Method for capturing organometallic impurities in the presence of trapped clumps on mesoporous and macroporous carriers.

Abstract

The present invention relates to a process for capturing organometallic impurities in a gasoline-type hydrocarbon feedstock containing sulfur compounds and olefins, comprising contacting the feedstock with a capture mass comprising a hydrogen- and nickel-based active phase and a mesoporous and macroporous alumina substrate having a bimodal distribution of mesopores, wherein the volume of mesopores having a diameter of 2 nm or more and less than 18 nm represents 10-30% by volume of the total pore volume of the substrate, the volume of mesopores having a diameter of 18 nm or more and less than 50 nm represents 30-50% by volume of the total pore volume of the substrate, and the volume of macropores having a diameter of 50 nm or more and less than 8000 nm represents 30-50% by volume of the total pore volume of the substrate.

Description

[Technical Field]

[0001] The present invention relates to a method for capturing organometallic impurities contained in gasoline-type hydrocarbon feedstocks containing sulfur compounds and olefins using nickel-based capture aggregates. [Background technology]

[0002] Automotive fuel specifications require a significant reduction in the sulfur content of these fuels, particularly gasoline. This reduction is aimed at limiting the content of sulfur and nitrogen oxides in vehicle exhaust gases. These specifications, currently in effect in Europe since 2009 for gasoline fuels, set the maximum sulfur content at 10 ppm (parts per million) by weight of sulfur. Similar specifications are in effect in other countries, such as the United States and China, which have required similar maximum sulfur content since January 2017. To meet these specifications, it is necessary to treat gasoline through desulfurization methods.

[0003] The primary source of sulfur in the gasoline base is "cracked" gasoline, which is primarily the gasoline fraction obtained from catalytic cracking of the residues of atmospheric or vacuum distillation of crude oil. While the gasoline fraction from catalytic cracking accounts for an average of 40% of the gasoline base, it actually accounts for over 90% of the sulfur in the gasoline. Consequently, the production of low-sulfur gasoline requires a desulfurization process of catalytically cracked gasoline. Specifically, the removal of sulfur from gasoline fractions involves treating these sulfur-rich gasolines via desulfurization methods in the presence of hydrogen. These are referred to as hydrodesulfurization (HDS) methods. However, these gasoline fractions, more specifically gasoline obtained from FCC, contain many unsaturated compounds in the form of monoolefins (approximately 20% to 50% by weight), diolefins (0.5% to 5% by weight), and aromatic compounds, which contribute to a good octane rating. These unsaturated compounds are unstable and react during the hydrodesulfurization process. Diolefins, in particular, polymerize during the hydrodesulfurization process to form gummy substances. The formation of this gum-like substance leads to the gradual deactivation of the hydrodesulfurization catalyst or the gradual blockage of the reactor. Therefore, diolefins must be removed by hydrogenation before any further processing of these gasolines is carried out. Conventional processing methods non-selectively desulfurize gasoline by hydrogenating most of the monoolefins, resulting in significant octane loss and large amounts of hydrogen consumption. Recent hydrodesulfurization methods make it possible to limit the hydrogenation of monoolefins and the resulting octane loss while desulfurizing cracked gasoline that is rich in monoolefins. Such methods are described, for example, in Patent Documents 1 and 2.

[0004] Hydrodesulfurization methods are operated continuously for a period of at least 3 to 5 years. The catalyst used for hydrodesulfurization of sulfur-containing gasoline, therefore, needs to have good activity, good selectivity, and good stability over time to enable continuous operation over several years. However, if heavy metals, such as mercury and arsenic, or contaminants, such as phosphorus and silicon, are present in the hydrocarbon feedstock to be desulfurized in the form of organometallic compounds, the hydrodesulfurization catalyst will be rapidly deactivated. Therefore, it is necessary to remove these contaminants from the feedstock before contact with the hydrodesulfurization catalyst.

[0005] Various solutions have been proposed for extracting these impurities, more specifically arsenic, from hydrocarbon feedstocks. Generally, the adsorbent is placed either in a reactor located upstream of the hydrodesulfurization unit, or in a hydrodesulfurization reactor upstream of the catalyst bed containing the hydrodesulfurization catalyst. Such adsorbents are described in Patent Documents 3 and 4. These adsorbents are used in the presence of hydrogen, but this presents problems when the gasoline to be processed contains unsaturated compounds. As a result, the octane rating decreases, leading to a decline in the quality of the gasoline from the stage of impurity adsorption. These adsorbents also have the disadvantage of being relatively catalytically inert to the hydrodesulfurization reaction. Furthermore, they occupy a considerable volume in the reactor, reducing the volume available for the hydrodesulfurization catalyst bed, thus leading to an overall decrease in the performance of the method. Therefore, it is necessary to seek solutions that can remove these impurities, such as arsenic, while having the objective of limiting the hydrogenation reaction that causes the decrease in the octane rating of the gasoline in question. These solutions must also be able to improve the hydrodesulfurization performance without impairing the selectivity of the hydrodesulfurization reaction for olefin hydrogenation.

[0006] Therefore, there remains a need for captured aggregates that possess adsorption characteristics and optimized catalytic properties for heavy metals, that is, those that have a good compromise between activity in hydrodesulfurization (HDS) and the maximum selectivity of the hydrodesulfurization reaction compared to olefin hydrogenation (HDS / HYD), and whose adsorption and catalytic activity characteristics after capture are stable over time.

[0007] Furthermore, prior art has shown that the pore distribution of the support material can have a beneficial effect on catalytic performance.

[0008] Patent Document 5 discloses a method for preparing a catalyst support, which does not contain macroporous regions and has a bimodal pore structure in the mesoporous regions, with the two peaks of the porosity region separated by only 1 to 20 nm. This support can be used in a number of catalytic applications, particularly in hydrogenation treatment, especially in hydrogenation denitrification.

[0009] Patent document 6 discloses a method for preparing a porous alumina support for use as a catalyst support for hydrodesulfurization or hydrodemetallation, wherein the total pore volume contained in the support is 0.65 to 1.30 cm³. 3 The porous support comprises two groups of macropores, of which approximately 2% to 20% relative to the total pore volume are in the form of macropores with a diameter of 10,000 angstroms to 100,000 angstroms (1,000 to 10,000 nm), of which approximately 5% to 30% relative to the total pore volume are in the form of macropores with a diameter of 1,000 angstroms to 10,000 angstroms (100 to 1,000 nm), and of which approximately 50% to 93% relative to the total pore volume are in the form of mesopores with a pore diameter of 30 angstroms to 1,000 angstroms (3 to 100 nm).

[0010] Patent Documents 7 to 9 disclose catalysts for various catalytic applications (propane dehydrogenation, esterification), and the carrier thereof has a trimodal pore distribution, and the population of mesopores is concentrated in three peaks with pore diameters of 2 to 4 nm, 5 to 15 nm, and 10 to 40 nm, respectively.

[0011] Patent Document 10 discloses alumina for the capture of halides, including a trimodal porosity part, and 40% to 49% by volume of this trimodal porosity part is in the form of pores with a diameter of 15 to 50 nm relative to the total pore volume of the carrier.

[0012] However, none of the prior art documents describe the implementation of a method for capturing organometallic impurities, particularly those contained in a hydrocarbon feedstock, in the presence of a capture mass containing a carrier having both a bimodal mesopore porosity part and a large mesopore volume, combined with a specific macropore volume.

[0013] In this context, one object of the present invention is to propose a method for capturing organometallic impurities in a gasoline-type hydrocarbon feedstock containing sulfur compounds and olefins, in which the capture mass contains an active phase containing at least nickel on a mesoporous and macroporous carrier, showing both a bimodal mesoporous porosity part and a high mesopore volume, combined with a predetermined macropore volume. This is because, surprisingly, the use of this capture mass enables efficient capture of organometallic impurities, particularly arsenic, contained in gasoline containing olefins and sulfur, while generally limiting the hydrogenation rate of olefins to a value of less than 30%, preferably less than 20%, and even more preferably less than 10%.

[0014] In fact, without being associated with any scientific theory, the use of such capture masses improves the phenomenon of internal diffusion of reactants and products due to the presence of a population of mesopores of different sizes. Furthermore, it is particularly advisable for a macroporous portion to be present in combination, when the feedstock to be processed contains a significant amount of reactive olefins (unsaturated compounds), especially diolefins, which is the case for gasoline and can lead to the formation of gum-like substances and would thus block the porosity of the capture mass without the presence of macroporosity.

Prior Art Documents

Patent Documents

[0015]

Patent Document 1

Patentent Documentent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Patent Document 9

Patent Document 10

Summary of the Invention

Means for Solving the Problems

[0016] (Subject matter of the invention) The subject of the present invention is a method for capturing organometallic impurities in a gasoline-type hydrocarbon feedstock containing sulfur compounds and olefins, wherein the captured mass is brought into contact with a flow of feedstock to be treated and hydrogen, at a temperature of 200°C to 400°C, a pressure of 0.2 to 5 MPa, and a hydrogen flow rate to hydrocarbon feedstock flow rate ratio of 50 to 800 Nm. 3 / m 3 The captured mass comprises a nickel-based active phase and a mesoporous and macroporous alumina carrier having a bimodal distribution of mesopores. - The volume of mesopores with a diameter of 2 nm or more and less than 18 nm corresponds to 10 to 30 volume percent of the total pore volume of the carrier; - The volume of mesopores with a diameter of 18 nm or more and less than 50 nm corresponds to 30 to 50 volume percent of the total pore volume of the carrier; - The volume of macropores with a diameter of 50 nm or more and less than 8000 nm corresponds to 30 to 50% of the total pore volume of the carrier. Regarding the method.

[0017] According to one or more embodiments, the specific surface area of ​​the carrier is 50 to 210 m². 2 It is / g.

[0018] According to one or more embodiments, the total pore volume contained in the carrier is 0.7 to 1.3 mL / g.

[0019] According to one or more embodiments, the volume of mesopores with a diameter of 2 nm or more and less than 18 nm corresponds to 15 to 25 volume percent of the total pore volume of the carrier.

[0020] According to one or more embodiments, the volume of mesopores with a diameter of 18 nm or more and less than 50 nm corresponds to 35 to 45 volume percent of the total pore volume of the carrier.

[0021] According to one or more embodiments, the volume of macropores with a diameter of 50 nm or more and less than 8000 nm corresponds to 35 to 50% of the total pore volume of the carrier.

[0022] According to one or more embodiments, the nickel content is expressed in the form of NiO and is 5 to 65% by weight relative to the total weight of the captured mass.

[0023] According to one or more embodiments, the active phase consists solely of nickel.

[0024] According to one or more embodiments, the active phase of the captured mass further comprises cobalt, molybdenum, and phosphorus.

[0025] According to one or more embodiments, the nickel content is expressed in the form of NiO oxide and is 5 to 65% by weight relative to the total weight of the captured mass; the cobalt content is expressed in the form of CoO and is 0.5 to 10% by weight relative to the total weight of the captured mass; the molybdenum content is expressed in the form of MoO3 and is 2 to 20% by weight relative to the total weight of the captured mass; and the phosphorus content is expressed in the form of P2O5 and is 0.2 to 10% by weight relative to the total weight of the captured mass.

[0026] According to one or more embodiments, the pore distribution of mesopores with a diameter of 2 nm or more and less than 18 nm is concentrated in the range of 10.5 to 14.5 nm.

[0027] According to one or more embodiments, the pore distribution of mesopores with a diameter of 18 nm or more and less than 50 nm is concentrated in the range of 22 to 28 nm.

[0028] According to one or more embodiments, the specific surface area of ​​the carrier is 70 to 180 m². 2 It is / g.

[0029] According to one or more embodiments, the carrier is in the form of beads having a diameter of 2 to 4 mm.

[0030] According to one or more embodiments, if the carrier is in the form of beads, the carrier is obtained by the following steps: s1) A step of obtaining alumina powder by dehydrating aluminum hydroxide or aluminum oxyhydroxide at a temperature of 400°C to 1200°C, preferably 600°C to 900°C, for a period of 0.1 seconds to 5 seconds, preferably 0.1 seconds to 4 seconds; s2) A step of shaping the alumina powder obtained in step s1) into the form of beads; s3) A step of heat-treating the alumina beads obtained in step s2) at a temperature of 200°C or higher; s4) A step in which the alumina beads obtained at the end of step s3) are hydrothermally treated by impregnating them with water or an aqueous solution and then occupying them in an autoclave at a temperature of 100°C to 300°C; s5) A process in which the alumina beads obtained at the end of process s4) are fired at a temperature of 500°C to 820°C.

[0031] According to one or more embodiments, the hydrocarbon feedstock is catalytic cracking gasoline containing 5% to 60% by weight of monoolefin, 50 to 6000 ppm by weight of sulfur compounds and 10 to 1000 ppb of arsenic, relative to the total weight of the feedstock.

[0032] According to one or more embodiments, the organometallic impurity is selected from heavy metals, silicon, phosphorus, and arsenic organometallic impurities. Preferably, the organometallic impurity is an organometallic arsenic impurity. [Modes for carrying out the invention]

[0033] (Detailed description of the invention) (1.Definition) Next, the groups of chemical elements are given by the CAS classification (CRC Handbook of Chemistry and Physics, published by CRC Press, editor-in-chief DR. Lide, 81st edition, 2000-2001). For example, Group VIII in the CAS classification corresponds to the metals in columns 8, 9, and 10 of the new IUPAC classification.

[0034] The BET specific surface area was measured by nitrogen physicoadsorption according to standard ASTM D3663-03, a method described in “Adsorption by Powders & Porous Solids: Principles, Methodology and Applications”, Academic Press, 1999, by Rouquerol F., Rouquerol J., and Singh K.

[0035] In this specification, in accordance with the IUPAC Agreement, “micropore” is understood to mean a pore with a diameter of less than 2 nm, i.e., less than 0.002 μm; “mesopore” is understood to mean a pore with a diameter greater than 2 nm, i.e., greater than 0.002 μm, and less than 50 nm, i.e., less than 0.05 μm; and “macropore” is understood to mean a pore with a diameter of 50 nm or more, i.e., 0.05 μm or more.

[0036] In the following description of the present invention, the “total pore volume” of the alumina or trapped mass is understood to mean the volume measured by intrusion using mercury porosimetry in accordance with ASTM D4284-83 standard, at a maximum pressure of 4000 bar (400 MPa), with a surface tension of 484 dyne / cm and a contact angle of 140°. The wetting angle was considered equal to 140° in accordance with the recommendation on pages 1050–1055 of the publication “Techniques de l'ingenieur, traite analysis et caracterisation” (Techniques for Engineers, Analysis and Characterization) written by Jean Charpin and Bernard Rasneur.

[0037] For greater accuracy, the total pore volume (mL / g) values ​​given herein hereafter correspond to the total mercury volume (total pore volume measured by mercury intrusion porosimetry) (mL / g) measured for the sample, minus the mercury volume (mL / g) measured for the same sample at a pressure equivalent to 30 psi (approximately 0.2 MPa).

[0038] The volumes of macropores and mesopores are measured by mercury intrusion porosimetry in accordance with standard ASTM D4284-83, using a maximum pressure of 4000 bar (400 MPa), a surface tension of 484 dyne / cm, and a contact angle of 140°.

[0039] The threshold for mercury to fill all intergranular voids, or exceed this threshold, is set at 0.2 MPa. Above this value, it is believed that mercury will penetrate the pores of the sample.

[0040] The macropore volume of a catalyst is defined as the cumulative volume of mercury introduced at a pressure of 0.2 MPa to 30 MPa, which corresponds to the volume contained within pores with an apparent diameter greater than 50 nm.

[0041] The mesopore volume of a catalyst is defined as the cumulative volume of mercury introduced at a pressure of 30 MPa to 400 MPa, which corresponds to the volume contained within pores with an apparent diameter of 2 to 50 nm.

[0042] When the incremental pore volume measured by mercury porosimetry is plotted as a function of pore diameter, the porosity mode corresponds to the inflection point of the represented function.

[0043] The content of metallic elements (Group VIII and Group VIB metals) and phosphorus is measured by X-ray fluorescence.

[0044] (2. Explanation) (Methods for capturing organometallic impurities) The present invention relates to a method for capturing organometallic impurities contained in a hydrocarbon feedstock, such as heavy metals, silicon, or phosphorus, and more particularly arsenic, using a capture mass as defined below, wherein the capture mass is brought into contact with the hydrocarbon feedstock in the presence of hydrogen. In the sense of the present invention, the capture method according to the present invention is a method for at least partially capturing arsenic and optionally silicon in a hydrocarbon feedstock in the presence of hydrogen to produce an effluent with a reduced heavy metal, particularly arsenic, content and limited octane loss. The capture method according to the present invention makes it possible to remove arsenic and to limit the hydrogenation rate of monoolefins. The hydrogenation rate of olefins is advantageously less than 50%, preferredly less than 30%, and even more preferably less than 20%.

[0045] The hydrocarbon feedstock to be processed is, advantageously, catalytically cracked gasoline from catalytic cracking, pyrolysis, or steam cracking units. This method can also be applied to the processing of mixtures of directly distilled gasoline, which may contain heavy metals derived from crude oil, and cracked gasoline containing monoolefins and diolefins. Preferably, the hydrocarbon feedstock to be processed is catalytically cracked gasoline containing 5% to 60% by weight of monoolefins, 50 ppm to 6000 ppm by weight of sulfur compounds, and 10 to 1000 ppb by weight of arsenic. The sulfur compounds contained in the hydrocarbon feedstock to be processed may be organosulfur compounds, such as thiols, thiophene compounds, benzothiophene compounds, and other aromatic sulfur compounds, disulfide compounds, etc. The arsenic compounds contained in the hydrocarbon feedstock to be processed may be organosarsenic compounds, such as trimethylarsine or triethylarsine. Monoolefins represent hydrocarbon molecules exhibiting a single carbon-carbon double bond, and diolefins represent hydrocarbon molecules exhibiting at least two carbon-carbon double bonds. Monoolefins and diolefins can be linear, branched, and / or cyclic hydrocarbon molecules.

[0046] The capture aggregate according to the present invention is advantageously carried out under operating conditions that maximize the arsenic capture rate while limiting the hydrogenation rate of the olefin. The temperature during which the contact operation is generally carried out is 200 to 400°C, the pressure is 0.2 to 5 MPa, and the ratio of the hydrogen flow rate to the hydrocarbon feedstock flow rate is 50 to 800 Nm³. 3 / m 3 The hydrogen used can be produced from any hydrogen source. Preferably, fresh hydrogen from a refinery and / or recycled hydrogen from a hydrodesulfurization unit, preferably from a unit for hydrodesulfurization of hydrocarbon fractions to be refined.

[0047] Several reactor technologies can be envisioned for carrying out arsenic capture from hydrocarbon feedstock in the presence of the capture mass according to the present invention, but the most traditional and widespread technology is the fixed-bed technology. In this case, the reactor is packed with the capture mass and hydrodesulfurization catalyst according to the present invention, and operations in arsenic adsorption and hydrodesulfurization are carried out until, in principle, arsenic appears in the outlet effluent (a phenomenon known to those skilled in the art as a breakthrough). In some cases, the entire amount of poisoned capture mass may be replaced with an equal amount of fresh capture mass. The choice of technology for replacing the capture mass according to the present invention is not considered an limiting factor in relation to the present invention. The capture mass may be used in a moving-bed reactor, i.e., used capture mass is continuously withdrawn and replaced with fresh capture mass. This type of technology makes it possible to maintain arsenic capture by the capture mass and avoid arsenic breakthrough into the resulting effluent. Among other solutions, the use of an expanding-bed reactor may be mentioned, which also allows for continuous withdrawal and replenishment of the capture mass and maintains the desulfurization activity of the capture mass.

[0048] The capture method according to the present invention is preferably associated with at least one additional step of selective hydrogenation or catalytic hydrodesulfurization performed on the effluent resulting from the contact operation with the capture mass according to the present invention. Therefore, the step of treating the hydrocarbon feedstock with the capture mass is considered a pretreatment that particularly enables the retention of the catalytic activity of the catalyst used in the subsequent steps of selective hydrogenation or hydrodesulfurization. Thus, the capture method according to the present invention comprises one or more additional steps of selective hydrogenation or hydrodesulfurization, in which the effluent resulting from contacting the hydrocarbon feedstock with the capture mass according to the present invention is contacted with at least one other catalyst for the selective hydrogenation or hydrodesulfurization of diolefins present in the feedstock. The additional hydrodesulfurization steps (one or more) make it possible to remove residual sulfur compounds contained in the effluent, where arsenic is depleted and the sulfur content is further reduced. Some of these residual sulfur compounds may originate from the addition of H2S to olefins present in the feedstock. H2S may form during the operation in which the hydrocarbon feedstock is in contact with the trapping mass, i.e., during arsenic capture. The additional hydrodesulfurization steps (one or more) are performed when the effluent obtained from the operation in which the hydrocarbon feedstock is in contact with the trapping mass generally 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 (less than 10 ppm in many countries). The effluent, from which some of the arsenic and sulfur compounds have been removed, is then treated in at least one of the additional steps of selective hydrodesulfurization. In the steps (one or more), the effluent is brought into contact with at least one other hydrodesulfurization catalyst under operating conditions that may be the same as or different from those under which the hydrocarbon feedstock was in contact with the trapping mass.

[0049] The catalyst(s) used in the aforementioned additional hydrodesulfurization step(s) (one or more) are protected from inactivation by arsenic present in the feedstock by the capture aggregate according to the present invention. Therefore, highly selective hydrodesulfurization catalysts sensitive to the presence of arsenic can be used in the aforementioned additional hydrodesulfurization step(s). Any hydrodesulfurization catalyst can be used in the aforementioned additional hydrodesulfurization step(s). Preferably, the catalyst used has high selectivity for the hydrodesulfurization reaction compared to the olefin hydrodesulfurization reaction. Such a catalyst comprises at least one porous and amorphous mineral support, a group VIB metal, and 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 generally selected from the group consisting of alumina, silica, silica-alumina, silicon carbide, titanium oxide (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 the group consisting of alumina, silica, and silica-alumina. Preferably, the hydrodesulfurization catalyst used in an additional hydrodesulfurization step (one or more times) has the following characteristics: - The content of elements in Group VIB is between 1% and 20% by weight of oxides of elements in Group VIB. - The content of Group VIII elements is 0.1% to 20% by weight of oxides of Group VIII elements. - The molar ratio (elements of Group VIII / elements of Group VIB) is between 0.1 and 0.8.

[0050] A highly suitable hydrodesulfurization catalyst contains cobalt and molybdenum and has the above-mentioned characteristics. 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 0.25 or higher, preferably 0.27 or higher.

[0051] In the said additional hydrodesulfurization stage(s), the arsenic-depleted effluent resulting from contacting the hydrocarbon feedstock with the capture mass according to the invention is contacted with at least one other selective hydrodesulfurization catalyst under the following operating conditions: - The temperature is from about 210 °C to about 410 °C, preferably from 240 °C to 360 °C, - The total pressure is from 0.2 to 5 MPa, more preferably from 0.5 to 3 MPa, - The volume of hydrogen per unit volume of the hydrocarbon feedstock is from 50 to 800 Nm 3 / m 3 , more preferably from 60 to 600 Nm 3 / m 3 .

[0052] In an alternative form of the method according to the invention, the operating conditions for contacting the hydrocarbon feedstock with the capture mass according to the invention are the same as those used in the said additional hydrodesulfurization stage(s).

[0053] According to another embodiment, the stage of hydrotreating the effluent resulting from the capture stage by the capture mass according to the invention is a selective hydrotreating, which not only enables the hydrogenation of diolefins giving olefins and optionally the hydrogenation of unsaturated sulfur compounds, but also the conversion (weight increase) of light sulfur compounds (i.e., having a temperature lower than that of thiophene) to sulfur compounds having a temperature higher than that of thiophene, for example, by the addition of thiols to olefins. This hydrogenation stage is carried out in the presence of hydrogen and a catalyst containing at least one metal of Group VIB and at least one non-noble metal of Group VIII deposited on a porous support. Preferably, the catalyst used is as follows: - The weight content of the oxide of the element of Group VIB is from 6% to 18% based on the weight of the catalyst, - The weight content of the oxide of the element of Group VIII is from 4% to 12% based on the weight of the catalyst, - The specific surface area of the catalyst is from 200 to 270 m 2 / g. - The density of the elements of Group VIB is expressed as the ratio of the weight content of the oxides of the elements of Group VIB to the specific surface area of ​​the catalyst, and is 4-6 × 10⁻⁶. -4 g / m 2 That is, - The molar ratio of Group VIII metals to Group VIB metals is between 0.6 and 3 moles / mol.

[0054] The metal of Group VIB is preferably selected from molybdenum and tungsten, and more preferably molybdenum. The metal of Group VIII is preferably nickel and / or cobalt, and more preferably nickel. Hydrogen is generally introduced in a slightly excess amount, up to a maximum of 5 moles / mol, compared to the stoichiometry required to hydrogenate the diolefin (1 mole of hydrogen per mole of diolefin). The mixture of gasoline and hydrogen is subjected to a pressure of 0.5 to 5 MPa, a temperature of 80°C to 220°C, and 1 to 10 hours. -1 The catalyst is brought into contact with the raw material at a liquid space velocity (LHSV), where the liquid space velocity is expressed as the volume of raw material per unit volume of catalyst (liters) and per unit time (liters) (L / L·h).

[0055] In an alternative embodiment of the method according to the present invention, the captured aggregate according to the present invention may be positioned in the protective bed of one or more reactors containing one or more catalysts used in the aforementioned additional steps (one or more) of selective hydrogenation and / or hydrodesulfurization. In another alternative embodiment of the method according to the present invention, the captured aggregate according to the present invention is positioned in a “capture” reactor. This reactor is separate from the reactor(s) containing one or more catalysts used in the aforementioned additional steps (one or more) of selective hydrogenation and / or hydrodesulfurization, and is positioned upstream of the reactor(s). In all alternative forms of the method according to the present invention that use at least one additional step of selective hydrogenation and / or hydrodesulfurization, the ratio of the volume of the captured mass according to the present invention to the volume of the catalyst(s) used in the additional step(s) of selective hydrogenation and / or hydrodesulfurization (one or more times) is advantageously 4% to 50%, preferably 5% to 40%, and more preferably 5% to 35%.

[0056] (captured mass) The captured aggregate used in connection with the method according to the present invention comprises an active phase, which comprises nickel, optionally at least one additional element from Group VIII, optionally at least one element from Group VIB, and optionally phosphorus.

[0057] The nickel content, expressed in the form of NiO, is favorably 5 to 65% by weight, preferably 10 to 30% by weight, relative to the total weight of the captured mass.

[0058] If additional Group VIII elements are present, their content is expressed in the form of oxides and is favorably 0.5–10% by weight relative to the total weight of the captured mass.

[0059] If group VIB elements are present, their content, expressed in oxide form, is favorably 2–20% by weight relative to the total weight of the captured mass.

[0060] If phosphorus is present, its content, expressed in the form of an oxide, is 0.2 to 10% by weight relative to the total weight of the captured mass.

[0061] In one embodiment of the present invention, the active phase consists solely of nickel. The nickel content is expressed in the form of NiO and is advantageously 5 to 65% by weight, preferably 10 to 30% by weight, relative to the total weight of the captured mass.

[0062] In one embodiment of the present invention, the active phase comprises nickel, cobalt, molybdenum, and phosphorus. The nickel content, expressed in the form of NiO oxide, is favorably 5 to 65% by weight, preferably 10 to 30% by weight, relative to the total weight of the captured mass. The cobalt content, expressed in the form of CoO, is favorably 0.5 to 10% by weight, preferably 0.5 to 5% by weight, relative to the total weight of the captured mass. The molybdenum content, expressed in the form of MoO3, is favorably 2 to 20% by weight, preferably 3 to 15% by weight, relative to the total weight of the captured mass. The phosphorus content, expressed in the form of P2O5, is favorably 0.2 to 10% by weight, preferably 0.5 to 5% by weight, relative to the total weight of the captured mass.

[0063] The specific surface area generally contained in the captured mass is 50-200 m². 2 / g, preferably 60-170m 2 / g, preferably 70-130m 2 It is / g.

[0064] The pore volume of the captured mass is generally 0.5 mL / g to 1.3 mL / g, preferably 0.6 mL / g to 1.1 mL / g.

[0065] (Alumina carrier) The alumina carrier used in connection with the method according to the present invention is a macroporous and mesoporous alumina carrier, which has a bimodal distribution of mesopores: - The volume of mesopores with a diameter of 2 nm or more and less than 18 nm corresponds to 10 to 30 volume percent of the total pore volume of the carrier; - The volume of mesopores with a diameter of 18 nm or more 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 of 50 nm or more and less than 8000 nm corresponds to 30 to 50% of the total pore volume of the carrier.

[0066] Preferably, the volume of the mesopores of the carrier, which have a diameter of 2 nm or more and less than 18 nm, corresponds to 15 to 25% of the total pore volume of the carrier.

[0067] Preferably, the volume of the mesopores of the carrier, which have a diameter of 18 nm or more and less than 50 nm, corresponds to 35 to 45% of the total pore volume of the carrier.

[0068] Preferably, the volume of the macropores of the carrier, which have a diameter of 50 nm or more and less than 8000 nm, corresponds to 35 to 50% of the total pore volume of the carrier.

[0069] In one embodiment of the present invention, the pore distribution of mesopores having a diameter of 2 nm or more and less than 18 nm is concentrated in the range of 10.5 to 14.5 nm, preferably 12 to 13 nm.

[0070] In one embodiment of the present invention, the pore distribution of mesopores having a diameter of 18 nm or more and less than 50 nm is concentrated in the range of 22 to 28 nm, preferably 23 to 27 nm.

[0071] The specific surface area typically contained in carriers is 50-210 m². 2 / g, preferably 70-180m 2 / g, more preferably 70-160m 2 It is / g.

[0072] The pore volume of the carrier is generally 0.7 mL / g to 1.3 mL / g, preferably 0.8 mL / g to 1.2 mL / g.

[0073] Advantageously, the carrier is in the form of beads with a diameter of 0.8–10 mm, preferably 1–5 mm, and more preferably 2–4 mm.

[0074] (Carrier preparation method) The alumina carrier for the captured mass used in connection with the method according to the present invention can be synthesized by any method known to those skilled in the art.

[0075] In a preferred embodiment, the alumina carrier used in accordance with the present invention is in the form of beads. In this preferred embodiment, the preparation of the carrier includes the following steps: s1) A step to obtain alumina powder by dehydrating aluminum hydroxide or aluminum oxyhydroxide at a temperature of 400°C to 1200°C, preferably 600°C to 900°C, for a period of 0.1 seconds to 5 seconds, preferably 0.1 seconds to 4 seconds; s2) A step of shaping the alumina powder obtained in step s1) into the form of beads; s3) A step of heat-treating the alumina beads obtained in step s2) at a temperature of 200°C or higher; s4) The alumina beads obtained at the end of step s3) are subjected to hydrothermal treatment by impregnating them with water or, preferably, an acidic aqueous solution, and then being kept in an autoclave at a temperature of 100°C to 300°C, preferably 150°C to 250°C. s5) A process in which the alumina beads obtained at the end of process s4) are fired at a temperature of 500°C to 820°C.

[0076] Steps s1) to s5) are described in detail below.

[0077] (Step s1)) According to step s1), dehydration of aluminum hydroxide or aluminum oxyhydroxide is carried out at a temperature of 400°C to 1200°C, preferably 600°C to 900°C, for a period of 0.1 seconds to 5 seconds, preferably 0.1 seconds to 4 seconds, to obtain alumina powder. Aluminum hydroxide may be selected from hydragillite, gibbsite, or bayerite. Aluminum oxyhydroxide may be selected from boehmite or diaspore.

[0078] Preferably, step s1) is carried out using hydragylite.

[0079] Generally, step s1) is carried out in the presence of a flow of high-temperature gas, such as dry or humid air, which allows for the rapid removal and entrainment of evaporated water.

[0080] Generally, activated alumina powder obtained after dehydration of aluminum hydroxide or oxyhydroxide is ground to a particle size of 10-200 μm.

[0081] Generally, the activated alumina powder obtained after dehydration of aluminum hydroxide or oxyhydroxide is washed with water or an acidic aqueous solution. When the washing step is carried out with an acidic aqueous solution, any inorganic or organic acid may be used, preferably inorganic acids such as nitric acid, hydrochloric acid, perchloric acid, or sulfuric acid, and organic acids such as carboxylic acids (formic acid, acetic acid, or malonic acid), sulfonic acids (para-toluenesulfonic acid), or sulfuric acid esters (sulfuric acid lauryl).

[0082] (Step s2)) According to step s2), the alumina powder obtained at the end of step s1) is shaped.

[0083] The alumina powder is then shaped to obtain beads, a process known as granulation, which is generally carried out using rotary technology, such as a rotary granulator or rotary drum. This type of method makes it possible to obtain beads with controlled diameter and pore distribution, which are generally created during the agglomeration process.

[0084] Porosity can be created by various means, such as selecting the particle size distribution of alumina powder or agglomerating several types of alumina powder having different particle size distributions. Another method involves mixing the alumina powder with one or more compounds known as pore-forming compounds before or during the agglomeration step. The pore-forming compounds disappear upon heating, thereby creating porosity in the beads. Possible pore-forming compounds used include, for example, wood flour, charcoal, activated carbon, carbon black, sulfur, tar, plastic materials or emulsions of plastic materials, such as polyvinyl chloride, polyvinyl alcohol, and naphthalene. The amount of pore-forming compound added depends on the untreated packing density of 500-1100 kg / m³. 3 Prioritizing 700-950 kg / m 3 The volume is determined by the desired volume to obtain beads with a diameter of 0.8 to 10 mm, preferably 1 to 5 mm, and more preferably 2 to 4 mm. Sieving of the obtained beads may be performed according to the desired particle size.

[0085] (Step s3)) According to step s3), the heat treatment is carried out on the alumina powder formed into beads at the end of step s2) at a temperature of 200°C or higher, preferably 200°C to 1200°C, preferably 300°C to 900°C, and very preferably 400°C to 750°C, for a period of generally 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 60-350mg 2 / g, more preferably 80-300m 2 It is / g.

[0086] (Step s4)) According to step s4), the alumina beads obtained at the end of step s3) undergo hydrothermal treatment. This treatment is carried out by impregnating them with water or preferably an acidic aqueous solution, and then holding them in an autoclave at a temperature of 100°C to 300°C, preferably 150°C to 250°C.

[0087] Hydrothermal treatment is generally carried out at a temperature of 100°C to 300°C, preferably 150°C to 250°C, for a duration of more than 45 minutes, preferably 1 to 24 hours, and very preferably 1.5 to 12 hours. Hydrothermal treatment is generally 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 a weak acid having a pH of less than 4, such as acetic acid or formic acid. Generally, the acidic aqueous solution also contains one or more compounds capable of releasing anions that can bind to aluminum ions, preferably compounds containing anions of general formula: R-COO, such as nitrate ions (aluminum nitrate, etc.), chlorides, sulfates, perchlorates, chloroacetates, trichloroacetates, bromoacetates, dibromoacetates, and formates and acetates.

[0088] (Step s5)) According to step s5), the alumina beads obtained at the end of step s4) are fired at a temperature of 500°C to 820°C, preferably 550°C to 750°C, for a period of generally 1 to 24 hours, preferably 1 to 6 hours. At the end of this step, the specific surface area of ​​the obtained alumina beads is 50 to 210 m². 2 / g, preferably 70-180m 2 / g, more preferably 70-160m 2 It is / g.

[0089] (Method for preparing captured masses) The metal of the active phase of the captured mass can be deposited onto the carrier, for example, by impregnation from a solution of metal precursors, according to techniques well known to those skilled in the art. Impregnation may be carried out, for example, according to known forms of dry impregnation, in which a desired amount of the element in the form of a soluble salt is introduced into a selected solvent, for example, desalination water, to fill the porous portions of the carrier as accurately as possible. The carrier thus filled with the solution is preferably dried.

[0090] Metals can be deposited by co-impregnation or by sequential addition. Phosphorus may be added to the impregnation solution(s) (one or more).

[0091] Advantageously, nickel nitrate, nickel hydroxide, or nickel carbonate can be used as precursors for the nickel active phase.

[0092] If the active phase contains cobalt as an additional Group VIII element, cobalt nitrate, cobalt hydroxide, or cobalt carbonate are favorably used as precursors.

[0093] When the active phase contains molybdenum as a group VIB metal, the precursor used is preferably ammonium heptamolybdate or molybdenum oxide (MoO3).

[0094] If phosphorus is present in the active phase, phosphoric acid is favorably used as a precursor. Any other salt known to those skilled in the art that is sufficiently soluble in aqueous solution and decomposes during the drying process or any type of oxidation treatment may also be used.

[0095] Following the introduction of nickel, optionally at least one group VIII metal, optionally at least one group VIB metal, and optionally phosphorus, the trapped mass is preferably subjected to a calcination treatment. The purpose of this treatment is to convert the molecular precursor of the metal into an oxide phase. In this case, the treatment is an oxidation treatment, but simple drying of the trapped mass may also be carried out. Preferably, the trapped mass is subjected to a calcination treatment before its use in the method according to the present invention. The calcination treatment is advantageously carried out in air or diluted 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 the form of an oxide.

[0096] Advantageously, the calcined captured mass is also subjected to sulfidation before use in the method according to the present invention. Sulfidation is carried out in a sulfo-reducing medium, i.e., in the presence of H2S and hydrogen, and converts the metal oxide to transition metal sulfides, e.g., MoS2, Ni3S2, and Co9S8. Sulfidation is carried out by injecting a stream containing H2S and hydrogen, or a sulfur compound that can decompose in the presence of the captured mass and hydrogen to yield H2S, onto the captured mass. Polysulfides, e.g., dimethyl disulfide, are H2S precursors commonly used in sulfide catalysts. The temperature is adjusted so that H2S reacts with the metal oxide to form a metal sulfide. This sulfidation can be carried out in situ or ex situ (inside or outside the hydrodesulfurization reactor) at a temperature of 200-600°C, more preferably 250-500°C. For reactivity, the metal is preferably substantially sulfided. The degree of sulfidation of the metal constituting the active phase of the trapped mass is advantageously at least equal to 60%, and preferably at least equal to 80%. The sulfur content in the sulfided material is measured by elemental analysis according to ASTM D5373. A metal is considered sulfided if its overall sulfidation rate, defined by the molar ratio of sulfur (S) present on the trapped mass to the metal, is at least equal to 60% of the theoretical molar ratio corresponding to complete sulfidation of the metal(s) under consideration. The total degree of sulfidation is defined by the following formula: (S / element) 捕捉塊≧0.6×(S / element) 理論 During the ceremony: (S / element) 捕捉塊 : The molar ratio between sulfur (S) and the element present on the trapped mass, (S / element) 理論 : The molar ratio of sulfur to the element corresponding to the total sulfidation of the element that produces the sulfide.

[0097] This theoretical molar ratio varies depending on the element being considered: - (S / Co) 理論 = 8 / 9 - (S / Ni) 理論 = 1 / 1 - (S / Mo) 理論 =2 / 1

[0098] After sulfidation, the captured mass is ready for use in the method according to the present invention.

[0099] The present invention is illustrated by the following embodiments.

[0100] (Examples) The present invention is illustrated by the following embodiments.

[0101] (Example 1: Captured mass A (compliant with the present invention)) The carrier S1 for arsenic-trapping aggregate A is prepared by dehydration using hydragillite (EMPLURA®, Merck) to obtain alumina powder. The temperature is set to 800°C, and the contact time between the material to be dehydrated and the flow of dry air is set to 1 second. The obtained alumina powder is pulverized to a particle size of 10-200 μm, and then washed three times with distilled water equal to twice the volume of powder used. The alumina powder is shaped in the presence of carbon black (N990 Thermax®) using a plate granulator (GRELBEX P30) equipped with a conical bowl at an angle of 30° and a rotation speed of 40 revolutions / minute. After sieving the solid, beads with a diameter mainly of 2-4 mm are obtained. The amount of carbon black is adjusted to obtain an untreated packing density of 800 kg / m³ of material. 3The beads are subjected to heat treatment at 720°C in air, and then coated with 200m 2 The specific surface area is given by / g. Next, the hydrothermal treatment is applied to the beads by impregnating the pore volume with an aqueous nitric acid solution (0.1N, Merck®). The hydrothermal treatment is carried out in a rotating basket autoclave at a temperature of 200°C for 6.5 hours. The beads thus obtained undergo a final calcination treatment in air at 650°C for 2 hours. The specific surface area of ​​the carrier S1 is 141m². 2 The pore volume is 0.97 mL / g, and it has the following pore distribution as determined by mercury porosimetry: - The pore distribution of mesopores with a diameter of 2 nm or more and less than 18 nm is concentrated at 13 nm, and the volume of mesopores is 0.15 mL / g, which corresponds to 15% of the total pore volume; - The pore distribution of mesopores with a diameter of 18 nm or more and less than 50 nm is concentrated at 26 nm, and the volume of mesopores is 0.43 mL / g, which corresponds to 44% of the total pore volume; - The volume of macropores with a diameter of 50 nm or more and less than 8000 nm is 0.39 mL / g, which corresponds to 40% of the total pore volume.

[0102] Arsenic-capturing aggregate A is obtained by double dry impregnation of an alumina support via an aqueous nickel nitrate solution. The water absorption volume of support S1 is 0.95 mL / g. The impregnation solution is prepared by diluting 18.24 grams of nickel nitrate (Ni(NO3)2·6H2O, 99.5%, Merck®) in 37.2 mL of distilled water. After dry impregnation of 40 grams of support and a 12-hour maturation process in a saturated water vapor atmosphere, the solid is dried at 120°C for 12 hours to obtain a catalyst precursor. The second impregnation step is carried out with a solution prepared by diluting 19.35 grams of nickel nitrate (Ni(NO3)2·6H2O, 99.5%, Merck®) in 33.7 mL of distilled water. After dry impregnation of the catalyst precursor and a 12-hour maturation process in a saturated water vapor atmosphere, the solid is dried at 120°C for 12 hours. The solid is then calcined in air at 450°C for 2 hours. The resulting arsenic-trapping mass A contains 20% by weight of NiO relative to the total weight of the trapping mass. The total pore volume of arsenic-trapping mass A is 0.87 mL / g, and the specific surface area is 112 m². 2 It is / g.

[0103] (Example 2: Captured mass B (not applicable; macroporous and large unimodal mesoporous captured mass) The carrier S2 of the captured aggregate B is prepared by dehydration with hydragillite (EMPLURA®, Merck®) to obtain activated alumina powder. The temperature is set to 800°C, and the contact time between the material to be dehydrated and the flow of dry air is set to 1 second. The obtained activated alumina powder is pulverized to a particle size of 10-200 μm, and then washed three times with distilled water equal to twice the volume of powder used. The activated alumina powder is shaped in the presence of carbon black (N990 Thermax) using a plate granulator (GRELBEX® P30) equipped with a conical bowl at an angle of 30° and a rotation speed of 40 revolutions / minute to obtain beads with a diameter mainly of 2-4 mm (after sieving the solid), and the untreated packing density of the material is 780 kg / m³. 3 The beads are subjected to heat treatment at 700°C in air, and then coated with 250m 2The specific surface area is given by / g. Next, the hydrothermal treatment is applied to the beads by impregnating the pore volume with an aqueous solution of nitric acid (0.1N, Merck®). The hydrothermal treatment is carried out in a rotating basket autoclave at a temperature of 200°C for 6.5 hours. The beads thus obtained undergo a final calcination treatment in air at 950°C for 2 hours. The specific surface area of ​​the carrier S2 is 71m². 2 The pore volume is 0.56 mL / g, and it has the following pore distribution as determined by mercury porosimetry: - The pore distribution of mesopores with a diameter of 10 nm or more and less than 50 nm is concentrated at 20 nm, and the volume of mesopores is 0.35 mL / g, which corresponds to 63% of the total pore volume; - The volume of macropores with a diameter of 50 nm or more and less than 8000 nm is 0.21 mL / g, which corresponds to 38% of the total pore volume.

[0104] Arsenic-capturing aggregate B is obtained by double dry impregnation of an alumina support via an aqueous solution of nickel nitrate. The water absorption volume of support S2 is 0.54 mL / g. The impregnation solution is prepared by diluting 18.24 grams of nickel nitrate hexahydrate (Sigma-Aldrich®, purity ≥ 98.5%) in 20.8 mL of distilled water. After dry impregnation of 40 grams of support and a 12-hour maturation process in a saturated water vapor atmosphere, the solid is dried at 120°C for 12 hours to obtain a catalyst precursor. The second impregnation step is carried out with a solution prepared by diluting 19.35 grams of nickel nitrate (Ni(NO3)2·6H2O, 99.5%, Merck®) in 17.5 mL of distilled water. The obtained arsenic-capturing aggregate B contains 20% by weight of NiO relative to the total weight of the capturing aggregate. The total pore volume of arsenic-trapping mass B is 0.48 mL / g, and its specific surface area is 66 m². 2 It is / g.

[0105] (Example 3: Evaluation of the arsenic capture performance of the captured mass) Prior to introduction into the reactor for arsenic capture testing, captured lumps A and B were subjected to in-situ sulfurization at 350°C for 2 hours under a flow of H2 / H2S mixture containing 15% by volume of H2S, and then cooled under high-purity hydrogen in a plateau at 200°C for 2 hours.

[0106] The arsenic capture performance test involves monitoring the rate of disappearance of arsenic compounds dissolved in the model feedstock. The reaction is carried out in static mode in a stirred, closed autoclave reactor at a temperature of 210°C, in the presence of hydrogen, and under a total pressure of 35 bar (3.5 MPa). The model feedstock is 250 cm³. 3 It consists of toluene by volume, i.e., 217 g, and triphenylarsine (AsPh3) at a concentration of 500 ppm by weight, equivalent to "As," i.e., approximately 1.45 mmol of As. The initial Ni / As molar ratio of 5 is obtained by adjusting the mass of the solids used.

[0107] [Table 1]

[0108] (Example 4: Evaluation of olefin hydrogenation performance) Fluid Catalytic Cracking (FCC) involves contacting gasoline (its characteristics are summarized in the table below) with different trapping materials. The reaction is carried out in a transverse-bed reactor under the following conditions: P=2MPa, H2 / HC=360 liters / liter (hydrocarbon feedstock), HSV=10h -1 The temperature is set to 250°C. The effluent is analyzed by gas chromatography to determine the hydrocarbon concentration.

[0109] [Table 2]

[0110] For all the lumps tested, the hydrogenation rate of the olefin was extremely low, less than 2% by weight relative to the total weight of the olefin.

Claims

1. A method for capturing organometallic impurities in a gasoline-type hydrocarbon feedstock containing sulfur compounds and olefins, wherein the captured mass is brought into contact with a flow of feedstock and hydrogen to be treated, the temperature being 200°C to 400°C, the pressure being 0.2 to 5 MPa, and the hydrogen flow rate to hydrocarbon feedstock flow rate being 50 to 800 Nm ３ / m ３ The captured mass comprises a nickel-based active phase and a mesoporous and macroporous alumina support having a bimodal distribution of mesopores. - The volume of mesopores with a diameter of 2 nm or more and less than 18 nm corresponds to 10 to 30 volume percent of the total pore volume of the carrier; - The volume of mesopores with a diameter of 18 nm or more and less than 50 nm corresponds to 30 to 50 volume percent of the total pore volume of the carrier; - The volume of macropores with a diameter of 50 nm or more and less than 8000 nm corresponds to 30 to 50% by volume of the total pore volume of the carrier. method.

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

3. The method according to claim 1 or 2, wherein the total pore volume contained in the carrier is 0.7 to 1.3 mL / g.

4. The method according to any one of claims 1 to 3, wherein the volume of mesopores with a diameter of 2 nm or more and less than 18 nm corresponds to 15 to 25 volume percent of the total pore volume of the carrier.

5. The method according to any one of claims 1 to 4, wherein the volume of mesopores having a diameter of 18 nm or more and less than 50 nm corresponds to 35% to 45% by volume of the total pore volume of the carrier.

6. The method according to any one of claims 1 to 5, wherein the volume of macropores having a diameter of 50 nm or more and less than 8000 nm corresponds to 35 to 50 volume percent of the total pore volume of the carrier.

7. The method according to any one of claims 1 to 6, wherein the nickel content is expressed in the form of NiO and is 5 to 65% by weight relative to the total weight of the captured mass.

8. The method according to any one of claims 1 to 7, wherein the active phase consists solely of nickel.

9. The method according to any one of claims 1 to 7, wherein the active phase of the captured mass further comprises cobalt, molybdenum, and phosphorus.

10. The nickel content is expressed in the form of NiO oxide and is 5 to 65% by weight relative to the total weight of the captured mass; the cobalt content is expressed in the form of CoO and is 0.5 to 10% by weight relative to the total weight of the captured mass; and the molybdenum content is MoO ３ It is expressed in the form of 2 to 20% by weight relative to the total weight of the captured mass, and the phosphorus content is P ２ O ５ The method according to claim 9, wherein it is expressed in the form of and is 0.2 to 10% by weight relative to the total weight of the captured mass.

11. The method according to any one of claims 1 to 10, wherein the pore distribution of mesopores having a diameter of 2 nm or more and less than 18 nm is concentrated in the range of 10.5 to 14.5 nm.

12. The method according to any one of claims 1 to 11, wherein the pore distribution of mesopores with a diameter of 18 nm or more and less than 50 nm is concentrated in the range of 22 to 28 nm.

13. The specific surface area of ​​the carrier is 70 to 180 m². 2 The method according to any one of claims 1 to 12, wherein the amount is / g.

14. The method according to any one of claims 1 to 13, wherein the carrier is in the form of beads having a diameter of 2 to 4 mm.

15. The carrier is obtained by the following steps, according to the method of claim 14: s1) A step of dehydrating aluminum hydroxide or aluminum oxyhydroxide at a temperature of 400°C to 1200°C for a period of 0.1 seconds to 5 seconds to obtain alumina powder; s2) A step of shaping the alumina powder obtained in step s1) into the form of beads; s3) A step of heat-treating the alumina beads obtained in step s2) at a temperature of 200°C or higher; s4) A step in which the alumina beads obtained at the end of step s3) are hydrothermally treated by impregnating them with water or an aqueous solution, and then immersing them in an autoclave at a temperature of 100°C to 300°C; s5) A process of firing the alumina beads obtained at the end of process s4) at a temperature of 500°C to 820°C.

16. The method according to any one of claims 1 to 15, wherein the hydrocarbon feedstock is catalytic cracking gasoline containing 5% to 60% by weight of monoolefin, 50 to 6000 ppm by weight of sulfur compounds and 10 to 1000 ppb of arsenic relative to the total weight of the feedstock.

17. The method according to any one of claims 1 to 16, wherein the organometallic impurity is selected from organometallic impurities of heavy metals, silicon, phosphorus, and arsenic.

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