VIIA (chlorine, fluorine for example), at least one element of group VIIB (manganese for example) ), and at least one element of the group VB (niobium for example).
  • the catalyst may also comprise, as inorganic binder, at least one porous or poorly crystallized oxide type mineral matrix.
  • inorganic binder 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 of the hydrocracking catalyst is generally provided by at least one element of the non-noble group VIII of the periodic table of elements (for example cobalt and / or nickel) and optionally at least one Group VIB element of the same classification (eg molybdenum and / or tungsten).
  • the hydro-dehydrogenating function of the hydrocracking catalyst is provided by at least one non-noble group VIII element (for example cobalt and / or nickel) and at least one group VIB element (for example molybdenum and / or tungsten)
  • group VIII element for example cobalt and / or nickel
  • group VIB element for example molybdenum and / or tungsten
  • the hydrocracking catalyst comprises at least one non-noble group VIII metal, at least one Group VIB metal, at least one zeolite and a mineral binder such as alumina.
  • the hydrocracking catalyst comprises essentially nickel, molybdenum, alumina and a zeolite selected from the group consisting of zeolite Y and zeolite NU-86.
  • 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 or palladium.
  • 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 or palladium.
  • ruthenium, rhodium, iridium, iron and other metals such as manganese, zinc, magnesium.
  • said catalyst further comprises at least one metal having a hydro-dehydrogenating function, and silicon deposited on said catalyst.
  • Peak levels and crystalline fractions are determined by X-ray diffraction against a reference zeolite, using a procedure derived from the ASTM method D3906-97 "Determination of Relative X-ray Diffraction Intensities of Faujasite-Type-Containing Materials ". We can refer to this method for the conditions general rules for the 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 essentially by the diffusion of the amorphous or micro-crystalline fraction of the sample (a weak diffusion signal is linked to the apparatus, air, sample holder, etc ).
  • the peak level of the sample is 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 zeolites. 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.
  • a catalyst comprising a zeolite Y not dealuminated globally and very acidic.
  • zeolite Y structural type FAU, faujasite
  • Atlas of zeolites structure types WM Meier, DH Olson and Ch. Baerlocher, 4th revised Edition 1996, Elsevier .
  • the crystalline parameter can be reduced by extraction of aluminum from the structure (or framework).
  • the overall SiO 2 / Al 2 O 3 ratio generally remains unchanged because the aluminum has not been chemically extracted.
  • Such a zeolite not dealuminated globally therefore has a global SiO 2 / Al 2 O 3 ratio which also remains unchanged.
  • This zeolite Y not dealuminated globally can be in the form either hydrogenated or at least partially exchanged with metal cations, for example using cations of alkaline earth metals rare earth metal cations of atomic number 57 to 71 included.
  • a zeolite devoid of rare earth and alkaline earth is generally preferred.
  • the zeolite Y globally not 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 from the sample, such as, for example, a steam treatment or treatment with SiCl 4 .
  • the hydrocracking catalyst contains a phosphate-doped alumina-type acidic amorphous oxide matrix, a non-dealuminated Y zeolite which is globally and highly acid dealalised, and optionally at least one group VIIA element. and in particular fluorine.
  • Beta zeolite of structural type BEA according to the nomenclature developed in " Atlas of Zeolite Structural Types ", WM Meier, DH Olson and Ch. Baerlocher, 4th revised 1996 Edition, Elsevier .
  • This zeolite Beta can be used in its H-beta acid form or partially exchanged with cations.
  • the Si / Al ratio of the zeolite Beta may be that obtained during its synthesis or it may undergo post-synthesis dealumination treatments known to those skilled in the art.
  • Zeolite NU-86 which can also be advantageously used in the process of the invention, is described in US Pat. US 5,108,579 .
  • This zeolite can be used in its acid form H-NU-86 or partially exchanged with cations.
  • the NU-86 zeolite can also be used after having undergone one or more post-synthesis dealumination treatments so as to increase its Si / Al ratio and thus adjust its catalytic properties.
  • Post-synthesis dealumination techniques are described in US Pat. US 6,165,439 .
  • the hydrocracking step is advantageously carried out at a pressure ranging from 5 to 15 MPa, preferably from 6 to 13 MPa, even more preferably from 7 to 11 MPa and at a temperature ranging from 290 to 400 ° C. preferably 310 ° C to 390 ° C, even more preferably 320 to 380 ° C.
  • the recycling of pure hydrogen can be between 200 and 2500 Nm 3 / m 3 , preferably between 300 and 2000 Nm 3 / m3.
  • the hydrorefining and / or hydrocracking catalyst may be subjected to a sulphurization treatment which makes it possible to transform, at least into part, the metal species sulphide before they come into contact with the load 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.
  • the effluent leaving the second reaction zone corresponding to the hydrocracking step of the process according to the invention may be subjected to a so-called final separation (for example an atmospheric distillation) so as to separate the gases (such as NH 3 ammonia and hydrogen sulphide (H 2 S), as well as other light gases present, hydrogen and conversion products (gasoline cut).
  • a so-called final separation for example an atmospheric distillation
  • the filler treated in this example is a naphtheno-aromatic gas oil obtained from a distillation and whose characteristics are as follows: Table 1: Physico-chemical characteristics of the load d15 / 4 0.9045 S content (% by weight) 2.2 Cetane engine 34 Content of aromatic compounds (including polyaromatics) 47.2 Polyaromatic content 20.4 T95% (ASTM D86) (° C) 351
  • This charge was introduced into a catalytic test unit comprising 2 reactors.
  • a catalyst comprising alumina, 3.6% by weight of nickel (oxide), 17.2% by weight of molybdenum (oxide) and 4% by weight of phosphorus (oxide) and in the downstream reactor a zeolitic hydrocracking catalyst comprising alumina, zeolite Y, nickel and molybdenum.
  • the yield of the gas oil fraction at 150 ° C + is 88% by weight (conversion of 12% by weight).
  • the table above shows that all the characteristics of the 150 ° C + gasoil fraction obtained by the process according to the invention are significantly improved and make it possible to meet the most severe future specifications.
  • the yield of the gas oil fraction at 150 ° C + is 92% by weight (conversion of 8% by weight).
  • the table above shows that all the characteristics of the 150 ° C + gasoil fraction obtained by the process according to the invention are also improved and make it possible to meet the most stringent future specifications.
  • Table 4 Characteristics of the 150 ° C ⁇ sup> + ⁇ / sup> cup after treatment d15 / 4 .8112 S content ppm weight 6 Cetane engine 44 Content of aromatic compounds (% by weight) 12.9 Content in polyaromatic compounds (% by weight) 1.2 T95% (ASTM D86) (° C) 281
  • the yield of the gas oil fraction at 150 ° C + is 43% by weight (conversion of 57% by weight).
  • the fuel obtained does not have a quality in accordance with the constraints imposed in the industrialized countries. In particular, it is noted that the cetane number is below 51.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP03290340A 2002-02-15 2003-02-11 Procédé d'amélioration de coupes gazoles aromatiques et naphteno-aromatiques Expired - Lifetime EP1336649B1 (fr)

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FR0201971A FR2836150B1 (fr) 2002-02-15 2002-02-15 Procede d'amelioration de coupes gazoles aromatiques et naphteno-aromatiques
FR0201971 2002-02-15

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EP1336649B1 true EP1336649B1 (fr) 2011-06-22

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BR (1) BR0300397B1 (pt)
ES (1) ES2367981T3 (pt)
FR (1) FR2836150B1 (pt)

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US20040159581A1 (en) 2004-08-19
ES2367981T3 (es) 2011-11-11
FR2836150A1 (fr) 2003-08-22
FR2836150B1 (fr) 2004-04-09
EP1336649A1 (fr) 2003-08-20
US7381321B2 (en) 2008-06-03
BR0300397B1 (pt) 2014-02-04

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