EP2598613A1

EP2598613A1 - Method for the selective hydrogenation of a gasoline fraction in the presence of a supported sulfide catalyst prepared using at least one cyclic oligosaccharide

Info

Publication number: EP2598613A1
Application number: EP11743261.7A
Authority: EP
Inventors: Fabrice Diehl; Elodie Devers
Original assignee: IFP Energies Nouvelles IFPEN
Current assignee: IFP Energies Nouvelles IFPEN
Priority date: 2010-07-29
Filing date: 2011-06-24
Publication date: 2013-06-05
Also published as: SA111320647B1; FR2963359B1; WO2012022849A1; US20130211163A1; FR2963359A1; US9206094B2; BR112013002162B1; BR112013002162A2; KR20130099017A; KR101886454B1

Abstract

The invention relates to a method for the selective hydrogenation of a gasoline fraction containing polyunsaturated hydrocarbons having at least two carbon atoms per molecule and having a final boiling point of no higher than 250°C, wherein said method consists of contacting said gasoline fraction with at least one catalyst, the active phase of which includes at least one Group VIII metal and one Group VIB metal deposited on a support, said catalyst being prepared according to a method including at least: i) a step of placing at least said support in contact with at least one solution containing at least one precursor of at least said Group VIII metal and at least one precursor of at least said Group VIB metal; ii) a step of placing at least said support in contact with at least one organic compound consisting of at least one cyclic oligosaccharide including at least six glucopyranose subunits bonded at α-(1,4); iii) a calcination step for obtaining at least said Group VIII metal and at least said Group VIB in oxide form; and iv) a sulfidation step, such that said active phase is provided in sulfide form, wherein steps i) and ii) can be carried out separately in any order, or simultaneously.

Description

METHOD FOR SELECTIVE HYDROGENATION OF A PETROL CUTTING IN THE PRESENCE OF A SUPPORTED SULFIDE CATALYST PREPARED BY MEANS OF AT LEAST ONE CYCLIC OLIGOSACCHARIDE

Field of the invention

The present invention relates to the field of petrol cutting hydrotreatment, including petrol cuts from fluidized bed catalytic cracking units (FCC). Hydroprocessing (HDT) is a general term used to designate all processes allowing the elimination of polyunsaturated compounds, especially diolefins (hydrogenation), as well as the elimination of organic compounds containing heteroatoms, in particular sulfur ( hydrodesulfurization, HDS), the presence of these compounds being undesirable in gasolines, which must meet ever more stringent automobile pollution standards. More specifically, the present invention relates to a process for the selective hydrogenation of a gasoline cut, mainly of a gasoline cut from a fluidized catalytic cracking unit, containing sulfur-containing organic compounds, in particular sulfur-containing organic compounds. light and saturated, and polyunsaturated compounds, especially diolefins. The content of polyunsaturated compounds, especially diolefins, as well as that of sulfur need to be reduced in order to be able to value said gasoline cut in the gasoline pool once it has been hydrotreated. The selective hydrogenation process according to the invention allows elimination of light sulfur compounds generally having from 1 to 3 carbon atoms per molecule by increasing the weight of said compounds without affecting the heavier sulfur compounds also present in the petrol fraction to be treated, said compounds heavier sulfur which can be converted to H ₂ S in a subsequent hydrodesulfurization step. To better situate the selective hydrogenation process according to the invention in a more global scheme, it is specified that the selective hydrogenation process according to the invention advantageously integrates into a technological complex in which the reaction unit carrying out said process of selective hydrogenation is placed upstream of a separation column making it possible to obtain a first stream formed of a light fuel cut, hydrogenated and substantially sulfur-depleted, having a good octane number and directly recoverable in the pool gasoline and a second stream formed of a heavy gasoline cut very enriched in sulfur, subsequently treated in a hydrodesulfurization unit, so as to obtain a gasoline also recoverable in the gasoline pool.

Prior art

The tightening of automotive pollution standards in 2009 in the European community forced refiners to very significantly reduce the sulfur content in gasoline, to a maximum of 10 parts per million weight (ppm) of sulfur since 1 January 2009, compared to 50 ppm as of January 1, 2005 (measured by ASTM D-4294). Else On the other hand, these new standards are also accompanied by constraints in terms of octane number.

The conversion gasolines, and more particularly those resulting from fluidized catalytic cracking (FCC gasoline, Fluid Catalytic Cracking according to English terminology), have high mono-olefin and sulfur contents and can represent 30 to 50% by volume. gasoline pool. The sulfur present in petrol is for this reason attributable, to nearly 90%, to gasolines resulting from fluidized catalytic cracking processes. The gasoline fractions, and more particularly the FCC gasolines, contain a large proportion of unsaturated compounds in the form of mono-olefins (approximately 20 to 50% by weight) and diolefins (0.5 to 5% by weight). Diolefins are unstable compounds which tend to form gums by polymerization and must therefore generally be removed by hydrogenation prior to any treatment of these species, in particular hydrodesulfurization (HDS) treatments intended to meet the specifications on the sulfur content in the species. However, it is essential that the hydrogenation is applied selectively to the diolefins in order to limit the hydrogenation of the mono-olefins which would lead to a loss of the octane number and to limit the consumption of hydrogen. Moreover, the gasoline cuts and more particularly the FCC gasolines, contain a significant part of sulfur in the form of sulfur-containing organic compounds (200 ppm to 0.5% by weight) which need to be eliminated in order to valorize said gasoline cuts in accordance with current regulations in terms of automotive pollution standards. Said sulfur-containing organic compounds are partly formed of saturated light sulfur compounds whose boiling point is below the boiling point of thiophene, which has a boiling point of 84 ° C., such as methanethiol, ethanethiol, sodium hydroxide and thiophene. dimethyl sulfide. It has already been proposed to eliminate such light sulfur compounds by weighing said compounds into sulfur compounds having a higher molecular weight which can be removed in a subsequent hydrodesulfurization step (EP 1 077.247 A1).

With the constant aim of obtaining gasoline of better quality and meeting the environmental requirements, catalytic formulations and processes for selectively hydrogenating diolefins to mono-olefins and / or transforming light sulfur compounds such as than mercaptans by weighting. For example, European Patent EP 0.685.552 B1 proposes a process for the hydrogenation of diolefins and for reducing the mercaptan content contained in a catalytic cracking gasoline based on a catalyst containing between 0.1 and 1% by weight of deposited palladium. on a support based on alumina. However, the catalytic performance of these prior catalysts are not entirely satisfactory in terms of activity in particular.

An effective way to increase the activity of the supported catalysts is to increase the amount of active phase in sulphide form, which results in prior to a maximum deposition of the active phase in oxide form associated with the surface of the support. However, this maximum amount (usually deposited by dry impregnation) is limited by the textural properties of the support and in particular its specific surface and its pore volume. In addition, in the particular case where the support used comprises the aluminum element, this high concentration of deposited oxide phase favors the formation of crystalline oxide phases of the type AI ₂ (MoO ₄ ) 3, CoAl ₂ O ₄ , NiAl ₂ O ₄ etc. which prove to be refractory to the sulphurization step. This logically results in an indirect loss of the catalytic activity since all the deposited oxide phase is not used to the maximum of its potential. On the other hand, an increase in the active phase content can lead to the formation of crystallites of o0 ₃ , NiO, CoO, Co ₃ 0 or CoMoO ₄ large enough to be detectable in XRD. These species are also known to reduce the sulfurization rate of hydrotreatment catalysts, and therefore their performance.

The composition and use of hydrogenation hydrotreatment catalysts are particularly well described in the article by B. S Clausen, HT Topsoe, and FE Massoth, from Catalysis Science and Technology, 1996, Volume 11, Springer-Verlag. Thus, these catalysts generally comprise at least one Group VI B metal and / or at least one Group VIII metal of the periodic table of the elements. The most common formulations are cobalt-molybdenum (CoMo), nickel-molybdenum (Ni o) and nickel-tungsten (NiW). These catalysts can be in mass form or in the supported state. In the latter case, the porous matrix is generally an amorphous or poorly crystallized oxide (alumina, silica-alumina, etc.) optionally combined with a zeolitic or non-zeolitic molecular sieve. After preparation, said catalysts are often in oxide form. Their active and stable form for the hydrotreatment processes and in particular for the hydrogenation processes being the sulfurized form, these catalysts are subjected to a sulphurization step.

However, the dispersion of the active phase or of these precursors oxide or oxy-hydroxide is directly related to the specific surface offered by the support: for high densities in molybdenum, the formation of refractory phases to sintering sulfurization has indeed been reported. New catalyst preparation techniques need to be developed to further improve the performance of these catalysts and meet future legislation. In particular, it is necessary to control the interactions between the support and the precursors of the active phase which result in species refractory to sulphidation (for example, ΑΙ ₂ (Μο0 ₄ ) ₃ , CoAI ₂ 0 ₄ or NiAl ₂ 0 ₄ ) , useless in the catalytic reaction and having undesirable effects on the catalytic activity.

The present invention proposes to develop a novel process for the selective hydrogenation of petrol cuts, particularly petrol cuts from the FCC, containing saturated light sulfur compounds and polyunsaturated compounds, especially diolefins, in the presence of a supported catalyst. whose preparation in the presence of an organic compound formed of at least one cyclic oligosaccharide leads to obtaining improved catalytic performance, especially in terms of activity.

Summary and interest of the invention

The subject of the present invention is a process for selective hydrogenation of an essence cut containing polyunsaturated hydrocarbons having at least 2 carbon atoms per molecule and having a final boiling point of less than or equal to 250 ° C., said cut having a weight content of polyunsaturated hydrocarbons of between 0.5 and 5% and a weight content of sulfur of between 200 and 5000 ppm, said method consisting in bringing said gasoline cut into contact with at least one catalyst whose active phase comprises at least a group VIII metal and at least one group VI B metal deposited on a support formed of at least one oxide, said catalyst being prepared according to a process comprising at least:

i) at least one step of contacting at least one of said support with at least one solution containing at least one precursor of at least said group VIII metal and at least one precursor of at least said group VIB metal,

ii) at least one step of contacting at least said support with at least one organic compound formed of at least one cyclic oligosaccharide composed of at least 6 α- (1,4) -linked glucopyranose subunits,

iii) at least one calcination step to obtain at least said group VIII metal and at least said group VIB metal in oxide form, and then

iv) at least one sulphurization step such that said active phase is in sulphide form,

steps i) and ii) can be performed separately, in any order, or simultaneously.

According to the selective hydrogenation process according to the invention, said group VIII metal present in the active phase is preferably nickel and said group VIB metal present in the active phase is preferably molybdenum. According to the selective hydrogenation process according to the invention, said catalyst is preferably prepared in the presence of a cyclodextrin as an organic compound. Surprisingly, it has been discovered that a sulfide catalyst whose active phase comprises at least one Group VIII metal, preferably a non-noble group VIII metal, and at least one Group VI B metal and prepared in the presence of at least one organic compound formed from at least one cyclic oligosaccharide composed of at least 6 α- (1,4) -linked glucopyranose subunits, preferably a cyclodextrin, which, when used in a process for selectively hydrogenating a gasoline cut, improved catalytic performance, especially in terms of catalytic activity and / or in terms of selectivity. In particular, such a catalyst has a substantially improved activity for conversion to polyunsaturated compounds, especially diolefins. This results in a better stability of said catalyst with respect to the formation of polymers, generated by the presence of the polyunsaturated compounds. In addition, the selectivity with respect to the selective hydrogenation of said polyunsaturated compounds, in particular of diolefinic compounds, is in no way affected, or even slightly improved: said catalyst prepared in the presence of at least one organic compound formed from at least one cyclic oligosaccharide composed of at least 6 α- (1,4) -linked glucopyranose subunits has, in addition to a substantially improved activity for the conversion towards the polyunsaturated compounds, a slightly improved selectivity towards the selective hydrogenation of said polyunsaturated compounds, especially diolefinic compounds, at the expense of the hydrogenation of the mono-olefinic compounds.

The selective hydrogenation process according to the invention also makes it possible, in addition to the selective hydrogenation of the polyunsaturated compounds, for the joint transformation of the sulfur-containing, light and saturated organic compounds present in the petrol fraction to be hydrotreated: said compounds are weighed down by in contact with the monoolefinic compounds present in said cut so as to form sulfur compounds, especially sulphides, of higher molecular weight. The sulfur compounds formed by weighing said sulfur compounds, light and saturated, are thus easily separated from the hydrogenated and sulfur-depleted gasoline cut by injection of the effluent of the selective hydrogenation process according to the invention into a separation train which leads to obtaining a first stream formed of said light gasoline fraction, hydrogenated and substantially sulfur-depleted, having a good octane number and directly recoverable in the gasoline pool without further treatment and a second stream consisting of a heavy gasoline fraction which is highly enriched in sulfur by the presence of said weighed sulfur compounds, said second stream being subsequently treated in a unit hydrodesulfurization, so as to obtain a gasoline also recoverable in the gasoline pool.

The selective hydrogenation process according to the invention thus makes it possible to obtain a light gasoline having a content of polyunsaturated compounds, in particular diolefins, and a content of light sulfur compounds, especially mercaptans, reduced. The gasoline thus produced, after separation, contains less than 1% by weight of polyunsaturated compounds, especially diolefins, and preferably less than 0.5% by weight of diolefins. It has an end point of less than 120 ° C, and preferably less than 100 ° C and very preferably less than 80 ° C. The light sulfur compounds whose boiling point is lower than that of thiophene (84 ° C.), present in the initial gasoline fraction to be hydrotreated according to the hydrogenation process according to the invention, are converted to more than 50%. Detailed description of the invention

The subject of the present invention is a process for selective hydrogenation of an essence cut containing polyunsaturated hydrocarbons having at least 2 carbon atoms per molecule and having a final boiling point of less than or equal to 250 ° C., said cut having a weight content of polyunsaturated hydrocarbons of between 0.5 and 5% and a weight content of sulfur of between 200 and 5000 ppm, said method consisting in bringing said gasoline cut into contact with at least one catalyst whose active phase comprises at least a Group VIII metal and at least one Group VIB metal deposited on a support formed of at least one oxide, said catalyst being prepared by a process comprising at least:

ii) at least one step of bringing at least one of said support into contact with at least one organic compound formed of at least one cyclic oligosaccharide composed of at least 6 α-linked glucopyranose subunits,

steps i) and ii) can be performed separately, in any order, or simultaneously. The gasoline cut, treated in the selective hydrogenation process according to the invention, has a lower final boiling point 250 ° C. It contains polyunsaturated hydrocarbons having at least 2 carbon atoms per molecule, and preferably at least 3 carbon atoms per molecule. Said gasoline cut is selected from gasolines from a coker unit, a visbreaking unit and a fluidized catalytic cracking unit (Fluid Cracking catalyst, FCC according to English terminology). Preferably, said gasoline cut, treated in the selective hydrogenation process according to the invention, comes from a catalytic cracking unit in a fluidized bed. More specifically, said polyunsaturated hydrocarbons present in said gasoline fraction treated according to the process of the invention are in particular compounds comprising at least one diene function, that is to say at least two double bonds. Preferably, said polyunsaturated hydrocarbons are diolefinic compounds, in particular isoprene, 2,4-butadiene and 1,3-pentadiene. The gasoline cut, treated in the selective hydrogenation process according to the invention, preferably the gasoline cut from a fluidized catalytic cracking unit, also contains monoolefinic compounds, for example 2,3-dimethyl- 1-butene, 4,4-dimethylcyclopentene, 2-methyl-2-heptene, 1-hexene, aromatic compounds, for example ethylbenzene and orthoxylene and saturated paraffin and / or naphthene compounds, for example, 2-methylhexane and 1-methylcyclopentane. Said essence cut, treated in the selective hydrogenation process according to the invention, and preferably said petrol cut resulting from a fluidized catalytic cracking unit, has a weight content of sulfur of between 200 and 5000 ppm, preferably between 500 and 2000 ppm. The sulfur present in said gasoline cut, preferably in said gasoline fluidized catalytic cracking gasoline cut, is in the form of sulfur-containing organic compounds, especially thiophene compounds, benzothiophenic compounds and sulfur compounds, light and saturated. The thiophene compounds are, for example, 3-methylthiophene and 3,4-dimethylthiophene. Of the benzothiophene compounds, benzothiophene is preferred. The sulfur compounds, light and saturated, present in said gasoline cut, are chosen from mercaptans (non-cyclic sulfur compounds having an SH bond) and light sulphides (compounds having an RS-R 'group, where R and R' are hydrocarbon groups). The most frequently encountered mercaptans in the gasoline cut, in particular in the gasoline catalytic cracking fluidized bed fraction, treated in the selective hydrogenation process according to the invention, are ethanethiol and propanethiol. Said mercaptans are concentrated in the light fraction of the gasoline to be hydrogenated and more precisely in the fraction whose boiling point is below 120 ° C. The light sulphides most frequently encountered in the gasoline cut, in particular in the fluidized catalytic cracking gasoline fraction, treated in the selective hydrogenation process according to the invention, are dimethylsulfide, methylethylsulfide and diethylsulphide, CS ₂ , COS, thiophane, methylthiophane.

A gasoline cut obtained from a catalytic cracking unit in a fluidized bed, advantageously used for carrying out the selective hydrogenation process according to the invention, has, for example, the following weight composition: from 0.5 to 5% by weight of di-olefinic compounds, from 20 to 50% by weight of monoolefinic compounds, from 30 to 60% by weight of aromatic compounds, from 20 to 50% by weight of saturated compounds (paraffins + naphthenes) and from 200 to 0.5% by weight sulfur weight. The content of light and saturated mercaptans having a boiling point below 84 ° C. preferably represents less than 300 ppm of said gasoline cut.

The selective hydrogenation process according to the invention consists mainly of selectively hydrogenating the polyunsaturated compounds, mainly diolefins, to mono-olefins and to convert the saturated light sulfur compounds, mainly mercaptans and light sulfides, into sulphides or mercaptans more heavy by reaction with monoolefins. The selective hydrogenation reaction of the polyunsaturated compounds, mainly diolefins, aims at eliminating said compounds present in said gasoline cut by converting said polyunsaturated compounds to the corresponding alkenes, avoiding the total saturation of said compounds so as to avoid the formation of the corresponding alkanes.

The sulfur-containing, light and saturated organic compounds which are to be converted in the process according to the invention are mainly mercaptans and light sulfides. The main transformation reaction of the mercaptans consists of thioetherification of the mono-olefins by the mercaptans. This reaction is illustrated below in the specific case of the addition of propane-2-thiol to pent-2-ene to form a propylpentylsulfide.

Since the process according to the invention is carried out in the presence of hydrogen, the transformation of the sulfur compounds present in the gasoline cut can also pass through the intermediate formation of H ₂ S which can then be added to the unsaturated compounds present in the cut. . This path is however a minority in the conditions of the reaction.

The light sulfides that can be converted and weighed according to the process of the invention are mainly dimethylsulfide, methylethylsulfide and diethylsulfide, CS ₂ , COS, thiophane, methylthiophane.

The technological implementation of the selective hydrogenation process according to the invention is carried out, for example, by injecting the petrol cut and hydrogen into at least one fixed bed, moving bed or bubbling bed reactor, in a preferred manner. in a fixed bed reactor. The entire gasoline fraction, treated according to the selective hydrogenation process according to the invention, is preferably injected at the reactor inlet where the selective hydrogenation reaction occurs. However, it may be advantageous, in some cases, to inject a fraction or all of said gasoline cut between two consecutive catalytic beds placed in said reactor. This embodiment makes it possible in particular to continue to keep the reactor operational even when the inlet of said reactor is clogged by deposits of polymers, particles or gums present in the gasoline cut.

The selective hydrogenation process according to the invention is carried out under the following operating conditions: a temperature of between 80 ° C. and 220 ° C., and preferably between 90 ° C. and 200 ° C., with a volume hourly velocity ( LHSV) of between 1 h ^"1 and 10 ^h ^-1, (the ratio of volume flow of gasoline cut on the volume of catalyst charged to the reactor in l / lh), a total pressure of between 0.5 MPa and 5 Pa and preferably between 1 and 4 MPa The pressure is adjusted so that the reaction mixture is predominantly in liquid form in the reactor The quantity of hydrogen introduced and injected is such that the molar ratio between hydrogen and the polyunsaturated compounds, preferably the diolefins to be hydrogenated is greater than 1 mol / mol and less than 10 mol / mol, and preferably between 1 and 5 mol / mol.

The catalyst used for the implementation of the selective hydrogenation process according to the invention comprises an active metal phase deposited on a support, said active phase comprising at least one metal of group VIII of the periodic table of the elements and at least one metal of group VI B of the periodic table of elements. Preferably, said catalyst contains no alkali metal or alkaline earth metal. In general, the metal content (ux) of group VIB in said oxide catalyst resulting from said step iii) is between 1 and 20% by weight of metal oxide (s) (ux) of group VIB, preferably between 5 and 15% by weight of Group VIB metal oxide (s). Preferably, the Group VIB metal is molybdenum or tungsten or a mixture of these two elements and more preferably the Group VIB metal consists solely of molybdenum or tungsten. The Group VIB metal is very preferably molybdenum.

In general, the metal content (ux) of group VIII in said oxide catalyst resulting from said step iii) is between 1 and 15% by weight of metal oxide (s) (ux) of group VIII, preferably between 1 and 10% by weight of Group VIII metal oxide (s). Preferably, the Group VIII metal is a non-noble metal of Group VIII of the Periodic Table of Elements. Very preferably, the Group VIII metal is selected from nickel, iron, cobalt and the mixture of at least two of these elements. More preferably, said Group VIII metal consists solely of cobalt or nickel. The Group VIII metal is very preferably nickel.

The molar ratio of metal (ux) of group VIII to metal (ux) of group VIB in the oxide catalyst from said step iii) is preferably between 1 and 2.5.

Advantageously, the catalyst obtained at the end of said step iv) has a total pore volume, measured by mercury porosimetry, of between 0.3 and 1.4 cm ³ / g, and very preferably between 0 , 4 and 1, 4 cm ³ / g. The mercury porosimetry is measured according to ASTM standard D4284-92 with a wetting angle of 140 °, for example by means of an Autopore III model apparatus of the Microméritics brand. The specific surface area of said catalyst is preferably between 40 and 300 m ² / g, preferably between 60 and 280 m ² / g.

The support on which the active phase is deposited is advantageously formed of at least one porous solid in oxide form selected from the group consisting of aluminas, silicas, silica-alumina or titanium or magnesium oxides used (s). ) alone or in admixture with alumina or silica-alumina. In a very preferred manner, the support consists essentially of a transition alumina. A support consisting essentially of a transition alumina comprises at least 51% by weight, preferably at least 60% by weight, very preferably at least 80% by weight, or even at least 90% by weight of said transition alumina. By transition alumina is meant for example an alpha phase alumina, a delta phase alumina, a gamma phase alumina. Even more preferred, said support consists entirely of a transition alumina. Said support formed of at least one oxide has a total pore volume, measured by mercury porosimetry, of between 0.4 and 1.4 cm ³ / g and preferably between 0.5 and 1.3 cm ³ / g. The specific surface area of said support is preferably between 40 and 350 m ² / g, preferably between 60 and 300 m ² / g. Said porous support is advantageously in the form of balls, extrudates, pellets, or irregular and non-spherical agglomerates, the specific shape of which may result from a crushing step. Very advantageously, said support is in the form of balls or extrudates. The catalyst used in the selective hydrogenation process according to the invention is prepared according to a process comprising at least:

iii) at least one calcination step to obtain at least said group VIII metal and at least said group VIB metal in oxide form, then,

iv) at least one suifuration step such that said active phase is in sulphide form,

steps i) and ii) can be performed separately, in any order, or simultaneously. The deposition of at least one of said group VIII metal and at least one of said group VIB metal on said support, in accordance with the implementation of said step i), may be carried out by any method well known to the man of the job. Said step i) is preferably carried out by impregnation of the support with at least one solution containing at least one precursor of said group VIII metal and at least one precursor of the group VIB metal. In particular, said step i) can be carried out by dry impregnation, by excess impregnation, or by deposition - precipitation according to methods well known to those skilled in the art. Preferably, said step i) is carried out by dry impregnation, which consists in bringing the support of the catalyst into contact with a solution containing at least one precursor of said group VIII metal and at least one precursor of said group VIB metal, whose volume is equal to the pore volume of the support to be impregnated. This solution contains the metal precursors of Group VIII metal (s) and Group VIB metal (s) at the desired concentration. Group VIII metal (s) and group VIB metal (s) are brought into contact with said support via any aqueous phase-soluble metal precursor or in the organic phase. Preferably, the said precursor (s) of the group VIII metal (s) and the precursor (s) precursor (s) of the metal (s) of the group VIB are introduced in aqueous solution. When the group VIII metal is cobalt, cobalt nitrate, cobalt hydroxide or cobalt carbonate are advantageously used as precursors. When the group VIII metal is nickel, nickel nitrate, nickel hydroxide or nickel carbonate are advantageously used as precursors. When said group VIB metal is molybdenum, it is advantageous to use ammonium heptamolybdate or molybdenum oxide. When said group VIB metal is tungsten, it is advantageous to use ammonium metatungstate. Any other salt known to those skilled in the art having sufficient solubility in aqueous solution and decomposable during a calcination step, in particular during the calcination step according to said step iii), can also be used.

The bringing into contact of said organic compound used for the implementation of said step ii) with said support is carried out by impregnation, in particular by dry impregnation or excess impregnation, preferably by dry impregnation. Said organic compound is preferably impregnated on said support after solubilization in aqueous solution. The impregnation solution advantageously comprises an acid, for example acetic acid.

Said organic compound is formed of at least one cyclic oligosaccharide composed of at least 6 α- (1,4) -linked glucopyranose subunits. A spatial representation of a subunit glucopyranose is given below:

Said organic compound is preferably chosen from cyclodextrins, substituted cyclodextrins, polymerized cyclodextrins and mixtures of cyclodextrins. Cyclodextrins are a family of cyclic oligosaccharides composed of α- (1,4) -linked glucopyranose subunits. It is about molecules-cages. According to the invention, the preferred cyclodextrins are Ρα-cyclodextrin, β-cyclodextrin and γ-cyclodextrin. respectively composed of 6, 7 and 8 α- (1,4) -linked glucopyranose subunits. The developed representations of Γα-cyclodextrin, β-cyclodextrin and γ-cyclodextrin are given below. Preferentially, for the implementation of said step ii), the β-cyclodextrin composed of 7 α- (1,4) -linked glucopyranose subunits. Cyclodextrins are marketed compounds.

γ-cyclodextrin

The substituted cyclodextrins advantageously employed for carrying out said step ii) consist of 6, 7 or 8 α- (1,4) -linked glucopyranose subunits, at least one of which is mono- or polysubstituted. Substituents can be attached to one or several hydroxyl group (s) present in the molecule, namely on the hydroxyl groups directly linked to the ring of a glucopyranose unit and / or on the hydroxyl bonded to the CH ₂ group itself linked to the ring of a glucopyranose unit. More preferably, said substituted cyclodextrins carry one or more substituent (s), identical (s) or different (s), selected (s) from saturated or unsaturated alkyl radicals, functionalized or not, and the functions ester, carbonyl, carboxyls, carboxylates, phosphates, ethers, polyethers, ureas, amides, amino, triazoles, ammoniums. Preferred substituted cyclodextrins are methylated, ethylated, propylated, allylated (i.e. possessing a function having the semi-developed formula -CH ₂ -CH = CH ₂ ), succinylated (i.e. having a function having the semi-developed formula R-OCO-CH ₂ -CH ₂ COOH), carboxylated, carboxymethylated, acetylated, 2-hydroxypropylated and polyoxyethylenated. The mono- or polysubstituent groups of the cyclodextrin may also be a monosaccharide or disaccharide molecule such as a maltose, glucose, fructose or sucrose molecule.

The substituted cyclodextrins that are particularly advantageous for the implementation of said step ii) are hydroxypropyl beta-cyclodextrin and methylated beta-cyclodextrins.

The polymerized cyclodextrins advantageously employed for the implementation of said step ii) are polymers whose monomers each consist of a cyclic oligosaccharide composed of 6, 7 or 8 α- (1,4) -linked glucopyranose subunits. substituted or not. A cyclodextrin in polymerized form, crosslinked or otherwise, which can be advantageously used for the implementation of said step ii) is for example of the type obtained by polymerization of beta-cyclodextrin monomers with epichlorohydrin or a polyacid.

The cyclodextrin mixtures advantageously employed for the implementation of said step ii) use substituted or unsubstituted cyclodextrins. Said mixtures may, by way of example, contain jointly and in variable proportions, each of the three types of cyclodextrins (alpha, beta and gamma).

The introduction of said organic compound, preferentially a cyclodextrin and very preferably beta-cyclodextrin, for the implementation of said step ii) is such that the molar ratio {(metal (ux) groups (VIII + VI B ) in the form of oxide present in the active phase of the catalyst obtained at the end of said step iii) / organic compound} is between 10 and 300 and preferably between 25 and 180. The metal (s) of the groups VIII and VIB taken into account for the calculation of said molar ratio are the metal (s) introduced for the implementation of said step i) and being in the form of oxide in the active phase of the catalyst resulting from said step iii). The said group VIII metal (s) and the group VIB metal (s) may consequently be in sulphide form: they will be sulphured prior to the implementation of the selective hydrogenation process according to the invention.

The process for preparing the catalyst used in the selective hydrogenation process according to the invention comprises several modes of implementation.

A first embodiment consists of carrying out said steps i) and ii) simultaneously so that said organic compound, preferably a cyclodextrin, and at least said precursor of at least said group VIII metal and at least said precursor of at least said group VIB metal present in the active phase are co-impregnated on said support (co-impregnation step). Said first embodiment advantageously comprises the implementation of one or more steps i). In particular, one or more steps i) advantageously (nt) and / or follow (nt) said co-impregnation step. According to said first embodiment, each of the (co) impregnation steps performed is preferably immediately followed by a maturation step and then at least one drying step and then at least one calcination step. In particular, said co-impregnation step is followed by at least one drying step and then at least one calcination step. Said first embodiment may comprise several steps of co-impregnation. Said step iii) of calcination is at least carried out when all the steps of deposition of at least said group VIII metal and at least said group VIB metal on the catalyst support have been carried out.

A second mode of implementation consists in performing said step i) prior to said step ii). According to said second embodiment, one or more steps i) of deposition of at least said group VIII metal and at least said group VIB metal present in the active phase of the catalyst precedes said step ii ). Preferably, each of said steps i) is immediately followed by a maturation step and then at least one drying step and optionally at least one calcination step. In particular, the last step i) is advantageously followed by at least one drying step, and possibly at least one calcination step, before the implementation of said step ii). Said step ii) is advantageously followed by a maturation step and then at least one drying step and very preferably at least one calcination step. Said calcination step according to said step iii) is at least carried out either following said step i) subsequent to the drying or following said ii) subsequently drying. A third mode of implementation consists in performing said step ii) prior to said step i). Said step ii) is preferably immediately followed by a maturation step and then at least one drying step and optionally at least one calcination step before the implementation of said step i). Advantageously, said step ii) is followed by several steps i). The preparation of the catalyst according to said third embodiment is advantageously terminated by said calcining step iii).

Each of the three implementation modes described above can be carried out independently so that the catalyst used in the process according to the invention is prepared either according to said first embodiment or according to said second embodiment. implemented again according to said third embodiment. However, it may be advantageous to associate said first mode with said second mode or with said third mode: both the Group VIII and Group VIB metals present in the active phase and the organic compound, preferably a cyclodextrin, are deposited at the same time. less than twice on the catalyst support, namely at least once by co-impregnation and at least once by successive impregnation.

Said drying steps, carried out for the preparation of the catalyst, prepared according to at least one embodiment described above, are carried out at a temperature of between 80 and 160 ° C. They are preferably carried out for a period of between 1 and 15 hours. The calcination step iii) is carried out at a temperature of between 200 and 660 ° C., preferably between 300 and 550 ° C. It is preferably carried out for a period of between 1 and 6 hours. The calcination steps used for the preparation of the catalyst, prepared according to at least one embodiment described above, are advantageously carried out under the same conditions as said step iii).

The catalyst obtained after said step iii), after implementing steps i) and ii) according to at least one of the three embodiments described above, is in the oxide state .

The preparation of the catalyst, used in the selective hydrogenation process according to the invention, comprises at least one sulphurization step iv) so that said active phase is in sulphide form.

Before contacting with the feedstock to be treated, the catalysts undergo a sulphurization step. The sulphurization is preferably carried out in a sulforeductive medium, ie in the presence of H ₂ S and hydrogen, in order to convert the metal oxides to sulphides, by for example, molybdenum oxides in MoS ₂ and nickel oxides in Ni ₃ S ₂ . Sulfurization is carried out by injecting onto the oxide catalyst a stream containing H ₂ S and hydrogen, or a sulfur compound capable of decomposing into H ₂ S in the presence of the catalyst and hydrogen. The H ₂ S precursors preferentially used for the implementation of said step iv) are polysulfides such as dimethyl disulphide. The temperature of said sulfurization step is adjusted so that the H ₂ S reacts with the metal oxides to form metal sulfides. Said step iv) of sulfurization can be carried out in situ (after loading the catalyst in the reaction unit of the selective hydrogenation process according to the invention) or ex situ (before loading the catalyst into the reaction unit of the hydrogenation process selective according to the invention) at a temperature between 200 and 600 ° C and more preferably between 300 and 500 ° C.

Said sulphurization step iv) is carried out so that the Group VIII and Group VIB metals are substantially sulphurized. An element is considered to be substantially sulphurated when the molar ratio between the sulfur (S) present on the catalyst resulting from said step iv) and said element is at least 60% (sulphidation ratio of at least 60%) of the ratio theoretical molar corresponding to the total sulphurisation of the element under consideration: (S / element) cataiyseur≥ 0.6 x (S / element), héorique

with:

(S / element) catayseur = molar ratio between the sulfur (S) and the element present on the catalyst resulting from said step iv)

(S / element) Theoretical = molar ratio between sulfur and the element corresponding to the total sulfurization of the sulphide element.

This theoretical molar ratio varies according to the element considered:

(S / Fe) theoretical ⁼ 1

(S / Co) theoretical = 8/9

- (S / Ni) _theoripue = 2/3

- (S / M0), _where _e = _2/1

- (S / W) _theoretical = 2/1

The catalyst comprising several metals, the molar ratio between the sulfur present on the catalyst resulting from said step iv) and all the elements must also be at least equal to 60% of the theoretical molar ratio corresponding to the total sulfurization of each element in sulphide, the calculation being made in proportion to the relative molar fractions of each element. For example, for a catalyst comprising molybdenum and nickel with a respective mole fraction of 0.7 and 0.3, the minimum molar ratio (S / Mo + Ni) is given by the _equation : (S / Mo + Ni) _cata i _yseur = 0.6 x {(0, 7 x 2) + (0.3 x (2/3)}

Very preferably, the sulphidation rate of the metals is greater than 80%. The catalyst resulting from said step iv) is before the implementation of the selective hydrogenation process according to the invention, at least partially in sulphide form. It may also comprise an oxide metal phase, which has not been converted during said sulphurization step iv). Said catalyst may be completely or partially freed from said organic compound formed of at least one cyclic oligosaccharide composed of at least 6 α- (1,4) -linked glucopyranose subunits.

The following examples specify the invention without limiting its scope.

EXAMPLES

The catalysts A, B, C and D respectively prepared in Examples 1, 2, 3 and 4 are prepared with iso-content of molybdenum and nickel elements. The support used for the preparation of each of the catalysts A, B, C and D is a gamma alumina support having a pore volume of 0.7 ml / g and a BET surface area of 280 m ² / g. Example 1 (comparative) Preparation of a supported catalyst A (oxide catalyst) and a supported catalyst A '(sulfide catalyst) of formula NiMo / AlgQ ₃

Catalyst A is obtained by dry impregnation of an aqueous solution prepared from ammonium heptamolybdate and nickel nitrate, the volume of the solution containing the molybdenum and nickel precursors being strictly equal to the pore volume of the alumina support mass. The concentrations of precursors in the aqueous solution are adjusted so as to deposit on the alumina support the weight contents of Ni and Mo desired. After a maturation step for 12 hours, the solid is dried for 12 hours at 120 ° C. and then calcined under air at 500 ° C. for 2 hours.

The catalyst A thus obtained in the oxide state, of NiMo / Al ₂ O ₃ formulation, has a molybdenum content of 7.2 expressed as a% by weight of MoO ₃ oxide, and a nickel content of 5.6 expressed as a% NiO oxide weight. The Ni / Mo molar ratio of this catalyst A is 1.50. Catalyst A is sulfurized ex situ at atmospheric pressure in a sulfurization bench under a H ₂ S / H ₂ mixture consisting of 15% by volume of H ₂ S to 1 1 / g of catalyst at 400 ° C. for two hours. A catalyst A 'is obtained in sulphide form (sulfidation rate greater than 60%). Example 2 (Invention): Preparation of a supported catalyst B (oxide catalyst) and a supported catalyst B '(sulfide catalyst) of the formula Ni o / AlgOa in the presence of B-cyclodextrin (co-impregnation)

Catalyst B is obtained by dry impregnation of an aqueous solution prepared from ammonium heptamolybdate and nickel nitrate, the volume of the solution containing the nickel and molybdenum precursors being strictly equal to the pore volume of the alumina support mass. The concentrations of precursors in the aqueous solution are adjusted so as to deposit on the alumina support the weight contents of Ni and Mo desired. Said aqueous solution also contains β-cyclodextrin (SIGMA-ALDRICH, purity of 98%) in a molar ratio (Ni + Mo) / p-cyclodextrin of 30. After a maturation step for 12 hours, the solid is then dried for 12 hours at 120 ° C and then calcined under air at 500 ° C for 2 hours.

The catalyst B thus obtained in the oxide state, of NiMo formulation has a molybdenum content of 7.1 expressed as% by weight of MoO ₃ oxide and a nickel content of 5.4 expressed in% by weight of NiO oxide. The Ni / Mo molar ratio of this catalyst B is 1.47.

Catalyst B is sulphurized ex situ at atmospheric pressure in a sulfurization bench under a H ₂ S / H ₂ mixture consisting of 15% by volume of H ₂ S to 1 1 / g of catalyst at 400 ° C. for two hours. A catalyst B 'in sulphide form (sulfidation rate greater than 60%) is obtained.

Example 3 (Invention): Preparation of a supported catalyst C (oxide catalyst) and a supported catalyst C (sulfide catalyst) of the formula NiMo / AlgQg in the presence of B-cyclodextrin (co-impregnation of Ni and Mo and subsequent impregnation Catalyst C is obtained by dry impregnation of an aqueous solution prepared from ammonium heptamolybdate and nickel nitrate, the volume of the solution containing the molybdenum and nickel precursors being rigorously equal. to the pore volume of the alumina support mass. The concentrations of precursors in the aqueous solution are adjusted so as to deposit on the alumina support the weight contents of Ni and Mo desired. After a 12 hour maturation step, the solid is dried for 12 hours at 120 ° C. A second dry impregnation stage makes it possible to add the β-cyclodextrin (SIGMA-ALDRICH, purity of 98%) dissolved in water to the dried solid obtained beforehand. The molar ratio (Ni + Mo) / -cyclodextrin is 30. After a maturation step for 12 hours, the catalyst is dried for 12 hours at 120 ° C. and then calcined in air at 500 ° C. for 2 hours to obtain the catalyst C. The catalyst C thus obtained in the oxide state, of NiMo formulation has a molybdenum content of 7.0 expressed as% by weight of MoO ₃ oxide, and a nickel content of 5.5 expressed in% by weight of NiO oxide. . The molar ratio Ni / Mo of this catalyst C is 1.50.

Catalyst C is sulphurized ex situ at atmospheric pressure in a sulfurization bench under a H ₂ S / H ₂ mixture consisting of 15% by volume of H ₂ S at 1 1 / g of catalyst at 400 ° C. for two hours. A catalyst C in sulphide form (sulfidation rate greater than 60%) is obtained.

EXAMPLE 4 (Non-compliant) Preparation of a Supported Catalyst D (Oxide Catalyst) and a Supported Catalyst (Sulphide Catalyst) of the Formula NiMo / Al 2 O 3 in the Presence of Cellobiose

Cellobiose or -D-glucopyranosyl (1-> 4) D-glucopyranose is the product of cellulose degradation. It is a diholoside of formula C ₁₂ H ₂₂ On. It is not a cyclic oligosaccharide. The structural formula of cellobiose is given below:

Catalyst D is obtained by dry impregnation of an aqueous solution prepared from ammonium heptamolybdate and nickel nitrate, the volume of the solution containing the molybdenum and nickel precursors being strictly equal to the pore volume of the alumina support mass. The concentrations of precursors in the aqueous solution are adjusted so as to deposit on the alumina support the weight contents of Ni and Mo desired. The solution also contains cellobiose (marketed by WWR) in a molar ratio (Ni + Mo) / cellobiose of 30. After a maturation step for 12 hours, the catalyst is dried for 12 hours at 120 ° C. and then calcined in air at room temperature. 500 ° C for 2 hours.

The catalyst D thus obtained in the oxide state, of NiMo formulation has a molybdenum content of 7.1 expressed in% by weight of MoO ₃ oxide, and a nickel content of 5.6 expressed in% by weight of NiO oxide. . The Ni / Mo molar ratio of this catalyst D is 1.52.

The catalyst D is sulphurized ex situ at atmospheric pressure in a sulfurization bench under a H ₂ S / H ₂ mixture consisting of 15% by volume of H ₂ S to 1 1 / g of catalyst at 400 ° C. for two hours. A catalyst D 'in sulfide form is obtained (sulfidation rate greater than 60%). EXAMPLE 5 Catalytic Performance of Catalysts A ', B', C and D 'in a Selective Hydrogenation Test of a Gasoline Cut from Model Molecules Representative of a Catalytic Cracking Gasoline

A representative model charge of a catalytic cracking gasoline (FCC) containing 1000 ppm by weight of sulfur in methyl-3-thiophene form, 100 ppm by weight of sulfur in the form of propane-2-thiol (mercaptan), 10% by weight of mono olefin in the form of hexene-1 and 1% by weight of diolefins in the form of isoprene in n-heptane is used to evaluate the catalytic performance of the various catalysts.

The selective hydrogenation reaction is carried out in a 500 ml stirred autoclave reactor. Each of the catalysts A ', B', C and D 'is successively placed in said reactor in contact with 250 ml of said model charge under a total pressure of 1.5 MPa and a temperature of 160 ° C. The time t = 0 of the test corresponds to the contacting of the catalyst with the charge and the hydrogen. The pressure is kept constant during the test by adding hydrogen. The duration of the test is set at 45 minutes and the gas phase chromatographic analysis of the liquid effluents collected on a regular basis makes it possible to evaluate the activities of each of the catalysts in hydrogenation of isoprene (selective formation of methylbutenes) and in hydrogenation of hexene-1 (formation of n-hexane). The activity of each catalyst for each of these two hydrogenation reactions is defined with respect to the rate constant obtained for each normalized hydrogenation reaction per gram of catalyst. The rate constant is calculated by considering an order 1 for the hydrogenation reaction. The activity of each catalyst for each of the two hydrogenation reactions is given by the formula: A (X) = k (X) / m

with A (X) = catalyst activity for the hydrogenation reaction of compound X, in min ^-1 / g of catalyst (in sulphide form), k = rate constant for the hydrogenation reaction under consideration, in min ^-1 . The constant k is calculated according to the formula k (X) = (1/45) ^* In (100 / (100 - Conv (X))), with 45 = duration of the test in minutes and Conv (X) = conversion of the compound X, X being isoprene or hexene-1; m = mass of catalyst (sulphide form) involved in the test The selectivity of the catalyst with respect to the hydrogenation of isoprene is equal to the ratio of the activities of the catalyst in hydrogenation of isoprene and hexene 1. It is noted as A (isoprene) / A (hexene-1).

The performances of the catalysts A ', B', C and D 'are given in Table 1. Catalyst performance in selective hydrogenation test

a model load.

The results in Table 1 demonstrate that the catalysts B 'and C, prepared in the presence of β-cyclodextrin, are substantially more active in hydrogenation of isoprene than the catalyst A' prepared in the absence of any organic compound and that the catalyst D 'prepared in the presence of cellobiose, which does not belong to the family of cyclic oligosaccharides. The results also demonstrate that the preparation of catalysts in the presence of β-cyclodextrin leads to the production of much more active catalysts for the hydrogenation of isoprene without the selectivity with respect to the hydrogenation of isoprene. not affected; on the other hand, the catalysts B 'and C are slightly more selective than the catalysts A' and D 'with respect to the hydrogenation of isoprene: the catalysts B' and C therefore favor slightly the selective hydrogenation of the isoprene to methylbutenes at the expense of the hydrogenation of hexene-1 to hexane.

Moreover, the chromatographic analyzes made it possible to prove that the conversion of the mercaptans present in the form of propane-2-thiol is rapid and total on all the catalysts A ', B ", C and D'.

Claims

claims

A process for the selective hydrogenation of a gasoline cut containing polyunsaturated hydrocarbons having at least 2 carbon atoms per molecule and having a final boiling point of less than or equal to 250 ° C, said cut having a weight content of polyunsaturated hydrocarbons between 0.5 and 5% and a weight content of sulfur of between 200 and 5000 phr, said process consisting in bringing said gasoline cut into contact with at least one catalyst whose active phase comprises at least one metal of group VIII and at least one group VIB metal deposited on a support formed of at least one oxide, said catalyst being prepared according to a process comprising at least: i) at least one step of contacting at least said support with at least one a solution containing at least one precursor of at least one Group VIII metal and at least one precursor of at least one of said Group VIB metal,

steps i) and ii) can be performed separately, in any order, or simultaneously.

2. Selective hydrogenation process according to claim 1, wherein said petrol fraction contains polyunsaturated hydrocarbons having at least 3 carbon atoms per molecule.

The selective hydrogenation process of claim 1 or claim 2 wherein said gasoline cut is from a fluidized catalytic cracking unit.

4. Selective hydrogenation process according to one of claims 1 to 3 such that the sulfur present in said gasoline cut is in the form of thiophene compounds, benzothiophenic and sulfur compounds, light and saturated.

5. Selective hydrogenation process according to claim 4 wherein said sulfur compounds, light and saturated, present in said gasoline cut, are selected from mercaptans and light sulfides.

6. Selective hydrogenation process according to one of claims 1 to 5 such that the metal group VIB is molybdenum or tungsten or a mixture of these two elements.

7. Selective hydrogenation process according to one of claims 1 to 6 such that the metal of group VIII is selected from nickel, iron, cobalt and the mixture of at least two of these elements.

8. Selective hydrogenation process according to one of claims 1 to 7 such that the support consists essentially of a transition alumina.

9. Selective hydrogenation process according to one of claims 1 to 8 such that said organic compound is selected from cyclodextrins, substituted cyclodextrins, polymerized cyclodextrins and mixtures of cyclodextrins.

10. Selective hydrogenation process according to claim 9, such that the cyclodextrins are Γα-cyclodextrin, β-cyclodextrin and γ-cyclodextrin respectively composed of

6, 7 and 8 α- (1,4) -linked glucopyranose subunits.

A selective hydrogenation process according to claim 9, such that the substituted cyclodextrins are hydroxypropyl beta-cyclodextrin and methylated beta-cyclodextrins.

12. Selective hydrogenation process according to one of claims 1 to 11 as said step iii) calcination is carried out at a temperature between 200 and 660 ° C.

13. Selective hydrogenation process according to one of claims 1 to 12 as implemented under the following operating conditions: a temperature between 80 ° C and 220 ° C, with a hourly volume velocity (VVH) between 1 h ^{~ 1} and 10 h ^"1 , a total pressure of between 0.5 MPa and 5 MPa, a quantity of hydrogen introduced and injected such that the molar ratio between the hydrogen and the polyunsaturated compounds to be hydrogenated is greater than at 1 mol / mol and less than 10 mol / mol.