Catalysts containing copper and Group IIIA elements

Abstract

The present invention relates to a catalyst comprising an active phase containing copper and Group IIIA elements, and an alumina support, wherein the copper content is 0.5% to 25% by weight of copper relative to the total weight of the catalyst, the atomic ratio of copper to Group IIIA elements is 1 mole / mol to 50 moles / mol, and the support is 10 to 250 m 2 It is characterized by being in the form of beads or extruded products having a specific surface area of ​​ / g.

Description

[Technical Field]

[0001] The present invention relates to a supported metal catalyst whose active phase is based on a Group IIIA element selected from copper, indium, and gallium, and is particularly intended for the hydrogenation of unsaturated hydrocarbons, and more specifically, for the selective hydrogenation of polyunsaturated compounds. [Background technology]

[0002] Monounsaturated organic compounds, such as ethylene and propylene, are sources for the production of polymers, plastics, and other value-added chemicals. These compounds are obtained from natural gas, naphtha, or gas oil, which have been treated by steam cracking or catalytic cracking. These methods are operated at high temperatures and yield, in addition to the desired monounsaturated compounds, polyunsaturated organic compounds, such as acetylene, propadiene and methylacetylene (or propyne), 1,2-butadiene and 1,3-butadiene, vinylacetylene and ethylacetylene, and other polyunsaturated compounds whose boiling points correspond to the C5+ gasoline fraction (gasoline containing hydrocarbon compounds with five or more carbon atoms), particularly styrene or indene compounds. These polyunsaturated compounds are highly reactive and lead to side reactions in polymerization units. Therefore, it is necessary to remove them before economic use of these fractions.

[0003] Selective hydrogenation is the primary treatment developed to specifically remove undesirable polyunsaturated compounds from these hydrocarbon feedstocks. This allows for the conversion of polyunsaturated compounds to their corresponding alkenes or aromatic compounds, while avoiding their total saturation and thus the formation of their corresponding alkanes or naphthenes.

[0004] The selective hydrogenation catalyst is generally based on a metal from Group VIII of the periodic table, preferably palladium or nickel. This metal is provided in the form of metal particles deposited on a support. The metal content, the size of the metal particles and the distribution of the active phase in the support are among the criteria related to the activity and selectivity of the catalyst.

[0005] Palladium catalysts are widely used in the selective hydrogenation reaction of C2-C4 light fractions.

[0006] Typically, the palladium content is low, generally less than 1 wt% of palladium relative to the catalyst. Palladium is distributed in the crust around the catalyst (referred to as an "egg-shell catalyst" as described in, for example, Patent Documents 1 and 2).

[0007] In recent years, the prices of precious metals, especially gold, ruthenium, platinum and palladium, have been rising. As a result, metal or multi-metal catalysts containing non-precious metals for the hydrogenation of acetylene and diolefins have been explored.

[0008] Therefore, the publication by Wang et al. (Non-Patent Document 1) describes the use of a catalyst containing iron supported on titanium oxide for the selective hydrogenation of butadiene to alkene at 175 °C.

[0009] Patent Document 3, which is a patent application, discloses the use of a catalyst containing a CuIn / ZrO2 alloy for the hydrogenation of CO2 to methanol. The catalyst is prepared by co-precipitation of the precursors of three elements.

[0010] Patent Document 4, which is a patent application, discloses the preparation of a catalyst for the hydrogenation of dimethyl oxalate. This catalyst contains a Cu-based active phase on a SiO2 support and is supplemented at a ratio of 0.2 to 1.5 based on the metal by another metal (or metal in the form of an oxide) selected from Ni, In, Mo, W, Fe, and Zn.

[0011] The publication by Onyestyak et al. (Non-Patent Document 2) describes the use of a γ-Al2O3-supported CuIn catalyst for the hydrogenation of organic acids. This catalyst contains 3 to 20% Cu and 3 to 20% In introduced by mechanical mixing. The catalyst is in powder form. The specific surface area is 203 m 2 / g.

[0012] The publication by Zhang et al. (Non-Patent Document 3) describes the use of a SiO2-supported CuIn catalyst for the hydrogenation of methyl acetate to ethanol. The addition of 0.2 to 2% indium is carried out on a catalyst containing 30% Cu / SiO2 corresponding to a Cu / In molar ratio of more than 66 mol / mol.

[0013] The publication by Dong et al. (Non-Patent Document 4) describes the use of a catalyst containing 10% Cu on SBA15-type silica and containing indium such that the Cu / In ratio is 0.01 to 15 for the hydrogenation of acetic acid to ethanol.

[0014] Surprisingly, the applicant has found that by using a catalyst for the selective hydrogenation of polyunsaturated compounds, which comprises an active phase containing copper and an element selected from Group IIIA, preferably an element selected from indium and gallium, and an alumina support in the form of beads or extrudates and having a specific surface area, a significant improvement in selectivity can be achieved while maintaining acceptable catalytic activity.

Prior Art Documents

Patent Documents

[0015]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

[0016] [Non-Patent Document 1] Wang et al., Chem. Commun., 2021, 57, 7031-7034. [Non-Patent Document 2] Onyestyak et al., Catalysis Communications, 2012, 26, 19-24 [Non-Patent Document 3] Zhang et al., Chinese Journal of Catalysis, 2018, 39, 99-108) [Non-Patent Document 4] Dong et al., Applied Catalysis B: Environmental, 2018, 244 [Overview of the Initiative] [Means for solving the problem]

[0017] (Subject of the invention) The first subject of the present invention is a catalyst comprising an active phase containing copper and a group IIIA element, and an alumina support, wherein the copper content is 0.5% to 25% by weight of copper relative to the total weight of the catalyst, and the atomic ratio of copper to group IIIA element is 1 to 50 mol / mol, wherein the support is 10 m 2 / g~250m 2 The present invention relates to a catalyst characterized by being provided in the form of beads or extruded objects having a specific surface area of ​​1 / g.

[0018] According to one or more embodiments of the present invention, the Group IIIA element is selected from indium or gallium.

[0019] According to one or more embodiments of the present invention, when the Group IIIA element is indium, the indium content is 0.02% to 25% by weight of indium relative to the total weight of the catalyst.

[0020] According to one or more embodiments of the present invention, when the Group IIIA element is gallium, the gallium content is 0.5% to 25% by weight of gallium relative to the total weight of the catalyst.

[0021] According to one or more embodiments of the present invention, when the Group IIIA element is indium, copper and indium exist in the form of an alloy.

[0022] According to one or more embodiments of the present invention, the carrier is an extruded product containing three or four leaves.

[0023] According to one or more embodiments of the present invention, the specific surface area of ​​the carrier is 160 m². 2 / g~210m 2 It is / g.

[0024] Another subject of the present invention relates to a method for preparing a catalyst according to the present invention, and includes the following steps: a) A process of providing alumina gel; b) A process of forming the alumina gel from step a); forming an alumina support; c) Perform the following steps to obtain the catalyst precursor: c1) A step of contacting an alumina support with a solution containing at least one precursor of the copper-active phase; c2) A step of contacting an alumina support with at least one solution containing at least one active phase precursor based on a group IIIA element: Steps c1) and c2) may be performed separately in either order or simultaneously; d) Dry the catalyst precursor obtained at the end of step c) at a temperature of less than 250°C; obtain the dried catalyst precursor.

[0025] According to one or more embodiments of the present invention, the molded alumina gel obtained at the end of step b) is subjected to a heat treatment including at least one hydrothermal treatment step in an autoclave at a temperature of 100°C to 800°C in the presence of an acid solution, followed by at least one calcination step at a temperature of 400°C to 1500°C after the hydrothermal treatment step to obtain an alumina support.

[0026] According to one or more embodiments of the present invention, if steps c1) and c2) are performed separately in either order, an intermediate drying step is performed between steps c1) and c2) or between steps c2) and c1), in which the catalyst precursor obtained at the end of step c1) or step c2) is dried at a temperature of less than 250°C.

[0027] According to one or more embodiments of the present invention, the catalyst precursor obtained at the end of the intermediate drying step is subjected to heat treatment at a temperature of 250°C to 1000°C.

[0028] In one or more embodiments of the present invention, steps c1) and c2) are performed simultaneously.

[0029] According to one or more embodiments of the present invention, the precursor of the copper active phase is selected from copper acetate, copper acetylacetonate, copper nitrate, copper sulfate, copper chloride, copper bromide, copper iodide, and copper fluoride.

[0030] According to one or more embodiments of the present invention, the Group IIIA element of the active phase is indium, and the precursor of the indium active phase is selected from indium acetate, indium acetylacetonate, indium nitrate, indium sulfate, indium sulfide, indium chloride, indium mercaptoacetate, indium bromide, indium iodide, indium fluoride, indium oxide, indium phosphide, and indium hydroxide.

[0031] According to one or more embodiments of the present invention, the Group IIIA element of the active phase is gallium, and the precursor of the gallium active phase is selected from gallium acetylacetonate, gallium nitrate, gallium sulfate, gallium sulfide, gallium chloride, gallium bromide, gallium iodide, gallium oxide, gallium nitride, gallium phosphide, gallium perchlorate, and organic precursors such as triethylgallium and trimethylgallium.

[0032] Another subject of the present invention relates to a method for the selective hydrogenation of polyunsaturated compounds containing at least 2 carbon atoms per molecule, which are contained in a hydrocarbon feedstock having a final boiling point of 300 °C or lower. When this method is carried out, the temperature is 0 °C to 300 °C, the pressure is 0.1 MPa to 10 MPa. When this method is carried out in the liquid phase, the molar ratio of hydrogen / (polyunsaturated compound to be hydrogenated) is 0.1 to 10, and the space-time velocity is 0.1 h -1 ~200 h -1 and when this method is carried out in the gas phase, the molar ratio of hydrogen / (polyunsaturated compound to be hydrogenated) is 0.5 to 1000, and the space-time velocity is 100 h -1 ~40,000 h -1 and it is carried out in the presence of a catalyst according to the present invention or a catalyst obtained by the preparation method according to the present invention.

Embodiments for Carrying Out the Invention

[0033] (Detailed Description of the Invention) (Definitions) In the following text, the groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, publisher CRC Press, editor-in-chief D. R. Lide, 81st edition, 2000 - 2001). For example, Group IIIA according to the CAS classification corresponds to the metals in column 13 according to the new IUPAC classification.

[0034] The specific surface area of ​​the BET (Bacterial Equivalent of Porous Solids) is measured by nitrogen physicoadsorption. The specific surface area of ​​the BET is measured by nitrogen physicoadsorption according to standard ASTM D3663-03, as described in Rouquerol F., Rouquerol J. and Sing K., “Adsorption by Powders & Porous Solids: Principle, Methodology and Applications”, Academic Press, 1999.

[0035] The total pore volume is measured by mercury porosimetry at a wetting angle of 140° according to standard ASTM D4284-92, for example, using an Autopore® III model device under the Micromeritics® brand.

[0036] The copper, indium, and gallium content is measured by X-ray fluorescence.

[0037] ( catalyst) (Catalytic active phase) The catalyst according to the present invention comprises an active phase containing copper and a group IIIA element, and an alumina support. The copper content is 0.5% to 25% by weight of copper relative to the total weight of the catalyst; the atomic ratio of copper to group IIIA element is 1 to 50 mol / mol. The catalyst is supported by a 10 m 2 / g~250m 2 It is characterized by being provided in the form of beads or extruded products having a specific surface area of ​​ / g.

[0038] The copper content in the catalyst, in the form of beads or extruded material, is 0.5% to 25% by weight, preferably 1% to 20% by weight, more preferably 2% to 18% by weight, more preferably 3% to 15% by weight, and even more preferably 5% to 15% by weight, relative to the total weight of the catalyst.

[0039] The content of Group IIIA elements in the catalyst is preferably 0.02% to 25% by weight, preferably 0.05% to 20% by weight, and more preferably 0.1% to 15% by weight, relative to the total weight of the catalyst.

[0040] The Group IIIA element is preferably selected from indium or gallium.

[0041] When the Group IIIA element is indium, the indium content is preferably 0.02% to 25% by weight, more preferably 0.05% to 20% by weight, and even more preferably 0.1% to 15% by weight, relative to the total weight of the catalyst.

[0042] When the Group IIIA element is gallium, the gallium content is preferably 0.5% to 25% by weight, more preferably 0.5% to 20% by weight, and even more preferably 1% to 15% by weight, relative to the total weight of the catalyst.

[0043] The atomic ratio of copper to group IIIA elements is 1 to 50 mol / mol, preferably 10 to 45 mol / mol, more preferably 15 to 45 mol / mol, and even more specifically 18 to 40 mol / mol. When the atomic ratio of copper to group IIIA elements is 10 to 45 mol / mol, preferably 15 to 45 mol / mol, and even more preferably 18 to 40 mol / mol, in addition to improved selectivity, the catalytic activity in the selective hydrogenation of polyunsaturated compounds is improved.

[0044] According to one or more embodiments, copper is uniformly distributed throughout the molded carrier.

[0045] According to one or more embodiments, the Group IIIA elements are preferably selected from indium and gallium and are uniformly distributed throughout the porous molded carrier.

[0046] In one embodiment of the present invention, the catalyst may include an alloy preferably containing copper and indium. In this embodiment, the average particle size of the metal crystallites containing copper and indium is advantageously 3.5 nm to 100 nm, preferably 4 nm to 50 nm.

[0047] The specific surface area of ​​the catalyst is advantageously 10 m². 2 / g~250m 2 / g, preferably 20m 2 / g~240m 2 / g, more preferably 40m 2 / g~230m 2 / g, more preferably 80ml 2 / g~220m 2 / g, even more preferably 160m 2 / g~210m 2 It is / g.

[0048] The total pore volume (TPV) of the catalyst is preferably 0.1 cm³. 3 / g~1.5cm 3 / g, preferably 0.2cm 3 / g~1.4cm 3 / g, more preferably 0.25cm 3 / g~1.3cm 3 It is / g.

[0049] (Catalyst support) The catalyst support according to the present invention is alumina, that is, the support contains at least 95% by weight, preferably at least 98% by weight, and particularly preferably at least 99% by weight of alumina relative to the weight of the support. Alumina generally has a δ-, γ-, or θ-alumina type crystallographic structure, either alone or in mixtures.

[0050] According to the present invention, the alumina support may contain impurities, such as metal oxides from Group IIA, Group IIIB, Group IVB, Group IIB, Group IIIA and Group IVA according to the CAS classification, preferably silica, titanium dioxide, zirconium dioxide, zinc oxide, magnesium oxide and calcium oxide, or alkali metals, preferably lithium, sodium or potassium, and / or alkaline earth metals, preferably magnesium, calcium, strontium or barium, or sulfur.

[0051] The specific surface area of ​​the carrier is 10 m². 2 / g~250m 2 / g, preferably 20m 2 / g~240m 2 / g, more preferably 40m 2 / g~230m 2 / g, more preferably 80ml 2 / g~220m 2 / g, even more preferably 160m 2 / g~210m 2 It is / g.

[0052] The total pore volume (TPV) of the porous support is preferably 0.1 cm³. 3 / g~1.5cm 3 / g, preferably 0.2cm 3 / g~1.4cm 3 / g, more preferably 0.25cm 3 / g~1.3cm 3 It is / g.

[0053] The carrier is supplied in either the form of beads or extruded material, the extruded material being advantageously tri-lobed or quadruple-lobed. When the carrier is supplied in the form of beads, the diameter of the beads is generally 1 mm to 10 mm, preferably 2 mm to 8 mm, and more preferably 2 mm to 6 mm. When the carrier is supplied in the form of tri-lobed extruded material, the length of the extruded material is generally 2 mm to 10 mm, preferably 2 mm to 8 mm, and more preferably 3 mm to 6 mm. When the carrier is supplied in the form of quadruple-lobed extruded material, the diameter of the extruded material is generally 0.5 mm to 10 mm, preferably 0.8 mm to 3.2 mm, and more preferably 1.0 mm to 2.5 mm, and the length is 0.5 mm to 2.0 mm.

[0054] (Preparation of catalyst) According to the present invention, a method for preparing a catalyst includes the following steps: a) A process of providing alumina gel; b) A process of forming the alumina gel from step a); obtaining an alumina support; c) Steps to obtain a catalyst precursor: c1) A step of contacting an alumina support with a solution containing at least one precursor of the copper-active phase; c2) A step of contacting an alumina support with at least one solution containing at least one active phase precursor based on a group IIIA element; Steps c1) and c2) may be performed separately in either order or simultaneously; d) The catalyst precursor obtained at the end of step c) is dried at a temperature of less than 250°C to obtain a dried catalyst precursor.

[0055] The different processes are described in detail below.

[0056] (Process a) Alumina gel) The alumina support contained in the catalyst according to the present invention is obtained from an alumina gel that essentially contains an aluminum oxy(hydroxide) (AlO(OH)) type precursor, also known as boehmite.

[0057] According to the present invention, alumina gel (or otherly known as boehmite gel) is synthesized by precipitation of aluminum salts from basic and / or acidic solutions induced by pH changes or any other method known to those skilled in the art (P. Euzen, P., Raybaud, X., Krokidis, H., Toulhoat, J.L. Le Loarer, J.P. Jolivet, and C. Froidefond, “Alumina”, in “Handbook of Porous Solids”, edited by F. Schuth, K.S. Wing, J. Weitkamp, ​​Wiley-V.C., Weinheim, Germany, 2002, pp. 1591-1677).

[0058] Precipitation reactions are generally carried out at temperatures of 5°C to 80°C and a pH of 6 to 10. Preferably, the temperature is 35°C to 70°C and the pH is 6 to 10.

[0059] According to one embodiment, an alumina gel is obtained by contacting an aqueous solution of an acidic salt of aluminum with a basic solution. For example, the acidic salt of aluminum is selected from the group consisting of aluminum sulfate, aluminum nitrate, or aluminum chloride, and preferably the acidic salt is aluminum sulfate. The basic solution is preferably selected from sodium hydroxide or potassium hydroxide.

[0060] Alternatively, an alkaline solution of an aluminum salt, which may be selected from the group consisting of sodium aluminate and potassium aluminate, may be brought into contact with an acidic solution. In a very preferred modification, the gel is obtained by bringing a sodium aluminate solution into contact with nitric acid. The concentration of the sodium aluminate solution is, advantageously, 10 -5 ~10 -1 mol·L -1 Preferably, this concentration is 10 -4 ~10 ー2 mol·L -1 That is the case.

[0061] According to another embodiment, an alumina gel is obtained by contacting an aqueous solution of an acidic salt of aluminum with an alkaline solution of an aluminum salt.

[0062] (Step b) Forming of the carrier) The carrier may be formed by any technique advantageously known to those skilled in the art. Forming may be achieved, for example, by kneading extrusion, by droplet coagulation (oil droplet) method, by rotary granulation, or by any other method known to those skilled in the art. The catalyst according to the present invention is produced and used in the form of an extruded product or beads. A forming method advantageous to the present invention is extrusion, and preferred extruded shapes are three-lobed or four-lobed.

[0063] In one particular embodiment, if the carrier is an extruded product, the alumina gel obtained at the end of step a) is subjected to a kneading step, preferably in an acidic medium. The acid used may be, for example, nitric acid. This step is carried out by known tools that enable the conversion of the gel into a product having the consistency of a paste, such as a Z-arm mixer, a grinding mixer, or a continuous single-screw or twin-screw mixer. According to one advantageous embodiment, one or more compounds called “pore-forming agents” are introduced into the kneading medium. These compounds have the property of decomposing upon heating and thus creating porosity in the carrier. For example, wood flour, charcoal, tar, and plastics can be used as pore-forming compounds. After kneading, the paste thus obtained is passed through an extrusion die.

[0064] After molding, the carrier is, in some cases, dried at a temperature of 50°C or higher but less than 250°C, preferably for a period of 4 to 16 hours.

[0065] The carrier obtained at the end of step b) is then, optionally, subjected to a hydrothermal treatment step, which can impart physical properties suitable for the intended application. The term “hydrothermal treatment” refers to treatment by autoclaving at a temperature above room temperature in the presence of water. During this hydrothermal treatment, the formed alumina may be treated in various ways. Therefore, the alumina can be impregnated with an acidic solution before autoclaving, and the hydrothermal treatment of the alumina can be carried out in either the vapor phase or the liquid phase, and this vapor phase or liquid phase of the autoclave can be acidic or non-acidic. This impregnation before hydrothermal treatment may be carried out dry or by immersing the alumina in an acidic aqueous solution. Dry impregnation is understood to mean contacting the alumina with a solution in a volume less than or equal to the total pore volume of the treated alumina. Preferably, the impregnation is carried out dry.

[0066] It is also possible to process the extruded carrier without pre-impregnation with an acidic solution, in which case the acidity is provided by an aqueous liquid in the autoclave. The acidic aqueous solution contains at least one acidic compound capable of dissolving at least a portion of the alumina in the extruded material. "An acidic compound capable of dissolving at least a portion of the alumina in the extruded material" is understood to mean any acidic compound that dissolves at least a portion of the aluminum ions when in contact with the alumina extruded material. Preferably, the acid should dissolve at least 0.5% by weight of alumina in the alumina extruded material.

[0067] Preferably, the acid is selected from strong acids such as nitric acid, hydrochloric acid, perchloric acid, sulfuric acid, or weak acids such as acetic acid, which are used at concentrations such that their aqueous solutions have a pH of less than 4, or mixtures of these acids.

[0068] According to a preferred embodiment, the hydrothermal treatment is carried out in the presence of nitric acid and acetic acid, either alone or as a mixture. The autoclave is preferably a rotating basket autoclave, such as the one defined in, for example, Japanese Patent Application EP-A-0 387 109.

[0069] The hydrothermal treatment may be carried out under saturated vapor pressure or under a partial pressure of water vapor equal to at least 70% of the saturated vapor pressure corresponding to the treatment temperature.

[0070] Preferably, the hydrothermal treatment is carried out at a temperature of 100°C to 800°C, preferably 200°C to 700°C, for a period of 30 minutes to 8 hours, and more preferably 30 minutes to 3 hours.

[0071] In some cases, the dried carrier is calcined at a temperature of 250°C to 1000°C, in or out of the presence of an airflow containing up to 150 grams of water per kilogram of dry air, preferably for a period of 3 to 8 hours.

[0072] At the end of step b), the obtained alumina support exhibits the specific texture characteristics described above.

[0073] (Step c) The support is brought into contact with the copper-active phase precursor. Step c) allows for the acquisition of a catalyst precursor and is characterized by the following procedure: c1) A step of contacting an alumina support with a solution containing at least one precursor of the copper active phase: c2) A step of contacting an alumina support with at least one solution containing at least one active phase precursor based on a group IIIA element: Steps c1) and c2) may be performed separately in either order or simultaneously.

[0074] Step c1) is characterized in that contact of the carrier with a solution containing a precursor of the copper-active phase can be achieved by dry impregnation, over-impregnation, or deposition-precipitation by methods well known to those skilled in the art. The pH of the solution can be modified by the addition of an optional acid or base.

[0075] The above step c1) is preferably carried out by impregnation of the carrier, and for example, by bringing the carrier into contact with at least one aqueous solution containing a copper precursor.

[0076] Preferably, step c1) is carried out by dry impregnation, which consists of contacting the carrier with at least one solution containing, preferably consisting of, at least one copper precursor, the volume of which is 0.25 to 1.5 times the pore volume of the carrier to be impregnated.

[0077] The copper precursor salt is preferably selected from copper acetate, copper acetylacetonate, copper nitrate, copper sulfate, copper chloride, copper bromide, copper iodide, or copper fluoride.

[0078] Preferably, the copper precursor salt is selected from copper nitrate, copper sulfate, or copper chloride.

[0079] The concentration of copper in the solution is adjusted according to the type of impregnation (dry impregnation or over-impregnation) and the pore volume of the support to obtain a copper content of 0.5% to 25% by weight, preferably 1% to 20% by weight, more preferably 2% to 18% by weight, more preferably 3% to 15% by weight, and even more preferably 5% to 15% by weight, relative to the total weight of the catalyst, for supported catalysts.

[0080] The aforementioned step c2) is characterized in that the contact of the support with a solution containing at least one precursor of a Group IIIA element, preferably selected from indium and gallium, by a method well known to those skilled in the art may be achieved by dry impregnation, over-impregnation, or deposition-precipitation.

[0081] Step c2) is carried out by impregnation of the molded carrier, which consists of contacting the carrier with at least one aqueous solution containing a precursor of a Group IIIA element, preferably selected from indium and gallium. The pH of the solution can be modified by the addition of an optional acid or base.

[0082] Preferably, step c2) is carried out by dry impregnation, which consists of contacting the carrier with at least one solution containing, preferably comprising, at least one precursor of a group IIIA element, preferably selected from indium and gallium, the volume of which is 0.25 to 1.5 times the pore volume of the carrier to be impregnated.

[0083] The indium precursor is preferably selected from indium acetate, indium acetylacetonate, indium nitrate, indium sulfate, indium sulfide, indium chloride, indium mercaptoacetate, indium bromide, indium iodide, indium fluoride, indium oxide, indium phosphide, and indium hydroxide.

[0084] The gallium precursor is selected from gallium acetylacetonate, gallium nitrate, gallium sulfate, gallium sulfide, gallium chloride, gallium bromide, gallium iodide, gallium oxide, gallium nitride, gallium phosphide, gallium perchlorate, and organic precursors, such as triethylgallium and trimethylgallium.

[0085] The concentration of the solution of a Group IIIA element, preferably selected from indium and gallium, is adjusted according to the type of impregnation (dry impregnation or over-impregnation) and the pore volume of the support, so that for supported catalysts, the content of a Group IIIA element, preferably selected from indium and gallium, is 0.02% to 25% by weight, preferably 0.05% to 20% by weight, and more preferably 0.1% to 15% by weight, relative to the total weight of the catalyst.

[0086] Similarly, the concentrations in solution of Group IIIA elements, preferably selected from indium and gallium, are provided such that the atomic ratio of copper to Group IIIA elements, preferably selected from indium and gallium, is 1 to 50 mol / mol, preferably 10 to 45 mol / mol, more preferably 15 to 45 mol / mol, and even more specifically 18 to 40 mol / mol.

[0087] If steps c1) and c2) are performed separately, an intermediate drying step is carried out between steps c1) and c2) or between steps c2) and c1) in which the catalyst precursor obtained at the end of step c1) or c2) is dried at a temperature of less than 250°C, preferably 70°C to 200°C. The drying time is generally 0.5 to 20 hours. Longer times are not ruled out, but do not necessarily result in any improvement.

[0088] Drying is generally carried out in combustion air containing hydrocarbons, preferably methane, or in heated air containing 0 to 80 grams of water per kilogram of combustion air, with an oxygen content of 5% to 25% by volume and a carbon dioxide content of 0% to 10% by volume.

[0089] In some cases, the catalyst precursor obtained at the end of the intermediate drying step is subjected to heat treatment in air, preferably combustion air, more preferably methane combustion air, the air containing 40 to 80 g of water per kg of air, with an oxygen content of 5 to 15 vol% and a CO2 content of 4 to 10 vol%. The calcination temperature is generally 250°C to 900°C, preferably about 300°C to about 500°C. The calcination time is generally 0.5 to 5 hours. The space-spatiotemporal velocity (HSV) is generally 150 to 3000 liters of combustion air per hour per volume of catalyst (liters), preferably 300 to 1500 liters.

[0090] In another embodiment, steps c1) and c2) are performed simultaneously. In this case, the impregnated carrier can be dried in step d).

[0091] (Step d) Dry the impregnated carrier. Step d), which involves drying the catalyst precursor obtained at the end of step c), is typically carried out at a temperature of less than 250°C, preferably 15–180°C, more preferably 30–160°C, even more preferably 50–150°C, and even more preferably 70–140°C, over a period of 10 minutes to 24 hours. Longer times are not ruled out, but do not necessarily result in any improvement.

[0092] The drying process can be carried out by any technique known to those skilled in the art. It is advantageously carried out in an inert atmosphere or an oxygen-containing atmosphere or a mixture of an inert gas and oxygen. It is advantageously carried out at atmospheric pressure or under reduced pressure. Preferably, this process is carried out at atmospheric pressure and in the presence of air or nitrogen.

[0093] (Heat treatment of dried catalyst (optional)) In some cases, the catalyst is calcined after drying (step d) in air, preferably in combustion air, more preferably in methane combustion air, where the air contains 40-80 g of water per kg of air, has an oxygen content of 5-15 vol%, and a CO2 content of 4-10 vol%. The calcination temperature is generally 250°C-900°C, preferably about 300°C-500°C. The calcination time is generally 0.5-5 hours. The space-spatiotemporal velocity (HSV) is generally 150-3000 liters of combustion air per hour and per volume (liters) of catalyst, preferably 300-1500 liters.

[0094] (Reduction by reducing gas (optional)) In some cases, the catalyst is reduced. This step is preferably carried out in situ, i.e., in the reactor where the catalyst conversion is performed, or ex situ, in the presence of a reducing gas. Preferably, this step is carried out at a temperature of 100°C to 600°C, more preferably 120°C to 500°C.

[0095] The reduction is carried out in the presence of a reducing gas containing 25% to 100% by volume of hydrogen, preferably 100% by volume of hydrogen. The hydrogen may be supplemented with an inert gas for reduction, preferably argon, nitrogen, or methane.

[0096] Reduction generally involves a warming phase followed by a plateau.

[0097] The plateau time in reduction is generally 1 to 10 hours, preferably 2 to 8 hours.

[0098] The space-spatiotemporal velocity (HSV) is generally 150 to 3000 liters of reducing gas per hour and per volume (liters) of catalyst, preferably 300 to 1500 liters.

[0099] (Selective hydrogenation method) Another subject of the present invention is a method for the selective hydrogenation of polyunsaturated compounds containing at least two carbon atoms per molecule, such as diolefins and / or acetylenes and / or alkenyl aromatic compounds (also known as styrene compounds), present in a hydrocarbon feedstock with a final boiling point of 300°C or less, wherein the temperature during the method is 0°C to 300°C, the pressure is 0.1 to 10 MPa, the molar ratio of hydrogen / (polyunsaturated compound to be hydrogenated) is 0.1 to 10 when the method is carried out in the liquid phase, and the spatiotemporal velocity is 0.1 to 200 h. -1 Furthermore, if this method is carried out in the gas phase, the molar ratio of hydrogen / (polyunsaturated compound to be hydrogenated) is 0.5 to 1000, and the spatiotemporal velocity is 100 to 40,000 h. -1 This is carried out in the presence of a catalyst according to the present invention or a catalyst prepared by the method according to the present invention described above.

[0100] Monounsaturated organic compounds, such as ethylene and propylene, are sources for the production of polymers, plastics, and other value-added chemicals. These compounds are obtained from natural gas, naphtha, or gas oils that have been treated by steam cracking or catalytic cracking. These methods are operated at high temperatures and yield, in addition to the desired monounsaturated compounds, polyunsaturated organic compounds, such as acetylene, propadiene and methylacetylene (or propyne), 1,2-butadiene and 1,3-butadiene, vinylacetylene and ethylacetylene, and other polyunsaturated compounds whose boiling points correspond to the C5+ fraction (hydrocarbon compounds having at least 5 carbon atoms), particularly diolefins or styrene or indene compounds. These polyunsaturated compounds are highly reactive and lead to side reactions in polymerization units. Therefore, it is necessary to remove them before economic use of these fractions.

[0101] Selective hydrogenation is a primary treatment developed to specifically remove undesirable polyunsaturated compounds from these hydrocarbon feedstocks. This allows for the conversion of polyunsaturated compounds to their corresponding alkenes or aromatic compounds while avoiding their total saturation and thus the formation of their corresponding alkanes or naphthenes. In cases where steam-cracked gasoline is used as feedstock, selective hydrogenation makes it possible to selectively hydrogenate alkenyl aromatic compounds to aromatic compounds while avoiding the hydrogenation of aromatic rings.

[0102] The hydrocarbon feedstock to be treated in the selective hydrogenation method has a final boiling point of 300°C or less, contains at least two carbon atoms per molecule, and contains at least one polyunsaturated compound. “Polyunsaturated compound” is understood to mean a compound having at least one acetylene functional group and / or at least one diene functional group and / or at least one alkenyl aromatic functional group.

[0103] More specifically, the raw materials used are steam-cracked gasoline, also known as pyrolytic gasoline, or C5+ fraction.

[0104] The steam-cracked gasoline or pyrolysis gasoline advantageously used in carrying out the selective hydrogenation method according to the present invention corresponds to a hydrocarbon fraction having a boiling point generally between 0 and 300°C, preferably between 10 and 250°C. The polyunsaturated hydrocarbons to be hydrogenated present in the steam-cracked gasoline are, in particular, diolefin compounds (butadiene, isoprene, cyclopentadiene, etc.), styrene compounds (styrene, α-methylstyrene, etc.), and indene compounds (indene, etc.). The steam-cracked gasoline generally contains a C5-C12 fraction together with trace amounts of C3, C4, C13, C14, and C15 (for example, 0.1% to 3% by weight for each of these fractions). For example, the composition of the feedstock formed from pyrolysis gasoline is generally as follows: 5% to 30% by weight of saturated compounds (paraffins and naphthenes), 40% to 80% by weight of aromatic compounds, 5% to 20% by weight of monoolefins, 5% to 40% by weight of diolefins, and 1% to 20% by weight of alkenyl aromatic compounds; these compounds together make up 100% by weight. It also contains 0 to 1000 ppm by weight of sulfur, preferably 0 to 500 ppm by weight of sulfur.

[0105] Technical implementation of the selective hydrogenation method is carried out, for example, by injecting polyunsaturated hydrocarbon feedstock and hydrogen in an upflow or downflow to at least one fixed-bed reactor. The reactor can be isothermal or adiabatic. An adiabatic reactor is preferred. The polyunsaturated hydrocarbon feedstock can be advantageously diluted by one or more reinjections of the effluent obtained from the reactor, in which the selective hydrogenation reaction takes place at various points in the reactor located between the reactor inlet and outlet, so as to limit the temperature gradient in the reactor. Technical implementation of the selective hydrogenation method according to the present invention can also be advantageously achieved via embedding of at least a supported catalyst in a reaction distillation column or exchanger reactor or slurry-type reactor. The hydrogen flow can be introduced simultaneously with and / or at one or more different points in the reactor to the feedstock to be hydrogenated.

[0106] In one embodiment of the present invention, when a selective hydrogenation method is performed, and the feedstock is steam-cracked gasoline containing a polyunsaturated compound, the molar ratio of (hydrogen) / (polyunsaturated compound to be hydrogenated) is generally 0.5 to 10, preferably 0.7 to 5.0, and more preferably 1.0 to 2.0; the temperature is 0°C to 200°C, preferably 20°C to 200°C, and more preferably 30°C to 180°C; and the space-spatiotemporal velocity (HSV) is generally 0.5 to 100 h. -1 Preferably 1 to 50 hours -1 The pressure is generally 0.3 MPa to 8.0 MPa, preferably 1.0 MPa to 7.0 MPa, and more preferably 1.5 MPa to 4.0 MPa.

[0107] More preferably, the feedstock is steam-cracked gasoline containing a polyunsaturated compound, the molar ratio of hydrogen to (polyunsaturated compound to be hydrogenated) is 0.7 to 5.0, the temperature is 20°C to 200°C, and the space-spatiotemporal velocity (HSV) is generally 1 to 50 h -1 Therefore, a selective hydrogenation method is performed with a pressure of 1.0 MPa to 7.0 MPa.

[0108] More preferably, the feedstock is steam-cracked gasoline containing a polyunsaturated compound, the molar ratio of hydrogen to (polyunsaturated compound to be hydrogenated) is 1.0 to 2.0, the temperature is 30°C to 180°C, and the space-spatiotemporal velocity (HSV) is generally 1 to 50 h. -1 Therefore, a selective hydrogenation method is performed with a pressure of 1.5 MPa to 4.0 MPa.

[0109] The hydrogen flow rate is adjusted to theoretically hydrogenate all of the polyunsaturated compound and to make enough hydrogen available to maintain an excess hydrogen at the reactor outlet.

[0110] (Examples) The present invention is illustrated here by the following examples, but these are not limiting.

[0111] (Example 1: Preparation of AL-1 alumina extruded material) The alumina gel is synthesized via a mixture of sodium aluminate and aluminum sulfate. The precipitation reaction is carried out at 60°C and pH 9 for 60 minutes with stirring at 200 rpm.

[0112] The resulting gel is kneaded in a Z-arm mixer to provide a paste. The paste is extruded by passing it through a die equipped with a 1.6 mm diameter trilobed orifice. The resulting extruded material is dried at 150°C for 12 hours and then calcined in a stream of dry air at 450°C for 5 hours. The dry air used in this example and all subsequent examples contains less than 5 grams of water per kilogram of air.

[0113] The specific surface area of ​​the AL-1 alumina support is 200 m². 2 The pore volume (determined by mercury porosimetry) is 0.85 mL / g, and the median mesopore diameter is 15 nm. Relative to the total weight of the carrier, the sodium content is 0.0350 wt%, and the sulfur content is 0.15 wt%.

[0114] (Example 2: Preparation of AL-2 alumina extruded material) The alumina gel is synthesized via a mixture of sodium aluminate and aluminum sulfate. The precipitation reaction is carried out at 50°C and pH 8.7 for 60 minutes with stirring at 200 rpm.

[0115] The resulting gel is kneaded in a Z-arm mixer to provide a paste. The paste is extruded by passing it through a die equipped with a 1.6 mm diameter trilobed orifice. The resulting extruded material is dried at 150°C for 12 hours and then baked in a stream of dry air at 450°C for 5 hours. The dry air used in this example and all subsequent examples contains less than 5 grams of water per kilogram of air.

[0116] The specific surface area of ​​the AL-2 alumina support is 300 m². 2 The pore volume (determined by mercury porosimetry) is 0.65 mL / g, and the median mesopore diameter is 8 nm. Relative to the total weight of the carrier, the sodium content is 0.0550 wt%, and the sulfur content is 0.20 wt%.

[0117] (Example 3: Preparation of a catalyst containing 10% Cu / AL-1 (not the present invention)) Dissolve 12.2 g of copper nitrate hydrate (Cu(NO3)2·2.5H2O, M=232.56 g / mol, 5.24 mmol) in 21 mL of deionized water at ambient temperature. This solution is then dropped onto 30 g of a pre-formed AL-1 carrier in a rotating coating pan at ambient temperature. Dry the material in air at 120°C for 16 hours, and then calcine it in an airflow at 400°C for 2 hours.

[0118] The copper content of catalyst A is 10% by weight relative to the total weight of the catalyst.

[0119] (Example 4: Preparation of a catalyst (not the present invention) containing 6.1% by weight of In / AL-1) Dissolve 6.7 g of indium nitrate hydrate (In(NO3)3·5H2O, M=391 g / mol, 1.71 mmol) in 21 mL of deionized water at ambient temperature. This solution is then dropped dropwise onto 30 g of pre-formed AL-1 carrier in a rotating coating pan at ambient temperature. Dry the material in air at 60°C for 12 hours, and then calcine it in a stream of air at 400°C for 2 hours.

[0120] The indium element content of catalyst B is 6.1% by weight relative to the total weight of the catalyst.

[0121] (Example 5: Preparation by co-impregnation of a catalyst containing 9.2 wt% Cu and 7.6 wt% In / AL-1 (Cu / In mol / mol ratio = 2.2, present invention)) Dissolve 9.3 g of indium nitrate hydrate (In(NO3)3·5H2O, M=391 g / mol, 2.37 mmol) and 12.2 g of copper nitrate hydrate (Cu(NO3)2·2.5H2O, M=232.6 g / mol, 5.24 mmol) in 21 mL of deionized water at ambient temperature. This solution is then dropped dropwise onto 30 g of pre-formed AL-1 carrier in a rotating coating pan at ambient temperature. Dry the material in air at 120°C for 16 hours, and then calcine it in an airflow at 400°C for 2 hours.

[0122] The copper content of catalyst C is 9.2% by weight relative to the total weight of the catalyst, and the indium content is 7.6% by weight relative to the total weight of the catalyst. The molar ratio of Cu / In is 2.2 mol / mol.

[0123] (Example 6: Preparation by co-impregnation of a catalyst containing 9.9 wt% Cu and 0.5 wt% In / AL-1 (Cu / In mol / mol ratio = 33, present invention)) Dissolve 0.6 g of indium nitrate hydrate (In(NO3)3·5H2O, M=391 g / mol, 0.15 mmol) and 12.2 g of copper nitrate hydrate (Cu(NO3)2·2.5H2O, M=232.6 g / mol, 5.24 mmol) in 21 mL of deionized water at ambient temperature. This solution is then dropped onto 30 g of a pre-formed AL-1 carrier in a rotating coating pan at ambient temperature. Dry the material in air at 120°C for 16 hours, and then calcine it in an airflow at 400°C for 2 hours.

[0124] The copper content of catalyst D is 9.9% by weight relative to the total weight of the catalyst, and the indium content is 0.5% by weight relative to the total weight of the catalyst. The molar ratio of Cu / In is 33 mol / mol.

[0125] (Example 7: Preparation by co-impregnation of a catalyst containing 9.9 wt% Cu and 0.5 wt% In / AL-2 (Cu / In mol / mol ratio = 33, not the present invention)) Dissolve 0.6 g of indium nitrate hydrate (In(NO3)3·5H2O, M=391 g / mol, 0.15 mmol) and 12.2 g of copper nitrate hydrate (Cu(NO3)2·2.5H2O, M=232.6 g / mol, 5.24 mmol) in 21 mL of deionized water at ambient temperature. This solution is then dropped dropwise onto 30 g of a pre-formed AL-2 carrier in a rotating coating pan at ambient temperature. Dry the material in air at 120°C for 16 hours, and then calcine it in an airflow at 400°C for 2 hours.

[0126] The copper content of catalyst E is 9.9% by weight relative to the total weight of the catalyst, and the indium content is 0.5% by weight relative to the total weight of the catalyst. The molar ratio of Cu / In is 33 mol / mol.

[0127] (Example 8: Catalyst Test: Performance in the selective hydrogenation of isoprene-containing mixtures) Catalysts A to E described in the above examples will be tested for the reaction of selective hydrogenation of isoprene.

[0128] The composition of the feedstock to be selectively hydrogenated is as follows: 10 wt% isoprene (supplied by Sigma Aldrich®, 99% purity) and 90 wt% n-heptane (solvent) (supplied by VWR®, >99% purity, Chromanorm HPLC). This composition corresponds to the initial composition of the reaction mixture.

[0129] The selective hydrogenation reaction is carried out in a 500 mL stainless steel autoclave. This autoclave is equipped with a magnetically driven mechanical stirrer and can be operated at a maximum pressure of 100 bar (10 MPa) and a temperature of 5°C to 200°C.

[0130] Before introducing the mixture into the autoclave, reduce 4 mL of catalyst (2.5-3 g) ex situ in a hydrogen stream of 1 L / h / g catalyst at 450°C for 2 hours (temperature gradient of 1°C / min), then remove the air and transfer to the autoclave. After adding 225 mL of n-heptane (153 g), close the autoclave, purge it, and then pressurize it with hydrogen to 35 bar (3.5 MPa) to reach the test temperature (90°C). At time t=0, introduce approximately 18 g of isoprene into the autoclave. The reaction mixture will have the above composition, and stirring will be started at 1600 rpm. Maintain a constant pressure of 35 bar (3.5 MPa) inside the autoclave using a storage cylinder located upstream of the reactor.

[0131] The progress of the reaction is monitored by taking samples of the reaction medium at regular time intervals: isoprene is hydrogenated to methylbutene. If the reaction is prolonged unnecessarily, methylbutene is hydrogenated to isopentane. Hydrogen consumption is also monitored over time through the decrease in pressure in a storage cylinder located upstream of the reactor. Catalytic activity is expressed as the number of moles of H2 consumed per minute and per weight (grams) of Cu.

[0132] The initial catalytic activity measured for catalysts A to E is reported in Table 1 below. These values ​​represent the conversion rate per second and per weight (grams) of catalyst. -3 It is expressed as moles of isoprene.

[0133] Activity = 10 -3 mol isoprene (initial) - mol isoprene (t) / t / mass of catalyst The isoprene conversion rate is determined according to the following formula.

[0134] Conversion rate (t, %) = 100 * [1 - (mol isoprene (t) / mol isoprene (initial))] Selectivity is expressed as selectivity for methylbutene.

[0135] Selectivity (%mol) = (methylbutene) / (methylbutene + isopentane) The selectivity of the catalysts for methylbutene will be compared using an 85% isoprene conversion rate.

[0136] [Table 1]

[0137] Monometallic catalyst B (not part of the present invention), which contains only indium, is inert in the reaction. Catalysts C and D of the present invention are highly selective in the selective hydrogenation of isoprene compared to catalyst A (not part of the present invention). The addition of indium makes it possible to reduce the amount of alkenes formed in the iso-conversion of isoprene. Furthermore, catalyst D exhibits very good activity, showing acceptable activity compared to catalyst C. Catalyst E is also active, having the same copper content, but is not selective at all. This is because the specific surface area of ​​alumina is too high, causing the copper and indium species to become isolated from each other. However, the selectivity achieved by the catalysts of the present invention is related to the strong interaction between copper and indium atoms.

Claims

1. A catalyst comprising an active phase containing copper and Group IIIA elements, and an alumina support, wherein the copper content is 0.5% to 25% by weight of copper relative to the total weight of the catalyst, the atomic ratio of copper to Group IIIA elements is 1 to 50 mol / mol, and the specific surface area of ​​the support is 10 m². ２ / g to 250m ２ A catalyst characterized by being provided in the form of beads or extruded products at a concentration of / g.

2. The catalyst according to claim 1, wherein the Group IIIA element is selected from indium or gallium.

3. The catalyst according to claim 1 or 2, wherein, when the group IIIA element is indium, the indium content is 0.02% to 25% by weight as indium relative to the total weight of the catalyst.

4. The catalyst according to claim 1 or 2, wherein, when the group IIIA element is gallium, the gallium content is 0.5% to 25% by weight as gallium element relative to the total weight of the catalyst.

5. The catalyst according to any one of claims 1 to 3, wherein, when the group IIIA element is indium, copper and indium exist in the form of an alloy.

6. The catalyst according to any one of claims 1 to 5, characterized in that the carrier is an extruded product containing three or four lobes.

7. The specific surface area of ​​the carrier is 160 m². ２ / g ~ 210m ２ The catalyst according to any one of claims 1 to 6, characterized in that it is / g.

8. A method for preparing a catalyst according to any one of claims 1 to 7, comprising the following steps: a) A step of providing alumina gel; b) A step of forming the alumina gel from step a); forming an alumina carrier; c) Steps to obtain a catalyst precursor: c1) A step of contacting an alumina support with a solution containing at least one precursor of the copper active phase; c2) A step of contacting an alumina support with at least one solution containing at least one active phase precursor based on a group IIIA element; Steps c1) and c2) may be performed separately or simultaneously, in either order; d) A step of drying the catalyst precursor obtained at the end of step c) at a temperature of less than 250°C; obtaining a dried catalyst precursor.

9. The method according to claim 8, wherein the molded alumina gel obtained at the end of step b) is subjected to a heat treatment including at least one hydrothermal treatment step in an autoclave in the presence of an acid solution at a temperature of 100°C to 800°C, and subsequently subjected to at least one calcination step at a temperature of 400°C to 1500°C performed after the hydrothermal treatment step to obtain the alumina carrier.

10. The method according to claim 8 or 9, wherein when steps c1) and c2) are performed separately in either order, an intermediate drying step is performed between step c1) and step c2) or between step c2) and step c1) to dry the catalyst precursor obtained at the end of step c1) or step c2) at a temperature of less than 250°C.

11. The method according to claim 10, wherein the catalyst precursor obtained at the end of the intermediate drying step is subjected to heat treatment at a temperature of 250°C to 1000°C.

12. The method according to claim 8 or 9, wherein steps c1) and c2) are performed simultaneously.

13. The method according to any one of claims 8 to 12, wherein the precursor of the copper active phase is selected from copper acetate, copper acetylacetonate, copper nitrate, copper sulfate, copper chloride, copper bromide, copper iodide, and copper fluoride.

14. The method according to any one of claims 8 to 13, wherein the group IIIA element of the active phase is indium, and the precursor of the indium active phase is selected from indium acetate, indium acetylacetonate, indium nitrate, indium sulfate, indium sulfide, indium chloride, indium mercaptoacetate, indium bromide, indium iodide, indium fluoride, indium oxide, indium phosphide, and indium hydroxide.

15. The method according to any one of claims 8 to 13, wherein the group IIIA element of the active phase is gallium, and the precursor of the gallium active phase is selected from gallium acetylacetonate, gallium nitrate, gallium sulfate, gallium sulfide, gallium chloride, gallium bromide, gallium iodide, gallium oxide, gallium nitride, gallium phosphide, gallium perchlorate, and organic precursors, such as triethylgallium and trimethylgallium.

16. A method for the selective hydrogenation of polyunsaturated compounds containing at least two carbon atoms per molecule, contained in a hydrocarbon feedstock with a final boiling point of 300°C or less, wherein the temperature during the method is 0°C to 300°C, the pressure is 0.1 MPa to 10 MPa, and when the method is carried out in the liquid phase, the molar ratio of hydrogen to (polyunsaturated compound to be hydrogenated) is 0.1 to 10, and the spatiotemporal velocity is 0.1 h. －１ ~200h －１ Furthermore, if this method is carried out in the gas phase, the molar ratio of hydrogen to (polyunsaturated compound to be hydrogenated) is 0.5 to 1000, and the spatiotemporal velocity is 100 h －１ ~40,000h －１ A method comprising the presence of a catalyst according to any one of claims 1 to 7 or a catalyst obtained by the preparation method according to any one of claims 8 to 15.

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