Metal-doped alumina supported basic catalyst, and preparation method therefor and use thereof

Abstract

Disclosed in the present invention are a metal-doped alumina supported basic catalyst, and a preparation method therefor and a use thereof. The catalyst comprises a support and a basic component supported on the support. The support comprises Al2O3, AgxOy and RemOn. By regulating one or more of the following parameters or conditions: the content and / or valence state of AgxOy and RemOn in the support, and the synergistic effect thereof with Al2O3 in the support, the supported basic component, and an optional modified component, the performance of the catalyst is significantly improved, so that the catalyst has better desulfurization efficiency and operation period, and can achieve adsorption removal and refining of different organic and inorganic sulfides under low temperature conditions. Moreover, the catalyst can be regenerated repeatedly, and the preparation method therefor is simple and easy to implement, and is suitable for industrial production.

Description

Metal-doped alumina supported alkaline catalysts, their preparation methods and applications Technical Field

[0001] This invention relates to the field of catalyst technology, and more specifically, to metal-doped alumina-supported alkaline catalysts, their preparation methods, and applications. Background Technology

[0002] The surface acid-base properties of supported basic catalysts are mainly influenced by the combined acid-base properties of the supported metal and the support itself. Due to differences in ionic radius, metallic properties, and the strength of their interactions with the support, the number and intensity of basic sites on the catalyst surface will vary accordingly. Solid supported basic catalysts possess a series of advantages, including large specific surface area, simple preparation process, and low deactivation rate, making them highly suitable for large-scale industrial production.

[0003] In existing common catalyst preparation methods, silver components are usually introduced using silver nitrate as a precursor through impregnation or spraying. However, this method tends to result in poor silver dispersion, causing the silver components to aggregate into a flake-like form, which then covers the surface of other active component particles, leading to a loss of catalytic activity and adsorption capacity.

[0004] Direct crude oil cracking technology struggles to remove and refine sulfur impurities at the cracking front end, limiting impurity removal to the cracked gas separation stage. While inorganic sulfur can be removed via alkaline scrubbing, removing organic sulfur fractions using existing technologies is challenging, negatively impacting downstream separation and catalyst stability. Currently, widely used industrial methods for organic sulfur removal primarily include hydrodesulfurization and catalytic hydrolysis.

[0005] Hydrodesulfurization catalysts typically use Co, Mo, and Ni as the main active components. For example, CN116196966A discloses an alumina-based desulfurization catalyst supported on Ni-Mo nitrides. This catalyst is suitable for the catalytic hydrodesulfurization reaction of dibenzothiophene in cyclohexane, achieving a maximum desulfurization rate of 79.14%. However, the desulfurization rate of this catalyst is still not high enough to meet the requirements of fine desulfurization.

[0006] Catalytic hydrolysis desulfurization refers to the process where sulfides are first hydrolyzed on a catalyst to convert into hydrogen sulfide, and then the generated hydrogen sulfide is adsorbed and removed. Currently, commercially available traditional organic sulfur hydrolysis desulfurizers mainly include alumina-based, titanium oxide-based, or activated carbon-based materials, such as iron oxide desulfurizers, zinc oxide desulfurizers, activated carbon desulfurizers, and nano-adsorbent materials. Organic sulfur (mainly COS) and inorganic sulfur (mainly H2S) present in blast furnace gas are typically removed using hydrolysis desulfurizers. However, many traditional desulfurizers (such as iron oxide desulfurizers, zinc oxide desulfurizers, activated carbon desulfurizers, and nano-adsorbent materials) suffer from insufficient desulfurization efficiency (e.g., desulfurization efficiency and precision), short service life, and high replacement costs. Therefore, there is an urgent need in this field to develop novel catalysts with improved desulfurization efficiency and shorter operating cycles. Summary of the Invention

[0007] The purpose of this invention is to overcome the problems of poor removal performance of desulfurization catalysts from sulfur-containing hydrocarbons such as crude oil cracking products, short catalytic cycle, and limited desulfurization conditions (requiring low-temperature desulfurization) in existing technologies. This invention provides a novel metal-doped alumina-supported alkaline catalyst, its preparation method, and its applications. The support for this metal-doped alumina-supported alkaline catalyst comprises Al2O3 and Ag. x O y and Re m O n By regulating Ag in the carrier x O y and Re m O n The content and / or valence state of the catalyst, as well as one or more parameters or conditions such as its synergistic effect with Al2O3 in the support, the supported alkaline components, and optional modifying components, enable the catalyst to have better catalytic performance.

[0008] To achieve the above objectives, a first aspect of the present invention provides a metal-doped alumina-supported alkaline catalyst, the catalyst comprising a support and an alkaline component supported on the support; the support comprises Al2O3 and Ag. x O y and Re m O n Ag x O y Includes one or more of elemental Ag and Ag oxides, wherein x is 1 or 2, and y is 0 or 1; Re m O nThe catalyst comprises one or more of elemental Re and Re oxides, wherein m is 1 or 2, and n is an integer selected from 0 to 7; in the catalyst, the weight ratio of Ag to Re, based on metal elements, is 1:0.3-5, preferably 1:0.5-2.05; the Al2O3 has a crystal form including θ phase and / or γ phase; the alkaline component is selected from one or more of alkali metals, alkaline earth metals, and organic alkaline compounds.

[0009] A second aspect of this invention provides a method for preparing a metal-doped alumina-supported alkaline catalyst, the method comprising the following steps:

[0010] S1. A mixture is obtained by mixing powdered raw materials with an acidic aqueous solution. After kneading and molding, the mixture is subjected to a first drying and a first calcination to obtain a carrier. The powdered raw materials include alumina precursor powder and one or more powders selected from silver perrhenate, silver nitrate, silver oxide, and rhenium oxide. In the mixture, the weight ratio of Ag to Re, based on metal elements, is 1:0.3-5, preferably 1:0.5-2.5. The temperature of the first calcination is 300-650℃, preferably 380-600℃.

[0011] S2, a precursor loaded with an alkaline component, is then subjected to a second drying and optional second calcination, as well as optional reduction.

[0012] A third aspect of the present invention provides a metal-doped alumina-supported alkaline catalyst prepared by the preparation method described in the second aspect above.

[0013] The fourth aspect of the present invention provides the application of the metal-doped alumina-supported alkaline catalyst as described in the first and third aspects above in catalytic desulfurization.

[0014] The fifth aspect of the present invention provides a method for removing sulfides contained in hydrocarbon materials, the method comprising: subjecting the hydrocarbon material to gas-solid contact or liquid-solid contact with the metal-doped alumina-supported alkaline catalyst described in the first or third aspect at a temperature of 20-80°C.

[0015] The beneficial technical effects achieved by the present invention through the above technical solution are as follows:

[0016] The support for the metal-doped alumina-supported alkaline catalyst of the present invention comprises Al2O3 and Ag. x O y and Re m O n By regulating Ag in the carrier x O y and Re m O nThe content and / or valence state of the catalyst, as well as one or more of the parameters or conditions such as its synergistic effect with Al2O3 in the support, the supported alkaline components, and optional modified components, significantly improve the performance of the catalyst, giving it better desulfurization precision and operating cycle. It can achieve adsorption, removal, and purification of different organic and inorganic sulfides under low temperature conditions. Furthermore, the catalyst can be repeatedly regenerated, and its preparation method is simple and easy to implement, facilitating industrial production.

[0017] Other features and advantages of this application will be described in detail in the following detailed description section. Attached Figure Description

[0018] Figure 1 is an X-ray photoelectron spectroscopy (XPS) spectrum of Re in the support of catalyst A-4 prepared in Example 4;

[0019] Figure 2 is an X-ray photoelectron spectroscopy (XPS) pattern of Ag in the support of catalyst A-4 prepared in Example 4. Detailed Implementation

[0020] The specific embodiments of this application will be described in detail below. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit this application.

[0021] Any specific numerical values ​​disclosed herein (including the endpoints of numerical ranges) are not limited to their exact values, but should be understood to also include values ​​close to the exact value, such as all possible values ​​within ±10% of the exact value. Furthermore, with respect to the disclosed numerical ranges, one or more new numerical ranges can be obtained by arbitrarily combining the endpoint values ​​of the range, the endpoint values ​​with specific point values ​​within the range, and the specific point values ​​themselves; these new numerical ranges should also be considered as specifically disclosed herein.

[0022] Unless otherwise stated, the terms used herein have the same meaning as commonly understood by those skilled in the art, and if a term is defined herein and its definition differs from the common understanding in the art, the definition herein shall prevail.

[0023] A first aspect of this invention provides a metal-doped alumina-supported alkaline catalyst, the catalyst comprising a support and an alkaline component supported on the support; the support comprises Al2O3 and Ag. x O y and Re m O n Ag x O y Includes one or more of elemental Ag and Ag oxides; Re m O nThe catalyst includes one or more of elemental Re and Re oxides; in the catalyst, the weight ratio of Ag to Re, based on metal elements, is 1:0.3-5; the alkaline component is selected from one or more of alkali metals, alkaline earth metals, and organic alkaline compounds.

[0024] The support for the metal-doped alumina-supported alkaline catalyst according to the present invention comprises Al2O3 and Ag. x O y and Re m O n Ag x O y Re m O n It is uniformly distributed with Al2O3. Through extensive research, the inventors discovered that Re and Ag have a significant synergistic effect; Re existing with Ag in a specific ratio can both prevent excessive Ag aggregation and alter the chemical shift of silver. On the other hand, due to the formation of rhenium oxide anions, the high-valence state Re... n+ This leads to an enhanced binding energy of the Ag 3d orbitals, making Ag electron-deficient and increasing its ability to acquire electrons from specific adsorbates.

[0025] According to some embodiments of the present invention, in the catalyst, the weight ratio of Ag to Re, based on metal elements, can be 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, 1:2.2, 1:2.5, 1:2.8, 1:3, 1:3.2, 1:3.5, 1:3.8, 1:4, 1:4.2, 1:4.5, 1:4.8, 1:5, or any value within a range of any two values, and is further preferably 1:0.5-2.5. By controlling the weight ratio of Ag to Re within a specific range, the dispersibility and chemical shift of Ag can be improved, thereby enhancing the desulfurization performance of the catalyst.

[0026] According to the present invention, the Ag x O y In the context, x = integers from 1 to 2, and y = integers from 0 to 1; the Re m O n In this context, m = integers from 1 to 2 and n = integers from 1 to 7.

[0027] According to some embodiments of the present invention, Ag x O y In the equation, x is 1 or 2, and y is 0 or 1.

[0028] According to some embodiments of the present invention, the Ag oxide includes Ag2O and AgO.

[0029] According to some preferred embodiments of the present invention, Ag x O y It includes elemental Ag and Ag₂O.

[0030] According to some preferred embodiments of the present invention, based on the total molar amount of Ag, the molar content of elemental Ag is ≥20%. For example, the molar content of elemental Ag can be 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 80%, 85%, 90%, 95%, 100%, or any value within any range of any two values, preferably 30-70%.

[0031] According to some preferred embodiments of the present invention, based on the total molar amount of Ag, the molar content of Ag₂O is ≥10%. For example, the molar content of Ag₂O can be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 80%, 85%, 90%, 95%, 100%, or any value within any range of any two values, preferably 30-70%.

[0032] According to some embodiments of the present invention, Re m O n In this context, m is either 1 or 2, and n is an integer selected from 0 to 7.

[0033] According to some preferred embodiments of the present invention, the Re oxide includes ReO2, ReO3 and Re2O7.

[0034] According to some preferred embodiments of the present invention, Re is expressed as Re. m O n Based on the total molar amount, the molar content of elemental Re is 20-70%.

[0035] According to some embodiments of the present invention, Re m O n It includes elemental Re, ReO2, ReO3, and Re2O7.

[0036] According to some preferred embodiments of the present invention, based on the total molar amount of Re, the molar content of elemental Re is ≥10%. For example, the molar content of elemental Re can be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, or any value within any range of any two values, preferably 15-70%, and more preferably 20-50%.

[0037] According to some preferred embodiments of the present invention, based on the total molar amount of Re element, the molar content of Re2O7 is ≥15%. For example, the molar content of Re2O7 can be 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or any value within any range of any two values, preferably 20-70%, and more preferably 20-50%.

[0038] According to some preferred embodiments of the present invention, based on the total molar amount of Re element, the molar content of ReO2 is ≥5%, for example, the molar content of ReO2 can be 5%, 10%, 15%, 20%, 25%, 30%, and any value in the range of any two values, preferably 5-25%.

[0039] According to some preferred embodiments of the present invention, based on the total molar amount of Re element, the molar content of ReO3 is ≥1%, for example, the molar content of ReO3 can be 1%, 5%, 10%, 15%, 20%, 25%, 30%, and any value in the range of any two values, preferably 1-30%.

[0040] The inventors, through extensive research, discovered that Ag containing a relatively high molar content in a specific valence state... x O y and / or Re m O n The catalyst exhibits a more efficient removal capacity for specific sulfides. For materials containing specific sulfides, the removal efficiency can be adjusted by controlling the Ag content in the catalyst. x O y and Re m O n The valence state and molar content are used to further optimize the low-temperature removal performance of various sulfides.

[0041] According to some embodiments of the present invention, Ag is calculated as Ag element based on the total weight of the catalyst. x O y The weight content is 0.2-15 wt%, for example, Ag. x O y The weight content can be 0.2wt%, 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 12wt%, 15wt%, or any value within any range of any two values, preferably 2-10wt%.

[0042] According to some embodiments of the present invention, Re is calculated as Re element based on the total weight of the catalyst.m O n The weight content is 0.2-15 wt%, for example, Re m O n The weight content can be 0.2wt%, 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 12wt%, 15wt%, or any value within any range of any two values, preferably 3-12wt%.

[0043] According to the present invention, the content of each element can be calculated based on the amount of feed, or it can be determined by detection methods such as inductively coupled plasma atomic emission spectrometry (ICP-AES) and X-ray fluorescence spectrometry (XRF).

[0044] According to some embodiments of the present invention, the Al2O3 in the carrier includes θ phase and / or γ phase crystal forms.

[0045] According to some preferred embodiments of the present invention, based on the total weight of Al2O3 and optionally Al(OH)3, the weight content of the θ phase crystal form is ≤20wt%, for example, the weight content of the θ phase crystal form can be 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 12wt%, 15wt%, 18wt%, 20wt%, and any value within the range of any two values, preferably 2-16wt%; the weight content of the γ phase crystal form is ≥70wt%, for example, the weight content of the γ phase crystal form can be 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, and any value within the range of any two values, preferably 75-88wt%.

[0046] According to some preferred embodiments of the present invention, the support further comprises Al(OH)3, with the weight content of Al(OH)3 being 5-15 wt% based on the total weight of Al2O3 and Al(OH)3. For example, the weight content of Al(OH)3 can be 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, or any value within any range of any two values. The inventors have discovered through extensive research that a small amount of Al(OH)3 is beneficial for the dissociation of COS and CS2 into H2S, promoting adsorption. Therefore, by controlling the weight content of Al(OH)3 in the support, the low-temperature catalytic desulfurization performance of the catalyst can be optimized.

[0047] According to some embodiments of the present invention, based on the total weight of the catalyst, the weight content of the alkaline component is 1-30 wt%, preferably 2-25 wt%, and more preferably 10-20 wt%. For example, the weight content of the alkaline component can be 1 wt%, 2 wt%, 5 wt%, 8 wt%, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, 25 wt%, 28 wt%, 30 wt%, or any value within a range of any two values. By adjusting the alkaline component and its weight content, the low-temperature catalytic desulfurization performance of the catalyst can be optimized.

[0048] According to some embodiments of the present invention, the alkali metal is selected from Li, Na, K, Cs and combinations thereof.

[0049] According to some embodiments of the present invention, the alkaline earth metal is selected from Mg, Ca, Sr and combinations thereof.

[0050] According to some embodiments of the present invention, the organic basic compound is selected from one or more organic amines, pyridines, and guanidines.

[0051] According to some preferred embodiments of the present invention, the organic basic compound is selected from one or more of dimethylamine, triethylamine, trifluoroacetamide, pyridine, 4-dimethylaminopyridine, triethanolamine and tetramethylguanidine.

[0052] According to some embodiments of the present invention, the catalyst further includes a modifying component supported on the support; the modifying component is selected from one or more of Group VIII elements, Group IIIA elements, Group IB elements excluding Ag, Group IIB elements, Group IIIB elements, Group IVB elements, Group VIIB elements excluding Re, and rare earth elements.

[0053] According to some preferred embodiments of the present invention, the modified component is selected from one or more of Ga, In, La, Zn, Fe, Ce, Y and Mn.

[0054] According to some embodiments of the present invention, based on the total weight of the catalyst, the weight content of the modified component is 0-20 wt%, preferably 0.1-15 wt%, and more preferably 1-12 wt%. For example, the weight content of the modified component can be 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%, 5 wt%, 8 wt%, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, or any value within any range of two such values. By adjusting the modified component and its weight content in the catalyst, the low-temperature desulfurization performance of the catalyst can be further optimized.

[0055] According to some embodiments of the present invention, the specific surface area of ​​the carrier is 100-500 m². 2 / g, preferably 150-450m 2 / g, more preferably 200-350m 2 / g.

[0056] According to some embodiments of the present invention, the catalyst does not contain metals with hydrogenation catalytic properties, such as Pd, Co, Mo, and Ni. By controlling the metal elements contained in the catalyst, it can be made to have excellent low-temperature desulfurization performance without triggering other reactions that crack hydrocarbon materials.

[0057] A second aspect of this invention provides a method for preparing a metal-doped alumina-supported alkaline catalyst, the method comprising the following steps:

[0058] S1. A mixture is obtained by mixing powdered raw materials with an acidic aqueous solution. After kneading and molding, the mixture is subjected to a first drying and a first calcination to obtain a carrier. The powdered raw materials include alumina precursor powder and one or more powders selected from silver perrhenate, silver nitrate, silver oxide and rhenium oxide. In the mixture, the weight ratio of Ag to Re, based on metal elements, is 1:0.3-5, preferably 1:0.5-2.5.

[0059] S2, a precursor loaded with an alkaline component, is then subjected to a second drying and optional second calcination, as well as optional reduction.

[0060] According to some embodiments of the present invention, the alumina precursor powder is selected from boehmite powder and optionally alumina powder.

[0061] According to some embodiments of the present invention, the alumina powder is obtained by calcining pseudoboehmite powder at a temperature selected from 450-900°C, and the amount of alumina powder accounts for 0-20 wt% of the total weight of the alumina precursor powder. For example, the amount of alumina powder can be 0 wt%, 0.5 wt%, 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt% of the total weight of the alumina precursor powder, or any value within a range of any two values.

[0062] According to the present invention, the method for preparing silver perrhenate comprises: adding a silver nitrate solution to an acidic solution of perrhenic acid or an ammonium perrhenate solution to produce a white precipitate. The molar ratio of silver nitrate to perrhenic acid or ammonium perrhenate is preferably 1:1. The acidic solution is preferably a nitric acid solution. The temperature at which the solution is added is preferably 30-50°C.

[0063] According to some embodiments of the present invention, the alkaline component is loaded in the form of an alkaline solution by means of spraying or equal-volume impregnation; the alkaline solution contains organic alkaline compounds and / or inorganic alkaline compounds.

[0064] According to some preferred embodiments of the present invention, the organic basic compound is selected from one or more organic amines, pyridines, and guanidines.

[0065] According to some preferred embodiments of the present invention, the organic basic compound is selected from one or more of dimethylamine, triethylamine, trifluoroacetamide, pyridine, 4-dimethylaminopyridine, triethanolamine and tetramethylguanidine.

[0066] According to some embodiments of the present invention, when the alkaline solution contains an organic alkaline compound, it is preferable not to perform a second calcination.

[0067] According to some preferred embodiments of the present invention, the inorganic basic compound is selected from one or more of the following: ammonium compounds, hydroxides, halides, citrates, oxalates, acetates, bicarbonates, carbonates, and organic compounds of Li, Na, K, Cs, Mg, Ca, and Sr.

[0068] According to some preferred embodiments of the present invention, the inorganic alkaline compound is selected from one or more of potassium chloride, lithium chloride, potassium acetate, sodium bicarbonate, sodium citrate, potassium carbonate, potassium hydroxide, magnesium hydroxide, and calcium hydroxide.

[0069] According to some preferred embodiments of the present invention, the solvent in the alkaline solution is selected from one or more of water, ethanol, acetone and tetrahydrofuran.

[0070] According to some preferred embodiments of the present invention, the concentration of organic alkaline compounds and / or inorganic alkaline compounds in the alkaline solution is 0.1-100 wt%.

[0071] According to some embodiments of the present invention, the acidic aqueous solution is a mixed aqueous solution of perrhenic acid and other acids; the other acids are selected from one or more of nitric acid, acetic acid, oxalic acid and citric acid.

[0072] According to some preferred embodiments of the present invention, the weight ratio of perrhenic acid to other acids is (0.2-10):1. For example, the weight ratio of perrhenic acid to other acids can be 0.2:1, 0.5:1, 1:1, 2:1, 5:1, 10:1, or any value within the range of any two values.

[0073] According to some preferred embodiments of the present invention, the weight ratio of the acidic aqueous solution to the powdered raw material is (0.4-2):1. For example, the weight ratio of the acidic aqueous solution to the powdered raw material can be 0.4:1, 0.6:1, 0.8:1, 1:1, 1.2:1, 1.5:1, 2:1, or any value within the range of any two values.

[0074] According to some embodiments of the present invention, the powdered raw material further includes a forming and pore-forming agent; the amount of the forming and pore-forming agent is 0-10 wt% of the total weight of the alumina precursor powder.

[0075] According to some preferred embodiments of the present invention, the molding pore-forming agent is selected from one or more of guar gum powder, starch, cellulose, urea, ethylenediamine and polymers.

[0076] According to some preferred embodiments of the present invention, the cellulose is selected from one or more of methylcellulose, hydroxypropyl methylcellulose and sodium hydroxymethylcellulose.

[0077] According to some preferred embodiments of the present invention, the polymer is selected from one or more of polyethylene microspheres, polystyrene, polyethylene glycol, polyvinyl alcohol, and polyethylene glycol.

[0078] According to some embodiments of the present invention, the temperature of the first drying is 60-120°C and the time is 8-24 hours.

[0079] According to some embodiments of the present invention, the temperature of the first calcination is 300-650°C, preferably 380-600°C. For example, the temperature of the first calcination can be 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, 650°C, or any value within a range of any two values.

[0080] According to some embodiments of the present invention, the first roasting time is 2-20 hours, preferably 3-10 hours.

[0081] According to some embodiments of the present invention, the pressure of the first calcination is 1-5 MPa, preferably 2-4 MPa.

[0082] According to some embodiments of the present invention, the atmosphere of the first calcination is selected from at least one of inert gas, nitrogen, air and oxygen.

[0083] According to some embodiments of the present invention, the atmosphere of the first roasting contains oxygen, wherein the oxygen content is >0-40 wt%, preferably 15-25 wt%.

[0084] According to some embodiments of the present invention, the temperature of the second drying is 60-260°C.

[0085] According to some embodiments of the present invention, the second calcination temperature is 200-550°C, preferably 350-450°C. For example, the second calcination temperature can be 200°C, 250°C, 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, or any value within a range of any two values.

[0086] According to some embodiments of the present invention, the atmosphere for the second calcination is selected from at least one of an inert gas, nitrogen, and air.

[0087] According to some embodiments of the present invention, the method further includes:

[0088] S3, the precursor of the loaded modified component, is then subjected to a third drying and a third calcination.

[0089] According to some embodiments of the present invention, step S3 is performed between steps S1 and S2.

[0090] According to some embodiments of the present invention, the modified component is loaded in the form of a solution containing a precursor of the modified component, and the loading method is spraying or equal volume impregnation.

[0091] According to some embodiments of the present invention, the precursor of the modified component is selected from at least one of the halides, nitrates, acetates, carbonates, sulfates, hydroxides, ammonides, and organometallic compounds of the modified component.

[0092] According to some embodiments of the present invention, the modified component is selected from one or more of Ga, In, La, Zn, Fe, Ce, Y and Mn.

[0093] According to some embodiments of the present invention, the third drying temperature is 80-140°C and the time is 8-24 hours.

[0094] According to some embodiments of the present invention, the temperature of the third calcination is 200-480°C. For example, the temperature of the third calcination can be 200°C, 250°C, 300°C, etc.

[0095] 350℃, 400℃, 450℃, 480℃, and any value within the range of any two values.

[0096] According to some embodiments of the present invention, the third calcination time is 4-20 hours, preferably 6-10 hours; the pressure is atmospheric pressure.

[0097] According to some embodiments of the present invention, the atmosphere of the third calcination is selected from at least one of inert gas, nitrogen, air and oxygen; preferably, the oxygen content in the atmosphere is 0-40 wt%, more preferably 15-25 wt%.

[0098] According to some embodiments of the present invention, the reducing atmosphere is selected from hydrogen, hydrogen-containing nitrogen, and hydrogen-containing methane.

[0099] According to some embodiments of the present invention, the volume content of hydrogen in the reducing atmosphere is 1-50%. For example, the volume content of hydrogen in the reducing atmosphere can be 1%, 2%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, or any value within a range of any two values.

[0100] According to some embodiments of the present invention, the reduction temperature is 50-370℃, preferably 100-320℃; the temperature fluctuation range is ±2℃, preferably ±1℃; the reduction time is 5min-10 hours, preferably 10min-4 hours.

[0101] According to some embodiments of the present invention, the reduction may be performed before or after loading the alkaline component.

[0102] The method of the present invention achieves Ag in the catalyst carrier by using a combination of powder kneading and spraying or impregnation. x O y Re m O n The uniform distribution of Al2O3 and Al(OH)3, as well as the basic components and optional modifying components on the support, and the obtaining of Ag in different valence states through optional reduction treatment. x O y and Re m O n The synergistic effect of the catalyst with the supported alkaline component and the modified component gives it improved low-temperature catalytic desulfurization performance. The preparation method of this invention is simple and easy to implement, facilitating industrial production.

[0103] A third aspect of the present invention provides a metal-doped alumina-supported alkaline catalyst prepared by the preparation method described in the second aspect above.

[0104] The fourth aspect of the present invention provides the application of the metal-doped alumina-supported alkaline catalyst as described in the first and third aspects above in catalytic desulfurization.

[0105] The catalyst of this invention can be used for the removal and refining of sulfides in various sulfur-containing hydrocarbon materials, such as those produced by direct cracking of crude oil.

[0106] According to some embodiments of the present invention, the sulfide is selected from one or more of inorganic sulfur and organic sulfur.

[0107] According to some embodiments of the present invention, the inorganic sulfur is selected from one or more of hydrogen sulfide and sulfur dioxide.

[0108] According to some embodiments of the present invention, the organic sulfur is selected from one or more of carbonyl sulfide, carbon disulfide, thiols, thioethers, and thiophenes. According to some preferred embodiments of the present invention, the organic sulfur is selected from one or more of carbonyl sulfide, carbon disulfide, C1-C4 thiols, and C1-C4 thioethers.

[0109] The fifth aspect of the present invention provides a method for removing sulfides contained in hydrocarbon materials, the method comprising: subjecting the hydrocarbon material to gas-solid contact or liquid-solid contact with the metal-doped alumina-supported alkaline catalyst described in the first or third aspect above under conditions of 20-80°C, so as to catalyze a desulfurization reaction.

[0110] According to some embodiments of the present invention, the hydrocarbon materials include hydrocarbon materials produced by direct cracking of crude oil, such as cracked gas from crude oil and C4 materials from crude oil.

[0111] The present invention also discloses the following embodiments:

[0112] Option 1: A metal-doped alumina-supported alkaline catalyst, characterized in that the catalyst comprises a support and an alkaline component supported on the support; the support contains Al2O3 and Ag. x O y and Re m O n Ag x O y Selected from one or more of elemental Ag and Ag oxides; Re m O n The basic component is selected from one or more of elemental Re and Re oxides; the basic component is selected from one or more of alkali metals, alkaline earth metals and organic basic compounds.

[0113] Option 2: The catalyst according to Option 1, wherein Ag x O y In the diagram, x is 1 and / or 2, and y is 0 and / or 1;

[0114] Preferably, Ag x O y Including elemental Ag and Ag₂O;

[0115] More preferably, Ag calculated as Ag x O yBased on the total molar amount, the molar content of elemental Ag is 30-70%.

[0116] Option 3: The catalyst according to Option 1 or 2, wherein Re m O n In this context, m is 1 and / or 2, and n is an integer selected from at least one of 0-7;

[0117] Preferably, the Re oxide includes ReO2, ReO3, and Re2O7;

[0118] More preferably, Re in Re terms m O n Based on the total molar amount, the molar content of elemental Re is 20-70%.

[0119] Option 4: The catalyst according to Option 3, wherein Re m O n Including elemental Re, ReO2, and Re2O7;

[0120] Preferably, Re is expressed as Re. m O n Based on the total molar amount, the molar content of elemental Re is 20-60%, and the molar content of Re2O7 is 20-50%.

[0121] Option 5: Based on the catalyst described in any one of Options 1-4, the Ag content, calculated as Ag element, is based on the total mass of the catalyst. x O y The mass content is 0.2-15 wt%, preferably 2-10 wt%;

[0122] And / or, based on the total mass of the catalyst, Re elemental concentration. m O n The mass content is 0.2-15 wt%, preferably 4-12 wt%.

[0123] Scheme 6: According to any one of Schemes 1-5, the crystal form of Al2O3 includes θ phase and / or γ phase; wherein, based on the total mass of Al2O3, the mass content of θ phase is <20wt% and the mass content of γ phase is >70wt%.

[0124] And / or, the carrier further contains Al(OH)3, with the Al(OH)3 content being 5-15 wt% based on the total mass of Al2O3 and Al(OH)3.

[0125] Scheme 7: The catalyst according to any one of Schemes 1-6, wherein, based on the total mass of the catalyst, the mass content of the alkaline component is 1-30 wt%, preferably 5-25 wt%, more preferably 10-20 wt%;

[0126] And / or, the alkali metal is selected from one or more of Li, Na, K and Cs;

[0127] And / or, the alkaline earth metal is selected from one or more of Mg, Ca, and Sr;

[0128] And / or, the organic basic compound is selected from one or more of organic amines, pyridines and guanidines; preferably, the organic basic compound is selected from one or more of dimethylamine, triethylamine, trifluoroacetamide, pyridine, 4-dimethylaminopyridine, triethanolamine and tetramethylguanidine.

[0129] Option 8: The catalyst according to any one of Options 1-7, wherein the catalyst further comprises a modifying component supported on the support; the modifying component is selected from one or more of Group VIII elements, Group IIIA elements, Group IB elements excluding Ag, Group IIB elements, Group IIIB elements, Group VIIB elements excluding Re, and rare earth elements.

[0130] Preferably, the modified component is selected from one or more of Ga, In, La, Ni, Zn, Fe, Ce, Y and Mn.

[0131] Scheme 9: The catalyst according to Scheme 8, wherein, based on the total mass of the catalyst, the mass content of the modified component is 0-20 wt%, preferably 2-15 wt%, and more preferably 5-15 wt%.

[0132] Option 10: The catalyst according to any one of Options 1-9, wherein the specific surface area of ​​the support is 100-500 m². 2 / g, preferably 150-450m 2 / g, more preferably 200-350m 2 / g.

[0133] Scheme 11: A method for preparing a metal-doped alumina-supported alkaline catalyst, characterized in that the preparation method includes the following steps:

[0134] S1. The powdered raw material is mixed with an acidic aqueous solution, kneaded and shaped, and then subjected to a first drying and a first calcination to obtain a carrier; wherein the powdered raw material includes alumina powder and one or more powders selected from silver perrhenate, silver nitrate, silver oxide and rhenium oxide.

[0135] S2. The precursor of the basic component and the precursor of the optional modified component are loaded onto the support obtained in step S1, and then subjected to a second drying and a second calcination, as well as optional reduction.

[0136] Scheme 12: The preparation method according to Scheme 11, wherein the alumina powder is selected from boehmite powder and optionally alumina powder;

[0137] Preferably, the alumina powder is obtained by calcining boehmite powder at a temperature selected from 450-900℃, and the amount of alumina powder accounts for 0-20 wt% of the total mass of the alumina powder.

[0138] Option 13: The preparation method according to Option 11 or 12, wherein the alkaline component is loaded in the form of an alkaline solution by spraying or equal-volume impregnation; the alkaline solution contains organic alkaline compounds and / or inorganic alkaline compounds;

[0139] Preferably, the organic basic compound is selected from one or more of organic amines, pyridines, and guanidines; more preferably, the organic basic compound is selected from one or more of dimethylamine, triethylamine, trifluoroacetamide, pyridine, 4-dimethylaminopyridine, triethanolamine, and tetramethylguanidine.

[0140] Preferably, the inorganic alkaline compound is selected from one or more of ammonia, hydroxides, halides, citrates, oxalates, acetates, bicarbonates, carbonates, and organic compounds of Li, Na, K, Cs, Mg, Ca, and Sr; more preferably, the inorganic alkaline compound is selected from one or more of potassium chloride, lithium chloride, potassium acetate, sodium bicarbonate, sodium citrate, potassium carbonate, potassium hydroxide, magnesium hydroxide, and calcium hydroxide.

[0141] Preferably, the solvent in the alkaline solution is selected from one or more of water, ethanol, acetone, and tetrahydrofuran;

[0142] Preferably, the concentration of organic alkaline compounds and / or inorganic alkaline compounds in the alkaline solution is 0.1-100 wt%.

[0143] Scheme 14: The preparation method according to any one of Schemes 11-13, wherein the modified component is loaded in the form of a solution containing a precursor of the modified component, and the loading method is spraying or equal volume impregnation.

[0144] Preferably, the precursor of the modified component is selected from at least one of the halides, nitrates, acetates, carbonates, sulfates, hydroxides, ammonium compounds, and organometallic compounds of the modified component;

[0145] Preferably, the modified component is selected from one or more of Ga, In, La, Ni, Zn, Fe, Ce, Y and Mn.

[0146] Option 15: The preparation method according to any one of Options 11-14, wherein the acidic aqueous solution is a mixed aqueous solution of perrhenic acid and other acids; the other acids are selected from one or more of nitric acid, acetic acid, oxalic acid and citric acid;

[0147] Preferably, the weight ratio of perrhenic acid to other acids is (0.2-10):1;

[0148] Preferably, the weight ratio of the acidic aqueous solution to the powdered raw material is (0.4-2):1.

[0149] Option 16: The preparation method according to any one of Options 11-15, wherein the powdered raw material further includes a forming pore-forming agent; the amount of the forming pore-forming agent is 0-10 wt% of the total mass of the alumina powder;

[0150] Preferably, the molding and pore-forming agent is selected from one or more of guar gum powder, starch, cellulose, urea, ethylenediamine, and polymers.

[0151] Preferably, the cellulose is selected from one or more of methylcellulose, hydroxypropyl methylcellulose, and sodium hydroxymethylcellulose;

[0152] Preferably, the polymer is selected from one or more of polyethylene microspheres, polystyrene, polyethylene glycol, polyvinyl alcohol, and polyethylene glycol.

[0153] Scheme 17: The preparation method according to any one of Schemes 11-16, wherein the temperature of the first drying is 60-120°C and the time is 8-24 hours;

[0154] And / or, the temperature of the first calcination is 300-600℃, preferably 380-520℃; the time is 4-20 hours, preferably 6-10 hours; and the pressure is 2-5 MPa, preferably 3-4 MPa.

[0155] And / or, the atmosphere of the first calcination is selected from at least one of inert gas, nitrogen, air and oxygen; preferably, the oxygen content in the atmosphere is 0-40 wt%, more preferably 15-25 wt%;

[0156] And / or, the temperature of the second drying is 60-260°C;

[0157] And / or, the temperature of the second calcination is 200-550°C;

[0158] And / or, the atmosphere for the second calcination is selected from at least one of an inert gas, nitrogen, and air.

[0159] Scheme 18: The preparation method according to any one of Schemes 11-17, wherein the reducing gas is hydrogen, hydrogen-containing nitrogen, or hydrogen-containing methane; preferably, the volume content of hydrogen in the reducing gas is 50-100%.

[0160] And / or, the reduction temperature is 20-370℃, preferably 60-320℃; the temperature fluctuation range is ±2℃, preferably ±1℃; the reduction time is greater than 2 hours, preferably 4-20 hours.

[0161] Scheme 19: A metal-doped alumina-supported alkaline catalyst prepared by any one of the preparation methods described in Schemes 11-18.

[0162] Option 20: Application of metal-doped alumina-supported alkaline catalysts as described in any one of Options 1-10 and 19 in catalytic desulfurization.

[0163] Option 21: The application according to Option 20, wherein the metal-doped alumina supported alkaline catalyst is used in the removal of sulfides from hydrocarbon products produced by direct cracking of crude oil.

[0164] Preferably, the sulfide is selected from inorganic sulfur and / or organic sulfur;

[0165] More preferably, the inorganic sulfur is selected from hydrogen sulfide and / or sulfur dioxide;

[0166] More preferably, the organic sulfur is selected from one or more of carbonyl sulfur, carbon disulfide, thiols, thioethers and thiophenes; more preferably, it is selected from one or more of carbonyl sulfur, carbon disulfide, C1-C4 thiols and C1-C4 thioethers.

[0167] Scheme 22, a method for removing sulfides from hydrocarbon materials, characterized in that the method includes: subjecting the hydrocarbon materials to gas-phase or liquid-phase contact with the metal-doped alumina-supported alkaline catalyst described in any one of Schemes 1-10 and 19 at a reaction temperature of 20-80°C to carry out a desulfurization reaction.

[0168] To facilitate understanding of the present invention, the following embodiments are provided. However, these embodiments are only for the purpose of helping to understand the present invention and should not be regarded as specific limitations of the present invention.

[0169] Example

[0170] The present invention will be further described below with reference to the embodiments, but the scope of the present invention is not limited to these embodiments.

[0171] Characterization methods:

[0172] X-ray photoelectron spectroscopy (XPS): In the following examples and comparative examples, the relative molar contents of elemental Ag, Ag oxides, elemental Re, and Re oxides in each catalyst or support were determined using X-ray photoelectron spectroscopy. The X-ray photoelectron spectroscopy analyzer used was a ThermoVG ESCALAB 250Xi model, with an optimal resolution of <3 μm, an optimal energy resolution of <0.45 eV, a C1s energy resolution of <0.82 eV, an ion source energy range of 0-5000 eV, a maximum beam current of 4 μA, and an optimal vacuum of 3 × 10⁻⁶. -9 mbar.

[0173] X-ray diffraction (XRD): In the following examples and comparative examples, the crystal form and relative weight content of Al2O3 in each catalyst or support were determined using XRD. The instrument used was a Bruker D8 ADVANCE high-power rotating target X-ray diffractometer with a tube voltage of 40 kV, a tube current of 300 mA, a slit system of 1.0-1.0-0.2 mm, a scanning step size of 0.02° / step, a scanning time of 0.5 s / step, an angular measurement (2θ) range of 10°-90°, and an angular measurement repeatability of 0.0001°.

[0174] Static volumetric nitrogen adsorption analysis: In the following examples and comparative examples, the specific surface area of ​​the samples was calculated using static volumetric nitrogen adsorption analysis combined with BET theoretical equations. The instrument used was a Quantachrome Autosorb-iQ-C adsorption analyzer (USA).

[0175] In the following examples and comparative examples, the pseudoboehmite powder was purchased from Sinopec Catalysts (Beijing) Co., Ltd., and had a specific surface area of ​​250 m². 2 / g or more.

[0176] Unless otherwise specified, the reagents used in the following examples and comparative examples are all conventionally used in the art, and the methods employed are all conventionally used in the art.

[0177] Preparation Example

[0178] Dissolve 100g of silver nitrate in 200ml of deionized water. Dissolve 150g of ammonium perrhenate in 500ml of deionized water. Under stirring at 40℃, slowly add the silver nitrate aqueous solution, producing a white precipitate. After all the solution has been added, let it stand for 30 minutes, then stop adding and cool to room temperature. Remove the filtrate, wash the white precipitate three times with ether, and dry it under vacuum at 80℃ to obtain silver perrhenate.

[0179] Example 1

[0180] (1) Weigh 217g of boehmite powder, 12.8g of silver perrhenate, 5g of silver nitrate, 4.5g of guar gum powder, 9g of methylcellulose, and 5g of polystyrene, and mix them in a mixer to obtain a uniform powdered raw material.

[0181] (2) Weigh 3g of citric acid and 11.4g of 75% perrhenic acid and add them to 290g of deionized water to prepare an acidic aqueous solution;

[0182] (3) The uniform powdered raw material was transferred to a kneader, and an acidic aqueous solution was slowly added. After kneading for 30 minutes, the mixture was extruded and pelletized to obtain toothed spherical carrier particles with a particle size of 4-5 mm. The particles were dried at 110℃ for 10 hours and then calcined at 430℃ for 4 hours in a nitrogen-oxygen mixed atmosphere with a pressure of 2.5 MPa and an oxygen content of 30% to obtain the carrier. The catalyst had a specific surface area of ​​246 m². 2 / g;

[0183] (4) Prepare 200 mL of sodium carbonate aqueous solution containing 26 g Na, immerse the support in the solution, dry at 120 °C for 8 h, and calcine at 400 °C for 6 h to obtain the catalyst precursor;

[0184] (5) The catalyst precursor was reduced at 200°C for 10 min using a mixed gas of hydrogen and nitrogen containing 1% hydrogen, with the temperature controlled within ±1°C, to obtain catalyst A-1, in which the content of Na element is 13wt%, the content of Ag element is 3.5wt%, and the content of Re element is 6.5wt% by weight.

[0185] XRD tests were performed on catalyst A-1. Based on the test results, it was determined that the catalyst support contained alumina θ phase, γ phase crystal form and Al(OH)3, with the weight content of θ phase crystal form being 5 wt%, the weight content of γ phase crystal form being 87 wt%, and the weight content of Al(OH)3 being 8 wt%.

[0186] Example 2

[0187] The method of Example 1 was followed, except that in step (1), 6.5 g of silver perrhenate, 15.5 g of silver nitrate, and 8.2 g of 75% perrhenic acid were used. Example 2 yielded catalyst A-2, in which, by weight, the content of Na was 13 wt%, the content of Ag was 5.9 wt%, and the content of Re was 4.0 wt%.

[0188] Example 3

[0189] The procedure was carried out according to Example 1, except that in step (1), 8g of silver perrhenate, 7g of silver nitrate, and 20g of 75% perrhenic acid were used. Example 3 yielded catalyst A-3, in which, by weight, the content of Na was 13wt%, the content of Ag was 3.43wt%, and the content of Re was 7.0wt%.

[0190] Example 4

[0191] The method of Example 1 was followed, except that 187g of pseudoboehmite powder was used in step (1); and the following step was added between steps (3) and (4): 190mL of a cerium nitrate aqueous solution containing 20g Ce was prepared, the support was immersed in the solution, dried at 120℃ for 8h, and calcined at 400℃ for 6h to obtain a catalyst precursor, which was then used to load Na in step (4). Catalyst A-4 was obtained in Example 4, wherein, by weight, the content of Na was 13wt%, the content of Ce was 10wt%, the content of Ag was 3.5wt%, and the content of Re was 6.5wt%.

[0192] Figure 1 shows the X-ray photoelectron spectroscopy (XPS) pattern of Re in the support of the catalyst A-4 prepared above. As can be seen from Figure 1, Re is distributed in the support in the forms of elemental Re, ReO2, ReO3, and Re2O7. Figure 2 shows the X-ray photoelectron spectroscopy (XPS) pattern of Ag in the support of the catalyst A-4 prepared above. As can be seen from Figure 2, Ag is distributed in the support in the forms of elemental Ag and Ag2O.

[0193] Example 5

[0194] (1) Prepare the carrier according to the method of steps (1)-(3) in Example 4;

[0195] (2) Prepare 200 mL of indium nitrate aqueous solution containing 10 g In, immerse the support in the solution, dry at 100 °C for 12 h, and calcine at 420 °C for 6 h to obtain catalyst precursor ①;

[0196] (3) Prepare 200 mL of potassium carbonate aqueous solution containing 36 g K, immerse catalyst precursor ① in the solution, dry at 100 °C for 12 h, and calcine at 420 °C for 6 h to obtain catalyst precursor ②;

[0197] (4) The catalyst precursor was reduced at 180°C for 15 min using a mixed gas of hydrogen and nitrogen containing 2% hydrogen, with the temperature controlled within ±1°C, to obtain catalyst A-5, in which the content of K element is 18wt%, the content of In element is 5wt%, the content of Ag element is 3.5wt%, and the content of Re element is 6.5wt%.

[0198] Example 6

[0199] The method of Example 1 was followed, except that in step (3), the toothed spherical support particles were dried and then calcined at 650°C for 7 hours in a nitrogen-oxygen mixed atmosphere with a pressure of 1.2 MPa and an oxygen content of 30% to obtain the support. Example 6 yielded catalyst A-6, wherein, by weight, the content of Na was 13 wt%, the content of Ag was 3.5 wt%, and the content of Re was 6.5 wt%.

[0200] XRD tests were performed on catalyst A-6. Based on the test results, it was determined that there were alumina θ phase and γ phase crystal forms in the catalyst support. The weight content of the θ phase crystal form was 16 wt%, the weight content of the γ phase crystal form was 84 wt%, and the weight content of Al(OH)3 was 0 wt%.

[0201] Example 7

[0202] (1) Weigh 217g of boehmite powder, 10.7g of silver perrhenate, 4.1g of silver oxide, 1.5g of rhenium dioxide, 0.4g of rhenium trioxide, 4.5g of guar gum powder, 9g of methylcellulose, and 5g of polystyrene, and mix them in a mixer to obtain a uniform powdered raw material.

[0203] (2) Weigh 5g of citric acid and 10.5g of 75% perrhenic acid and add them to 290g of deionized water to prepare an acidic aqueous solution;

[0204] (3) The uniform powdered raw material is transferred to the kneader and the acidic aqueous solution is slowly added. After kneading for 30 minutes, it is extruded and granulated to obtain toothed spherical carrier particles with a particle size of 4-5 mm. It is dried at 110℃ for 10 hours and calcined at 400℃ for 4 hours in a nitrogen-oxygen mixed atmosphere with a pressure of 3.0 MPa and an oxygen content of 30% to obtain the carrier.

[0205] (4) Prepare 200 mL of sodium carbonate aqueous solution containing 26 g Na, immerse the support in the solution, dry at 120 °C for 8 h, and calcine at 400 °C for 6 h to obtain the catalyst precursor;

[0206] (5) The catalyst precursor was reduced at 200°C for 10 min using a mixed gas of hydrogen and nitrogen containing 1% hydrogen, with the temperature controlled within ±1°C, to obtain catalyst B-1, in which the content of Na element was 13wt%, the content of Ag element was 3.5wt%, and the content of Re element was 6.5wt% by weight.

[0207] Example 8

[0208] (1) Weigh 217g of boehmite powder, 9.7g of silver perrhenate, 6.5g of silver nitrate, 4.8g of rhenium dioxide, 1.77g of rhenium trioxide, 4.5g of guar gum powder, 9g of methylcellulose, and 5g of polystyrene, and mix them in a mixer to obtain a uniform powdered raw material.

[0209] (2) Weigh 10g of citric acid and 4.4g of 75% perrhenic acid and add them to 290g of deionized water to prepare an acidic aqueous solution;

[0210] (3) The uniform powdered raw material is transferred to the kneader and the acidic aqueous solution is slowly added. After kneading for 30 minutes, it is extruded and granulated to obtain toothed spherical carrier particles with a particle size of 4-5 mm. It is dried at 110℃ for 10 hours and calcined at 450℃ for 4 hours in a nitrogen-oxygen mixed atmosphere with a pressure of 2.5 MPa and an oxygen content of 30% to obtain the carrier.

[0211] (4) Prepare 200 mL of sodium carbonate aqueous solution containing 26 g Na, immerse the support in the solution, dry at 120 °C for 8 h, and calcine at 400 °C for 6 h to obtain the catalyst precursor;

[0212] (5) The catalyst precursor was reduced at 200°C for 10 min using a mixed gas of hydrogen and nitrogen containing 1% hydrogen, with the temperature controlled within ±1°C, to obtain catalyst B-2, in which the content of Na element was 13wt%, the content of Ag element was 3.5wt%, and the content of Re element was 6.5wt% by weight.

[0213] Example 9

[0214] (1) Weigh 196.9g of boehmite powder, 13.8g of silver perrhenate, 1.5g of rhenium dioxide, 0.4g of rhenium trioxide, 4.4g of silver oxide, 4g of guar gum powder, 4g of methylcellulose, and 4g of polyethylene microspheres, and mix them in a mixer to obtain a uniform powdered raw material.

[0215] (2) Weigh 13g of 75% perrhenic acid and add it to 200g of deionized water to prepare an acidic aqueous solution;

[0216] (3) The uniform powdered raw material is transferred to the kneader and the acidic aqueous solution is slowly added. After kneading for 1 hour, it is extruded and granulated to obtain toothed spherical carrier particles with a particle size of 4-5 mm. It is dried at 120℃ for 10 hours and calcined at 400℃ for 4 hours under an air atmosphere at a pressure of 3.0 MPa to obtain the carrier with an Ag content of 4 wt% and a Re content of 7.8 wt%.

[0217] (4) Prepare 220 mL of aqueous solution of cerium ammonium nitrate containing 16 g Ce, immerse the support in the solution, and dry at 120 °C for 10 h to obtain catalyst precursor ①;

[0218] (5) Prepare 210 mL of K2CO3 aqueous solution containing 16 g K, immerse catalyst precursor ① in the solution, dry at 120 °C for 10 h, and calcine at 390 °C for 12 h to obtain catalyst precursor ②;

[0219] (6) Using a mixture of nitrogen and hydrogen containing 5% hydrogen, reduce catalyst precursor ② at 150°C for 1 hour, with the temperature controlled within ±2°C, to obtain catalyst C-1, wherein by weight, the content of K is 8wt%, the content of Ce is 8wt%, the content of Ag is 4wt%, and the content of Re is 8wt%.

[0220] Example 10

[0221] (1) Prepare the carrier according to the method of steps (1)-(3) in Example 9;

[0222] (2) Prepare 180 mL of an aqueous solution containing 12 g In indium nitrate, immerse the support in the solution, dry at 105 °C for 8 h, and calcine at 380 °C for 8 h to obtain catalyst precursor ①;

[0223] (3) Use a mixture of nitrogen and hydrogen containing 5% hydrogen to reduce catalyst precursor ① at 150℃ for 40 minutes, with the temperature controlled within ±2℃, to obtain catalyst precursor ②;

[0224] (4) Prepare 100 mL of tetrasodium ethylenediaminetetraacetate aqueous solution containing 20 g Na, immerse catalyst precursor ② in the solution, and dry at 160 °C for 10 h to obtain catalyst C-2, wherein the content of Na is 10 wt%, the content of In is 6 wt%, the content of Ag is 4 wt%, and the content of Re is 8 wt% by weight.

[0225] Example 11

[0226] (1) Weigh 206g of boehmite powder, 19.4g of silver perrhenate, 5g of silver nitrate, 6.1g of rhenium dioxide, 4.5g of guar gum powder, 12g of hydroxypropyl methylcellulose, and 3g of polyethylene microspheres, and mix them in a mixer to obtain a uniform powdered raw material.

[0227] (2) Weigh 10g of acetic acid and 4.9g of 75% perrhenic acid and add them to 310g of deionized water to prepare an acidic aqueous solution;

[0228] (3) The uniform powdered raw material is transferred to the kneader and the acidic aqueous solution is slowly added. After kneading for 30 minutes, it is extruded and granulated to obtain spherical carrier particles with a particle size of 4-5 mm. It is dried at 110℃ for 10 hours and calcined at 450℃ for 4 hours in a nitrogen-oxygen mixed atmosphere with a pressure of 2.5 MPa and an oxygen content of 15% to obtain the carrier.

[0229] (4) Prepare 195 mL of gallium nitrate aqueous solution containing 7 g Ga, immerse the support in the solution, dry at 120 °C for 8 h, and calcine at 450 °C for 4 h to obtain catalyst precursor ①;

[0230] (5) Prepare 200 mL of magnesium nitrate aqueous solution containing 20 g Mg, immerse catalyst precursor ① in the solution, dry at 120 °C for 8 h, and calcine at 450 °C for 4 h to obtain catalyst precursor ②;

[0231] (6) Using a mixture of hydrogen and methane containing 1% hydrogen, reduce catalyst precursor ② at 150℃ for 25 min, with the temperature controlled within ±1℃, to obtain catalyst D, wherein by weight, the content of Mg is 10wt%, the content of Ga is 3.5wt%, the content of Ag is 4.5wt%, and the content of Re is 9wt%.

[0232] Example 12

[0233] (1) Weigh 245g of boehmite powder, 6.3g of silver nitrate, 6.9g of silver oxide, 2.34g of rhenium dioxide, 3.77g of rhenium trioxide, 10g of starch, 1g of methylcellulose, and 1g of polyethylene microspheres, and mix them in a mixer to obtain a uniform powdered raw material.

[0234] (2) Weigh 20g of citric acid and 3.6g of 75% perrhenic acid, add them to 350g of deionized water, and prepare an acidic aqueous solution;

[0235] (3) The uniform powdered raw material is transferred to the kneader and the acidic aqueous solution is slowly added. After kneading for 4 hours, it is extruded and granulated to obtain toothed spherical carrier particles with a particle size of 3-4 mm. It is dried at 105℃ for 8 hours and calcined at 500℃ for 6 hours under an air atmosphere at a pressure of 3.2 MPa to obtain the carrier.

[0236] (4) Prepare 280 mL of an aqueous solution containing 2 g Y of yttrium nitrate, immerse the support in the solution, dry at 160 °C for 4 h, and calcine at 450 °C for 4 h to obtain catalyst precursor ①;

[0237] (5) Prepare 280 mL of an aqueous solution of magnesium nitrate containing 14 g Mg, immerse the catalyst precursor ① in the solution, dry at 105 °C for 8 h, and calcine at 400 °C for 6 h to obtain catalyst precursor ②;

[0238] (6) Using a mixture of nitrogen and hydrogen containing 15% hydrogen, reduce catalyst precursor ② at 260°C for 30 hours, with the temperature controlled within ±1°C, to obtain catalyst E, wherein by weight, the content of Mg is 7wt%, the content of Y is 1wt%, the content of Ag is 5.2wt%, and the content of Re is 3.5wt%.

[0239] Example 13

[0240] (1) Weigh 210g of boehmite powder, 25.2g of silver nitrate, 11.7g of rhenium dioxide, 3g of guar gum powder, 5g of sodium hydroxymethyl cellulose, and 12g of polystyrene, and mix them in a mixer to obtain a uniform powdered raw material.

[0241] (2) Weigh 7g of citric acid and 14.4g of 75% perrhenic acid and add them to 220g of deionized water to prepare an acidic aqueous solution;

[0242] (3) The uniform powdered raw material is transferred to the kneader and the acidic aqueous solution is slowly added. After kneading for 1 hour, it is extruded and granulated to obtain spherical carrier particles with a particle size of 4-5 mm. It is dried at 120℃ for 8 hours and calcined at 400℃ for 5 hours in a nitrogen-oxygen mixed atmosphere with a pressure of 4 MPa and an oxygen content of 35% to obtain the carrier.

[0243] (4) Prepare 270 mL of an aqueous solution of ferrous nitrate containing 10 g Fe, immerse the support in the solution, and dry at 140 °C for 8 h to obtain catalyst precursor ①;

[0244] (5) Prepare 260 mL of LiOH aqueous solution containing 4 g Li, immerse catalyst precursor ① in the solution, dry at 140 °C for 4 h, and calcine at 390 °C for 8 h to obtain catalyst precursor ②;

[0245] (6) Using a mixture of nitrogen and hydrogen containing 80% hydrogen, reduce catalyst precursor ② at 310℃ for 8 hours, with the temperature controlled within ±1℃, to obtain catalyst F, wherein by weight, the content of Li is 2wt%, the content of Fe is 5wt%, the content of Ag is 8wt%, and the content of Re is 9wt%.

[0246] Example 14

[0247] (1) Weigh 203 pseudoboehmite powder, 2.7g silver perrhenate, 10.6g silver oxide, 5g guar gum powder, 7g hydroxypropyl methylcellulose, and 2g polyvinyl alcohol, and mix them in a mixer to obtain a uniform powdered raw material.

[0248] (2) Weigh 4g of citric acid and 12g of 75% perrhenic acid and add them to 240g of deionized water to prepare an acidic aqueous solution;

[0249] (3) The uniform powdered raw material is transferred into the kneader and the acidic aqueous solution is slowly added. After kneading for 2 hours, it is extruded and granulated to obtain columnar carrier particles with a particle size of 3-4 mm.

[0250] (4) Dry at 110℃ for 8h; calcine at 420℃ for 6h under a pressure of 2MPa and a nitrogen-oxygen mixed atmosphere with 14% oxygen content to obtain the carrier;

[0251] (5) Prepare 240 mL of an aqueous solution of zirconium nitrate containing 20 g Zr, immerse the support in the solution, dry at 130 °C for 4 h, and calcine at 350 °C for 4 h to obtain the catalyst precursor;

[0252] (6) Prepare 200 mL of ethanol solution containing 15 g of 4-aminopyridine, immerse the catalyst precursor in the solution, and dry at 100 °C for 4 h to obtain catalyst G, wherein the content of Zr is 10 wt%, the content of Ag is 5.3 wt%, the content of Re is 4 wt%, and the content of 4-aminopyridine is 7.5% by weight.

[0253] Comparative Example 1

[0254] The procedure was carried out according to Example 1, except that silver perrhenate and silver nitrate were not added in step (1), and 5g of concentrated nitric acid was used instead of 75% perrhenic acid in step (2). Catalyst R-1 was obtained in Comparative Example 1, wherein the Na content was 13wt% by weight.

[0255] Comparative Example 2

[0256] The procedure was carried out according to Example 1, except that silver perrhenate was not added in step (1), and 11.1 g of silver nitrate was added instead. In step (2), 5 g of concentrated nitric acid was used instead of 75% perrhenic acid. Catalyst R-2 was obtained in Comparative Example 2, wherein the content of Na was 13 wt% and the content of Ag was 3.5 wt% by weight.

[0257] Comparative Example 3

[0258] The procedure was carried out according to Example 1, except that silver perrhenate and silver nitrate were not added in step (1), 5g of concentrated nitric acid was used instead of 75% perrhenic acid in step (2), and the following steps were added between steps (3) and (4): 150mL of an aqueous solution containing 7g Ag of AgNO3 was prepared, the Al2O3 support obtained in step (3) was impregnated in the solution, dried at 120℃ for 8h, and calcined at 440℃ for 12h. Catalyst R-3 was obtained in Comparative Example 3, wherein the content of Na was 13wt% and the content of Ag was 3.5wt% by weight.

[0259] Comparative Example 4

[0260] The method of Example 1 was followed, except that silver perrhenate and silver nitrate were not added in step (1), and 5g of concentrated nitric acid was used instead of 75% perrhenic acid in step (2). The following steps were added between steps (3) and (4): 150mL of an aqueous solution containing 7g Ag of AgNO3 was prepared, and the Al2O3 support obtained in step (3) was immersed in this solution, dried at 120°C for 8h, and calcined at 440°C for 12h; 150mL of an aqueous solution containing 13g Re of perrhenic acid was prepared, and the Ag-loaded Al2O3 support obtained in the previous step was immersed in this solution, dried at 120°C for 8h, and calcined at 440°C for 12h. Comparative Example 4 yielded catalyst R-4, wherein, by weight, the content of Na was 13wt%, the content of Ag was 3.5wt%, and the content of Re was 6.5wt%.

[0261] Comparative Example 5

[0262] The method of Example 1 was followed, except that 3.0 g of silver perrhenate and 9.6 g of silver nitrate were used in step (1), and 0.2 g of 75% concentration perrhenic acid was used in step (2). Catalyst R-5 was obtained in Comparative Example 5, wherein the content of Na was 13 wt%, the content of Ag was 3.5 wt%, and the content of Re element was 1.6 wt% by weight.

[0263] The catalysts prepared in the above examples and comparative examples were subjected to XPS tests. The Ag and Re valence states were determined based on the test results, and the molar percentage of each valence state was calculated.

[0264] Table 1. Valence states and molar percentage distribution of Ag and Re

[0265] Test Example 1

[0266] This test case illustrates the evaluation of the desulfurization effect of gas phase pyrolysis gas materials.

[0267] The trace sulfur removal process for pyrolysis gas from the outlet of the five-stage pyrolysis gas compressor employs a single-stage adiabatic fixed-bed reactor. The inlet temperature of the single-stage adiabatic fixed-bed reactor is 60℃, the pressure is 3.3MPa, and the gas hourly space velocity is 3500 h⁻¹. -1 The composition of the cracked gas feedstock at the reactor inlet includes 10 ppm hydrogen sulfide, 28 ppm carbonyl sulfide, 5 ppm CS2, 3 ppm methanethiol, 2 ppm ethanethiol, 4 ppm dimethyl sulfide, 15 mol% hydrogen, 600 ppm CO, 43 mol% ethylene, 0.65 mol% acetylene, 16 mol% propylene, 0.4 mol% methylacetylene (MA), and 0.4 mol% propadiene (PD).

[0268] The operating cycle refers to the time the system can operate when the total sulfur content at the reactor outlet is controlled below 1 ppm; for catalysts R-2 to R-4, the operating cycle refers to the time the system can operate when the total sulfur content at the reactor outlet is controlled below 5 ppm.

[0269] Table 2 Comparison of gas-phase desulfurization performance of various catalysts

[0270] Table 2 shows the desulfurization performance of the catalysts obtained in the examples and comparative examples for cracked gas feedstocks from sulfur-containing crude oil, mainly composed of hydrogen sulfide, carbonyl sulfide, and carbon disulfide. As can be seen from Table 2, compared with the comparative examples, the desulfurization catalysts prepared in the examples exhibit significantly improved desulfurization accuracy and operating cycle for gaseous feedstocks. This improvement is achieved by adjusting the Ag content in the catalyst. x O y and Re m O n The valence state and molar percentage of Al(OH)3, the weight content of Al(OH)3, and the types and contents of alkaline and modified components can be used to optimize the low-temperature catalytic desulfurization performance of gaseous materials.

[0271] Test Example 2

[0272] This test case is used to illustrate the evaluation of the desulfurization effect of liquid-phase C4 materials.

[0273] The C4 residue after butadiene extraction of sulfur-containing mixed C4 material was used as raw material, and the content of each component is shown in Table 3.

[0274] Table 3 Composition of C4 material in sulfur-containing extraction residue

[0275] The raked C4 material was fed into a single-stage trickle bed reactor packed with desulfurization catalyst for desulfurization. The total sulfur content of the C4 material was 56 ppm. The inlet temperature of the single-stage trickle bed reactor was 45°C, the pressure was 2.2 MPa, and the liquid hourly space velocity was 2.0 h⁻¹. -1 .

[0276] The operating cycle refers to the time the system can operate when the total sulfur content at the reactor outlet is controlled below 2 ppm; for catalysts R-2 to R-4, the operating cycle refers to the time the system can operate when the total sulfur content at the reactor outlet is controlled below 15 ppm.

[0277] Table 4 Comparison of liquid-phase desulfurization performance of various catalysts

[0278] Table 5 shows the desulfurization performance of the catalysts obtained in the examples and comparative examples for C4 production from sulfur-containing crude oil, mainly composed of low-carbon thiols and thioethers. As can be seen from Table 5, compared with the comparative examples, the desulfurization catalysts prepared in the examples exhibit significantly improved desulfurization accuracy and operating cycle for liquid-phase materials. This improvement is achieved by adjusting the Ag content in the catalyst. x O y and Re m O n The valence state and molar percentage of Al(OH)3, the weight content of Al(OH)3, and the types and contents of alkaline and modified components can optimize the low-temperature catalytic desulfurization performance of liquid materials.

[0279] The specific embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combining the various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

A metal-doped alumina-supported basic catalyst characterized in that, The catalyst comprises a carrier and a basic component supported on the carrier; the carrier comprises Al2O3, Ag x O y and Re m O n ; Ag x O y including one or more of elemental Ag and Ag oxides, wherein x is 1 or 2, y is 0 or 1; Re m O n including one or more of elemental Re and Re oxides, wherein m is 1 or 2, n is selected from integers from 0 to 7; in the catalyst, the weight ratio of Ag to Re, in terms of metal elements, is 1:0.3-5, preferably 1:0.5-2.5, the crystal form of the Al2O3 includes theta phase crystal form and / or gamma phase crystal form; the basic component is selected from one or more of alkali metals, alkaline earth metals and organic basic compounds. The catalyst according to claim 1, wherein, Ag x O y elemental Ag and Ag20; preferably, the molar content of elemental Ag is 30-70%, and the molar content of Ag20 is 30-70%, based on the total molar amount of Ag element. And / or, where, Re m O n Re, Re02, Re03, and Re207; preferably, the molar content of Re is 15 to 70% and the molar content of Re207 is 20 to 50% based on the total moles of Re element. Catalyst according to any one of claims 1-2, having a Ag content of 0.2-15 wt%, preferably 2-10 wt%, based on the total weight of the catalyst, calculated as Ag element x O y wt% and / or the Re content, calculated as Re, is 0.1 to 10 wt.-%, based on the total weight of the catalyst m O n is 0.2 to 15 wt.-%, preferably 3 to 12 wt.-%. The catalyst according to any one of claims 1 to 3, wherein The carrier further comprises Al(OH)3. Preferably, based on the total weight of Al2O3 and Al(OH)3, the weight content of the θ phase crystal form is ≤20wt%, the weight content of the γ phase crystal form is ≥70wt%, and the weight content of Al(OH)3 is 5-15wt%. The catalyst according to any one of claims 1 to 4, wherein Based on the total weight of the catalyst, the weight content of the alkaline component is 1-30 wt%, preferably 2-25 wt%, and more preferably 10-20 wt%. And / or, the alkali metal is selected from Li, Na, K, Cs and combinations thereof; And / or, the alkaline earth metal is selected from Mg, Ca, Sr and combinations thereof; And / or, the organic basic compound is selected from one or more of organic amines, pyridines and guanidines; preferably, the organic basic compound is selected from one or more of dimethylamine, triethylamine, trifluoroacetamide, pyridine, 4-dimethylaminopyridine, triethanolamine and tetramethylguanidine. The catalyst according to any one of claims 1 to 5, wherein The catalyst further includes a modifying component supported on the support; the modifying component is selected from one or more of Group VIII elements, Group IIIA elements, Group IB elements excluding Ag, Group IIB elements, Group IIIB elements, Group IVB elements, Group VIIB elements excluding Re, and rare earth elements; Preferably, the modifying component is selected from one or more of Ga, In, La, Zn, Fe, Ce, Y, Zr and Mn; Preferably, based on the total weight of the catalyst, the weight content of the modified component is 0-20 wt%, more preferably 0.1-15 wt%, and more preferably 1-12 wt%. The catalyst according to any one of claims 1 to 6, wherein The specific surface area of the support is between 100 and 500 m2 / g, preferably between 150 and 450 m2 / g 2 The specific surface area of the support is between 100 and 500 m2 / g, preferably between 150 and 450 m2 / g 2 The specific surface area of the support is between 100 and 500 m2 / g, preferably between 150 and 450 m2 / g 2 The specific A method for preparing a metal-doped alumina-supported basic catalyst, characterized in that, The preparation method includes the following steps: S1. A mixture is obtained by mixing powdered raw materials with an acidic aqueous solution. After kneading and molding, the mixture is subjected to a first drying and a first calcination to obtain a carrier. The powdered raw materials include alumina precursor powder and one or more powders selected from silver perrhenate, silver nitrate, silver oxide, and rhenium oxide. In the mixture, the weight ratio of Ag to Re, based on metal elements, is 1:0.3-5, preferably 1:0.5-2.

5. The temperature of the first calcination is 300-650℃, preferably 380-600℃. S2, a precursor loaded with an alkaline component, is then subjected to a second drying and optional second calcination, as well as optional reduction. The production method according to claim 8, wherein The alumina precursor powder is selected from boehmite powder and optionally alumina powder. Preferably, the alumina powder is obtained by calcining boehmite powder at a temperature selected from 450-900℃, and the amount of alumina powder accounts for 0-20 wt% of the total weight of the alumina precursor powder. The production method according to claim 8 or 9, wherein The alkaline component is loaded in the form of an alkaline solution, and the loading method is spraying or equal volume impregnation. The alkaline solution contains organic alkaline compounds and / or inorganic alkaline compounds; Preferably, the organic basic compound is selected from one or more of organic amines, pyridines, and guanidines; more preferably, the organic basic compound is selected from one or more of dimethylamine, triethylamine, trifluoroacetamide, pyridine, 4-dimethylaminopyridine, triethanolamine, and tetramethylguanidine. Preferably, the inorganic alkaline compound is selected from one or more of the following: ammonium compounds, hydroxides, halides, citrates, oxalates, acetates, bicarbonates, carbonates, and organic compounds of Li, Na, K, Cs, Mg, Ca, and Sr; more preferably, the inorganic alkaline compound is selected from one or more of the following: potassium chloride, lithium chloride, potassium acetate, sodium bicarbonate, sodium citrate, potassium carbonate, potassium hydroxide, magnesium hydroxide, and calcium hydroxide. Preferably, the solvent in the alkaline solution is selected from one or more of water, ethanol, acetone, and tetrahydrofuran; Preferably, the concentration of organic alkaline compounds and / or inorganic alkaline compounds in the alkaline solution is 0.1-100 wt%. The production method according to any one of claims 8 to 10, wherein The acidic aqueous solution is a mixed aqueous solution of perrhenic acid and other acids; the other acids are selected from one or more of nitric acid, acetic acid, oxalic acid and citric acid; Preferably, the weight ratio of perrhenic acid to other acids is (0.2-10):1; Preferably, the weight ratio of the acidic aqueous solution to the powdered raw material is (0.4-2):

1. The production method according to any one of claims 8 to 11, wherein The powdered raw material also includes a forming and pore-forming agent; the amount of the forming and pore-forming agent is 0-10 wt% of the total weight of the alumina precursor powder; Preferably, the molding and pore-forming agent is selected from one or more of guar gum powder, starch, cellulose, urea, ethylenediamine, and polymers. Preferably, the cellulose is selected from one or more of methylcellulose, hydroxypropyl methylcellulose, and sodium hydroxymethylcellulose; Preferably, the polymer is selected from one or more of polyethylene microspheres, polystyrene, polyvinyl alcohol, and polyethylene glycol. The production method according to any one of claims 8 to 12, wherein The first drying temperature is 60-120℃, and the time is 8-24 hours; And / or, the first calcination time is 2-20 hours, preferably 3-10 hours; the pressure is 1-5 MPa, preferably 2-4 MPa; And / or, the atmosphere of the first calcination is selected from at least one of inert gas, nitrogen, air and oxygen; preferably, the oxygen content in the atmosphere is 0-40 wt%, more preferably 15-25 wt%; And / or, the temperature of the second drying is 60-260°C; And / or, the temperature of the second calcination is 200-550°C; And / or, the atmosphere for the second calcination is selected from at least one of an inert gas, nitrogen, and air. The production method according to any one of claims 8 to 13, wherein The method further includes: S3, the precursor of the loaded modified component, is then subjected to a third drying and a third calcination; Preferably, step S3 is performed between steps S1 and S2; Preferably, the modified component is loaded in the form of a solution containing a precursor of the modified component, and the loading method is spraying or equal volume impregnation. Preferably, the precursor of the modified component is selected from at least one of the halides, nitrates, acetates, carbonates, sulfates, hydroxides, ammonium compounds, and organometallic compounds of the modified component; Preferably, the modifying component is selected from one or more of Ga, In, La, Zn, Fe, Ce, Y, and Mn; The third drying process is carried out at a temperature of 80-140℃ for 8-24 hours. And / or, the temperature of the third calcination is 200-480°C, and the time is 4-20 hours, preferably 6-10 hours; And / or, the atmosphere of the third calcination is selected from at least one of inert gas, nitrogen, air and oxygen; preferably, the oxygen content in the atmosphere is 0-40 wt%, more preferably 15-25 wt%. The production method according to any one of claims 8 to 14, wherein The reducing atmosphere is selected from hydrogen, hydrogen-containing nitrogen, and hydrogen-containing methane; preferably, the volume content of hydrogen in the reducing atmosphere is 1-50%. And / or, the reduction temperature is 50-370℃, preferably 100-320℃; the temperature fluctuation range is ±2℃, preferably ±1℃; the reduction time is 5min-10 hours, preferably 10min-4 hours. The application of the metal-doped alumina supported alkaline catalyst according to any one of claims 1-7 or the metal-doped alumina supported alkaline catalyst prepared by the preparation method according to any one of claims 8-15 in catalytic desulfurization. The use according to claim 16, wherein The metal-doped alumina-supported alkaline catalyst is used to remove sulfides contained in hydrocarbon materials. Preferably, the hydrocarbon material is a hydrocarbon produced by direct cracking of crude oil; Preferably, the sulfide is selected from one or more of inorganic sulfur and organic sulfur; More preferably, the inorganic sulfur is selected from one or more of hydrogen sulfide and sulfur dioxide; More preferably, the organic sulfur is selected from one or more of carbonyl sulfide, carbon disulfide, thiols, thioethers and thiophenes; more preferably, it is selected from one or more of carbonyl sulfide, carbon disulfide, C1-C4 thiols and C1-C4 thioethers. A method for removing sulfides contained in a hydrocarbon material, characterized by, The method includes: subjecting the hydrocarbon material to gas-solid or liquid-solid contact with the metal-doped alumina-supported alkaline catalyst according to any one of claims 1-7 or the metal-doped alumina-supported alkaline catalyst prepared by the preparation method according to any one of claims 8-15, at a temperature of 20-80°C.

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