Coated hydrogenation catalyst

Abstract

An embodiment of the present disclosure relates to a coated hydrogenation catalyst comprising: a porous support and at least one metal supported on the porous support, wherein the porous support is made of silica, alumina, titania, or a combination thereof, and the at least one metal is selected from IUPAC Groups 6, 9, and 10 metals; a catalyst activator comprising at least one sulfur-containing compound, a catalyst deactivator comprising at least one nitrogen-containing compound, or both, loaded onto the pores of the porous support; and a coating layer on a surface of the hydrogenation catalyst, the coating layer encapsulating the catalyst activator, the catalyst deactivator, or both within the hydrogenation catalyst, the coating layer being made of a polymer or a paraffinic oil.

Description

Description of related applications

[0001] This application claims priority to U.S. Patent Application No. 17 / 165415, filed on 2 February 2021, entitled “Coated Hydrogenation Catalyst,” the entirety of which is incorporated herein by reference. [Technical Field]

[0002] Embodiments of the present disclosure broadly relate to coated hydrogenation catalysts having a coating layer that encapsulates a catalyst activator, a catalyst deactivator, or both within the hydrogenation catalyst. [Background technology]

[0003] Hydrogenation catalysts are used to remove impurities from hydrocarbon feedstocks, which are typically derived from crude oil distillation. Common impurities include sulfur compounds and nitrogen compounds. These impurities are catalytically converted to hydrogen sulfide and ammonia, and then removed from the hydrocarbon feedstock.

[0004] Generally, hydrogenation catalysts consist of a support on which metals such as molybdenum, tungsten, nickel, and cobalt are deposited. Conventional methods for preparing these hydrogenation catalysts are characterized by the fact that the support is compounded with the metal components, for example, by impregnation. These metal components are active only when they are in sulfide form. Therefore, hydrogenation catalysts are generally subjected to sulfidation treatment.

[0005] Conventional sulfidation processes include laboratory-based and in-situ sulfidation. Laboratory-based sulfidation processes take place outside the reactor where a catalyst is used to hydrogenate hydrocarbon raw materials. In such processes, the catalyst is brought into contact with a sulfur compound (catalyst activation precursor) outside the reactor, and the metal is converted into a metal sulfide. In-situ sulfidation processes take place inside the reactor where a catalyst is used to hydrogenate hydrocarbon raw materials. Here, the catalyst is brought into contact with a hydrogen gas stream mixed with a sulfidating agent (catalyst activation precursor) inside the high-temperature reactor, and the metal is converted into a metal effluent. In both laboratory-based and in-situ sulfidation processes, a catalyst activation precursor is required to activate the metal component in the catalyst. [Overview of the project] [Problems that the invention aims to solve]

[0006] Therefore, there is a continued need for hydrogenation catalysts with improved catalytic activity, while avoiding the excessive supply of catalyst activation and deactivation precursors. [Means for solving the problem]

[0007] Embodiments of this disclosure satisfy this need by encapsulating a catalyst activation precursor, a catalyst deactivation precursor, or both on the pores of the hydrogenation catalyst through a coating layer. This eliminates or significantly reduces the need to introduce the catalyst activation precursor and catalyst deactivation precursor into the purification process.

[0008] According to one or more aspects of the present disclosure, a coated hydrogenation catalyst is a hydrogenation catalyst comprising a porous support and at least one metal supported on the porous support, wherein the porous support is made of silica, alumina, titania, or a combination thereof, and the at least one metal is selected from metals of Groups 6, 9, and 10 of the International Union of Pure and Applied Chemistry (IUPAC); a catalyst activator comprising at least one sulfur-containing compound filled on the pores of the porous support, a catalyst deactivator comprising at least one nitrogen-containing compound, or both; and a coating layer on the surface of the hydrogenation catalyst, the coating layer encapsulating the catalyst activator, the catalyst deactivator, or both within the hydrogenation catalyst and comprising a coating layer made of a polymer or a paraffinic oil.

[0009] Additional features and advantages of the described embodiments are set forth in the following detailed description, some of which will be readily apparent to those skilled in the art from that description or will be recognized by practicing the described embodiments, which include the following detailed description and the claims.

Brief Description of the Drawings

[0010] The following detailed description of specific embodiments of the present disclosure can be best understood when read in conjunction with the accompanying drawings. [Figure 1] Generalized flowchart of a method for manufacturing an encapsulated hydrogenation catalyst according to one or more embodiments of the present disclosure [Figure 2] Generalized flowchart of another embodiment of a method for manufacturing an encapsulated hydrogenation catalyst according to one or more embodiments of the present disclosure [Figure 3] Graph showing thermogravimetric analysis (TGA) of Example 3 [Figure 4] Graph showing TGA of Examples 6 and 8. Here, for a detailed reference to various embodiments, some of which embodiments are shown in the accompanying drawings.

Modes for Carrying Out the Invention

[0011] As used in this disclosure, “catalyst” refers to any substance that increases the rate of a particular chemical reaction. The catalysts described in this disclosure can be used to accelerate a variety of reactions, including, but are not limited to, hydrocracking, hydrodemetallation, hydrodesulfurization, hydrodenitrification, hydrogenation, or combinations thereof. As used in this disclosure, “cracking” generally refers to a chemical reaction in which a molecule having a carbon-carbon bond is cleaved into multiple molecules by the cleavage of one or more carbon-carbon bonds, or a compound containing a cyclic part, such as an aromatic compound, is converted into a compound that does not contain a cyclic part. “Hydrocracking” refers to the decomposition of hydrocarbons in the presence of hydrogen.

[0012] As used in this disclosure, “catalytic activity” with respect to a hydrogenation catalyst refers to the ability of a hydrogenation catalyst to catalyze hydrogenation reactions, such as hydrocracking, hydrodemetallation, hydrodesulfurization, hydrodenitrification, and hydrogenation.

[0013] As used in this disclosure, “packed hydrogenation catalyst” refers to a catalyst comprising a hydrogenation catalyst and a catalyst activator, a catalyst deactivator, or both on the pores of the hydrogenation catalyst.

[0014] As used in this disclosure, “polymer” refers to polymer compounds prepared by polymerizing monomers, whether of the same or different types.

[0015] Coated hydrogenation catalyst Embodiments of the present disclosure relate to coated hydrogenation catalysts. The coated hydrogenation catalysts of the present disclosure are hydrogenation catalysts comprising a porous support and at least one metal supported on the porous support, wherein the porous support is made of alumina, silica, titania, or a combination thereof, and the at least one metal is a hydrogenation catalyst selected from Group 6, Group 9, and Group 10 metals of the International Union of Pure and Applied Chemistry (IUPAC); a catalyst activator comprising at least one sulfur compound, a catalyst deactivator comprising at least one nitrogen compound, or both, packed on the pores of the porous support; and a coating layer on the surface of the hydrogenation catalyst, which may include a coating layer made of a polymer, paraffinic oil, or both, encapsulating the catalyst activator, catalyst deactivator, or both within the hydrogenation catalyst. While not intended to be theoretically restrictive, encapsulating the hydrogenation catalyst with a coating layer reduces the need for additional catalyst deactivators because the coating layer slows down the desorption or decomposition of the catalyst deactivator packed on the porous support.

[0016] As mentioned earlier, the coated hydrogenation catalyst includes a hydrogenation catalyst. This hydrogenation catalyst may include a porous support and at least one metal.

[0017] The porous support may include alumina (Al2O3), silica (SiO2), titania (TiO2), zeolite, or a combination thereof. In one or more embodiments, the porous support may include zeolite. As used herein, "zeolite" refers to a porous crystalline aluminosilicate material. The zeolite of the present disclosure may have a FAU, MFI, MOR, or BEA structure type as defined by the Structure Commission of the International Zeolite Association (IZA). In one or more embodiments, the porous support may include alumina (Al2O3), silica (SiO2), titania (TiO2), or a combination thereof. The porous support may have an alumina to silica molar ratio of from 5 to 1000, from 5 to 500, from 5 to 300, from 5 to 200, from 5 to 100, from 2 to 1000, from 2 to 500, from 2 to 300, from 2 to 200, from 2 to 100, from 1 to 1000, from 1 to 500, from 1 to 300, from 1 to 200, or from 1 to 100.

[0018] The porous support may have a pore volume of from 0.4 ml / g to 1.5 ml / g, from 0.4 ml / g to 1.25 ml / g, from 0.4 ml / g to 1.0 ml / g, from 0.4 ml / g to 0.75 ml / g, or from 0.4 ml / g to 0.5 ml / g. The pore volume of the porous support can be measured by the Brunauer-Emmett-Teller ("BET") method, which measures the amount of nitrogen adsorbed on the support.

[0019] The porous support is up to 1000 square meters per gram (m 2 , 2 , 2 , 2 , 2 , 2 / g), or from 100 m 2 / g to 1000 m 2 / g, from 100 m 2 / g to 900 m 2 / g, from 100 m 2 / g to 800 m 2 / g, from 100 m 2 / g to 500 m 2 / g, from 120 m 2 / g to 1000 m 2 / g, from 120 m 2 / g to 900 m 2 / g, from 120 m 2 / g to 800 m2 / g, 120m 2 / g to 500m 2 / g, 150m 2 / g to 1000m 2 / g, 150m 2 / g to 900m 2 / g, 150m 2 / g to 800m 2 / g, 150m 2 / g to 500m 2 / g, 180m 2 / g to 1000m 2 / g, 180m 2 / g to 900m 2 / g, 180m 2 / g to 800m 2 / g, 180m 2 / g to 500m 2 / g, 200m 2 / g to 1000m 2 / g, 200m 2 / g to 900m 2 / g, 200m 2 / g to 800m 2 / g, or 200m 2 / g to 500m 2 It may have a surface area of ​​ / g. The binder is 100m 2 / g to 200m 2 / g, 100m 2 / g to 150m 2 / g, or 150m 2 / g to 200m 2 It may have a surface area of ​​ / g.

[0020] Porous carriers may have average pore diameters ranging from 10 angstroms (Å) to 10,000 Å, 10 Å to 9,000 Å, 10 Å to 8,000 Å, 10 Å to 5,000 Å, 50 Å to 10,000 Å, 50 Å to 9,000 Å, 50 Å to 8,000 Å, 50 Å to 5,000 Å, 100 Å to 10,000 Å, 100 Å to 9,000 Å, 100 Å to 8,000 Å, and 100 Å to 5,000 Å. This average pore diameter can be calculated using the formula Ps = 4V / S, where Ps = pore diameter, V = pore volume, and S = surface area.

[0021] Porous carriers can be formed into shapes selected from the group of spherical, cylindrical, trefoil, twisted trefoil, and tetrafoil forms. Examples of methods for forming porous carriers include extrusion, spray drying, granulation, agglomeration, and oil droplets. As used here, the "oil droplet" process refers to the process in which precipitation occurs when a liquid is poured into an immiscible liquid.

[0022] As mentioned earlier, at least one type of metal can be supported on a porous support. This at least one type of metal may include metals from IUPAC Group 6, Group 9, and Group 10. In some embodiments, the metals from IUPAC Group 6, Group 9, and Group 10 may include Co, Mo, Ni, W, or combinations thereof. In one embodiment, at least one type of metal may be in oxide form, such as CoO, MoO3, NiO, or WO3. In other embodiments, at least one type of metal may be in sulfide form, such as Co9S8, MoS2, Ni3S2, or WS2.

[0023] A hydrogenation catalyst may be a dual-function catalyst possessing both decomposition and hydrogenation functions. The decomposition function may be provided by decomposition components such as zeolites, alumina, silica, titania, or combinations thereof. The hydrogenation function may be provided by at least one metal, including metals of IUPAC Group 6, 9, and 10. In some embodiments, at least one metal can be added to a porous support by mixing or impregnation. For example, metals of IUPAC Group 6, 9, and 10 may be introduced into a porous support by mixing and converted in situ to oxides by calcination.

[0024] Hydrogenation catalysts can be used as catalysts in hydrogenation reactions. Examples of hydrocarbon feedstocks that can be treated with the hydrogenation catalysts described here include crude oil fractions such as naphtha, diesel, vacuum diesel, and vacuum residue, or intermediate refined flows such as deasphalt oil, coker naphtha, diesel, and fluid catalytic cracking circulating oil. In hydrogenation reactions, the main reactions may involve the removal of sulfur, nitrogen, and metals. Hydrogenation catalysts may have one or more functionalities: hydrodesulfurization (HDS), hydrodenitrification (HDN), or hydrodemetallation (HDM), hydrocracking (HCR), or hydrogenation (HYD).

[0025] In one or more embodiments, the hydrogenation catalyst may have an average cross-sectional dimension of 0.01 mm to 5.0 mm, 0.1 mm to 5.0 mm, 0.5 mm to 5.0 mm, 0.01 mm to 3.0 mm, 0.1 mm to 3.0 mm, 0.5 mm to 3.0 mm, 0.01 mm to 2.5 mm, 0.1 mm to 2.5 mm, 0.5 mm to 2.5 mm, 0.01 mm to 2.0 mm, 0.1 mm to 2.0 mm, or 0.5 mm to 2.0 mm. The cross-sectional dimension of the hydrogenation catalyst can be measured using transmission electron microscopy (TEM), dry sieving, or laser light scattering techniques.

[0026] As previously mentioned, the coated hydrogenation catalyst contains a catalyst activator, a catalyst deactivator, or both. The catalyst activator, catalyst deactivator, or both may be impregnated into or absorbed into the pores of the porous support.

[0027] Catalyst activators may include sulfur-containing compounds. In one embodiment, catalyst activators may include organic sulfides, organic disulfides, organic polysulfides, elemental sulfur, or their oxidized forms. For example, catalyst activators may include methanethiol, thiophene, dialkyl disulfide, diaryl disulfide, or combinations thereof. Dimethyl disulfide (DMDS) may be an example of a catalyst activator. Catalyst activators may include disulfide oils from mercaptan oxidation (Merox) units. Disulfide oils from Merox units may have the general formula RSS-R', where R and R' are alkyl groups having 1 to 20 carbon atoms. In some embodiments, this general formula may include DMDS.

[0028] Catalyst deactivators may include nitrogen-containing compounds. In one embodiment, an organic nitrogen compound may be used as the catalyst deactivator. For example, amines, carbazoles, indoles, quinolines, amides, acridines, anilines, ammonia, or their oxidized forms may be used as catalyst deactivators. Methyldiethanolamine (MDEA) may be used as a catalyst deactivator.

[0029] A coated hydrogenation catalyst may also include a coating layer. This coating layer can encapsulate a catalyst activator, a catalyst deactivator, or both within the hydrogenation catalyst.

[0030] The coating layer may contain a polymer, a paraffinic oil, or both. In one or more embodiments, the polymer may be a polymer material derived from olefins, carbonates, aromatic compounds, sulfones, fluorinated hydrocarbons, chlorinated hydrocarbons, acrylonitrides, or combinations thereof. The polymer material may be polystyrene, polyethylene, polypropylene, or combinations thereof. In one or more embodiments, the paraffinic oil may be N-paraffin wax having 20 to 50 carbon atoms.

[0031] In one or more embodiments, the coating layer may have an average thickness of 50 μm to 100 μm, 50 μm to 90 μm, 50 μm to 80 μm, 40 μm to 100 μm, 40 μm to 90 μm, or 40 μm to 80 μm.

[0032] In one or more embodiments, the coating layer may have a melting point up to 350°C, 20°C to 350°C, 30°C to 350°C, 40°C to 350°C, 50°C to 350°C, 100°C to 350°C, 20°C to 300°C, 30°C to 300°C, 40°C to 300°C, 50°C to 300°C, 100°C to 300°C, 20°C to 250°C, 30°C to 250°C, 40°C to 250°C, 50°C to 250°C, or 100°C to 250°C.

[0033] In one or more embodiments, the coated hydrogenation catalyst may have an average cross-sectional dimension of 0.05 mm to 6.0 mm, 0.06 mm to 6.0 mm, 0.1 mm to 6.0 mm, 0.5 mm to 6.0 mm, 0.05 mm to 3.0 mm, 0.06 mm to 3.0 mm, 0.1 mm to 3.0 mm, or 0.5 mm to 3.0 mm.

[0034] Method for producing a coated hydrogenation catalyst Further embodiments of this disclosure relate to a method for producing the encapsulated hydrogenation catalyst (coated hydrogenation catalyst) described above. As previously stated, an encapsulated hydrogenation catalyst can be produced by coating a hydrogenation catalyst to encapsulate the catalyst activation precursor, catalyst deactivation precursor, or both on the pores of the hydrogenation catalyst. Encapsulated hydrogenation catalysts produced by coating a hydrogenation catalyst with a polymer or paraffinic oil enable the preparation of a hydrogenation catalyst with improved catalytic activity without supplying an excess of the catalyst activation precursor, catalyst deactivation precursor, or both. While not intended to be theoretically restrictive, encapsulating the hydrogenation catalyst with a coating layer reduces the need for additional catalyst deactivators because the coating layer slows down the desorption or decomposition of the catalyst deactivator packed on the porous support.

[0035] The above method may include a step of preparing a hydrogenation catalyst comprising the porous support described above and at least one metal supported on the porous support. Referring to Figures 1 and 2, the preparation step may include a step of preparing a binder 110 and a step of preparing at least one of alumina, silica, titania, or a combination thereof. The binder can be mixed with at least one of alumina, silica, titania, or a combination thereof to produce a blend. This binder can hold the components of the hydrogenation catalyst together. Various binders are considered suitable. For example, binders may include clay, minerals, alumina, silica, titania, or a combination thereof. Kaolin may be an example of clay. Alumina may include attapulgite, boehmite, or one or more partially acid-peptized alumina.

[0036] In some embodiments, the zeolite may be prepared before mixing at least one of alumina, silica, titania, or a combination thereof with a binder, and then mixed with a blend containing at least one of alumina, silica, titania, or a combination thereof and a binder. In alternative embodiments, the zeolite may be added together with at least one of alumina, silica, titania, or a combination thereof.

[0037] Referring further to Figures 1 and 2, in some embodiments, the blend can be extruded to produce catalyst particles containing 300, zeolite, alumina, silica, titania, or a combination thereof. In other embodiments, the catalyst particles may be produced by spray drying, granulation, agglomeration, oil droplets, or a combination thereof. In some embodiments, the process of producing catalyst particles may include the process of producing a porous carrier. The porous carrier may be produced by precipitation, kneading, mixing 200, or a combination thereof. The kneaded or mixed carrier may be subjected to heat treatment at temperatures of 10°C to 50°C, 10°C to 40°C, 20°C to 50°C, or from 20°C. At least one metal may be added to the porous carrier by mixing or impregnation to produce catalyst particles. For example, at least one metal may be introduced into the porous carrier by mixing and converted in situ to an oxide form by calcination. Alternatively, at least one metal in oxide form may be introduced into the porous carrier by mixing to produce catalyst particles.

[0038] Catalyst particles can be calcined to produce calcined catalyst particles. The calcination temperature may range from 500°C to 650°C, or from 500°C to 600°C. The calcination process may last from 0.5 hours to 6 hours, from 0.5 hours to 3 hours, from 1 hour to 6 hours, or from 1 hour to 3 hours. The calcination process may be carried out in an oxygen-containing atmosphere.

[0039] Impregnated catalyst particles can be produced by impregnating calcined catalyst particles with at least one metal 500. The impregnation step 500 described herein is based on induce wetness impregnation of at least one metal. Other methods for impregnating calcined catalyst particles with at least one metal 500 may also be used, such as immersion impregnation and evaporation impregnation.

[0040] Alternatively, the calcined catalyst particles can be brought into contact with a solution containing at least one metal. As previously mentioned, the at least one metal may be a metal from IUPAC Group 6, Group 9, or Group 10. In some embodiments, the metals from IUPAC Group 6, Group 9, or Group 10 may be Co, Mo, Ni, W, or a combination thereof. In one embodiment, the at least one metal may be in oxide form, such as CoO, MoO3, NiO, or WO3. In other embodiments, the at least one metal may be in sulfide form, such as Co9S8, MoS2, Ni3S2, or WS2.

[0041] The calcined catalyst particles can be brought into contact with a solution under ambient conditions. The solution may be mixed for a period of time before the calcined catalyst particles are brought into contact with the solution. After contacting the calcined catalyst particles with a solution containing at least one metal, excess liquid such as the solution or solvent can be removed from the mixture to produce impregnated catalyst particles. The step of removing the liquid component may include removing excess solution from the impregnated catalyst particles and drying the impregnated catalyst particles. The step of removing excess solution from the impregnated catalyst particles may include decantation, filtration, vacuum filtration, or a combination thereof of the mixture. In some embodiments, drying may be carried out at temperatures of 50°C to 200°C, 50°C to 180°C, 50°C to 150°C, 100°C to 200°C, 100°C to 180°C, or 100°C to 150°C. The drying period may be 3 hours to 30 hours, 3 hours to 20 hours, or 3 hours to 10 hours.

[0042] In one or more embodiments, the step 500 of impregnating with calcined catalyst particles may be carried out at a temperature of 20°C to 40°C, 20°C to 35°C, or 20°C to 30°C. In one or more embodiments, the step 500 of impregnating with calcined catalyst particles may be carried out at a pressure of 0.5 bar (50 kPa) to 3 bar (300 kPa), 0.5 bar (50 kPa) to 2.5 bar (250 kPa), 1 bar (100 kPa) to 3 bar (300 kPa), 1 bar (100 kPa) to 2.5 bar (250 kPa), 1.5 bar (150 kPa) to 3 bar (300 kPa), or 1.5 bar (150 kPa) to 2.5 bar (250 kPa).

[0043] The impregnated catalyst particles can be calcined to produce a hydrogenation catalyst. The calcination temperature may range from 500°C to 700°C, 500°C to 650°C, or 500°C to 600°C. The calcination time may range from 0.5 hours to 6 hours, 0.5 hours to 5 hours, 0.5 hours to 3 hours, 1 hour to 6 hours, 1 hour to 5 hours, or 1 hour to 3 hours. The calcination process may be carried out in an oxygen-containing atmosphere.

[0044] The method described above may further include a step of applying a catalyst activation precursor, a catalyst deactivation precursor, or both, to the pores of a hydrogenation catalyst to form a packed hydrogenation catalyst. In some embodiments, the catalyst activation precursor, the catalyst deactivation precursor, or both may be packed into the pores of a porous support, on the surface of the porous support, or both. Once the catalyst activation precursor and the catalyst deactivation precursor are packed into the pores of the porous support, on the surface of the porous support, or both, they can constitute a catalyst activator and a catalyst deactivator, respectively.

[0045] The catalyst activation precursor, catalyst deactivation precursor, or both may be applied for a sufficiently long period of time to achieve sufficient adsorption or desorption of the catalyst activation precursor, catalyst deactivation precursor, or both into the pores of the porous support, on the surface of the porous support, or both. In some embodiments, the catalyst activation precursor, catalyst deactivation precursor, or both may be applied in the gas phase, liquid phase, or gas-liquid phase.

[0046] Referring further to Figures 1 and 2, in one or more embodiments, the process may include impregnating the hydrogenation catalyst with a catalyst activation precursor, a catalyst deactivation precursor, or both to produce a packed hydrogenation catalyst. The process described herein is based on the impregnation of the catalyst activation precursor, a catalyst deactivation precursor, or both into the pores of a porous support, on the surface of the porous support, or both. Other methods for impregnating the hydrogenation catalyst with a catalyst activation precursor, a catalyst deactivation precursor, or both, such as immersion impregnation or evaporation impregnation, may also be used.

[0047] The impregnation step 700 may include contacting the hydrogenation catalyst with a solution containing a catalyst activation precursor, a catalyst deactivation precursor, or both. As previously mentioned, the catalyst activation precursor may include sulfur-containing compounds. In one embodiment, the catalyst activation precursor may be an organic sulfide, organic disulfide, organic polysulfide, elemental sulfur, or an oxidized form thereof. For example, the catalyst activation precursor may be methanethiol, thiophene, dialkyl disulfide, diaryl disulfide, or a combination thereof. Dimethyl disulfide (DMDS) may be an example of a catalyst activation precursor. The catalyst activation precursor may include a disulfide oil from a Merox unit. The disulfide oil from a Merox unit may have the general formula RSS-R', where R and R' are alkyl groups having 1 to 20 carbon atoms. In some embodiments, this general formula may include DMDS. The catalyst deactivation precursor may include a nitrogen-containing compound. In one embodiment, the catalyst deactivation precursor may be an organic nitrogen compound. For example, catalyst deactivation precursors could include amines, carbazoles, indoles, quinolines, amides, acridines, anilines, ammonia, or their oxidized forms. Methyldiethanolamine (MDEA) could also be considered a catalyst deactivation precursor.

[0048] In one or more embodiments, the impregnation step 700 may be carried out at temperatures of 20 to 80 degrees Celsius, 20 to 75 degrees Celsius, 20 to 70 degrees Celsius, 25 to 80 degrees Celsius, 25 to 75 degrees Celsius, 25 to 70 degrees Celsius, 30 to 80 degrees Celsius, 30 to 75 degrees Celsius, or 30 to 70 degrees Celsius. In one or more embodiments, the impregnation process 700 may be carried out at a pressure of 1 bar (100 kPa) to 3 bar (300 kPa), 1 bar (100 kPa) to 2.5 bar (250 kPa), 1 bar (100 kPa) to 2 bar (200 kPa), 1.5 bar (150 kPa) to 3 bar (300 kPa), 1.5 bar (150 kPa) to 2.5 bar (250 kPa), or 1.5 bar (150 kPa) to 2 bar (200 kPa).

[0049] The hydrogenation catalyst may be brought into contact with the solution under ambient conditions. Before bringing the hydrogenation catalyst into contact with the solution, the solution may be mixed for a period of time. The mixture containing the hydrogenation catalyst dispersed in the solution may be mixed for a sufficiently long period of time to allow sufficient adsorption or desorption of the catalyst activation precursor, catalyst deactivation precursor, or both into the pores of the porous support, on the surface of the porous support, or both.

[0050] A hydrogenation catalyst can be brought into contact with a solution containing a catalyst activation precursor, a catalyst deactivation precursor, or both, and then excess liquid, such as the solution or solvent, can be removed from the mixture to produce a filled hydrogenation catalyst. The step of removing the liquid component may include removing excess solution from the filled hydrogenation catalyst and drying the filled hydrogenation catalyst. The step of removing excess solution from the filled hydrogenation catalyst may include decantation, filtration, vacuum filtration, or a combination thereof, of the mixture. In some embodiments, drying may be carried out at temperatures of 50°C to 200°C, 50°C to 180°C, 100°C to 200°C, or 100°C to 180°C. The drying period may be 3 hours to 30 hours, 3 hours to 20 hours, or 3 hours to 10 hours.

[0051] In some embodiments, the process may include spraying a catalyst activation precursor, a catalyst deactivation precursor, or both onto the hydrogenation catalyst. For example, the catalyst activation precursor, the catalyst deactivation precursor, or both may be sprayed onto the hydrogenation catalyst on a conveyor belt. In one or more embodiments, the process may include pouring a catalyst activation precursor, a catalyst deactivation precursor, or both onto the hydrogenation catalyst. In one or more embodiments, the process may include immersing the hydrogenation catalyst in the catalyst activation precursor, the catalyst deactivation precursor, or both. The liquid may be drained from the immersed hydrogenation catalyst. In one or more embodiments, the process may include soaking the hydrogenation catalyst in the catalyst activation precursor, the catalyst deactivation precursor, or both. The liquid may be drained from the immersed hydrogenation catalyst.

[0052] In some embodiments, when the catalyst activation precursor is packed into the pores of the hydrogenation catalyst, on the surface of the hydrogenation catalyst, or both, at least one metal contained in the hydrogenation catalyst may be a sulfide to maximize the hydrodesulfurization (HDS), hydrodenitrification (HDN), hydrodemetallation (HDM), hydrocracking (HCR), and hydrogenation (HYD) functionality. The sulfidation treatment may be carried out in situ or in a laboratory setting. In-situ sulfidation may be carried out by treating at least one metal in oxide form with the catalyst activation precursor in the presence of hydrogen. The catalyst activation precursor may produce hydrogen sulfide, which converts the metal oxide into metal sulfides such as Co9S8, MoS2, Ni3S2, and WS2. In some embodiments, in-situ sulfidation may be carried out under hydrogen pressure. In one or more embodiments, in-situ sulfidation may be carried out at temperatures of 20°C to 250°C, 20°C to 200°C, 30°C to 250°C, or 30°C to 200°C. In one or more embodiments, in-facility sulfidation may be carried out by providing an organic polysulfide as a catalyst activation precursor. Examples of organic polysulfides include dialkyl polysulfides having the formula R-Sn-R', where R and R' are alkyls having 1 to 20 carbon atoms, and n is a number in the range of 3 to 10. In some embodiments, di-tert-butyl polysulfide (TBPS454) may be an example of an organic polysulfide. In other embodiments, the hydrogenation catalyst may be impregnated with elemental sulfur at a temperature below the melting point of sulfur. Under these conditions, the sulfur may sublimate and be substantially incorporated into the pores of the hydrogenation catalyst. Sulfur-impregnated catalysts can be brought into contact with a hydrocarbon solvent to pre-wet the mixture and react to convert metal oxides into metal sulfides.

[0053] In some embodiments, when the catalyst deactivation precursor is packed into the pores of the hydrogenation catalyst, on the surface of the hydrogenation catalyst, or both, the catalyst deactivation precursor may modulate the activity of the hydrogenation catalyst. In some embodiments, nitrogen may be injected into the reactor in the form of aqueous ammonia or anhydrous ammonia to modulate the activity of the hydrogenation catalyst. In some embodiments, to minimize the hazardous situations of high-pressure ammonia injection, such as ammonia leaking or overflowing from a tank or pipe, the catalyst deactivation precursor may contain methyldiethanolamine (MDEA). For example, when injected into the reactor at a temperature above 180°C in the presence of hydrogen, the amine may readily decompose to form ammonia necessary to deactivate the hydrogenation catalyst.

[0054] Referring to Figure 2, the method further includes the step of coating the packed hydrogenation catalyst with a coating material 710 to produce an encapsulated hydrogenation catalyst 800. The step of coating the packed hydrogenation catalyst with a coating material containing a polymer or paraffinic oil 710 can create a coating layer on the packed hydrogenation catalyst. As mentioned earlier, the polymer may be a polymer material derived from olefins, carbonates, aromatic compounds, sulfones, fluorinated hydrocarbons, chlorinated hydrocarbons, acrylonitrides, or combinations thereof. The polymer material may be polystyrene, polyethylene, polypropylene, or combinations thereof. The paraffinic oil may be N-paraffin wax with 20 to 50 carbon atoms.

[0055] The process of coating the filled hydrogenation catalyst 710 may be carried out by spraying a coating material onto the filled hydrogenation catalyst.

[0056] In some embodiments, the coating layer may completely surround the packed hydrogenation catalyst. The coating layer may completely surround the hydrogenation catalyst, a catalyst activation precursor, a catalyst deactivation precursor, or a combination thereof.

[0057] In one or more embodiments, the coating layer may have an average thickness of 50 μm to 100 μm, 50 μm to 90 μm, 50 μm to 80 μm, 40 μm to 100 μm, 40 μm to 90 μm, or 40 μm to 80 μm. [Examples]

[0058] The following embodiments illustrate one or more additional features of the present disclosure. It should be understood that these embodiments are not intended to limit the scope of the present disclosure or the accompanying claims in any way.

[0059] Example 1 - Hydrogenation Catalyst A hydrogenation catalyst was prepared from 30% by mass of zeolite and 70% by mass of binder. USY zeolite having a FAU structure was used as the zeolite, and alumina was used as the binder. The zeolite and binder were mixed to form a support. This support was then mixed with 4% by mass of nickel and 16% by mass of molybdenum, respectively, based on the total amount of the support. The mixture was extruded and dried at 130°C for 20 hours, and then calcined at 600°C for 1 hour to produce the hydrogenation catalyst.

[0060] Example 2 - DMDS-filled hydrogenation catalyst The hydrogenation catalyst was dried in a furnace at 150°C for 1 hour to remove volatile substances. 2.5 grams (g) of the dried hydrogenation catalyst was mixed with an aliquot of dimethyl disulfide (DMDS) as a catalyst activation precursor. 1.6 g of DMDS was absorbed into the pores of the hydrogenation catalyst to produce a packed hydrogenation catalyst.

[0061] Example 3 - TGA of DMDS-filled hydrogenation catalyst A 10 mg pre-packed hydrogenation catalyst was analyzed by thermogravimetric analysis (TGA) under a gaseous flow. TGA data was obtained using TA Instruments (model number TGA Q500) at a heating rate of 20 °C / min over a range of 25 to 900 °C. As shown in Figure 3, based on the total amount of DMDS and hydrogenation catalyst, only 1 mass% of DMDS was released at 50 °C, 5 mass% at 100 °C, and then 10 to 12 mass% of DMDS were released from the pre-packed hydrogenation catalyst at 300 °C. After 300 °C, the curve flattens, indicating that all of the DMDS were desorbed and / or decomposed under a gaseous flow.

[0062] Example 4 - Encapsulated DMDS-filled hydrogenation catalyst (coated hydrogenation catalyst) A 4.1 g DMDS-filled hydrogenation catalyst was coated with 0.26 g n-paraffin wax. The coating layer encapsulated the DMDS on the pores of the filled hydrogenation catalyst.

[0063] Example 5 - TBA-filled hydrogenation catalyst The hydrogenation catalyst was dried in a furnace at 150°C for 1 hour to remove volatile substances. An aliquot of t-butylamine (TBA) was added to 6.4 grams (g) of the dried hydrogenation catalyst as a catalyst activation precursor. 2.5 g of TBA was absorbed into the pores of the hydrogenation catalyst to produce a pre-filled hydrogenation catalyst.

[0064] Example 6 - TGA of TBA-filled hydrogenation catalyst In Example 6, 40.35 mg of the pre-packed hydrogenation catalyst from Example 5 was analyzed by TGA under a flow of air. TGA data was obtained using TA Instruments (model number TGA Q500) at a heating rate of 20°C / min over a range of 25 to 900°C. As shown in Figure 4, based on the total amount of TBA and hydrogenation catalyst, only 0.94 mass% of TBA was released at 50°C, 4.4 mass% at 100°C, and then 13 to 14 mass% of TBA was released from the pre-packed hydrogenation catalyst at 310°C. After 310°C, the curve flattens, indicating that all of the TBA was desorbed and / or decomposed under a flow of air.

[0065] Example 7 - Encapsulated TBA-filled hydrogenation catalyst (coated hydrogenation catalyst) In Example 7, 15.9 g of TBA-filled hydrogenation catalyst was coated with 0.8 g of n-paraffin wax. The coating layer encapsulated the TBA on the pores of the filled hydrogenation catalyst.

[0066] Example 8 - TGA of encapsulated and filled hydrogenation catalyst In Example 8, the 40.35 mg pre-packed hydrogenation catalyst from Example 7 was analyzed by TGA under a stream of air. TGA data was obtained using TA Instruments (model number TGA Q500) at a heating rate of 20°C / min over a range of 25 to 900°C. As shown in Figure 4, based on the total amounts of TBA, hydrogenation catalyst, and n-paraffin wax, only 0.21 mass% of TBA was released at 50°C, 0.81 mass% at 100°C, and then around 650°C, 15.0 mass% of TBA and paraffin wax were released from the coated hydrogenation catalyst. After 650°C, the curve flattens, indicating that all of the TBA and wax were desorbed and / or decomposed under a stream of air.

[0067] A first aspect of the present disclosure relates to a coated hydrogenation catalyst comprising a porous support and at least one metal supported on the porous support, wherein the porous support is made of silica, alumina, titania, or a combination thereof, and the at least one metal is selected from metals of IUPAC Group 6, Group 9, and Group 10; a catalyst activator comprising at least one sulfur-containing compound, a catalyst deactivator comprising at least one nitrogen-containing compound, or both, packed into the pores of the porous support; and a coating layer on the surface of the hydrogenation catalyst, the coating layer being made of a polymer or paraffinic oil, which encapsulates the catalyst activator, catalyst deactivator, or both within the hydrogenation catalyst.

[0068] A second aspect of this disclosure may include the first aspect, wherein the catalyst activator, catalyst deactivator, or both are impregnated into or absorbed into the pores of a porous carrier.

[0069] A third aspect of this disclosure may include either one of the first or second aspects, wherein at least one metal exists in the form of an oxide or a sulfide.

[0070] A fourth aspect of this disclosure may include any one of the first to third aspects, wherein the metals of IUPAC Group 6, Group 9, and Group 10 include Co, Mo, Ni, W, or combinations thereof.

[0071] A fifth aspect of this disclosure may include any one of the first to fourth aspects, wherein the hydrogenation catalyst has an average cross-sectional dimension of 0.01 millimeters (mm) to 5.0 mm.

[0072] A sixth aspect of this disclosure may include any one of the first to fifth aspects, wherein the porous carrier comprises a zeolite having a FAU, MFI, MOR, or BEA structure.

[0073] A seventh aspect of this disclosure may include any one of the first to sixth aspects, wherein the coating layer has a thickness of 50 micrometers (μm) to 100 μm.

[0074] An eighth aspect of this disclosure may include any one of the first to seventh aspects, wherein the catalyst activator comprises at least one of an organic sulfide, organic disulfide, organic polysulfide, or elemental sulfur.

[0075] A ninth aspect of this disclosure may include any one of the first to eighth aspects, wherein the catalyst activator includes methanethiol, thiophene, dialkyl disulfide, diaryl disulfide, or a combination thereof.

[0076] A tenth aspect of this disclosure may include any one of the first to ninth aspects, wherein the catalyst activator comprises dimethyl disulfide (DMDS).

[0077] An eleventh aspect of this disclosure may include any one of the first to tenth aspects, wherein the catalyst deactivator comprises an organic nitrogen-containing compound.

[0078] A twelfth aspect of this disclosure may include any one of the first to eleventh aspects, wherein the catalyst deactivator includes amines, carbazoles, indoles, quinolines, amides, acridines, anilines, ammonia, or their oxidized forms.

[0079] A thirteenth aspect of this disclosure may include any one of the first to twelfth aspects, wherein the catalyst deactivator comprises methyldiethanolamine (MDEA).

[0080] A fourteenth aspect of this disclosure may include any one of the first to thirteenth aspects, wherein the polymer comprises polymer materials derived from olefins, carbonates, aromatic compounds, sulfones, fluorinated hydrocarbons, chlorinated hydrocarbons, acrylonitrides, or combinations thereof.

[0081] A fifteenth aspect of this disclosure may include any one of the first to fourteenth aspects, wherein the paraffinic oil comprises N-paraffin wax having 20 to 50 carbon atoms.

[0082] Note that the term “wherein,” “where,” or “in which”” may be used as a transitional clause in one or more of the following claims. Note that for the purposes of defining this Art, this term is introduced into the claims as an unrestricted transitional clause used to introduce an enumeration of a set of structural features and should be interpreted similarly to the more commonly used unrestricted postscript “comprising.” For the purposes of defining this Art, the transitional clause “consisting of” may be introduced into the claims as a closed preamble term that limits the scope of the claim to the enumerated components or processes and naturally occurring impurities. For the purposes of defining this Art, the transitional clause “consisting essentially of” may be introduced into the claims to limit the scope of one or more claims to the enumerated elements, components, materials, or processes of a method, as well as to unenumerated elements, components, materials, or processes of a method that do not materially affect the novel features of the subject matter of the claim. The transitional phrases “comprising” and “substantially consisting of” can be interpreted as part of unrestrictive transitional phrases such as “comprising” and “including,” and therefore, the use of unrestrictive phrases to introduce an enumeration of a set of elements, components, materials, or processes should also be interpreted as disclosing an enumeration of a set of elements, components, materials, or processes using the closed terms “comprising” and “substantially consisting of.” For example, a description of a composition “comprising” components A, B, and C should also be interpreted as disclosing a composition “comprising” components A, B, and C, as well as a composition “substantially consisting of” components A, B, and C. Any quantitative values ​​expressed in this application are considered to include unrestrictive embodiments that coincide with the transitional phrases “comprising” and “including,” as well as closed or partially closed embodiments that coincide with the transitional phrases “comprising” and “substantially consisting of.”

[0083] As used herein and in the accompanying claims, nouns include multiple subjects unless the context clearly indicates otherwise. The verb “comprises” and its conjugations should be interpreted as referring to elements, components, or processes in a non-exclusive manner. The elements, components, or processes referred to may exist, be utilized, or be combined with other elements, components, or processes not expressly mentioned.

[0084] Furthermore, where quantities, concentrations, or other values ​​or parameters are given as a range, a preferred range, or a list of preferred upper and lower limits, this should be understood to specifically disclose all ranges formed from any pair of upper or preferred values ​​of any range and lower or preferred values ​​of any range, regardless of whether the ranges are disclosed separately. Where numerical ranges are enumerated herein, unless otherwise specified, the range is intended to include its endpoints and all integers and fractions within that range. The ranges of the present invention are not intended to be limited to specific values ​​enumerated when defining ranges. Where a component is indicated to exist in a range starting from 0, such a component is an optional component (i.e., it may or may not exist). If an optional component is present, it may be at least 0.1% by mass of the composition or copolymer.

[0085] Where a material, method, or apparatus is described herein using the terms “known to those skilled in the art,” “prior art,” or synonyms or phrases thereof, such terms indicate that the material, method, and apparatus described herein are those prior art at the time of filing of this application.

[0086] Any two quantitative values ​​given to a property may constitute a range for that property, and it should be understood that all combinations of ranges formed from all listed quantitative values ​​for a given property are conceivable in this disclosure. The subject matter of this disclosure has been described in detail and with reference to specific embodiments. It should be understood that no detailed description of a component or feature of one or more embodiments necessarily implies that the component or feature is essential to that particular embodiment or any other embodiment. Furthermore, it should be apparent to those skilled in the art that various modifications and changes can be made to the described embodiments without departing from the spirit and scope of the subject matter of the claims. Preferred embodiments of the present invention are described below in separate sections. Embodiment 1 In a coated hydrogenation catalyst, A hydrogenation catalyst comprising a porous carrier and at least one metal supported on the porous carrier, The porous carrier is made from silica, alumina, titania, or a combination thereof. The aforementioned at least one metal is selected from the metals of Groups 6, 9, and 10 of the International Union of Pure and Applied Chemistry (IUPAC). Hydrogenation catalyst, A catalyst activator containing at least one sulfur-containing compound, a catalyst deactivator containing at least one nitrogen-containing compound, or both, are packed onto the pores of the porous carrier, A coating layer on the surface of the hydrogenation catalyst, wherein the hydrogenation catalyst contains the catalyst activator, the catalyst deactivator, or both, and the coating layer is made of a polymer or paraffin-based oil. A coated hydrogenation catalyst equipped with the following features. Embodiment 2 The coated hydrogenation catalyst according to Embodiment 1, wherein the catalyst activator, the catalyst deactivator, or both are impregnated into or absorbed into the pores of the porous support. Embodiment 3 The coated hydrogenation catalyst according to Embodiment 1 or 2, wherein the at least one of the metals is in oxide or sulfide form. Embodiment 4 A coated hydrogenation catalyst according to any one of Embodiments 1 to 3, wherein the metals of Group 6, Group 9, and Group 10 of the IUPAC include Co, Mo, Ni, W, or a combination thereof. Embodiment 5 The coated hydrogenation catalyst according to any one of Embodiments 1 to 4, wherein the hydrogenation catalyst has an average cross-sectional dimension of 0.01 millimeters (mm) to 5.0 mm. Embodiment 6 The coated hydrogenation catalyst according to any one of Embodiments 1 to 5, wherein the porous support comprises a zeolite having a FAU, MFI, MOR, or BEA structure. Embodiment 7 The coated hydrogenation catalyst according to any one of Embodiments 1 to 6, wherein the coating layer has a thickness of 50 micrometers (μm) to 100 μm. Embodiment 8 The coated hydrogenation catalyst according to any one of Embodiments 1 to 7, wherein the catalyst activator comprises at least one of an organic sulfide, an organic disulfide, an organic polysulfide, or elemental sulfur. Embodiment 9 The coated hydrogenation catalyst according to any one of Embodiments 1 to 8, wherein the catalyst activator comprises methanethiol, thiophene, dialkyl disulfide, diaryl disulfide, or a combination thereof. Embodiment 10 The coated hydrogenation catalyst according to any one of Embodiments 1 to 9, wherein the catalyst activator comprises dimethyl disulfide (DMDS). Embodiment 11 The coated hydrogenation catalyst according to any one of Embodiments 1 to 10, wherein the catalyst deactivator comprises an organic nitrogen-containing compound. Embodiment 12 The coated hydrogenation catalyst according to any one of Embodiments 1 to 11, wherein the catalyst deactivator comprises an amine, carbazole, indole, quinoline, amide, acridine, aniline, ammonia, or an oxidized form thereof. Embodiment 13 The coated hydrogenation catalyst according to any one of Embodiments 1 to 12, wherein the catalyst deactivator comprises methyldiethanolamine (MDEA). Embodiment 14 The coated hydrogenation catalyst according to any one of Embodiments 1 to 13, wherein the polymer comprises a polymer material derived from an olefin, carbonate, aromatic compound, sulfone, fluorinated hydrocarbon, chlorinated hydrocarbon, acrylonitride, or a combination thereof. Embodiment 15 The coated hydrogenation catalyst according to any one of Embodiments 1 to 14, wherein the paraffin-based oil contains N-paraffin wax having 20 to 50 carbon atoms.

Claims

1. In a coated hydrogenation catalyst, A hydrogenation catalyst comprising a porous carrier and at least one metal supported on the porous carrier, The porous carrier is made from silica, alumina, titania, or a combination thereof, and the porous carrier contains a zeolite having a FAU, MFI, MOR, or BEA structure type. The aforementioned at least one metal is selected from the metals of Groups 6, 9, and 10 of the International Union of Pure and Applied Chemistry (IUPAC). Hydrogenation catalyst, A catalyst activation precursor containing at least one sulfur-containing compound, a catalyst deactivation precursor containing at least one nitrogen-containing compound, or both, are packed on the pores of the porous carrier, A coating layer on the surface of the hydrogenation catalyst, wherein the hydrogenation catalyst contains the catalyst activation precursor, the catalyst deactivation precursor, or both, and the coating layer is made from paraffinic oil. A coated hydrogenation catalyst equipped with the following features.

2. The coated hydrogenation catalyst according to claim 1, wherein the catalyst activation precursor, the catalyst deactivation precursor, or both are impregnated into or absorbed into the pores of the porous carrier.

3. The coated hydrogenation catalyst according to claim 1, wherein the at least one metal is in oxide or sulfide form.

4. The coated hydrogenation catalyst according to claim 1, wherein the metals of Group 6, Group 9, and Group 10 of the IUPAC include Co, Mo, Ni, W, or a combination thereof.

5. The coated hydrogenation catalyst according to claim 1, wherein the hydrogenation catalyst has an average cross-sectional dimension of 0.01 millimeters (mm) to 5.0 mm.

6. The coated hydrogenation catalyst according to claim 1, wherein the coating layer has a thickness of 50 micrometers (μm) to 100 μm.

7. The coated hydrogenation catalyst according to any one of claims 1 to 6, wherein the catalyst activation precursor comprises at least one of an organic sulfide, an organic disulfide, an organic polysulfide, or elemental sulfur.

8. The coated hydrogenation catalyst according to any one of claims 1 to 6, wherein the catalyst activation precursor comprises methanethiol, thiophene, dialkyl disulfide, diaryl disulfide, or a combination thereof.

9. The coated hydrogenation catalyst according to any one of claims 1 to 6, wherein the catalyst activation precursor comprises dimethyl disulfide (DMDS).

10. The coated hydrogenation catalyst according to any one of claims 1 to 6, wherein the catalyst deactivation precursor comprises an organic nitrogen-containing compound.

11. The coated hydrogenation catalyst according to any one of claims 1 to 6, wherein the catalyst deactivation precursor comprises an amine, carbazole, indole, quinoline, amide, acridine, aniline, ammonia, or an oxidized form thereof.

12. The coated hydrogenation catalyst according to any one of claims 1 to 6, wherein the catalyst deactivation precursor comprises methyldiethanolamine (MDEA).

13. The coated hydrogenation catalyst according to any one of claims 1 to 6, wherein the paraffin-based oil comprises N-paraffin wax having 20 to 50 carbon atoms.

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