Hydrogenation catalysts, and methods for preparing and using same

Abstract

A dry gas hydrogenation catalyst and a preparation method are disclosed. The catalyst comprises a support component and a hydrogenation active component, the support component including alumina. The hydrogenation active component is present in the catalyst in a sulfided form, with the average number of lamellar crystal layers of the sulfide being less than 1.5, and the proportion of single layers being 65% to 80%. The preparation method includes the following steps: (1) roasting alumina powder A at high temperature in an oxygen-containing atmosphere to obtain alumina drysol powder B; (2) immersing alumina drysol powder B in a hydrogenation active component soaking solution C, drying, and roasting it at high temperature in an oxygen-containing atmosphere, followed by sulfurization to obtain powder E; and (3) molding, drying, and roasting powder E prepared in step II). The high-temperature roasting temperatures for steps I and II are both 800°C or higher. The catalyst prepared by this method exhibits excellent performance in removing impurities such as oxygen, CO, and CO2, and also exhibits excellent performance in hydrogenating organic sulfur and olefins.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of Chinese Patent Application No. 202211569861.2, filed on December 8, 2022, the contents of which are incorporated herein by reference. [Technical Field]

[0002] The present invention relates to the field of hydrogenation, and in particular to hydrogenation catalysts, as well as methods for their preparation and use. [Background technology]

[0003] China has many refineries and chemical companies and is rich in light hydrocarbon resources, such as catalytic dry gas and coking dry gas. For example, coking dry gas contains high impurities such as oxygen, sulfur, CO, and CO2, making it unusable for purposes other than fuel and hydrogen production. Coking dry gas can be hydrogenated to saturate the diolefins and olefins contained therein and remove impurities such as sulfur and oxygen. This allows it to be used as a high-quality feedstock for olefin production, resulting in a high triene yield and thus alleviating the shortage of ethylene raw materials while also improving economic benefits.

[0004] CN200910230393.4 discloses a bifunctional hydrogenation catalyst that has excellent organic sulfur hydrocracking and olefin saturation performance when used in the hydrorefining process of feedstocks with high olefin content, such as coked dry gas and catalytic dry gas. This catalyst uses Co-Mo-Ni-Cu-rare earth active metals supported on titanium oxide-alumina, and can effectively hydrogenate the organic sulfur and olefins in coked dry gas and catalytic dry gas.

[0005] CN201911052623.2 discloses a dry gas hydrodesulfurization catalyst, as well as its preparation and use. The catalyst comprises raspberry-shaped particles composed of an active component (a), a structural additive (b), and other additives (c). The raspberry-shaped particles are hollow microspheres with a single micropore on the surface. The hollow microspheres have an internal hollow structure, and the micropore and hollow structure are connected to form a cavity with one open end. The metal element of the active component (a) is selected from Ni and Mo, and the structural additive (b) is one or more selected from alumina, silicon oxide, titanium oxide, and zirconium oxide. The metal element of the other additives (c) is one or more selected from Cu, La, Ce, W, Mn, and Zn.

[0006] CN201911053316.6 discloses a dry gas hydrogenation saturated olefin and desulfurization catalyst, and its preparation and use. The catalyst comprises a carrier and an active metal component supported on the carrier, the active metal component comprising molybdenum and a Group VIII metal, the molybdenum content being 10-45 wt %, the Group VIII metal content being 1-10 wt %, and the carrier oxide content being 50-89 wt %, preferably 55-80 wt %, based on the catalyst, calculated as oxide.

[0007] Numerous research experiments have shown that the content of impurities such as oxygen, CO, and CO2 in dry gas affects the catalyst's activity in hydrogenating organic sulfur and olefins. Therefore, when the content of impurities such as oxygen, CO, and CO2 in dry gas is high, the catalyst must have excellent impurity removal performance. Summary of the Invention [Problem to be solved by the invention]

[0008] In view of the shortcomings of the prior art, the present invention proposes a hydrogenation catalyst and a preparation method thereof. The catalyst has excellent hydrogenation performance, particularly for the hydrogenation of organic sulfur and olefins, and is particularly suitable for application to hydrotreating processes of low-carbon hydrocarbons, such as the hydrogenation of ethylene cracking raffinate, liquefied gas, or dry gas. In a preferred embodiment, by introducing an activator according to the components to be removed from the reaction feed, the catalyst has good performance in the hydrogenation of organic sulfur and olefins, and also has good performance in removing impurities such as oxygen, CO, and CO2. [Means for solving the problem]

[0009] The present invention provides a hydrogenation catalyst comprising a support component and a hydrogenation-active component, wherein the support component comprises alumina, the hydrogenation-active component is present in the catalyst in a sulfided form, the average number of lamellar layers of the sulfide is less than 1.5, preferably 1.2 to 1.3, and the proportion of single layers is 65% to 80%, for example, 65%, 70%, 72%, 75%, 78%, or 80%. The catalyst of the present invention having the above structural characteristics has the advantage of excellent resistance to carbon deposition. When applied to hydrogenation, it provides excellent stability and a long process operating life.

[0010] In order for the catalyst to have good performance in removing impurities such as oxygen, CO, and CO2, it is preferable that the hydrogenation catalyst contains an activator. The range of options for the activator is relatively wide, and examples will be described below, but the advantages of the present invention are not limited thereto. The activator includes one or more of Cu, Ag, Ni, Co, W, and Mo. In the present invention, one or two of Cu, Ag, Ni, Co, and W are used to explain the advantages of the present invention, but the scope of the present invention is not limited thereto.

[0011] According to a preferred embodiment of the present invention, the activator is preferably present in the catalyst in a metallic state, which allows impurities such as oxygen, CO, and CO to be removed by hydrogenation at a relatively low temperature.

[0012] In the present invention, the content of the activating agent can be selected within a relatively wide range, and the object of the present invention can be achieved within a commonly used content range. The following provides an illustrative example, but the scope of the present invention is not limited thereby. According to one preferred embodiment of the present invention, the content of the activating agent in the catalyst is preferably 0.1 wt% to 4 wt%, preferably 0.3 wt% to 4 wt%, preferably 0.5 wt% to 3 wt%, for example, 0.5 wt%, 0.8 wt%, 1 wt%, 1.4 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 2.0 wt%, 2.5 wt%, 2.8 wt%, 3 wt%, etc.

[0013] In the present invention, the content of the hydrogenation active component can be selected within a relatively wide range, and the object of the present invention can be achieved within a commonly used content range. The following provides an illustrative explanation, but the scope of the present invention is not limited thereto. According to one preferred embodiment of the present invention, the content of the hydrogenation active component, calculated as sulfide based on the weight of the catalyst, is preferably 1.5 wt% to 30 wt%, more preferably 10 wt% to 20 wt%, for example, 10 wt%, 11 wt%, 12 wt%, 14 wt%, 16 wt%, 17 wt%, 18 wt%, 20 wt%, etc., of the total mass of the catalyst.

[0014] In the present invention, there are no special requirements for the selection of the hydrogenation active component, and any commonly used hydrogenation active component can be applied to the present invention. An exemplary explanation will be given below, but the scope of the present invention is not limited thereby. According to one preferred embodiment of the present invention, the hydrogenation active component contains a Group VIB and Group VIII metal, and preferably, the Group VIB metal contains Mo and / or W, and the Group VIII metal contains Co and / or Ni. In the examples of the present invention, Mo and Co, Mo and Ni, W, Mo and Ni are used as examples to explain the advantages of the present invention, but the scope of the present invention is not limited thereby.

[0015] In the present invention, there is no special requirement for the amount of the hydrogenation active component, and all commonly used amount ranges are applicable to the present invention. The following provides an illustrative explanation, but the scope of the present invention is not limited thereby. According to one preferred embodiment of the present invention, the Group VIB metal sulfide is preferably 1 wt% to 20 wt%, preferably 8 wt% to 16 wt%, of the total mass of the catalyst, and the Group VIII metal sulfide is preferably 0.5 wt% to 10 wt%, preferably 2 wt% to 4 wt%, of the total mass of the catalyst, based on the weight of the catalyst.

[0016] According to one preferred embodiment of the present invention, the total acid content of the catalyst is 0.1-0.4 mmol / g, with 5%-15% being a strong acid at 400-500°C, 10%-20% being a medium-strength acid at 250-400°C, and the remainder being a weak acid at 150-250°C. A catalyst with the above acid content characteristics has the advantage of reducing acid decomposition side reactions and carbon deposition on the catalyst. When applied to hydrogenation, this can result in a favorable result of extending the operating life of the catalyst.

[0017] In the present invention, there is no special requirement for the method of preparing the hydrogenation catalyst, and the object of the present invention can be achieved as long as the catalyst satisfies the requirements of the above characteristics. Step I) of roasting the alumina powder A at high temperature in an oxygen-containing atmosphere to obtain an alumina drysol powder B; Step II) of immersing the alumina dry sol powder B in a hydrogenation active component immersion solution C, drying the resultant, roasting the resultant at a high temperature in an oxygen-containing atmosphere, and then sulfurizing the resultant to obtain a powder E; and step III) of shaping, drying and roasting the powder E prepared in step (2), The present invention provides a method for preparing a hydrogenation catalyst, in which the high-temperature roasting temperatures in steps I) and II) are each 800°C or higher. In step I), alumina powder is first roasted to promote alumina lattice deformation. Roasting in step II) prevents migration and aggregation of the hydrogenation active components during the sulfiding process, thereby making it possible to reduce the average number of lamellae layers in the sulfide of the present invention to less than 1.5 layers.

[0018] In the present invention, preferably, the method further comprises the steps of immersing alumina powder A in an activator immersion solution D, drying, and reducing to obtain powder F, and step III) comprises mixing said powder E and said powder F, followed by molding, drying, and roasting.

[0019] In the present invention, there are no special requirements for either the drying or reduction steps. The following is an illustrative explanation, but the scope of the present invention is not limited thereto.

[0020] According to one preferred embodiment of the present invention, the reduction treatment comprises roasting in a reducing atmosphere, preferably in a hydrogen atmosphere.

[0021] According to one preferred embodiment of the present invention, the roasting conditions in the reduction treatment include a roasting temperature of 300 to 700° C. and a roasting time of 2 to 5 hours.

[0022] According to one preferred embodiment of the present invention, preferably, the drying conditions before reduction include a drying time of 1 to 5 hours and a drying temperature of 80 to 120°C.

[0023] In the present invention, there is no particular requirement for the immersion method. The following is an example, but the scope of the present invention is not limited thereto. Preferably, the immersion method for the immersion with the activator is saturated immersion or supersaturated immersion.

[0024] In the present invention, activated alumina is required for the alumina powder A, and the physical and chemical parameters of the preferred alumina powder A of the present invention are a specific surface area of ​​100 to 480 m 2 / g, pore volume 0.4~1.2cm 3 / g, pore size of 4.0 to 35.0 nm, and content on a dry basis of, for example, 60 to 80 wt%. Illustratively, the alumina powder A is, for example, a dry sol powder of pseudo-boehmite. The pseudo-boehmite dry sol powder A is a commonly available product and can be prepared by methods such as an alcohol aluminum method, a sodium aluminate neutralization method, or a carbonization method.

[0025] In the present invention, there are no special requirements for the oxygen-containing atmosphere in step I). An exemplary explanation will be given below, but the scope of the present invention is not limited thereto. According to one preferred embodiment of the present invention, the oxygen content in the oxygen-containing atmosphere is preferably 10v% to 30v%, and an air atmosphere is preferably used.

[0026] In the present invention, the object of the present invention can be achieved by selecting the high-temperature roasting conditions in step I) within a roasting temperature range of 800°C or higher, and specifically, the high-temperature roasting conditions are determined as needed. In the present invention, preferably, the high-temperature roasting conditions include a roasting temperature of 800 to 1100°C, for example, 800°C, 850°C, 900°C, 950°C, 1000°C, 1050°C, or 1100°C, and a roasting time determined as needed, for example, a roasting time of 0.5 to 5 hours, for example, 0.5 h, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, or 5 h.

[0027] In the present invention, there is no special requirement for the oxygen-containing atmosphere in step II), and although an exemplary description will be given below, the scope of the present invention is not limited thereby. According to one preferred embodiment of the present invention, preferably, in step II), the oxygen content in the oxygen-containing atmosphere is 10v% to 30v%, and preferably, an air atmosphere is used.

[0028] In the present invention, the object of the present invention can be achieved by selecting the high-temperature roasting conditions in step II) within a roasting temperature range of 800°C or higher, and the specific conditions are determined as needed. In the present invention, the high-temperature roasting conditions preferably include a roasting temperature of 800 to 1100°C, e.g., 800°C, 850°C, 900°C, 950°C, 1000°C, 1050°C, or 1100°C, and a roasting time determined as needed, e.g., 0.5 to 5 hours, e.g., 0.5 h, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, or 5 h.

[0029] In the present invention, there are no special requirements for the sulfurization treatment step, and the main purpose is sulfurization. An exemplary explanation will be given below, but the scope of the present invention is not limited thereby. According to one preferred embodiment of the present invention, the sulfurization treatment in step II) comprises roasting in a sulfurizing atmosphere, preferably roasting in a mixed atmosphere of H2S and H2, and preferably, the H2S in the mixed atmosphere of H2S and H2 occupies 0.1v% to 2v%. In the examples of the present invention, 1v% will be used as an example, but the scope of the present invention is not limited thereby.

[0030] In the present invention, there are no special requirements for the sulfurization roasting, and commonly used sulfurization roasting temperatures can be applied to the present invention. In the present invention, preferred roasting conditions in a sulfurization atmosphere include roasting in a sulfurization atmosphere, a roasting temperature of 250 to 550°C, and a roasting time determined as necessary, for example, 3 to 8 hours.

[0031] In the present invention, there is no special requirement for the immersion method. An example will be explained below, but the scope of the present invention is not limited thereto. Preferably, the immersion method in step II) is saturated immersion or supersaturated immersion.

[0032] In the present invention, the conditions for forming, drying, and roasting in step III) may all be those of the prior art. The following examples are provided for illustrative purposes, but the scope of the present invention is not limited thereto.

[0033] Specifically, for example, the catalyst molding process in step III) is to add extrusion aid, gel solvent and water to the composite powder to mix it into a plastic, and then knead and mold it.

[0034] There is no particular requirement for the type of the extrusion aid, and it may be, for example, one or more of methyl cellulose, sesbania gum powder, starch, and polyvinyl alcohol.

[0035] There is no particular requirement for the type of the gel solvent, and it may be, for example, one or more of diluted nitric acid, diluted phosphoric acid, and silicic acid.

[0036] In the present invention, there are no particular requirements for the drying conditions, and for example, the drying conditions in steps II) and III) include a drying time of 1 to 5 hours and a drying temperature of 80 to 120°C, respectively.

[0037] In the present invention, there are no particular requirements for the roasting conditions, and the roasting conditions in step III) include a roasting temperature of 200 to 350°C and a roasting time that is determined as necessary, for example, 1 to 4 hours.

[0038] In the present invention, the roasting atmosphere in step III) is an inert atmosphere, for example, one or more gases selected from N2, He or Ar.

[0039] In the method of the present invention, the active ingredient impregnation solution and the activator impregnation solution are both aqueous solutions prepared by conventional methods. For example, the active ingredient impregnation solution can be an aqueous solution prepared using salts such as ammonium molybdate, ammonium metatungstate, cobalt nitrate, nickel nitrate, basic cobalt carbonate, and basic nickel carbonate. The activator impregnation solution can be an aqueous solution prepared using salts such as copper nitrate, silver nitrate, ammonium molybdate, ammonium metatungstate, cobalt nitrate, nickel nitrate, basic cobalt carbonate, and basic nickel carbonate. The selected metal salts are all water-soluble, but are not limited to the above salts. The amount of each component added to the impregnation solution is calculated based on the content of each component on the catalyst.

[0040] The inventors have found through research that metal sulfides with a small number of layers have excellent hydrodesulfurization activity. When the alumina support has little interaction with the hydrogenation-active metal, the metal sulfide produced by sulfidation has a multilayer structure. Heat is released during the hydrogenation process, causing the multilayered sulfide to migrate and aggregate. The acidity of alumina powder is significantly reduced after high-temperature treatment. After impregnating the hydrogenation-active metal, the powder is roasted again at high temperature to strengthen the interaction between the alumina and the metal. The number of layers in the metal sulfide stack produced by sulfidation is significantly reduced, while the number of single layers is significantly increased, improving the stability of the catalyst's hydrogenation activity.

[0041] The hydrogenation catalyst of the present invention is suitable for use in various hydrogenation processes such as hydrogenation of ethylene cracking raffinate, liquefied gas or dry gas, and is particularly suitable for use in the preparation of low-carbon hydrocarbons by dry gas hydrogenation.

[0042] In the present invention, there are no special requirements for the reaction conditions of the reaction for preparing low-carbon hydrocarbons by dry gas hydrogenation, and all commonly used conditions are applicable to the present invention. In the present invention, the reaction conditions for the reaction for preparing low-carbon hydrocarbons by dry gas hydrogenation are preferably a reaction pressure of 0.1 to 10 MPa, a space velocity of 300 to 10,000 h -1 , reaction temperature 150 to 400°C.

[0043] According to one preferred embodiment of the present invention, the dry gas hydrogenation catalyst of the present invention comprises a support component, an active component, and an activity aid, wherein the support component is alumina, the active component is a Group VIB and Group VIII metal, the Group VIB metal is preferably Mo and / or W, the Group VIII metal is preferably Co and / or Ni, the activity aid is one or more of Cu, Ag, Ni, Co, W, and Mo, the active component is present in the catalyst in a sulfide state, the average number of lamellar crystal layers of the sulfide is less than 1.5 layers, and the proportion of single layers is 65% to 80%, and the activity aid is present in the catalyst in a metallic state.

[0044] According to one preferred embodiment of the present invention, based on the weight of the catalyst, the Group VIB metal sulfide is 1 wt% to 20 wt% of the total mass of the catalyst, and the Group VIII metal sulfide is 0.5 wt% to 10 wt% of the total mass of the catalyst.

[0045] According to one preferred embodiment of the present invention, the content of the activation aid in the catalyst is 0.1 wt% to 4 wt%, preferably 0.3 wt% to 4 wt%.

[0046] According to one preferred embodiment of the present invention, the total acid content of the catalyst is 0.1-0.4 mmol / g, the amount of strong acid at 400-500°C accounts for 5%-15%, the amount of medium strength acid at 250-400°C accounts for 10%-20%, and the amount of weak acid at 150-250°C accounts for 65%-85%.

[0047] According to one preferred embodiment of the present invention, the method for preparing the dry gas hydrogenation catalyst of the present invention comprises: Step (1) of preparing pseudoboehmite dry sol powder A and roasting it at a high temperature in an oxygen-containing atmosphere to obtain alumina dry sol powder B; Step (2) of immersing the alumina dry sol powder B in the active ingredient immersion solution C, drying it, and roasting it at a high temperature in an oxygen-containing atmosphere, and then roasting it in a mixed atmosphere of H2S and H2 to obtain powder E; Step (3) of immersing the pseudo-boehmite dry sol powder A in an activator immersion solution D, drying, and roasting in a hydrogen atmosphere to obtain powder F; and step (4) of uniformly mixing the powder E prepared in step (2) with the powder F prepared in step (3), followed by molding, drying, and roasting to obtain a dry gas hydrogenation catalyst.

[0048] In the method of the present invention, the pseudo-boehmite dry sol powder A in step (1) is a commercially available product and can be prepared by methods such as the aluminum alcohol method, the sodium metaaluminate neutralization method, and the carbonization method.

[0049] In the method of the present invention, the oxygen content in the oxygen-containing atmosphere in step (1) is 10v% to 30v%, preferably an air atmosphere is used, and the high-temperature roasting conditions are a roasting temperature of 800 to 1100°C and a roasting time of 0.5 to 5 hours.

[0050] In the method of the present invention, the oxygen content in the oxygen-containing atmosphere in step (2) is 10v% to 30v%, preferably an air atmosphere is used, and the high-temperature roasting conditions are a roasting temperature of 800 to 1100°C and a roasting time of 0.5 to 5 hours.

[0051] In the method of the present invention, the roasting conditions in the mixed atmosphere of H2S and H2 in step (2) are a roasting temperature of 250 to 550°C and a roasting time of 3 to 8 hours, and H2S in the mixed atmosphere of H2S and H2 accounts for 0.1 v% to 2 v%.

[0052] In the method of the present invention, the roasting conditions in a hydrogen atmosphere in step (3) are a roasting temperature of 300 to 700°C and a roasting time of 2 to 5 hours.

[0053] In the method of the present invention, the active ingredient impregnation solution C in step (2) and the activator impregnation solution D in step (3) are both aqueous solutions prepared by conventional methods. For example, the active ingredient impregnation solution C can be an aqueous solution prepared using salts such as ammonium molybdate, ammonium metatungstate, cobalt nitrate, nickel nitrate, basic cobalt carbonate, and basic nickel carbonate. The activator impregnation solution D can be an aqueous solution prepared using salts such as copper nitrate, silver nitrate, ammonium molybdate, ammonium metatungstate, cobalt nitrate, nickel nitrate, basic cobalt carbonate, and basic nickel carbonate. The selected metal salts are all water-soluble, but are not limited to the above salts. The amount of each component in the impregnation solution is calculated according to the content of each component on the catalyst.

[0054] In the method of the present invention, the soaking method in steps (2) and (3) is saturated soaking or supersaturated soaking, which are well known to those skilled in the art. The drying process is also well known to those skilled in the art, such as conventional drying or vacuum drying.

[0055] In the method of the present invention, the catalyst molding process in step (4) is a method well known in the art, for example, by adding an extrusion aid, a gel solvent, and water to the composite powder to mix it into a plastic material, and then kneading and molding it. Here, the extrusion aid is one or more of methyl cellulose, sesbania gum powder, starch, and polyvinyl alcohol. The gel solvent is one or more of dilute nitric acid, dilute phosphoric acid, and silicic acid.

[0056] In the method of the present invention, the drying conditions in steps (2), (3), and (4) are a drying time of 1 to 5 hours and a drying temperature of 80 to 120°C.

[0057] In the method of the present invention, the roasting conditions in step (4) are a roasting temperature of 200 to 350°C and a roasting time of 1 to 4 hours. The roasting atmosphere is an inert atmosphere of one or more gases selected from N2, He, and Ar.

[0058] The dry gas hydrogenation catalyst of the present invention is used in a reaction for preparing low-carbon hydrocarbons by dry gas hydrogenation, and the reaction conditions are a reaction pressure of 0.1 to 10 MPa and a space velocity of 300 to 10,000 h -1 The reaction temperature is 150 to 400°C. The specific process conditions may be adjusted according to the quality of the raw materials.

[0059] The inventors discovered that the majority of organic sulfur in dry gas is carbonyl sulfide, and that metal sulfides with a small number of layers also have excellent hydrodesulfurization activity. When alumina as a support has low interaction with Group VIB and Group VIII active metals, the metal sulfides produced by sulfidation have a multilayer structure. During the dry gas hydrogenation process, olefins rapidly saturate and rapidly release heat, leading to migration and aggregation of the multilayered sulfides. Furthermore, the catalyst surface is highly acidic and contains impurities such as oxygen, CO, and CO2, which cause olefin polymerization and carbon deposition. These factors reduce the catalyst's desulfurization and olefin saturation activity. Alumina drysol powder's acidity is significantly reduced after high-temperature treatment. After impregnation with Group VIB and / or Group VIII active metals, it is roasted again at high temperatures to strengthen the interaction between the alumina and the metals. The number of layers in the metal sulfide stack produced by sulfidation is significantly reduced, while the number of single layers is significantly increased, improving the stability of the catalyst's desulfurization and olefin saturation activity.

[0060] Furthermore, if the dry gas contains excessive impurities such as oxygen, CO, and CO2, especially CO, they are adsorbed by the active metal, reducing the hydrogenation and desulfurization performance of the catalyst. The inventors have found that the use of an active metal adjuvant has the advantage of adsorbing impurities such as oxygen, CO, and CO2 and removing them through the hydrogenation reaction. Furthermore, compared with alumina powder that has been roasted at high temperatures, pseudo-boehmite powder that has not been roasted at high temperatures has better deflocculation properties. This allows it to be directly molded with alumina powder that has been roasted at high temperatures to prepare a catalyst. The resulting catalyst has more weak acids and less strong acids. The weak interaction of the active metal adjuvant with the pseudo-boehmite powder facilitates the reduction and dispersion of the active metal adjuvant at lower temperatures, thereby improving the performance of the active metal adjuvant in removing impurities such as oxygen, CO, and CO2 through hydrogenation. [Brief explanation of the drawings]

[0061] [Figure 1] 1 is an X-ray photoelectron spectroscopy (XPS) spectrum of the catalyst of Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0062] The solution and effect of the present invention will be further illustrated by the following examples, which are not intended to limit the present invention. In this invention, a commercially available pseudo-boehmite dry sol powder purchased from China Petrochemical Chemicals Dalian Branch was selected. This pseudo-boehmite dry sol powder has a specific surface area of ​​392 m 2 / g, pore volume 0.95 cm 3 / g, pore size 9.7nm, 70wt% on a dry basis. XPS spectrum analysis was used to characterize the valence state of each active metal on the catalyst. The acidity of the catalyst was tested using the NH3-TPD method. The number of sulfide lamellae on the catalyst was calculated using TEM images. The specific statistical formula is as follows:

[0063]

number

[0064] In the formula, N is the average number of layers in the sheet stack, and N i is the number of stack layers of the ith sheet, and n i is the statistical N i Represents the number of.

[0065] The components of the raw materials and products are obtained by normalization and calculation using chromatographic analysis.

[0066] Example 1 17.2 g of ammonium heptamolybdate and 18.8 g of cobalt nitrate hexahydrate were dissolved in an appropriate amount of water to prepare 70 mL of active ingredient aqueous solution C. Similarly, 5.8 g of copper nitrate and 10.4 g of nickel nitrate hexahydrate were dissolved in an appropriate amount of water to prepare 70 mL of auxiliary ingredient aqueous solution D. A certain amount of the pseudoboehmite dry sol powder A was then roasted in an air atmosphere at 1000°C for 1.5 hours to obtain alumina dry sol powder B. 100 g of the roasted alumina dry sol powder B was immersed in solution C, dried at 100°C for 3 hours, roasted in an air atmosphere at 1000°C for 1.5 hours, and then treated at 350°C for 6 hours in a 1% H2S mixed atmosphere of H2S and H2 to obtain powder E. 100 g of pseudoboehmite dry sol powder A was immersed in aqueous solution D and dried at 100°C for 3 hours. It was then roasted at 650°C for 4 hours in a hydrogen atmosphere to obtain powder F. Powders E and F were mixed homogeneously, crushed, and sieved (200 mesh). Then, 2 g of sesbania rubber powder, 15 g of 10% nitric acid, and 150 mL of deionized water were added, molded, dried at 100°C for 3 hours, and roasted at 350°C for 2 hours in a nitrogen atmosphere to obtain final catalyst C-1. A query of the NIST XPS database revealed that the metal Mo shown in Figure 1 is in the +4 state of MoS2, Co is in the +2 state of CoS, and Cu and Ni are in the 0-valent state.

[0067] Example 2 29.0 g of ammonium heptamolybdate and 26.0 g of nickel nitrate hexahydrate were dissolved in an appropriate amount of water to prepare 90 mL of active ingredient aqueous solution C. Similarly, 3.2 g of silver nitrate and 6.3 g of ammonium metatungstate were dissolved in an appropriate amount of water to prepare 42 mL of auxiliary ingredient aqueous solution D. A certain amount of the pseudoboehmite dry sol powder A was then roasted in an air atmosphere at 900°C for 3 hours to obtain alumina dry sol powder B. 120 g of the roasted alumina dry sol powder B was immersed in aqueous solution C, dried at 110°C for 3 hours, roasted in an air atmosphere at 1050°C for 1 hour, and then treated at 400°C for 5 hours in a 1% H2S and H2 mixed atmosphere to obtain powder E. 60 g of pseudoboehmite dry sol powder A was immersed in aqueous solution D, dried at 110°C for 3 hours, and then roasted at 550°C for 3 hours in a hydrogen atmosphere to obtain powder F. Powders E and F were mixed uniformly, crushed, and sieved (200 mesh). 2.5 g of sesbania rubber powder, 17 g of 10% nitric acid, and 190 mL of deionized water were added, molded, dried at 110°C for 3 hours, and then roasted at 250°C for 2 hours in a nitrogen atmosphere to obtain final catalyst C-2.

[0068] Example 3 19.1 g of ammonium metatungstate, 7.3 g of ammonium heptamolybdate, and 10.6 g of nickel nitrate hexahydrate were dissolved in an appropriate amount of water to prepare 80 mL of active ingredient aqueous solution C. Similarly, 1.6 g of cobalt nitrate and 2.5 g of nickel nitrate were dissolved in an appropriate amount of water to prepare 35 mL of auxiliary ingredient aqueous solution D. A certain amount of the pseudoboehmite dry sol powder A was then roasted in an air atmosphere at 800°C for 5 hours to obtain alumina dry sol powder B. 100 g of the roasted alumina dry sol powder B was immersed in aqueous solution C, dried at 110°C for 2 hours, roasted in an air atmosphere at 900°C for 4 hours, and then treated at 500°C for 4 hours in a 1% H2S and H2 mixed atmosphere to obtain powder E. 50 g of pseudoboehmite dry sol powder A was immersed in aqueous solution D, dried at 110°C for 2 hours, and then roasted at 450°C for 2 hours in a hydrogen atmosphere to obtain powder F. Powders E and F were mixed uniformly, crushed, and sieved (200 mesh). 2.5 g of sesbania rubber powder, 17 g of 10% nitric acid, and 170 mL of deionized water were added, molded, dried at 110°C for 2 hours, and then roasted at 300°C for 2 hours in a nitrogen atmosphere to obtain final catalyst C-3.

[0069] Example 4 24.4 g of ammonium metatungstate, 9.3 g of ammonium heptamolybdate, and 13.5 g of nickel nitrate hexahydrate were dissolved in an appropriate amount of water to prepare 80 mL of active ingredient aqueous solution C. Similarly, 9.3 g of copper nitrate was dissolved in an appropriate amount of water to prepare 70 mL of auxiliary ingredient aqueous solution D. A certain amount of the pseudoboehmite dry sol powder A was then roasted in an air atmosphere at 900°C for 5 hours to obtain alumina dry sol powder B. 100 g of the roasted alumina dry sol powder B was immersed in aqueous solution C, dried at 90°C for 4 hours, roasted in an air atmosphere at 850°C for 4 hours, and then treated at 300°C for 7 hours in a mixed atmosphere of 1% H2S and H2 to obtain powder E. 100 g of pseudoboehmite dry sol powder A was immersed in aqueous solution D, dried at 90°C for 4 hours, and then roasted at 600°C for 3 hours in a hydrogen atmosphere to obtain powder F. Powders E and F were mixed uniformly, crushed, and sieved (200 mesh). 2.5 g of sesbania rubber powder, 20 g of 10% nitric acid, and 210 mL of deionized water were added, molded, dried at 90°C for 4 hours, and then roasted at 300°C for 2 hours in a nitrogen atmosphere to obtain final catalyst C-4.

[0070] Example 5 A certain amount of the pseudoboehmite dry sol powder A was roasted in an air atmosphere at 950°C for 1.5 hours to obtain alumina dry sol powder B. Then, 12.8 g of ammonium heptamolybdate and 13.0 g of cobalt nitrate hexahydrate were dissolved in an appropriate amount of water to prepare 100 mL of active ingredient aqueous solution C. After the roasting, 100 g of alumina dry sol powder B was immersed in solution C, dried at 100°C for 3 hours, roasted in an air atmosphere at 1050°C for 1.5 hours, and then treated at 400°C for 6 hours in a mixed atmosphere of 1% H2S and H2 to obtain powder D. Powder D was crushed and sieved (200 mesh), and then 2.5 g of sesbania rubber powder, 20 g of 10% nitric acid, and 100 mL of deionized water were added. The mixture was molded, dried at 100°C for 3 h, and then roasted at 350°C in a nitrogen atmosphere for 2 h to obtain the final catalyst C-5.

[0071] Comparative Example 1 The preparation method of Example 1 was followed, except that the pseudoboehmite powder was not roasted at high temperatures during the preparation process. 13.7 g of ammonium heptamolybdate and 14.9 g of cobalt nitrate hexahydrate were dissolved in an appropriate amount of water to prepare 100 mL of active ingredient aqueous solution C. Similarly, 4.6 g of copper nitrate and 8.2 g of nickel nitrate hexahydrate were dissolved in an appropriate amount of water to prepare 70 mL of auxiliary ingredient aqueous solution D. Subsequently, 142.9 g of pseudoboehmite dry sol powder A was immersed in solution C, dried at 100°C for 3 hours, roasted in an air atmosphere at 1000°C for 1.5 hours, and then treated at 350°C for 6 hours in a mixed atmosphere of 1% H2S and H2 to obtain powder E. 100 g of pseudoboehmite dry sol powder A was immersed in aqueous solution D, dried at 100°C for 3 hours, and then roasted at 650°C for 4 hours in a hydrogen atmosphere to obtain powder F. Powders E and F were mixed uniformly, crushed, and sieved (200 mesh). 2 g of sesbania rubber powder, 15 g of 10% nitric acid, and 150 mL of deionized water were added, molded, dried at 100°C for 3 hours, and then roasted at 350°C for 2 hours in a nitrogen atmosphere to obtain final catalyst D-1.

[0072] Comparative Example 2 The preparation method of Example 1 was followed, except that the high-temperature roasting in step (1) was replaced by low-temperature roasting of pseudoboehmite powder to form γ-alumina. 13.7 g of ammonium heptamolybdate and 14.9 g of cobalt nitrate hexahydrate were dissolved in a suitable amount of water to prepare 100 mL of active ingredient aqueous solution C. Similarly, 4.6 g of copper nitrate and 8.2 g of nickel nitrate hexahydrate were dissolved in a suitable amount of water to prepare 70 mL of auxiliary ingredient aqueous solution D. A certain amount of pseudo-boehmite dry sol powder A was then roasted in an air atmosphere at 550°C for 3 hours to obtain γ-alumina dry sol powder. Next, 100 g of the γ-alumina powder was immersed in solution C to support the powder, dried at 100°C for 3 hours, and then roasted in an air atmosphere at 1000°C for 1.5 hours. Next, it was treated in a 1% HS and H mixed atmosphere at 350°C for 6 hours to obtain powder E. 100 g of pseudo-boehmite dry sol powder A was immersed in aqueous solution D to support the powder, dried at 100°C for 3 hours, and then roasted in a hydrogen atmosphere at 650°C for 4 hours to obtain powder F. Powder E and powder F were mixed uniformly, crushed, and sieved (200 mesh). Then, 2 g of sesbania rubber powder, 15 g of 10% nitric acid, and 150 mL of deionized water were added, molded, dried at 100°C for 3 hours, and then roasted at 350°C in a nitrogen atmosphere for 2 hours to obtain the final catalyst D-2.

[0073] Comparative Example 3 The preparation method of Example 1 was followed, except that the powders impregnated with Group VIB and / or Group VIII metals were not roasted at high temperatures during the preparation process. 13.7 g of ammonium heptamolybdate and 14.9 g of cobalt nitrate hexahydrate were dissolved in an appropriate amount of water to prepare 100 mL of active ingredient aqueous solution C. Similarly, 4.6 g of copper nitrate and 8.2 g of nickel nitrate hexahydrate were dissolved in an appropriate amount of water to prepare 70 mL of auxiliary ingredient aqueous solution D. A certain amount of the pseudoboehmite dry sol powder A was roasted in an air atmosphere at 1000°C for 1.5 hours to obtain alumina dry sol powder B. Subsequently, 100 g of alumina dry sol powder B was immersed in solution C, dried at 100°C for 3 hours, and then treated at 350°C for 6 hours in a 1% H2S mixed atmosphere of H2S and H2 to obtain powder E. 100 g of pseudoboehmite dry sol powder A was immersed in aqueous solution D to support it, dried at 100°C for 3 hours, and then roasted at 650°C for 4 hours in a hydrogen atmosphere to obtain powder F. Powder E and powder F were mixed uniformly, crushed, and sieved (200 mesh). 2 g of sesbania rubber powder, 15 g of 10% nitric acid, and 150 mL of deionized water were added, molded, dried at 100°C for 3 hours, and then roasted at 350°C for 2 hours in a nitrogen atmosphere to obtain final catalyst D-3.

[0074] Comparative Example 4 The preparation method of Example 1 was followed, except that the active metal component and auxiliary component were gradually impregnated after the support was prepared. A certain amount of the above pseudoboehmite dry sol powder A was roasted in an air atmosphere at 1000°C for 1.5 hours to obtain alumina dry sol powder B. 100 g of the roasted alumina dry sol powder B and 100 g of pseudoboehmite dry sol powder A were then homogeneously mixed, pulverized, and sieved (200 mesh). Then, 2 g of sesbania rubber powder, 15 g of 10% nitric acid, and 150 mL of deionized water were added, molded, dried at 100°C for 3 hours, and then roasted in an air atmosphere at 250°C for 2 hours to obtain a catalyst support. 13.7 g of ammonium heptamolybdate and 14.9 g of cobalt nitrate hexahydrate were dissolved in an appropriate amount of water to prepare 70 mL of active component aqueous solution C. Similarly, 4.6 g of copper nitrate and 8.2 g of nickel nitrate hexahydrate were dissolved in an appropriate amount of water to prepare 35 mL of auxiliary component aqueous solution D. The prepared support was immersed in solution C to support the catalyst, dried at 100°C for 3 hours, and then roasted in an air atmosphere at 1000°C for 1.5 hours. This was then treated at 350°C for 6 hours in a 1% H2S and H2 mixed atmosphere to obtain first-stage catalyst E. This first-stage catalyst E was then immersed in aqueous solution D to support the catalyst, dried at 100°C for 3 hours, and then roasted in a nitrogen atmosphere at 350°C for 2 hours to obtain final catalyst D-4.

[0075] Comparative Example 5 12.8 g of ammonium heptamolybdate and 13.0 g of cobalt nitrate hexahydrate were dissolved in an appropriate amount of water to prepare 100 mL of active ingredient aqueous solution C. Next, 142.9 g of the pseudoboehmite dry sol powder A was immersed in solution C, dried at 100°C for 3 hours, and then roasted at 450°C for 1.5 hours in an air atmosphere. This was then treated at 400°C for 6 hours in a 1% H2S and H2 mixed atmosphere to obtain powder D. Powder D was crushed and sieved (200 mesh), and then 2.5 g of sesbania rubber powder, 20 g of 10% nitric acid, and 100 mL of deionized water were added. The mixture was molded, dried at 100°C for 3 hours, and then roasted at 350°C for 2 hours in a nitrogen atmosphere to obtain the final catalyst D-5.

[0076] The content and performance of each catalyst component are shown in Table 1.

[0077] [Table 1]

[0078] Hydrogenation of coked dry gas For the above catalyst, a 10 mL reactor was used, with a reaction pressure of 3.0 MPa, a reaction temperature of 190°C, and a space velocity of 700 h -1 The performance of the raw material is shown in Table 2, the evaluation results after 500 hours of reaction are shown in Table 3, and the amount of carbon deposition on the catalyst is shown in Table 4.

[0079] [Table 2]

[0080] [Table 3]

[0081] [Table 4]

[0082] The evaluation results in Table 3 demonstrate that the catalyst of the present invention is superior to the catalyst of the comparative example in olefin saturation activity and in removing impurities such as sulfur, oxygen, CO, and CO2, making it more suitable for the hydrogenation reaction of coked dry gas. The carbon deposition amount on the catalyst after hydrogenation in Table 4 indicates that the catalyst of the present invention has significantly lower carbon deposition amount after 500 hours of reaction than the catalyst of the comparative example, demonstrating that the catalyst of the present invention has better stability and is more suitable for long-term industrial operation.

[0083] Hydrogenation of liquefied gas For the above catalyst, the reaction pressure was 1.5 MPa in a 10 mL reactor, the reaction temperature was 180°C, and the liquid hourly space velocity was 4.0 h -1 The activity evaluation test was carried out at a hydrogen to oil volume ratio of 200:1. The feedstock had a total olefin content of 20v% and a total sulfur content of 203mg / m 3The evaluation results after 500 hours of reaction are shown in Table 5, and the amount of carbon deposited on the catalyst after hydrogenation is shown in Table 6.

[0084] [Table 5]

[0085] [Table 6]

[0086] From the evaluation results in Table 5 and the amount of carbon deposition on the catalyst after hydrogenation in Table 6, it was found that the olefin saturation activity and desulfurization activity of the catalyst of the present invention were superior to those of the catalyst of the comparative example, the amount of carbon deposition after 500 hours of reaction was low, and the catalyst stability was also excellent.

[0087] Although the preferred embodiments of the present invention have been described in detail above, the present invention is not limited thereto. Without departing from the scope of the technical concept of the present invention, the technical solutions of the present invention may be modified in a number of simple ways, including combining each technical feature in any other suitable manner, and these simple modifications and combinations shall also be regarded as the disclosure content of the present invention and all fall within the protection scope of the present invention.

Claims

1. A hydrogenation catalyst comprising: a support component; and a hydrogenation active component, wherein the support component comprises alumina; the hydrogenation active component is present in the catalyst in a sulfide state; the average number of lamellar crystal layers of the sulfide is less than 1.5 layers; and the proportion of single layers is 65% to 80%.

2. The average number of lamellae of the sulfide is 1.2 to 1.3 layers, and / or The hydrogenation catalyst includes an activator, and the activator includes one or more of Cu, Ag, Ni, Co, W, and Mo; Preferably, the activator is present in the catalyst in metallic form, The catalyst according to claim 1, characterized in that the content of the activation aid in the catalyst is preferably 0.1 wt% to 4 wt%, preferably 0.3 wt% to 4 wt%, more preferably 0.5 wt% to 3 wt%.

3. 3. The catalyst according to claim 1, wherein the content of the hydrogenation active component, calculated as sulfide, based on the weight of the catalyst, is 1.5 wt % to 30 wt %, preferably 10 wt % to 20 wt %, of the total mass of the catalyst.

4. the hydrogenation active component comprises a Group VIB and a Group VIII metal; Preferably, the Group VIB metals include Mo and / or W and the Group VIII metals include Co and / or Ni; 4. A catalyst according to any one of claims 1 to 3, characterized in that, preferably based on the weight of the catalyst, the Group VIB metal sulphide represents from 1 wt % to 20 wt %, preferably from 8 wt % to 16 wt %, of the total mass of the catalyst, and the Group VIII metal sulphide represents from 0.5 wt % to 10 wt %, preferably from 2 wt % to 4 wt %, of the total mass of the catalyst.

5. 5. The catalyst according to claim 1, wherein the total amount of acid in the catalyst is 0.1-0.4 mmol / g, the amount of strong acid at 400-500°C accounts for 5%-15%, the amount of medium strength acid at 250-400°C accounts for 10%-20%, and the rest is weak acid at 150-250°C.

6. A method for preparing a hydrogenation catalyst, comprising the steps of: Step I) roasting the alumina powder A at a high temperature in an oxygen-containing atmosphere to obtain an alumina drysol powder B; Step II) of immersing the alumina dry sol powder B in a hydrogenation active component immersion solution C, drying the alumina dry sol powder B, roasting the alumina dry sol powder B at a high temperature in an oxygen-containing atmosphere, and then sulfurizing the alumina dry sol powder B to obtain a powder E; and step III) of shaping, drying and roasting the powder E prepared in step (2), The method for preparing a hydrogenation catalyst, wherein the high-temperature roasting temperatures in steps I) and II) are each 800°C or higher.

7. The method further comprises the steps of soaking the alumina powder A with an activator soak solution D, drying, and reducing to obtain a powder F; Step III) includes mixing the powder E and the powder F, followed by molding, drying, and roasting; Preferably, The reduction treatment includes roasting in a reducing atmosphere, preferably in a hydrogen atmosphere; In the reduction treatment, the roasting conditions include a roasting temperature of 300 to 700°C and a roasting time of 2 to 5 hours; Preferably, before reduction, the drying conditions include a drying time of 1 to 5 hours and a drying temperature of 80 to 120°C; The preparation method according to claim 6, wherein the immersion method of the immersion with the active agent is saturated immersion or supersaturated immersion.

8. The physical and chemical parameters of alumina powder A are: specific surface area 100-480 m ２ / g, pore volume 0.4-1.2 cm ３ / g, and a pore size of 4.0 to 35.0 nm.

9. In step I), The oxygen content in the oxygen-containing atmosphere is 10% to 30% by volume, and preferably an air atmosphere is used; and / or The method according to any one of claims 6 to 8, wherein the high-temperature roasting conditions include a roasting temperature of 800 to 1100°C and a roasting time of 0.5 to 5 hours.

10. In step II), The oxygen content in the oxygen-containing atmosphere is 10% to 30% by volume, and preferably an air atmosphere is used; and / or The method according to any one of claims 6 to 9, wherein the high-temperature roasting conditions include a roasting temperature of 800 to 1100°C and a roasting time of 0.5 to 5 hours.

11. The sulfurization treatment in step II) is carried out by roasting in a sulfurizing atmosphere, preferably H ２ S and H ２ and preferably in a mixed atmosphere of H ２ S and H ２ H in a mixed atmosphere ２ S accounts for 0.1v% to 2v%; The method according to any one of claims 6 to 10, wherein the roasting conditions are preferably a roasting temperature of 250 to 550°C and a roasting time of 3 to 8 hours.

12. The method according to any one of claims 6 to 11, wherein the immersion method of step II) is saturated immersion or supersaturated immersion.

13. Step III) the catalyst molding process is to add extrusion aid, gel solvent and water to the composite powder to mix it into a plastic, and then knead and mold it; Preferably, the extrusion aid is one or more of methyl cellulose, sesbania gum powder, starch, and polyvinyl alcohol; 13. The method according to any one of claims 6 to 12, wherein the gel solvent is preferably one or more of dilute nitric acid, dilute phosphoric acid, and silicic acid.

14. The method according to any one of claims 6 to 13, wherein the drying conditions in steps II) and III) comprise a drying time of 1 to 5 hours and a drying temperature of 80 to 120°C, respectively.

15. The roasting conditions in step III) include a roasting temperature of 200 to 350°C and a roasting time of 1 to 4 hours; The roasting atmosphere was N ２ 15. The method according to claim 6, wherein the inert atmosphere is one or more gases selected from the group consisting of Ar, He, and Ar.

16. Use of the hydrogenation catalyst according to any one of claims 1 to 5 in a reaction for preparing low-carbon hydrocarbons by hydrogenation of ethylene cracking raffinate, liquefied gas or dry gas, preferably dry gas hydrogenation, comprising: Preferably, the reaction conditions for the low-carbon hydrocarbon preparation reaction by dry gas hydrogenation are a reaction pressure of 0.1 to 10 MPa and a space velocity of 300 to 10,000 h －１ , reaction temperature 150-400°C, including use.

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