Method for capturing organometallic impurities in the presence of trapping substances on mesoporous-macroporous supports

Abstract

This invention relates to a method for capturing organometallic impurities in gasoline-type hydrocarbon feedstocks containing sulfur compounds and olefins, wherein the feedstock is contacted with hydrogen and a capturing substance comprising a nickel-based active phase and a mesoporous-macroporous alumina substrate having a bimodal mesoporous pore distribution, wherein: - the volume of mesopores with a diameter greater than or equal to 2 nm and less than 18 nm corresponds to 10 vol% to 30 vol% of the total pore volume of the substrate; - the volume of mesopores with a diameter greater than or equal to 18 nm and less than 50 nm corresponds to 30 vol% to 50 vol% of the total pore volume of the substrate.

Description

Technical Field

[0001] This invention relates to a method for capturing organometallic impurities contained in gasoline-type hydrocarbon feedstocks containing sulfur compounds and olefins using nickel-based capturing substances. Existing technology

[0002] Automotive fuel regulations require a significant reduction in the sulfur content of these fuels, especially gasoline. This reduction specifically targets the limits on sulfur and nitrogen oxides in vehicle exhaust. Since 2009, the current European gasoline fuel regulations have set a maximum sulfur content of 10 ppm (parts per million by weight). Similar regulations are in effect in other countries, such as the United States and China, which have required the same maximum sulfur content since January 2017. To meet these regulations, gasoline must be treated with desulfurization methods.

[0003] The primary source of sulfur in gasoline base is "cracked" gasoline, mainly gasoline fractions obtained from the catalytic cracking of residues from crude oil atmospheric or vacuum distillation. Gasoline fractions from catalytic cracking account for an average of 40% of the gasoline base and, in fact, over 90% of the sulfur in gasoline. Therefore, the production of low-sulfur gasoline requires a desulfurization step from catalytic cracked gasoline. Sulfur removal from gasoline fractions involves specially treating these sulfur-rich gasolines in the presence of hydrogen using desulfurization methods. These are subsequently known as hydrodesulfurization (HDS). However, these gasoline fractions, especially those from FCC, contain a large proportion of monoolefins (approximately 20% to 50% by weight, contributing to a good octane number), dienes (0.5% to 5% by weight), and unsaturated compounds in the form of aromatics. These unsaturated compounds are unstable and react during hydrodesulfurization. Diolefins polymerize during hydrodesulfurization to form gums. This gum formation leads to gradual deactivation of the hydrodesulfurization catalyst or gradual blockage of the reactor. Therefore, before any processing of these gasolines, diolefins must be removed by hydrotreating. Conventional processing methods desulfurize gasoline by hydrotreating most monoolefins rather than selectively, resulting in high octane number loss and high hydrogen consumption. Newer hydrodesulfurization methods can desulfurize cracked gasoline rich in monoolefins while limiting the hydrotreating of monoolefins and thus limiting octane number loss. Such methods are described, for example, in documents EP-A-1077247 and EP-A-1174485.

[0004] Hydrodesulfurization methods require continuous operation for at least 3 to 5 years. Therefore, catalysts used for hydrodesulfurization of sulfur-containing gasoline must possess good activity, selectivity, and time stability to enable continuous operation for several years. However, the presence of heavy metals (such as mercury or arsenic) or contaminants (such as phosphorus and silicon) in the hydrocarbon feedstock can lead to rapid deactivation of the hydrotreatment catalyst. Therefore, these contaminants must be removed from the feedstock before it is brought into contact with these hydrodesulfurization catalysts.

[0005] Various schemes have been proposed for the extraction of these impurities, particularly arsenic from hydrocarbon feedstocks. Typically, the captured material (adsorbent) is placed in a reactor upstream of the hydrodesulfurization unit, or upstream of the catalytic bed containing the hydrodesulfurization catalyst within the hydrodesulfurization reactor. These adsorbents are described in documents FR2794381 and WO2006 / 037884. The use of these adsorbents in the presence of hydrogen presents a disadvantage when the gasoline to be treated contains unsaturated compounds. This leads to a decrease in octane number and a decline in gasoline quality from the perspective of impurity adsorption. These adsorbents also have the disadvantage of relatively no catalytic activity for the hydrodesulfurization reaction. Furthermore, they occupy a non-negligible volume in the reactor, reducing the available volume of the hydrodesulfurization catalyst bed, thus resulting in an overall loss of performance for the method. Therefore, it is necessary to find schemes capable of eliminating these impurities, such as arsenic, with the aim of limiting the hydrodesulfurization reaction that leads to a decrease in the octane number of the gasoline of interest. These schemes must also be able to improve hydrodesulfurization performance without sacrificing the selectivity of the hydrodesulfurization reaction relative to olefin hydrogenation.

[0006] Therefore, there is still a need for capture materials with the following properties: adsorption properties for heavy metals and optimized catalytic properties, i.e., a good trade-off between hydrodesulfurization (HDS) activity and maximum selectivity of the hydrodesulfurization reaction compared to the olefin hydrogenation reaction (HDS / HYD), and whose adsorption properties and post-capture catalytic activity are stable over time.

[0007] Furthermore, it is known from existing technologies that the pore distribution of the support can have a beneficial effect on catalytic performance.

[0008] US document 6,589,908 discloses a method for preparing a catalyst support that is free of macropores and has a bimodal pore structure within mesopores, such that the two pore peaks are separated by 1 to 20 nm. This support can be used in many catalytic applications, particularly for hydrogenation processes, especially for hydrodenitrification.

[0009] US 5,266,300 discloses a method for preparing a porous alumina support, which is used as a catalyst support for hydrodesulfurization or hydrodemetallization, wherein the support comprises 0.65 to 1.30 cm³ of... 3 The porous carrier comprises two macropore groups, wherein approximately 2% to 20% of the total pore volume is a macropore form with a diameter of 10,000 to 100,000 angstroms (1,000 to 10,000 nm), approximately 5% to 30% of the total pore volume is a macropore form with a diameter of 1,000 to 10,000 angstroms (100 to 1,000 nm), and approximately 50% to 93% of the total pore volume is a mesopore form with a pore size of 30 to 1,000 angstroms (3-100 nm).

[0010] Documents CN108855197, CN104248987 and CN104248985 disclose catalysts for various catalytic applications (propane dehydrogenation, esterification), whose supports have a three-peak pore distribution, with the mesopore group concentrated on three peaks, which are 2 to 4 nm, 5 to 15 nm and 10 to 40 nm, respectively.

[0011] Document US7,790,130 discloses alumina for capturing halides, which comprises trimodal porosity, wherein 40 vol% to 49 vol% of the total pore volume relative to the carrier is in the form of pores with a diameter of 15 to 50 nm.

[0012] However, no existing literature describes the implementation of methods for capturing organometallic impurities, particularly those contained in hydrocarbon feedstocks, in the presence of a capturing substance comprising a carrier having bimodal mesoporous pores, high-medium pore volumes, and specific macroporous volumes.

[0013] In this context, one objective of the present invention is to provide a method for capturing organometallic impurities in gasoline-type hydrocarbon feedstocks containing sulfur compounds and olefins, wherein the capturing material is contained in an active phase comprising at least nickel on a mesoporous-macroporous support exhibiting a bimodal mesoporous pore size, a high-medium pore volume, and a defined macroporous volume. This is because it has been surprisingly found that using such a capturing material allows for the effective capture of organometallic impurities, particularly arsenic contained in gasoline containing olefins and sulfur, while limiting the rate of hydrogenation of olefins to typically less than 30%, preferably less than 20%, and even more preferably less than 10%.

[0014] In fact, without being tied to any particular scientific theory, the use of such trapping materials improves the internal diffusion of reactants and products through the presence of mesopore groups of varying sizes. Furthermore, the presence of a combination of macropores is particularly advantageous when the feedstock contains significant amounts of reactive olefins (unsaturated compounds), especially dienes. In the case of gasoline, dienes can cause gum formation, thus blocking the pores of the trapping material in the absence of macropores.

[0015] Invention Theme

[0016] The subject of this invention is a method for capturing organometallic impurities in gasoline-type hydrocarbon feedstocks containing sulfur compounds and olefins, wherein the captured material is subjected to a temperature of 200 to 400°C, a pressure of 0.2 to 5 MPa, and a flow rate of 50 to 800 Nm. 3 / m 3 The hydrogen flow rate is contacted at a ratio to the hydrocarbon feed flow rate, and the captured material comprises a nickel-based active phase and a mesoporous-macroporous alumina support with a bimodal mesoporous distribution, wherein:

[0017] - The volume of mesopores with a diameter greater than or equal to 2 nm and less than 18 nm corresponds to 10 to 30% of the total pore volume of the carrier;

[0018] - The volume of mesopores with a diameter greater than or equal to 18 nm and less than 50 nm corresponds to 30 to 50% of the total pore volume of the carrier;

[0019] - The volume of macropores with a diameter greater than or equal to 50 nm and less than 8000 nm corresponds to 30 to 50% of the total pore volume of the carrier.

[0020] According to one or more embodiments, the specific surface area of ​​the carrier is 50 to 210 m². 2 / g.

[0021] According to one or more embodiments, the total pore volume of the carrier is 0.7 to 1.3 mL / g.

[0022] According to one or more embodiments, the volume of the mesopore with a diameter greater than or equal to 2 nm and less than 18 nm corresponds to 15 to 25% of the total pore volume of the carrier.

[0023] According to one or more embodiments, the volume of the mesopore with a diameter greater than or equal to 18 nm and less than 50 nm corresponds to 35 to 45% of the total pore volume of the carrier.

[0024] According to one or more embodiments, the volume of macropores with a diameter greater than or equal to 50 nm and less than 8000 nm corresponds to 35 to 50% of the total pore volume of the carrier.

[0025] According to one or more embodiments, the nickel content, expressed in NiO form, is 5 to 65% by weight relative to the total weight of the captured material.

[0026] According to one or more embodiments, the active phase consists of only nickel.

[0027] According to one or more embodiments, the active phase of the captured substance further comprises cobalt, molybdenum, and phosphorus.

[0028] According to one or more embodiments, the nickel content, expressed as NiO oxide, is 5 to 65% by weight relative to the total weight of the captured material; the cobalt content, expressed as CoO, is 0.5 to 10% by weight relative to the total weight of the captured material; the molybdenum content, expressed as MoO3, is 2 to 20% by weight relative to the total weight of the captured material; and the phosphorus content, expressed as P2O5, is 0.2 to 10% by weight relative to the total weight of the captured material.

[0029] According to one or more embodiments, the pore distribution of mesopores with a diameter greater than or equal to 2 nm and less than 18 nm is concentrated in the numerical range of 10.5 to 14.5 nm.

[0030] According to one or more embodiments, the pore distribution of mesopores with a diameter greater than or equal to 18 nm and less than 50 nm is concentrated in the numerical range of 22 to 28 nm.

[0031] According to one or more embodiments, the specific surface area of ​​the carrier is 70 to 180 m². 2 / g.

[0032] According to one or more embodiments, the carrier is in the form of beads with a diameter of 2 to 4 mm.

[0033] According to one or more embodiments, when the carrier is in the form of beads, the carrier is obtained according to the following steps:

[0034] s1) Dehydrate aluminum hydroxide or aluminum hydroxide at a temperature of 400°C to 1200°C, preferably 600°C to 900°C, for 0.1 seconds to 5 seconds, preferably 0.1 seconds to 4 seconds, to obtain aluminum oxide powder;

[0035] s2) The alumina powder obtained in step s1) is shaped into beads;

[0036] s3) Alumina beads obtained in step s2) are heat-treated at a temperature greater than or equal to 200°C;

[0037] s4) Alumina beads obtained by immersion in water or an aqueous solution and then retention in an autoclave at a temperature of 100°C to 300°C at the end of hydrothermal treatment step s3);

[0038] s5) Calcine the alumina beads obtained at the end of step s4) at a temperature of 500°C to 820°C.

[0039] According to one or more embodiments, the hydrocarbon feedstock is catalytic cracked gasoline containing 5% to 60% by weight of monoolefins, 50 to 6000 ppm by weight of sulfur compounds and 10 to 1000 ppb of arsenic relative to the total weight of the feedstock.

[0040] According to one or more embodiments, the organometallic impurity is selected from organometallic impurities of heavy metals, silicon, phosphorus, and arsenic. Preferably, the organometallic impurity is an organometallic arsenic impurity. Invention Details

[0042] 1. Definition

[0043] Subsequently, chemical elements are assigned groups according to the CAS classification (CRC Handbook of Chemistry and Physics, published by CRC Press, edited by DRLide, 81st edition, 2000-2001). For example, Group VIII according to the CAS classification corresponds to metals in columns 8, 9, and 10 according to the new IUPAC classification.

[0044] BET specific surface area is measured by physical adsorption of nitrogen gas according to standard ASTM D3663-03, as described in the book "Adsorption by Powders & Porous Solids: Principles, Methodology and Applications" by Rouquerol F., Rouquerol J. and Singh K., Academic Press, 1999.

[0045] In this specification, according to IUPAC convention, "micropore" should be understood as a pore with a diameter less than 2 nm, i.e., 0.002 μm; "medium pore" should be understood as a pore with a diameter greater than 2 nm, i.e., 0.002 μm, and less than 50 nm, i.e., 0.05 μm; and "large pore" should be understood as a pore with a diameter greater than or equal to 50 nm, i.e., 0.05 μm.

[0046] In the following description of the invention, the “total pore volume” of alumina or the trapping material should be understood as the volume measured by mercury intrusion porosimetry at a maximum pressure of 4000 bar (400 MPa), using a surface tension of 484 dynes / cm and a contact angle of 140°, according to ASTM D4284-83. Following the recommendation in the publication “Techniques de l′ingénieur, traité analyze et caractérisation” [Techniques of the Engineer, Analysis and Characterization Treatise], pp. 1050-5, by Jean Charpin and Bernard Rasneur, the wetting angle is taken as 140°.

[0047] To obtain better accuracy, the total pore volume values ​​(in ml / g) given below correspond to the total mercury volume measured on the sample (total pore volume measured by mercury porosimetry) (in ml / g) minus the mercury volume measured on the same sample at a pressure corresponding to 30 psi (approximately 0.2 MPa) (in ml / g).

[0048] The volumes of macro- and meso-orifices were measured by mercury intrusion porosimetry under a maximum pressure of 4000 bar (400 MPa), using a surface tension of 484 dynes / cm and a contact angle of 140°, according to standard ASTM D4284-83.

[0049] When the value is equal to or higher than a certain value, mercury fills all interparticle voids. This value is set at 0.2 MPa, and it is believed that when the value is higher than this, mercury penetrates into the pores of the sample.

[0050] The macropore volume of a catalyst is defined as the cumulative volume of mercury introduced under pressures ranging from 0.2 MPa to 30 MPa, corresponding to the volume contained in pores with an apparent diameter greater than 50 nm.

[0051] The mesopore volume of a catalyst is defined as the cumulative volume of mercury introduced under pressures of 30 MPa to 400 MPa, corresponding to the volume contained in pores with apparent diameters of 2 to 50 nm.

[0052] When the incremental pore volume measured by mercury intrusion porosimetry is plotted as a function of pore diameter, the pore peak corresponds to the inflection point of the function it represents.

[0053] The contents of metallic elements (Group VIII metals and Group VIB metals) and phosphorus were measured by X-ray fluorescence method.

[0054] 2. Description

[0055] Methods for capturing organometallic impurities

[0056] This invention relates to a method for capturing organometallic impurities, such as heavy metals, silicon, or phosphorus, and more particularly arsenic, contained in hydrocarbon feedstocks using a capturing substance defined as follows, wherein the capturing substance is contacted with the hydrocarbon feedstock in the presence of hydrogen. Within the scope of this invention, the capturing method according to the invention is a method for at least partially capturing arsenic and optionally silicon from hydrocarbon feedstocks in the presence of hydrogen to produce an effluent with reduced heavy metal and, particularly, arsenic content, while limiting octane number loss. The capturing method according to the invention allows for the removal of arsenic and also limits the hydrogenation rate of monoolefins. The hydrogenation rate of olefins is advantageously less than 50%, preferably less than 30%, and even more preferably less than 20%.

[0057] Advantageously, the hydrocarbon feedstock to be treated is catalytically cracked gasoline from a catalytic cracking, thermal cracking, or steam cracking unit. This method can also be used to treat mixtures of direct distilled gasoline and cracked gasoline, wherein the direct distilled gasoline may contain heavy metals from crude oil, and the cracked gasoline contains mono-olefins and dienes. Preferably, the hydrocarbon feedstock to be treated is catalytically cracked gasoline containing 5% to 60% by weight of mono-olefins, 50 ppm to 6000 ppm by weight of sulfur compounds, and 10 ppb to 1000 ppb by weight of arsenic. The sulfur compounds in the hydrocarbon feedstock to be treated can be organosulfur compounds, such as thiols, thiophene compounds, benzothiophene compounds, and other aromatic sulfur compounds, disulfide compounds, etc. The arsenic compounds in the hydrocarbon feedstock to be treated can be organoarsenic compounds, such as trimethylarsene or triethylarsene. Mono-olefins refer to hydrocarbon molecules having a single carbon-carbon double bond, and dienes are hydrocarbon molecules containing at least two carbon-carbon double bonds. Mono-olefins and dienes can be straight-chain, branched, and / or cyclic hydrocarbon molecules.

[0058] The capture material according to the invention is advantageously carried out under operating conditions that maximize arsenic capture while limiting the hydrogenation rate of olefins. Contact operation is typically performed at temperatures of 200 to 400°C, pressures of 0.2 to 5 MPa, and 50 to 800 Nm. 3 / m 3 The process is carried out at a ratio of hydrogen flow rate to hydrocarbon feed flow rate. The hydrogen used can come from any hydrogen source. Preferably, fresh hydrogen from the refinery and / or recycled hydrogen from the hydrodesulfurization unit, more preferably from the hydrodesulfurization unit used for the hydrocarbon fraction to be purified, is used.

[0059] Several reactor technologies are conceivable for capturing arsenic from hydrocarbon feedstocks in the presence of the capture substance according to the invention, with the most conventional and widely used being the fixed-bed technology. In this case, the reactor is charged with the capture substance according to the invention and a hydrodesulfurization catalyst, and operation is performed in the adsorption and hydrodesulfurization of arsenic, in principle until arsenic appears in the effluent (a phenomenon known to those skilled in the art under the term "breakthrough"). In some cases, the total amount of poisoned capture substance can be replaced by an equal amount of fresh capture substance. The choice of technology for replacing the capture substance according to the invention is not considered a limiting element in the context of the invention. The capture substance can be used in a moving-bed reactor, that is, the used capture substance is continuously removed and replaced with new capture substance. This type of technology allows for the maintenance of arsenic capture by the capture substance and avoids arsenic breakthrough into the resulting effluent. Among other solutions, the use of an expanded-bed reactor can be mentioned, which also allows for continuous removal and topping-up of the capture substance to maintain its hydrodesulfurization activity.

[0060] The capture method according to the invention is preferably combined with at least one additional stage of selective hydrotreating or catalytic hydrodesulfurization, said additional stage being performed on the effluent generated from the operation of contacting the capture substance according to the invention. Thus, the stage of treating the hydrocarbon feedstock with the capture substance is considered a pretreatment, which in particular allows the catalytic activity of the catalyst used in the subsequent selective hydrotreating or hydrodesulfurization stage to be maintained. Therefore, the capture method according to the invention includes one or more additional stages of selective hydrotreating or hydrodesulfurization, wherein the effluent generated from contacting the hydrocarbon feedstock with the capture substance according to the invention is contacted with at least one other catalyst for the selective hydrotreating or hydrodesulfurization of dienes present in the feedstock. The one or more additional hydrodesulfurization stages allow the removal of residual sulfur compounds contained in the effluent, which is arsenic-poor and has a low sulfur content. Some of these residual sulfur compounds may be generated by the addition of H₂S to olefins present in the feedstock. H₂S may be formed during the operation of contacting the hydrocarbon feedstock with the capture substance, i.e., during the capture of arsenic. When the effluent from the operation involving contact between the hydrocarbon feedstock and the captured substance typically exhibits a sulfur content greater than 10 ppm, and when it is necessary to produce gasoline with a low sulfur content that meets current specifications (below 10 ppm in many countries), the aforementioned additional hydrodesulfurization stage(s) is implemented. The effluent, after the removal of arsenic and a portion of sulfur compounds, is then treated in at least one of the aforementioned additional selective hydrodesulfurization stages. In said stage(s), the effluent is contacted with at least one other hydrodesulfurization catalyst under operating conditions that are the same as or different from those used to contact the hydrocarbon feedstock and the captured substance.

[0061] The trapping material according to the invention protects the catalyst(s) used in the one or more additional hydrodesulfurization stages from deactivation due to arsenic present in the feedstock. Therefore, a highly selective hydrodesulfurization catalyst sensitive to the presence of arsenic can be used in the one or more additional hydrodesulfurization stages. Any hydrodesulfurization catalyst can be used in the one or more additional hydrodesulfurization stages. Preferably, a catalyst exhibiting high selectivity for hydrodesulfurization compared to olefin hydrogenation is used. Such a catalyst comprises at least one porous amorphous inorganic support, a Group VIB metal, or a Group VIII metal. The Group VIB metal is preferably molybdenum or tungsten, and the Group VIII metal is preferably nickel or cobalt. The support is typically selected from alumina, silica, silica-alumina, silicon carbide, titanium dioxide (alone or as a mixture with alumina or silica-alumina), and magnesium oxide (alone or as a mixture with alumina or silica-alumina). Preferably, the support is selected from alumina, silica, and silica-alumina. Preferably, the hydrodesulfurization catalyst used in one or more additional hydrodesulfurization steps has the following characteristics:

[0062] - The content of Group VIb elements is 1% to 20% by weight of the oxides of Group VIb elements;

[0063] - The content of Group VIII elements is 0.1% to 20% by weight of the oxides of Group VIII elements;

[0064] - The molar ratio (Group VIII elements / Group VIb elements) is 0.1 to 0.8.

[0065] A highly preferred hydrodesulfurization catalyst comprises cobalt and molybdenum and has the characteristics described above. Furthermore, the hydrodesulfurization catalyst may contain phosphorus. In this case, the phosphorus content is preferably 0.1% to 10% by weight of P₂O₅ relative to the total weight of the catalyst, and the molar ratio of phosphorus to Group VIB elements is greater than or equal to 0.25, preferably greater than or equal to 0.27.

[0066] In the one or more additional hydrodesulfurization stages, the arsenic-poor effluent generated from contacting the hydrocarbon feedstock with the trapping substance according to the invention is contacted with at least one other selective hydrodesulfurization catalyst under the following operating conditions:

[0067] - From about 210°C to about 410°C, preferably at a temperature of 240°C to 360°C;

[0068] The total pressure is -0.2 to 5 MPa, more preferably 0.5 to 3 MPa;

[0069] -50 to 800 Nm 3 / m 3 More preferably 60 to 600 Nm3 / m 3 The ratio of hydrogen volume to hydrocarbon feedstock volume.

[0070] In an alternative form of the method according to the invention, the operating conditions for contacting the hydrocarbon feedstock with the capture substance according to the invention are the same as those used in the (one or more) additional hydrodesulfurization stages.

[0071] According to another embodiment, the hydrotreating stage of the effluent produced by the capture stage using the capture substance according to the invention is selective hydrogenation, which allows dienes to be hydrogenated to yield olefins and optionally unsaturated sulfur compounds, and allows light sulfur compounds (i.e., having a temperature lower than that of thiophene) to be converted (by weight) to sulfur compounds having a temperature higher than that of thiophene, for example by adding thiols to olefins. This hydrogenation stage is carried out in the presence of hydrogen and a catalyst containing at least one Group VIb metal and at least one Group VIII non-noble metal deposited on a porous support. Preferably, a catalyst is used, for which:

[0072] - The weight content of oxides of group VIb elements is 6% to 18% relative to the weight of the catalyst;

[0073] - The weight content of oxides of group VIII elements is 4% to 12% relative to the weight of the catalyst;

[0074] - The specific surface area of ​​the catalyst is 200 to 270 m². 2 / g;

[0075] The density of Group VIb elements, expressed as the ratio of the weight content of the oxides of the Group VIb elements to the specific surface area of ​​the catalyst, is between 4 and 6.10. -4 g / m 2 ;

[0076] The molar ratio of Group VIII metals to Group VIb metals is 0.6 to 3 mol / mol.

[0077] Group VIb metals are preferably selected from molybdenum and tungsten; molybdenum is very preferably a Group VIb metal. Group VIII metals are preferably nickel and / or cobalt, with nickel being very preferred. Hydrogen is typically introduced in a slight excess (up to 5 mol / mol relative to stoichiometry) necessary for the hydrogenation of dienes (one mole of hydrogen per mole of diene). The mixture of gasoline and hydrogen is subjected to a catalyst at a pressure of 0.5 to 5 MPa, a temperature of 80 to 220 °C, and for 1 to 10 h. -1 Contact at the liquid hourly space velocity (LHSV), which is expressed as liters of catalyst and liters of feed per hour (l / lh).

[0078] In one alternative form of the method according to the invention, the captured material according to the invention may be placed in the location of a guard bed of one or more reactors containing one or more catalysts used in the one or more additional selective hydrogenation and / or hydrodesulfurization stages. In another alternative form of the method according to the invention, the captured material according to the invention is placed in a “capture” reactor. This reactor is separate from and located upstream of one or more reactors containing one or more catalysts used in the one or more additional selective hydrogenation and / or hydrodesulfurization stages. In all alternative forms of the method according to the invention using at least one additional selective hydrogenation and / or hydrodesulfurization stage, the volume ratio of the captured material according to the invention to the volume of one or more catalysts used in the one or more additional selective hydrogenation and / or hydrodesulfurization stages is advantageously 4% to 50%, preferably 5% to 40%, more preferably 5% to 35%.

[0079] Remove substances

[0080] The capturing material used in the method according to the invention comprises an active phase comprising nickel, optionally at least one additional Group VIII element, optionally at least one Group VIb element, and optionally phosphorus.

[0081] The nickel content, expressed in NiO form, is advantageously 5% to 65% by weight, preferably 10% to 30% by weight, relative to the total weight of the captured material.

[0082] When additional Group VIII elements are present and expressed in oxide form, their content is advantageously 0.5% to 10% by weight relative to the total weight of the captured material.

[0083] When a Group VIb element is present and expressed in oxide form, its content is advantageously 2% to 20% by weight relative to the total weight of the captured substance.

[0084] When phosphorus is present and expressed in the form of oxides, its content is 0.2% to 10% by weight relative to the total weight of the captured substances.

[0085] In one embodiment of the invention, the active phase consists solely of nickel. The nickel content, expressed as NiO, is advantageously 5% to 65% by weight, preferably 10% to 30% by weight, relative to the total weight of the captured material.

[0086] In one embodiment of the invention, the active phase comprises nickel, cobalt, molybdenum, and phosphorus. The nickel content, expressed as NiO oxide, is advantageously 5% to 65% by weight, preferably 10% to 30% by weight, relative to the total weight of the captured material. The cobalt content, expressed as CoO, is advantageously 0.5% to 10% by weight, preferably 0.5% to 5% by weight, relative to the total weight of the captured material. The molybdenum content, expressed as MoO3, is advantageously 2% to 20% by weight, preferably 3% to 15% by weight, relative to the total weight of the captured material. The phosphorus content, expressed as P2O5, is advantageously 0.2% to 10% by weight, preferably 0.5% to 5% by weight, relative to the total weight of the captured material.

[0087] The specific surface area of ​​the captured material is typically 50 to 200 m². 2 / g, preferably 60 to 170m 2 / g, preferably 70 to 130m 2 / g.

[0088] The pore volume of the captured substance is typically from 0.5 mL / g to 1.3 mL / g, preferably from 0.6 mL / g to 1.1 mL / g.

[0089] Alumina carrier

[0090] The alumina support used in the method according to the invention for capturing the substance is a macroporous-mesoporous alumina support with a bimodal mesoporous distribution, wherein:

[0091] - The volume of mesopores with a diameter greater than or equal to 2 nm and less than 18 nm corresponds to 10 to 30% of the total pore volume of the carrier;

[0092] - The volume of mesopores with a diameter greater than or equal to 18 nm and less than 50 nm corresponds to 30 to 50% of the total pore volume of the carrier;

[0093] - The volume of macropores with a diameter greater than or equal to 50 nm and less than 8000 nm corresponds to 30 to 50% of the total pore volume of the carrier.

[0094] Preferably, the volume of the mesopores in the carrier with a diameter greater than or equal to 2 nm and less than 18 nm corresponds to 15 to 25% of the total pore volume of the carrier.

[0095] Preferably, the volume of the mesopores in the carrier with a diameter greater than or equal to 18 nm and less than 50 nm corresponds to 35 to 45% of the total pore volume of the carrier.

[0096] Preferably, the volume of macropores in the carrier with a diameter greater than or equal to 50 nm and less than 8000 nm corresponds to 35% to 50% of the total pore volume of the carrier.

[0097] In one embodiment of the invention, the pore distribution of mesopores with a diameter greater than or equal to 2 nm and less than 18 nm is concentrated in the range of 10.5 to 14.5 nm, preferably 12 to 13 nm.

[0098] In one embodiment of the invention, the pore distribution of mesopores with a diameter greater than or equal to 18 nm and less than 50 nm is concentrated in the range of 22 to 28 nm, preferably 23 to 27 nm.

[0099] The specific surface area of ​​the carrier is typically 50 to 210 m². 2 / g, preferably 70 to 180m 2 / g, or even more preferably 70 to 160 mg 2 / g.

[0100] The pore volume of the carrier is typically from 0.7 mL / g to 1.3 mL / g, preferably from 0.8 mL / g to 1.2 mL / g.

[0101] Advantageously, the carrier is in the form of beads having a diameter of 0.8 to 10 mm, preferably 1 to 5 mm, more preferably 2 to 4 mm.

[0102] Carrier preparation method

[0103] The alumina carrier for the captured material used in the method according to the invention can be synthesized by any method known to those skilled in the art.

[0104] According to a preferred embodiment, the alumina support used according to the present invention is in bead form. According to this preferred embodiment, the preparation of the support includes the following steps:

[0105] s1) Dehydrate aluminum hydroxide or aluminum hydroxide at a temperature of 400°C to 1200°C, preferably 600°C to 900°C, for 0.1 seconds to 5 seconds, preferably 0.1 seconds to 4 seconds, to obtain aluminum oxide powder;

[0106] s2) The alumina powder obtained in step s1) is shaped into beads;

[0107] s3) Alumina beads obtained in step s2) are heat-treated at a temperature greater than or equal to 200°C;

[0108] s4) Alumina beads obtained by impregnation with water or preferably an acidic aqueous solution, followed by retention in an autoclave at a temperature of 100°C to 300°C, preferably 150°C to 250°C, at the end of hydrothermal treatment step s3);

[0109] s5) Calcine the alumina beads obtained at the end of step s4) at a temperature of 500°C to 820°C.

[0110] Steps s1) to s5) are described in detail below.

[0111] Step s1)

[0112] According to step s1), aluminum hydroxide or aluminum hydroxide is dehydrated at a temperature of 400°C to 1200°C, preferably 600°C to 900°C, for a duration of 0.1 seconds to 5 seconds, preferably 0.1 seconds to 4 seconds, to obtain alumina powder. Aluminum hydroxide may be selected from hydrargillite, gibbsite, or bayerite. Aluminum hydroxide may be selected from boehmite or diaspore.

[0113] Preferably, step s1) is performed using hydrated bauxite.

[0114] Typically, step s1) is carried out in the presence of a hot airflow (e.g., dry or humid air) to quickly eliminate and entrain evaporated water.

[0115] Typically, activated alumina powder obtained by dehydrating aluminum hydroxide or aluminum hydroxide is ground to a particle size of 10 to 200 μm.

[0116] Typically, the activated alumina powder obtained after dehydrating aluminum hydroxide or aluminum hydroxide is washed with water or an acidic aqueous solution. When using an acidic aqueous solution for the washing step, any inorganic or organic acid can be used, preferably nitric acid, hydrochloric acid, perchloric acid, or sulfuric acid for inorganic acids, and carboxylic acids (formic acid, acetic acid, or malonic acid), sulfonic acids (p-toluenesulfonic acid), or sulfate esters (lauryl sulfate) for organic acids.

[0117] Step s2)

[0118] According to step s2), the alumina powder obtained at the end of step s1) is shaped.

[0119] The process of shaping the alumina powder into beads, known as granulation, is typically carried out using rotary techniques such as rotary granulators or drums. These methods allow for the production of beads with controlled diameter and pore distribution, dimensions and distributions that are usually generated during the agglomeration step.

[0120] Pores can be created in various ways, such as by selecting the particle size distribution of the alumina powder or by agglomerating several alumina powders with different particle size distributions. Another method involves mixing one or more compounds, called pore-forming compounds, with the alumina powder before or during the agglomeration stage. These pore-forming compounds are dissolved by heating, thereby creating pores in the beads. Pore-forming compounds used can be mentioned as, for example, wood flour, charcoal, activated carbon, carbon black, sulfur, tar, plastic materials, or emulsions of plastic materials, such as polyvinyl chloride, polyvinyl alcohol, naphthalene, etc. The amount of pore-forming compound added is determined by the desired volume to obtain a porosity of 500 to 1100 kg / m³. 3 Preferred weight is 700 to 950 kg / m³ 3 The raw filling density and the beads have a diameter of 0.8 to 10 mm, preferably 1 to 5 mm, and even more preferably 2 to 4 mm. The selection of beads obtained by sieving can be based on the desired particle size.

[0121] Step s3)

[0122] According to step s3), the shaped alumina powder in bead form obtained at the end of step s2) is heat-treated at a temperature greater than or equal to 200°C, preferably 200°C to 1200°C, preferably 300°C to 900°C, and most preferably 400°C to 750°C, for a period typically of 1 to 24 hours, preferably 1 to 6 hours. The specific surface area of ​​the beads obtained in this intermediate step is 50 to 420 m². 2 / g, preferably 60 to 350m 2 / g, or even more preferably 80 to 300 mg 2 / g.

[0123] Step s4)

[0124] According to step s4), the alumina beads obtained at the end of step s3) are subjected to hydrothermal treatment by immersion in water or preferably an acidic aqueous solution and then retention in an autoclave at a temperature of 100°C to 300°C, preferably 150°C to 250°C.

[0125] Hydrothermal treatment is typically carried out at temperatures between 100°C and 300°C, preferably between 150°C and 250°C, for more than 45 minutes, preferably 1 to 24 hours, and most preferably 1.5 to 12 hours. The hydrothermal treatment is usually carried out using an acidic aqueous solution containing one or more inorganic and / or organic acids, preferably nitric acid, hydrochloric acid, perchloric acid, sulfuric acid, and weak acids, with a pH below 4, such as acetic acid or formic acid. Typically, the acidic aqueous solution also contains one or more compounds capable of releasing anions that can bind to aluminum ions, preferably including nitrate ions (e.g., aluminum nitrate), chloride ions, sulfate ions, perchlorate ions, chloroacetic acid ions, trichloroacetic acid ions, bromoacetic acid ions, dibromoacetic acid ions, and compounds with anions of the general formula R-COO (such as formate and acetate ions).

[0126] Step s5)

[0127] According to step s5), the alumina beads obtained at the end of step s4) are calcined at a temperature of 500°C to 820°C, preferably 550°C to 750°C, for a period of time typically from 1 hour to 24 hours, preferably from 1 hour to 6 hours. At the end of this step, the specific surface area of ​​the resulting alumina beads is 50 to 210 m². 2 / g, preferably 70 to 180m 2 / g, or even more preferably 70 to 160 mg 2 / g.

[0128] Methods for preparing capture substances

[0129] The active phase of the metal that captures the substance can be deposited on a support according to techniques known to those skilled in the art, for example, by impregnation from a solution of a metal precursor. Impregnation can be carried out, for example, according to a known dry impregnation method, in which the desired amount of the element in the form of a soluble salt is introduced into a selected solvent, such as softened water, to fill the pores of the support as precisely as possible. Preferably, the support thus filled with the solution is dried.

[0130] Metals can be deposited by co-impregnation or by sequential addition. Phosphorus can be added to one or more impregnation solutions.

[0131] Advantageously, nickel nitrate, nickel hydroxide, or nickel carbonate can be used as precursors for the nickel active phase.

[0132] When the active phase contains cobalt as an additional Group VIII element, cobalt nitrate, cobalt hydroxide, or cobalt carbonate are advantageously used as precursors.

[0133] When the active phase contains molybdenum as a Group VIb metal, the precursor used is advantageously ammonium heptamolybdate or molybdenum oxide (MoO3).

[0134] Phosphoric acid is advantageously used as a precursor when phosphorus is present in the active phase. Any other salt known to those skilled in the art that has sufficient solubility in aqueous solution and can be decomposed during a drying step or any type of oxidation treatment may also be used.

[0135] After introducing nickel, optionally at least one Group VIII metal, optionally at least one Group VIb metal, and optionally phosphorus, the captured material is preferably subjected to calcination. The purpose of this treatment is to convert the molecular precursor of the metal into an oxide phase. In this case, this treatment is an oxidation treatment, but simple drying of the captured material can also be performed. Preferably, the captured material is subjected to calcination before use in the method according to the invention. The calcination treatment is advantageously carried out in air or dilute oxygen at a temperature of 200°C to 550°C, preferably 300°C to 500°C. After calcination, the metal deposited on the support is in oxide form.

[0136] Advantageously, the calcined captured material is further subjected to sulfidation before being used in the method according to the invention. Sulfidation is carried out in a sulfur-reducing medium, i.e., in the presence of H₂S and hydrogen, to convert the metal oxide into transition metal sulfides, such as MoS₂, Ni₃S₂, and Co₉S₈. Sulfidation is performed by injecting a stream containing H₂S and hydrogen, or a sulfur compound capable of decomposing to produce H₂S in the presence of the captured material and hydrogen, onto the captured material. Polysulfides, such as dimethyl disulfide, are H₂S precursors commonly used in sulfide catalysts. The temperature is adjusted to allow H₂S to react with the metal oxide to form metal sulfides. This sulfidation can be carried out in situ or ex-situ (inside or outside the hydrodesulfurization reactor) at temperatures from 200°C to 600°C and more preferably from 250°C to 500°C. For reactivity, the metal should preferably be substantially sulfided. The degree of sulfidation of the metal constituting the active phase of the captured material is advantageously at least 60%, preferably at least 80%. The sulfur content in a sulfurized material is measured by elemental analysis according to ASTM D5373. A metal is considered sulfurized when the total degree of sulfidation, defined by the molar ratio between sulfur (S) present on the trapping material and the metal, is at least 60% equal to the theoretical molar ratio corresponding to complete sulfidation of the metal(s) under consideration. The total degree of sulfidation is defined by the following equation:

[0137] (S / Element) 捕获物质 >= 0.6 × (S / element) 理论

[0138] in:

[0139] (S / Element) 捕获物质 The molar ratio between sulfur (S) present in the captured substance and the element.

[0140] (S / Element) 理论This corresponds to the molar ratio between sulfur and the element that produces sulfides when the element is fully sulfided.

[0141] The theoretical molar ratio varies depending on the elements considered:

[0142] -(S / Co) 理论 =8 / 9

[0143] -(S / Ni) 理论 =1 / 1

[0144] -(S / Mo) 理论 =2 / 1

[0145] After vulcanization, the captured material is prepared for use in the method according to the invention.

[0146] The present invention is illustrated by the following embodiments. Example

[0147] The present invention is illustrated by the following embodiments.

[0148] Example 1: Capturing Substance A (according to the present invention)

[0149] The carrier S1 for arsenic-capturing substance A is hydrated boehmite ( The alumina powder was prepared by dehydration using Merck (a type of carbon black) to obtain alumina powder. The temperature was set at 800°C, and the contact time between the dehydrated material and the dry air stream was 1 second. The obtained alumina powder was ground to a particle size of 10 to 200 μm and then washed three times with distilled water with a volume equal to twice the volume of the powder used. In the presence of carbon black, the alumina powder is shaped using a plate granulator (GRELBEX P30) equipped with a conical cylindrical bowl at a 30° angle and a rotation speed of 40 rpm to obtain beads with a diameter primarily of 2 to 4 mm after sieving the solids. The amount of carbon black is adjusted to obtain 800 kg / m³. 3 The original filling density of the object. The beads were heat-treated in air at 720°C to give them a density of 200 μm. 2 The specific surface area was measured in g. Next, the surface area was determined by using a nitric acid aqueous solution (0.1N, Merck). TM The volume of the impregnated pores was determined, and the beads were subjected to hydrothermal treatment. The hydrothermal treatment was carried out in a rotating basket autoclave at 200°C for 6.5 hours. The resulting beads were then subjected to a final calcination treatment in air at 650°C for 2 hours. The carrier S1 has a diameter of 141m. 2The specific surface area per g, the total pore volume of 0.97 mL / g, and the following pore distribution given by mercury porosity determination:

[0150] - The volume of mesopores with a diameter greater than or equal to 2 nm and less than 18 nm is 0.15 mL / g, and their pore distribution is concentrated at 13 nm, corresponding to 15% of the total pore volume;

[0151] - The volume of mesopores with a diameter greater than or equal to 18 nm and less than 50 nm is 0.43 mL / g, and their pore distribution is concentrated at 26 nm, corresponding to 44% of the total pore volume;

[0152] - The volume of macropores with a diameter greater than or equal to 50 nm and less than 8000 nm is 0.39 mL / g, corresponding to 40% of the total pore volume.

[0153] Arsenic trapping material A was obtained by double dry impregnation of an alumina support via an aqueous nickel nitrate solution. Support S1 exhibited a water absorption volume of 0.95 mL / g. This was achieved by impregnating an alumina support with 18.24 g of nickel nitrate (Ni(NO3)2,6H2O, 99.5%, Merck). TM The impregnation solution was prepared by diluting the solid in 37.2 mL of distilled water. After dry impregnation of 40 g of support and aging in a humidified atmosphere for 12 hours, the solid was dried at 120 °C for 12 hours to obtain the catalyst precursor. The second impregnation step was carried out by impregnating 19.35 g of nickel nitrate (Ni(NO3)2,6H2O, 99.5%) with Merck. TM The solution was prepared by diluting it in 33.7 mL of distilled water. After dry impregnation of the catalyst precursor and aging in a humid atmosphere for 12 hours, the solid was dried at 120 °C for 12 hours. The solid was then calcined in air at 450 °C for 2 hours. The obtained arsenic trapping material A contained 20 wt% NiO relative to the total weight of the trapping material. Arsenic trapping material A had a total pore volume of 0.87 mL / g and a pore size of 112 m... 2 Specific surface area per g.

[0154] Example 2: Capture material B (macropore-large single-peak mesopore capture material) not according to the present invention

[0155] The carrier S2 that captures substance B passes through hydrated alumina ( Merck TM The activated alumina powder was prepared by dehydration. The temperature was set at 800°C, and the contact time between the dehydrated material and the dry air stream was 1 second. The obtained activated alumina powder was ground to a particle size of 10 to 200 μm, and then washed three times with distilled water with a volume equal to twice the volume of the powder used. The activated alumina powder was then processed using a disc granulator (GRELBEX) equipped with a conical cylindrical disc. TMP30) is formed at a 30° angle and a rotation speed of 40 rpm to obtain an initial fill density of 780 kg / m³, with a diameter primarily of 2 to 4 mm (after sieving solids). 3 The beads are heat-treated in air at 700°C to give them a 250µm diameter. 2 The specific surface area was measured in g. Next, the surface area was determined by using a nitric acid aqueous solution (0.1N, Merck). TM The volume of the impregnated pores was determined, and the beads were subjected to hydrothermal treatment. The hydrothermal treatment was carried out in a rotary basket autoclave at 200°C for 6.5 hours. The resulting beads were then subjected to a final calcination treatment in air at 950°C for 2 hours. The carrier S2 has a diameter of 71m. 2 The specific surface area per g, the total pore volume of 0.56 mL / g, and the following pore distribution given by mercury porosity determination:

[0156] - The volume of mesopores with a diameter greater than or equal to 10 nm and less than 50 nm is 0.35 mL / g, and their pore distribution is concentrated at 20 nm, corresponding to 63% of the total pore volume;

[0157] - The volume of macropores with a diameter greater than or equal to 50 nm and less than 8000 nm is 0.21 mL / g, corresponding to 38% of the total pore volume.

[0158] Arsenic trapping material B was obtained by a double dry impregnation of an alumina support via an aqueous nickel nitrate solution. Support S2 exhibited a water absorption volume of 0.54 mL / g. This was achieved by impregnating an alumina support with 18.24 g of nickel nitrate hexahydrate (Sigma-Aldrich). TM The impregnation solution was prepared by dissolving 40 g of the support (purity ≥ 98.5%) in 20.8 mL of distilled water. After dry impregnation of 40 g of support and aging in a saturated humidity atmosphere for 12 hours, the solid was dried at 120 °C for 12 hours to obtain the catalyst precursor. The second impregnation step was carried out by dissolving 19.35 g of nickel nitrate (Ni(NO3)2,6H2O, 99.5%, Merck) in 20.8 mL of distilled water. TM The solution was diluted in 17.5 mL of distilled water. The obtained arsenic trapping material B contained 20% by weight NiO relative to the total weight of the trapping material. Arsenic trapping material B had a total pore volume of 0.48 mL / g and a pore size of 66 m. 2 Specific surface area per g.

[0159] Example 3: Evaluation of Arsenic Capture Performance of the Captured Substance

[0160] Before introducing capture substances A and B into the reactor for arsenic capture tests, they were subjected to in-situ sulfidation for 2 hours under a flow of H2 / H2S mixture containing 15 vol% H2S at 350 °C, and then cooled to a plateau at 200 °C for 2 hours under pure hydrogen.

[0161] Arsenic capture performance tests included monitoring the disappearance rate of arsenic compounds dissolved in the model feedstock. The reaction was carried out in a static mode in a stirred and sealed autoclave reactor at 210°C, in the presence of hydrogen, and at a total pressure of 35 bar (3.5 MPa). The model feedstock consisted of a volume of 250 cm³. 3 The mixture consisted of toluene (217 g) and triphenylarsine (AsPh3) (containing 500 ppm by weight, or approximately 1.45 mmol As, in "As" equivalent). The mass of the solids used was adjusted to obtain an initial Ni / As molar ratio of 5.

[0162] Table 1

[0163]

[0164] Example 4: Evaluation of Olefin Hydrogenation Performance

[0165] Catalytic cracking (FCC or fluidized bed catalytic cracking) gasoline (characteristics summarized in the table below) is contacted with different capture substances. The reaction is carried out in a traversed bed reactor under the following conditions: P = 2 MPa, H2 / HC = 360 L / L feedstock, HSV = 10 h⁻¹. -1 The temperature was set at 250℃. The hydrocarbon concentration was determined by analyzing the effluent using gas chromatography.

[0166] Table 2

[0167]

[0168]

[0169] For all the substances tested, the hydrogenation of alkenes was extremely low, less than 2 wt% relative to the total weight of the alkenes.

Claims

1. A method for capturing organometallic impurities in gasoline-type hydrocarbon feedstocks containing sulfur compounds and olefins, wherein the capturing material is subjected to a temperature of 200 to 400°C, a pressure of 0.2 to 5 MPa, and a flow rate of 50 to 800 Nm. 3 / m 3 The hydrogen flow rate is contacted at a ratio to the hydrocarbon feed flow rate, and the captured material comprises a nickel-based active phase and a mesoporous-macroporous alumina support with a bimodal mesoporous distribution, wherein: - The volume of mesopores with a diameter greater than or equal to 2 nm and less than 18 nm corresponds to 10% to 30% of the total pore volume of the carrier; - The volume of mesopores with a diameter greater than or equal to 18 nm and less than 50 nm corresponds to 30% to 50% of the total pore volume of the carrier; - The volume of macropores with a diameter greater than or equal to 50 nm and less than 8000 nm corresponds to 30 to 50% of the total pore volume of the carrier.

2. The method of claim 1, wherein the specific surface area of ​​the carrier is 50 to 210 m² / g.

3. The method of any one of claims 1 and 2, wherein the total pore volume of the carrier is 0.7 to 1.3 mL / g.

4. The method of any one of claims 1 and 2, wherein the volume of the mesopores with a diameter greater than or equal to 2 nm and less than 18 nm corresponds to 15 to 25% of the total pore volume of the carrier.

5. The method of any one of claims 1 and 2, wherein the volume of the mesopores with a diameter greater than or equal to 18 nm and less than 50 nm corresponds to 35% to 45% of the total pore volume of the carrier.

6. The method of any one of claims 1 and 2, wherein the volume of macropores with a diameter greater than or equal to 50 nm and less than 8000 nm corresponds to 35 to 50% of the total pore volume of the carrier.

7. The method of any one of claims 1 and 2, wherein the nickel content, expressed in the form of NiO, is 5 to 65% by weight relative to the total weight of the captured material.

8. The method of any one of claims 1 and 2, wherein the active phase consists only of nickel.

9. The method of any one of claims 1 and 2, wherein the active phase of the captured substance further comprises cobalt, molybdenum and phosphorus.

10. The method of claim 9, wherein the nickel content, expressed as NiO oxide, is 5 to 65% by weight relative to the total weight of the captured material; the cobalt content, expressed as CoO, is 0.5 to 10% by weight relative to the total weight of the captured material; the molybdenum content, expressed as MoO3, is 2 to 20% by weight relative to the total weight of the captured material; and the phosphorus content, expressed as P2O5, is 0.2 to 10% by weight relative to the total weight of the captured material.

11. The method of any one of claims 1 and 2, wherein the pore distribution of mesopores with a diameter greater than or equal to 2 nm and less than 18 nm is concentrated in the numerical range of 10.5 to 14.5 nm.

12. The method of any one of claims 1 and 2, wherein the pore distribution of mesopores with a diameter greater than or equal to 18 nm and less than 50 nm is concentrated in the numerical range of 22 to 28 nm.

13. The method of any one of claims 1 and 2, wherein the specific surface area of ​​the carrier is 70 to 180 m² / g.

14. The method of any one of claims 1 and 2, wherein the carrier is in the form of beads having a diameter of 2 to 4 mm.

15. The method of claim 14, wherein the carrier is obtained according to the following steps: s1) Dehydrate aluminum hydroxide or aluminum hydroxide at a temperature of 400°C to 1200°C for 0.1 to 5 seconds to obtain aluminum oxide powder; s2) The alumina powder obtained in step s1) is shaped into beads; s3) Alumina beads obtained in step s2) are heat-treated at a temperature greater than or equal to 200°C; s4) Alumina beads obtained at the end of hydrothermal treatment step s3) by impregnation with water or aqueous solution and then retention in an autoclave at a temperature of 100°C to 300°C; s5) Calcine the alumina beads obtained at the end of step s4) at a temperature of 500°C to 820°C.

16. The method of claim 15, wherein in step s1), aluminum hydroxide or aluminum hydroxide is dehydrated at a temperature of 600°C to 900°C for 0.1 seconds to 4 seconds.

17. The method of any one of claims 1 and 2, wherein the hydrocarbon feedstock is catalytic cracked gasoline containing 5% to 60% by weight of monoolefins, 50 to 6000 ppm by weight of sulfur compounds and 10 to 1000 ppb of arsenic relative to the total weight of the hydrocarbon feedstock.

18. The method of any one of claims 1 and 2, wherein the organometallic impurity is selected from organometallic impurities of heavy metals.

19. The method of any one of claims 1 and 2, wherein the organometallic impurity is selected from organometallic impurities of arsenic.

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