Oxygen-containing compound removing agent as well as preparation method and application thereof

Abstract

The invention relates to the technical field of removal agents, in particular to an oxygen-containing compound removal agent and a preparation method and application thereof. According to the oxygen-containing compound removal agent provided by the invention, the oxygen-containing compound removal agent comprises a molecular sieve subjected to acid treatment, attapulgite subjected to acid treatment and a metal compound; the metal oxide comprises a gallium metal compound, a zinc metal compound and a strontium metal compound. The oxygen-containing compound removing agent is large in particle strength, high in adsorption capacity, high in activation performance, capable of effectively enhancing selectivity to dimethyl ether, methyl alcohol and methyl tert-butyl ether (MTBE) and high in oxygen-containing compound removing efficiency.

Description

Technical Field

[0001] The present invention relates to the technical field of removers, and in particular to an oxygen-containing compound remover, a preparation method thereof and an application thereof. Background Art

[0002] As important by-products of chemical production, C3 and C4 hydrocarbons have considerable output and are extremely valuable chemical raw materials. Their scope of application has been continuously expanded with the development of science and technology and market demand, showing great potential. Among them, C3 hydrocarbons mainly include propylene, propane, etc., and C4 hydrocarbons include butane, butene, isobutylene, etc. However, in the processing of C3 and C4 hydrocarbons (such as isomerization, cracking, etherification, and polymerization), the oxygen-containing compounds contained in them, such as methanol, dimethyl ether (DME), methyl ethyl ketone, and methyl tert-butyl ether, will destroy the active center of the remover or react with it, resulting in reduced activity and selectivity of the remover, seriously affecting product quality, production efficiency and economic benefits. In addition, these oxygen-containing compounds will generate water and carbon monoxide in the reaction system, and some heavy oxide-containing impurities will also form gum-like substances.

[0003] To eliminate the effects of oxygen-containing compounds, the industry currently mainly uses adsorption to purify low-carbon hydrocarbons (such as C3 and C4 hydrocarbons), with granular NaX molecular sieves as the core adsorbent. However, this technology has many shortcomings: a "pre-load" treatment is required before the adsorption operation to avoid excessive heat release during the adsorption process, which may lead to device failure or safety accidents. This increases the complexity and risk of operation. When deeply removing oxygen-containing compounds, the physical structure of NaX molecular sieve particles leads to large mass transfer resistance, low adsorption efficiency, and slow rate. The removal effect of oxygen-containing compounds still needs to be improved. In addition, the effective adsorption capacity and utilization rate of the adsorbent are low, and frequent regeneration or replacement is required; its regeneration process (usually high-temperature desorption) consumes a lot of energy, which increases operating costs. Ultimately, faced with increasingly stringent purification requirements (such as lower oxygen-containing impurity limits and higher olefin retention rates), the existing adsorption technology based on granular NaX molecular sieves can no longer meet the needs and its application scope is limited. Summary of the Invention

[0004] Therefore, the technical problem to be solved by the present invention is to overcome the defects of the removers used in the existing removal of oxygenated compounds, such as poor particle strength, low adsorption capacity, and the removal effect of oxygenated compounds still needs to be improved, thereby providing a remover for removing oxygenated compounds and its preparation method and application.

[0005] In a first aspect, the present invention provides an oxygen-containing compound removing agent, wherein the oxygen-containing compound removing agent comprises an acid-treated molecular sieve, an acid-treated attapulgite, and a metal compound;

[0006] The metal oxides include gallium metal compounds, zinc metal compounds and strontium metal compounds.

[0007] Preferably, the specific surface area of ​​the oxygen-containing compound removing agent is 238-403m 2 / g, pore volume 0.32-0.43cm 3 / g, average pore size 7-11nm;

[0008] Preferably, the specific surface area of ​​the oxygen-containing compound removing agent is 264-403m 2 / g, pore volume 0.36-0.43cm 3 / g, average pore diameter 8-11nm.

[0009] In a second aspect, the present invention provides a method for preparing the above-mentioned oxygen-containing compound removing agent, comprising the following steps:

[0010] 1) treating the molecular sieve and the attapulgite with acid to obtain the acid-treated molecular sieve and the acid-treated attapulgite;

[0011] 2) mixing the template, gallium salt, zinc salt, strontium salt and water to form a mixed solution, heating and stirring to form a gel, and then drying and grinding to obtain a gel powder;

[0012] 3) The acid-treated molecular sieve obtained in step 1), the acid-treated attapulgite, the gel powder obtained in step 2) and a molding aid are mixed, molded, cured, and then calcined to obtain the oxygen-containing compound removing agent.

[0013] Preferably, in step 1), the molecular sieve and the attapulgite are placed in an acid solution, respectively, and subjected to heat treatment to obtain the acid-treated molecular sieve and the acid-treated attapulgite.

[0014] Preferably, the concentration of the acid in the acid solution is 1-3 mol / L;

[0015] The acid in the acid solution includes at least one of nitric acid, hydrochloric acid, and sulfuric acid;

[0016] The molecular sieve and acid solution ratio is 1: (1-3), the unit is g / mL;

[0017] The dosage ratio of the attapulgite to the acid solution is 1:(1-3), and the unit is g / mL.

[0018] Preferably, the molecular sieve includes at least one of aluminum phosphate molecular sieve, silicoaluminophosphate molecular sieve, ZSM-5 molecular sieve, Y-type molecular sieve, X-type molecular sieve, and A-type molecular sieve;

[0019] The heating temperature is 150-200°C and the heating time is 2-12h;

[0020] Optionally, a drying step is further included after the heating treatment step is completed.

[0021] Preferably, in step 2), the molar ratio of gallium ions in the gallium salt, zinc ions in the zinc salt and strontium ions in the strontium salt is (0.5-3): (0.5-3): (0.5-3);

[0022] The ratio of the total molar amount of gallium ions in the gallium salt, zinc ions in the zinc salt and strontium ions in the strontium salt to the molar amount of the template is 1:(1-3);

[0023] The total molar content of gallium ions of the gallium salt, zinc ions of the zinc salt, and strontium ions of the strontium salt in the mixed solution is 0.6-1.8 mol / L;

[0024] The heating and stirring temperature is 70-100°C, the heating and stirring speed is 200-500r / min, and the heating and stirring time is 3-6h;

[0025] In step 2), the drying temperature is 100-120° C. and the drying time is 8-16 hours.

[0026] In step 2), the template comprises at least one of citric acid, tartaric acid, ethylenediaminetetraacetic acid, and gluconic acid;

[0027] Preferably, the template is citric acid;

[0028] It should be noted that the core advantage of citric acid as a template is that it contains three carboxyl groups and one hydroxyl group, and the hydroxyl group is located on the β carbon atom. This structure enables it to provide acidic sites and form hydrogen bonds or coordination bonds with the molecular sieve surface through the hydroxyl group, thereby enhancing the interaction. The unique -OH structure of citric acid can achieve the rearrangement of the skeleton Al, realize the aluminum supplementation effect of the molecular sieve, and does not destroy the structure of the molecular sieve, so it can be used as a template. The prepared remover has strong activation performance, effectively enhances the selectivity for dimethyl ether, methanol and methyl tert-butyl ether (MTBE), and increases the adsorption capacity of oxygen-containing compounds. Although both tartaric acid and gluconic acid contain hydroxyl groups, the position and number of hydroxyl groups may affect their interaction with the molecular sieve. The hydroxyl groups of tartaric acid are located on adjacent carbon atoms, which may form intramolecular hydrogen bonds, reducing its binding ability with the molecular sieve surface. The hydroxyl groups of gluconic acid are more dispersed and may not form an effective structural guidance effect. At the same time, compared with ethylenediaminetetraacetic acid, citric acid has moderate coordination ability and is easy to control, leaves no residue after thermal decomposition, is environmentally friendly, and has more precise control over materials, especially in the preparation of high-performance removers under mild conditions.

[0029] The gallium salt includes at least one of gallium nitrate nonahydrate, gallium sulfate, gallium chloride, and gallium iodide;

[0030] The zinc salt includes at least one of zinc nitrate hexahydrate, zinc sulfate, and zinc chloride;

[0031] The strontium salt includes at least one of strontium nitrate tetrahydrate, strontium chloride, strontium acetate, and strontium hydroxide.

[0032] In step 3), the mass percentages of the acid-treated molecular sieve, the acid-treated attapulgite, the gel powder obtained in step 2), and the molding aid are (100-300): (200-500): (100-300): (300-500);

[0033] The molding aid includes at least one of alumina, silica, magnesium oxide, and clay;

[0034] In step 3), the curing temperature is 40-80°C and the curing time is 6-48h;

[0035] The calcination temperature is 350-750°C and the calcination time is 2-6 hours;

[0036] Optionally, after the health-preserving step is completed, a drying step is further included;

[0037] Optionally, the forming includes water-added strip extrusion forming or water-added ball rolling forming.

[0038] It should be noted that the present invention does not impose any specific restrictions on the amount of water used in the water-added strip extrusion or water-added ball forming process, as long as the forming purpose is achieved. Typically, but not limiting, the mass ratio of the total mass of the acid-treated molecular sieve obtained in step 1), the acid-treated attapulgite obtained in step 1), the gel powder obtained in step 2), and the forming aid to water is 1000:(40-70).

[0039] In a third aspect, the present invention provides a use of the above-mentioned oxygen-containing compound removal agent in removing oxygen-containing compounds from hydrocarbon compounds;

[0040] Optionally, the hydrocarbon compound includes a C3-C5 hydrocarbon compound;

[0041] Optionally, the C3-C5 hydrocarbon compound includes C3-C5 alkane and / or C3-C5 olefin;

[0042] Optionally, the oxygen-containing compound includes at least one of methanol, dimethyl ether, methyl ethyl ketone, butyraldehyde, and methyl tert-butyl ether.

[0043] The technical solution of the present invention has the following advantages:

[0044] 1. The present invention provides an oxygenate-removing agent comprising an acid-treated molecular sieve, an acid-treated attapulgite, and a metal compound; the metal oxide comprises a gallium metal compound, a zinc metal compound, and a strontium metal compound. The oxygenate-removing agent of the present invention has high particle strength, high adsorption capacity, and strong activation, effectively enhancing selectivity for dimethyl ether, methanol, and methyl tert-butyl ether (MTBE), and achieving high oxygenate removal efficiency.

[0045] 2. The present invention provides a method for preparing an oxygen-containing compound remover, comprising the following steps: 1) treating a molecular sieve and attapulgite with acid to obtain an acid-treated molecular sieve and an acid-treated attapulgite; 2) mixing a template, a gallium salt, a zinc salt, a strontium salt, and water to form a mixed solution, heating and stirring to form a gel, and then drying and grinding to obtain a gel powder; 3) mixing the acid-treated molecular sieve and the acid-treated attapulgite obtained in step 1), the gel powder obtained in step 2), and a molding aid, molding, curing, and then calcining to obtain the oxygen-containing compound remover. This method, by acid-treating the molecular sieve and attapulgite, can unclog the internal pores of the molecular sieve and attapulgite, thereby increasing the specific surface area of ​​the attapulgite carrier and the number of hydroxyl groups on its surface; simultaneously, a sol-gel method is used to prepare a gel powder from the gallium salt, zinc salt, and strontium salt, and the gel powder is granulated and molded with the acid-treated molecular sieve, the acid-treated attapulgite, and the molding aid. This process helps to improve the oxygen-containing compound removal activity, adsorption capacity, and mechanical strength of the resulting remover. The acid-treated attapulgite used has a large specific surface area and abundant surface groups; the added specific gallium salts, zinc salts, and strontium salts help to improve the catalytic adsorption activation and stability of the adsorption process. The powder is made by the sol-gel method, and the process of rolling ball molding with other raw materials has the characteristics of improving catalytic adsorption activity, high adsorption capacity and mechanical strength. The remover for removing oxygen-containing compounds in low-molecular hydrocarbons prepared by the present invention has a large specific surface area and a large number of surface hydroxyl groups. On the basis of high particle strength and no destruction of the structure of the molecular sieve, the remover has a high adsorption capacity and strong activation performance, effectively enhancing the selectivity for dimethyl ether, methanol and methyl tert-butyl ether (MTBE), and improving the removal efficiency of oxygen-containing compounds.

[0046] 3. In the preparation method of the oxygen-containing compound removal agent provided by the present invention, in step 2), the template agent includes at least one of citric acid, tartaric acid, ethylenediaminetetraacetic acid, and gluconic acid; preferably, the template agent is citric acid; the citric acid template agent has a specific -OH structure, which can achieve the rearrangement and aluminum supplementation of the framework Al without destroying the molecular sieve structure, thereby further enhancing the adsorption capacity and activation performance of the removal agent, and further effectively improving the selectivity and adsorption capacity of oxygen-containing compounds such as dimethyl ether, methanol and MTBE.

[0047] 4. The preparation method of the oxygen-containing compound removing agent provided by the present invention can be used to remove oxygen-containing compounds from various raw materials without causing substantial loss of olefins. DETAILED DESCRIPTION

[0048] The following examples are provided for a better understanding of the present invention and are not intended to limit the best mode of implementation. They do not limit the content and scope of protection of the present invention. Any product identical or similar to the present invention obtained by anyone under the guidance of the present invention or by combining the features of the present invention with other prior arts shall fall within the scope of protection of the present invention.

[0049] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in this field can be used. If the manufacturer of the reagents or instruments is not specified, they are all commercially available conventional reagents.

[0050] Example 1

[0051] This embodiment provides a method for preparing an oxygen-containing compound removing agent, comprising the following steps:

[0052] 1) Weigh 800 ml of 1 mol / L hydrochloric acid, add 400 g of ZSM-5 molecular sieve, transfer to a stainless steel reactor, heat treat at 150° C. for 8 h, filter and dry to obtain acid-treated ZSM-5 molecular sieve; weigh 1200 ml of 1 mol / L hydrochloric acid, add 600 g of attapulgite, transfer to a stainless steel reactor, heat treat at 150° C. for 8 h, filter and dry to obtain acid-treated attapulgite;

[0053] 2) Take citric acid and zinc nitrate hexahydrate, gallium nitrate nonahydrate, and strontium nitrate tetrahydrate, and dissolve them in 1L of deionized water to form a mixed solution. The total molar concentration of gallium ions, zinc ions, and strontium ions in the mixed solution is 0.6 mol / L, the molar ratio of citric acid to the total molar amount of zinc ions in zinc nitrate hexahydrate, gallium ions in gallium nitrate nonahydrate, and strontium ions in strontium nitrate tetrahydrate is 1:1, and the molar ratio of zinc ions in zinc nitrate hexahydrate, gallium ions in gallium nitrate nonahydrate, and strontium ions in strontium nitrate tetrahydrate is 1:1:1. Subsequently, the mixed solution is vigorously stirred in a water bath at 90°C, with a speed of 400r / min and a stirring time of 4h until a gel is formed. Subsequently, the obtained gel is placed in a blast drying oven, dried at a temperature of 120°C for 12h, and then ground to obtain gel powder;

[0054] 3) 100 g of the acid-treated ZSM-5 molecular sieve obtained in step 1), 200 g of the acid-treated attapulgite obtained in step 1), 200 g of the gel powder obtained in step 2), and 500 g of activated alumina were mixed, 60 g of water was added, and the mixture was rolled into balls. The mixture was cured in a closed environment at 60°C for 12 h, then dried, and then calcined at 500°C for 2 h to obtain the oxygen-containing compound removing agent.

[0055] Example 2

[0056] This embodiment provides a method for preparing an oxygen-containing compound removing agent, comprising the following steps:

[0057] 1) Weigh 800 ml of 1 mol / L hydrochloric acid, add 400 g of ZSM-5 molecular sieve, transfer to a stainless steel reactor, heat treat at 150° C. for 8 h, filter and dry to obtain acid-treated ZSM-5 molecular sieve; weigh 1200 ml of 1 mol / L hydrochloric acid, add 600 g of attapulgite, transfer to a stainless steel reactor, heat treat at 150° C. for 8 h, filter and dry to obtain acid-treated attapulgite;

[0058] 2) Take citric acid and zinc nitrate hexahydrate, gallium nitrate nonahydrate, and strontium nitrate tetrahydrate, and dissolve them in 1L of deionized water to form a mixed solution. The total molar concentration of gallium ions, zinc ions, and strontium ions in the mixed solution is 1.2 mol / L, the molar ratio of citric acid to the total molar amount of zinc ions in zinc nitrate hexahydrate, gallium ions in gallium nitrate nonahydrate, and strontium ions in strontium nitrate tetrahydrate is 2:1, and the molar ratio of zinc ions in zinc nitrate hexahydrate, gallium ions in gallium nitrate nonahydrate, and strontium ions in strontium nitrate tetrahydrate is 1:1:1. Subsequently, the mixed solution is vigorously stirred in a water bath at 80°C, with a speed of 400r / min and a stirring time of 4h until a gel is formed. Subsequently, the obtained gel is placed in a blast drying oven, dried at a temperature of 120°C for 12h, and then ground to obtain gel powder;

[0059] 3) 100 g of the acid-treated ZSM-5 molecular sieve obtained in step 1), 200 g of the acid-treated attapulgite obtained in step 1), 200 g of the gel powder obtained in step 2), and 500 g of activated alumina were mixed, 60 g of water was added, and the mixture was rolled into balls. The mixture was cured in a closed environment at 60°C for 12 h, then dried, and then calcined at 650°C for 2 h to obtain the oxygen-containing compound removing agent.

[0060] Example 3

[0061] This embodiment provides a method for preparing an oxygen-containing compound removing agent, comprising the following steps:

[0062] 1) Weigh 800 ml of 2 mol / L hydrochloric acid, add 400 g of ZSM-5 molecular sieve, transfer to a stainless steel reactor, heat treat at 180° C. for 8 h, filter and dry to obtain acid-treated ZSM-5 molecular sieve; weigh 1200 ml of 1 mol / L hydrochloric acid, add 600 g of attapulgite, transfer to a stainless steel reactor, heat treat at 150° C. for 8 h, filter and dry to obtain acid-treated attapulgite;

[0063] 2) Take citric acid and zinc nitrate hexahydrate, gallium nitrate nonahydrate, and strontium nitrate tetrahydrate, and dissolve them in 1L of deionized water to form a mixed solution. The total molar concentration of gallium ions, zinc ions, and strontium ions in the mixed solution is 1.2 mol / L, the molar ratio of citric acid to the total molar amount of zinc ions in zinc nitrate hexahydrate, gallium ions in gallium nitrate nonahydrate, and strontium ions in strontium nitrate tetrahydrate is 2:1, and the molar ratio of zinc ions in zinc nitrate hexahydrate, gallium ions in gallium nitrate nonahydrate, and strontium ions in strontium nitrate tetrahydrate is 1:1:1. Subsequently, the mixed solution is vigorously stirred in a water bath at 80°C, with a speed of 400r / min and a stirring time of 4h until a gel is formed. Subsequently, the obtained gel is placed in a blast drying oven, dried at a temperature of 120°C for 12h, and then ground to obtain gel powder;

[0064] 3) 100 g of the acid-treated ZSM-5 molecular sieve obtained in step 1), 200 g of the acid-treated attapulgite obtained in step 1), 200 g of the gel powder obtained in step 2), and 500 g of activated alumina were mixed, 60 g of water was added, and the mixture was rolled into balls. The mixture was cured in a closed environment at 60° C. for 24 h, then dried, and then calcined at 350° C. for 2 h to obtain the oxygen-containing compound removing agent.

[0065] Example 4

[0066] This embodiment provides a method for preparing an oxygen-containing compound removing agent, comprising the following steps:

[0067] 1) Weigh 800 ml of 2 mol / L hydrochloric acid, add 400 g of ZSM-5 molecular sieve, transfer to a stainless steel reactor, heat treat at 180° C. for 8 h, filter and dry to obtain acid-treated ZSM-5 molecular sieve; weigh 1200 ml of 1 mol / L hydrochloric acid, add 600 g of attapulgite, transfer to a stainless steel reactor, heat treat at 150° C. for 8 h, filter and dry to obtain acid-treated attapulgite;

[0068] 2) Take citric acid and zinc nitrate hexahydrate, gallium nitrate nonahydrate, and strontium nitrate tetrahydrate, and dissolve them in 1L of deionized water to form a mixed solution. The total molar concentration of gallium ions, zinc ions, and strontium ions in the mixed solution is 1.8 mol / L, the molar ratio of citric acid to the total molar amount of zinc ions in zinc nitrate hexahydrate, gallium ions in gallium nitrate nonahydrate, and strontium ions in strontium nitrate tetrahydrate is 3:1, and the molar ratio of zinc ions in zinc nitrate hexahydrate, gallium ions in gallium nitrate nonahydrate, and strontium ions in strontium nitrate tetrahydrate is 1:1:1. Subsequently, the mixed solution is vigorously stirred in a water bath at 80°C, with a speed of 400r / min and a stirring time of 4h until a gel is formed. Subsequently, the obtained gel is placed in a blast drying oven, dried at a temperature of 120°C for 12h, and then ground to obtain gel powder;

[0069] 3) 100 g of the acid-treated ZSM-5 molecular sieve obtained in step 1), 200 g of the acid-treated attapulgite obtained in step 1), 200 g of the gel powder obtained in step 2), and 500 g of activated alumina were mixed, 60 g of water was added, and the mixture was rolled into balls. The mixture was cured in a closed environment at 60° C. for 24 h, then dried, and then calcined at 350° C. for 2 h to obtain the oxygen-containing compound removing agent.

[0070] Example 5

[0071] This embodiment provides a method for preparing an oxygen-containing compound removing agent, comprising the following steps:

[0072] 1) Weigh 800 ml of 2 mol / L hydrochloric acid, add 400 g of ZSM-5 molecular sieve, transfer to a stainless steel reactor, heat treat at 200° C. for 8 h, filter and dry to obtain acid-treated ZSM-5 molecular sieve; weigh 1200 ml of 1 mol / L hydrochloric acid, add 600 g of attapulgite, transfer to a stainless steel reactor, heat treat at 150° C. for 8 h, filter and dry to obtain acid-treated attapulgite;

[0073] 2) Take citric acid and zinc nitrate hexahydrate, gallium nitrate nonahydrate, and strontium nitrate tetrahydrate, and dissolve them in 1L of deionized water to form a mixed solution. The total molar concentration of gallium ions, zinc ions, and strontium ions in the mixed solution is 1.2 mol / L, the molar ratio of citric acid to the total molar amount of zinc ions in zinc nitrate hexahydrate, gallium ions in gallium nitrate nonahydrate, and strontium ions in strontium nitrate tetrahydrate is 2:1, and the molar ratio of zinc ions in zinc nitrate hexahydrate, gallium ions in gallium nitrate nonahydrate, and strontium ions in strontium nitrate tetrahydrate is 1:1:1. Subsequently, the mixed solution is vigorously stirred in a water bath at 70°C at a speed of 400r / min for 4 hours until a gel is formed. Subsequently, the obtained gel is placed in a blast drying oven, dried at a temperature of 120°C for 12 hours, and then ground to obtain gel powder;

[0074] 3) 100 g of the acid-treated ZSM-5 molecular sieve obtained in step 1), 200 g of the acid-treated attapulgite obtained in step 1), 200 g of the gel powder obtained in step 2), and 500 g of activated alumina were mixed, 60 g of water was added, and the mixture was rolled into balls. The mixture was cured in a closed environment at 80°C for 24 h, then dried, and then calcined at 350°C for 2 h to obtain the oxygen-containing compound removing agent.

[0075] Example 6

[0076] This embodiment provides a method for preparing an oxygen-containing compound removing agent, comprising the following steps:

[0077] 1) Weigh 800 ml of 2 mol / L hydrochloric acid, add 400 g of ZSM-5 molecular sieve, transfer to a stainless steel reactor, heat treat at 180° C. for 8 h, filter and dry to obtain acid-treated ZSM-5 molecular sieve; weigh 1200 ml of 1 mol / L hydrochloric acid, add 600 g of attapulgite, transfer to a stainless steel reactor, heat treat at 150° C. for 8 h, filter and dry to obtain acid-treated attapulgite;

[0078] 2) Take citric acid and zinc nitrate hexahydrate, gallium nitrate nonahydrate, and strontium nitrate tetrahydrate, and dissolve them in 1L of deionized water to form a mixed solution. The total molar concentration of gallium ions, zinc ions, and strontium ions in the mixed solution is 1.2 mol / L, the molar ratio of citric acid to the total molar amount of zinc ions in zinc nitrate hexahydrate, gallium ions in gallium nitrate nonahydrate, and strontium ions in strontium nitrate tetrahydrate is 2:1, and the molar ratio of zinc ions in zinc nitrate hexahydrate, gallium ions in gallium nitrate nonahydrate, and strontium ions in strontium nitrate tetrahydrate is 1:1:1. Subsequently, the mixed solution is vigorously stirred in a water bath at 80°C, with a speed of 400r / min and a stirring time of 4h until a gel is formed. Subsequently, the obtained gel is placed in a blast drying oven, dried at a temperature of 120°C for 12h, and then ground to obtain gel powder;

[0079] 3) 100 g of the acid-treated ZSM-5 molecular sieve obtained in step 1), 200 g of the acid-treated attapulgite obtained in step 1), 200 g of the gel powder obtained in step 2), and 500 g of activated alumina were mixed, 60 g of water was added, and the mixture was rolled into balls. The mixture was cured in a closed environment at 40°C for 6 h, then dried, and then calcined at 650°C for 2 h to obtain the oxygen-containing compound removing agent.

[0080] Example 7

[0081] This embodiment provides a method for preparing an oxygen-containing compound removing agent, comprising the following steps:

[0082] 1) Weigh 800 ml of 2 mol / L hydrochloric acid, add 400 g of ZSM-5 molecular sieve, transfer to a stainless steel reactor, heat treat at 180° C. for 8 h, filter and dry to obtain an acid-treated ZSM-5 molecular sieve; weigh 1200 ml of 1 mol / L hydrochloric acid, add 600 g of attapulgite, transfer to a stainless steel reactor, heat treat at 150° C. for 8 h, filter and dry to obtain an acid-treated attapulgite;

[0083] 2) Take citric acid and zinc nitrate hexahydrate, gallium nitrate nonahydrate, and strontium nitrate tetrahydrate, and dissolve them in 1L of deionized water to form a mixed solution. The total molar concentration of gallium ions, zinc ions, and strontium ions in the mixed solution is 0.6 mol / L, the molar ratio of citric acid to the total molar amount of zinc ions in zinc nitrate hexahydrate, gallium ions in gallium nitrate nonahydrate, and strontium ions in strontium nitrate tetrahydrate is 1:1, and the molar ratio of zinc ions in zinc nitrate hexahydrate, gallium ions in gallium nitrate nonahydrate, and strontium ions in strontium nitrate tetrahydrate is 1:1:1. Subsequently, the mixed solution is vigorously stirred in a water bath at 70°C at a speed of 400r / min for 4 hours until a gel is formed. Subsequently, the obtained gel is placed in a blast drying oven, dried at a temperature of 120°C for 12 hours, and then ground to obtain gel powder;

[0084] 3) 100 g of the acid-treated ZSM-5 molecular sieve obtained in step 1), 200 g of the acid-treated attapulgite obtained in step 1), 200 g of the gel powder obtained in step 2), and 500 g of activated alumina were mixed, 60 g of water was added, and the mixture was rolled into balls. The mixture was cured in a closed environment at 60° C. for 24 h, then dried, and then calcined at 350° C. for 2 h to obtain the oxygen-containing compound removing agent.

[0085] Example 8

[0086] This embodiment provides a method for preparing an oxygen-containing compound removing agent, comprising the following steps:

[0087] 1) Weigh 800 ml of 1 mol / L hydrochloric acid, add 400 g of ZSM-5 molecular sieve, transfer to a stainless steel reactor, heat treat at 150° C. for 4 h, filter and dry to obtain an acid-treated ZSM-5 molecular sieve; weigh 1200 ml of 1 mol / L hydrochloric acid, add 600 g of attapulgite, transfer to a stainless steel reactor, heat treat at 150° C. for 8 h, filter and dry to obtain an acid-treated attapulgite;

[0088] 2) Take citric acid and zinc nitrate hexahydrate, gallium nitrate nonahydrate, and strontium nitrate tetrahydrate, and dissolve them in 1L of deionized water to form a mixed solution. The total molar concentration of gallium ions, zinc ions, and strontium ions in the mixed solution is 0.6 mol / L, the molar ratio of citric acid to the total molar amount of zinc ions in zinc nitrate hexahydrate, gallium ions in gallium nitrate nonahydrate, and strontium ions in strontium nitrate tetrahydrate is 1:1, and the molar ratio of zinc ions in zinc nitrate hexahydrate, gallium ions in gallium nitrate nonahydrate, and strontium ions in strontium nitrate tetrahydrate is 1:1:1. Subsequently, the mixed solution is vigorously stirred in a water bath at 90°C, with a speed of 400r / min and a stirring time of 4h until a gel is formed. Subsequently, the obtained gel is placed in a blast drying oven, dried at a temperature of 120°C for 12h, and then ground to obtain gel powder;

[0089] 3) 100 g of the acid-treated ZSM-5 molecular sieve obtained in step 1), 200 g of the acid-treated attapulgite obtained in step 1), 200 g of the gel powder obtained in step 2), and 500 g of activated alumina were mixed, 60 g of water was added, and the mixture was rolled into balls. The mixture was cured in a closed environment at 40°C for 12 h, then dried, and then calcined at 650°C for 2 h to obtain the oxygen-containing compound removing agent.

[0090] Example 9

[0091] This embodiment provides a method for preparing an oxygen-containing compound removing agent, comprising the following steps:

[0092] 1) Weigh 800 ml of 2 mol / L hydrochloric acid, add 400 g of ZSM-5 molecular sieve, transfer to a stainless steel reactor, heat treat at 180° C. for 8 h, filter and dry to obtain an acid-treated ZSM-5 molecular sieve; weigh 1200 ml of 1 mol / L hydrochloric acid, add 600 g of attapulgite, transfer to a stainless steel reactor, heat treat at 150° C. for 8 h, filter and dry to obtain an acid-treated attapulgite;

[0093] 2) Take citric acid and zinc nitrate hexahydrate, gallium nitrate nonahydrate, and strontium nitrate tetrahydrate, and dissolve them in 1L of deionized water to form a mixed solution. The total molar concentration of gallium ions, zinc ions, and strontium ions in the mixed solution is 1.2 mol / L, the molar ratio of citric acid to the total molar amount of zinc ions in zinc nitrate hexahydrate, gallium ions in gallium nitrate nonahydrate, and strontium ions in strontium nitrate tetrahydrate is 2:1, and the molar ratio of zinc ions in zinc nitrate hexahydrate, gallium ions in gallium nitrate nonahydrate, and strontium ions in strontium nitrate tetrahydrate is 1:1:1. Subsequently, the mixed solution is vigorously stirred in a water bath at 80°C, with a speed of 400r / min and a stirring time of 4h until a gel is formed. Subsequently, the obtained gel is placed in a blast drying oven, dried at a temperature of 120°C for 12h, and then ground to obtain gel powder;

[0094] 3) Mix 200 g of the acid-treated ZSM-5 molecular sieve obtained in step 1), 500 g of the acid-treated attapulgite obtained in step 1), 100 g of the gel powder obtained in step 2), and 300 g of activated alumina, add 60 g of water, roll into balls, cure in a closed environment at 60°C for 24 h, then dry, and then calcine at 350°C for 2 h to obtain the oxygen-containing compound remover.

[0095] Example 10

[0096] This embodiment provides a method for preparing an oxygen-containing compound removing agent, comprising the following steps:

[0097] 1) Weigh 800 ml of 1 mol / L hydrochloric acid, add 400 g of ZSM-5 molecular sieve, transfer to a stainless steel reactor, heat treat at 150° C. for 8 h, filter and dry to obtain an acid-treated ZSM-5 molecular sieve; weigh 1200 ml of 1 mol / L hydrochloric acid, add 600 g of attapulgite, transfer to a stainless steel reactor, heat treat at 150° C. for 8 h, filter and dry to obtain an acid-treated attapulgite;

[0098] 2) Take ethylenediaminetetraacetic acid and zinc nitrate hexahydrate, gallium nitrate nonahydrate, and strontium nitrate tetrahydrate, and dissolve them in 1L of deionized water to form a mixed solution. The total molar concentration of gallium ions, zinc ions, and strontium ions in the mixed solution is 0.6 mol / L, the molar ratio of ethylenediaminetetraacetic acid to the total molar amount of zinc ions in zinc nitrate hexahydrate, gallium ions in gallium nitrate nonahydrate, and strontium ions in strontium nitrate tetrahydrate is 1:1, and the molar ratio of zinc ions in zinc nitrate hexahydrate, gallium ions in gallium nitrate nonahydrate, and strontium ions in strontium nitrate tetrahydrate is 1:1:1. Subsequently, the mixed solution is vigorously stirred in a water bath at 90°C, with a speed of 400r / min and a stirring time of 4h until a gel is formed. Subsequently, the obtained gel is placed in a blast drying oven, dried at a temperature of 120°C for 12h, and then ground to obtain a gel powder;

[0099] 3) 100 g of the acid-treated ZSM-5 molecular sieve obtained in step 1), 200 g of the acid-treated attapulgite obtained in step 1), 200 g of the gel powder obtained in step 2), and 500 g of activated alumina were mixed, 60 g of water was added, and the mixture was rolled into balls. The mixture was cured in a closed environment at 60°C for 12 h, then dried, and then calcined at 500°C for 2 h to obtain the oxygen-containing compound removing agent.

[0100] Comparative Example 1

[0101] This comparative example provides a method for preparing an oxygen-containing compound removing agent, comprising the following steps:

[0102] 1) Take citric acid and zinc nitrate hexahydrate, gallium nitrate nonahydrate, and strontium nitrate tetrahydrate, and dissolve them in 1L of deionized water to form a mixed solution. The total molar concentration of gallium ions, zinc ions, and strontium ions in the mixed solution is 0.6 mol / L, the molar ratio of citric acid to the total molar amount of zinc ions in zinc nitrate hexahydrate, gallium ions in gallium nitrate nonahydrate, and strontium ions in strontium nitrate tetrahydrate is 1:1, and the molar ratio of zinc ions in zinc nitrate hexahydrate, gallium ions in gallium nitrate nonahydrate, and strontium ions in strontium nitrate tetrahydrate is 1:1:1. Subsequently, the mixed solution is vigorously stirred in a water bath at 90°C, with a speed of 400r / min and a stirring time of 4h until a gel is formed. Subsequently, the obtained gel is placed in a blast drying oven, dried at a temperature of 120°C for 12h, and then ground to obtain gel powder;

[0103] 2) 100 g of ZSM-5 molecular sieve, 200 g of attapulgite, 200 g of the gel powder obtained in step 1), and 500 g of activated alumina were mixed, 60 g of water was added, and the mixture was rolled into balls. The mixture was cured in a closed environment at 60° C. for 12 h, then dried, and calcined at 500° C. for 2 h to obtain the oxygen-containing compound removing agent.

[0104] Comparative Example 2

[0105] This comparative example provides a method for preparing an oxygen-containing compound removing agent, comprising the following steps:

[0106] 1) Weigh 1200 ml of 1 mol / L hydrochloric acid, add 600 g of attapulgite, transfer to a stainless steel reactor, heat treat at 150° C. for 8 h, filter and dry to obtain acid-treated attapulgite;

[0107] 2) Take citric acid and zinc nitrate hexahydrate, gallium nitrate nonahydrate, and strontium nitrate tetrahydrate, and dissolve them in 1L of deionized water to form a mixed solution. The total molar concentration of gallium ions, zinc ions, and strontium ions in the mixed solution is 0.6 mol / L, the molar ratio of citric acid to the total molar amount of zinc ions in zinc nitrate hexahydrate, gallium ions in gallium nitrate nonahydrate, and strontium ions in strontium nitrate tetrahydrate is 1:1, and the molar ratio of zinc ions in zinc nitrate hexahydrate, gallium ions in gallium nitrate nonahydrate, and strontium ions in strontium nitrate tetrahydrate is 1:1:1. Subsequently, the mixed solution is vigorously stirred in a water bath at 90°C, with a speed of 400r / min and a stirring time of 4h until a gel is formed. Subsequently, the obtained gel is placed in a blast drying oven, dried at a temperature of 120°C for 12h, and then ground to obtain gel powder;

[0108] 3) 200 g of the acid-treated attapulgite obtained in step 1), 200 g of the gel powder obtained in step 2), and 500 g of activated alumina were mixed, 600 g of water was added, and the mixture was rolled into balls. The mixture was cured in a closed environment at 60° C. for 12 h, then dried, and calcined at 500° C. for 2 h to obtain the oxygen-containing compound removing agent.

[0109] Comparative Example 3

[0110] This comparative example provides a method for preparing an oxygen-containing compound removing agent, comprising the following steps:

[0111] 1) Weigh 800 ml of 1 mol / L hydrochloric acid, add 400 g of ZSM-5 molecular sieve, transfer to a stainless steel reactor, heat treat at 150° C. for 8 h, filter and dry to obtain an acid-treated ZSM-5 molecular sieve; weigh 1200 ml of 1 mol / L hydrochloric acid, add 600 g of attapulgite, transfer to a stainless steel reactor, heat treat at 150° C. for 8 h, filter and dry to obtain an acid-treated attapulgite;

[0112] 2) Mix 100 g of the acid-treated ZSM-5 molecular sieve obtained in step 1), 200 g of the acid-treated attapulgite obtained in step 1), and 500 g of activated alumina, add 60 g of water, roll into balls, cure in a closed environment at 60° C. for 12 h, then dry, and calcine at 500° C. for 2 h to obtain the oxygen-containing compound removing agent.

[0113] Comparative Example 4

[0114] This comparative example provides a method for preparing an oxygen-containing compound removing agent, comprising the following steps:

[0115] 1) Weigh 800 ml of 1 mol / L hydrochloric acid, add 400 g of ZSM-5 molecular sieve, transfer to a stainless steel reactor, heat treat at 150° C. for 8 h, filter and dry to obtain an acid-treated ZSM-5 molecular sieve; weigh 1200 ml of 1 mol / L hydrochloric acid, add 600 g of attapulgite, transfer to a stainless steel reactor, heat treat at 150° C. for 8 h, filter and dry to obtain an acid-treated attapulgite;

[0116] 2) Take citric acid, zinc nitrate hexahydrate and strontium nitrate tetrahydrate, and dissolve them in 1L of deionized water to form a mixed solution. The total molar concentration of zinc ions and strontium ions in the mixed solution is 0.6 mol / L, the molar ratio of citric acid to the total molar amount of zinc ions in zinc nitrate hexahydrate and strontium ions in strontium nitrate tetrahydrate is 1:1, and the molar ratio of zinc ions in zinc nitrate hexahydrate and strontium ions in strontium nitrate tetrahydrate is 1:1. Subsequently, the mixed solution is vigorously stirred in a water bath at 90°C, with a speed of 400r / min and a stirring time of 4h until a gel is formed. Subsequently, the obtained gel is placed in a blast drying oven, dried at a temperature of 120°C for 12h, and then ground to obtain gel powder;

[0117] 3) 100 g of the acid-treated ZSM-5 molecular sieve obtained in step 1), 200 g of the acid-treated attapulgite obtained in step 1), 200 g of the gel powder obtained in step 2), and 500 g of activated alumina were mixed, 60 g of water was added, and the mixture was rolled into balls. The mixture was cured in a closed environment at 60°C for 12 h, then dried, and then calcined at 500°C for 2 h to obtain the oxygen-containing compound removing agent.

[0118] Comparative Example 5

[0119] This comparative example provides a method for preparing an oxygen-containing compound removing agent, comprising the following steps:

[0120] 1) Weigh 800 ml of 1 mol / L hydrochloric acid, add 400 g of ZSM-5 molecular sieve, transfer to a stainless steel reactor, heat treat at 150° C. for 8 h, filter and dry to obtain an acid-treated ZSM-5 molecular sieve; weigh 1200 ml of 1 mol / L hydrochloric acid, add 600 g of attapulgite, transfer to a stainless steel reactor, heat treat at 150° C. for 8 h, filter and dry to obtain an acid-treated attapulgite;

[0121] 2) Take citric acid, gallium nitrate nonahydrate and strontium nitrate tetrahydrate, and dissolve them in 1L of deionized water to form a mixed solution. The total molar concentration of gallium ions and strontium ions in the mixed solution is 0.6 mol / L, the molar ratio of citric acid to the total molar amount of gallium ions in gallium nitrate nonahydrate and strontium ions in strontium nitrate tetrahydrate is 1:1, and the molar ratio of gallium ions in gallium nitrate nonahydrate to strontium ions in strontium nitrate tetrahydrate is 1:1. Subsequently, the mixed solution is vigorously stirred in a water bath at 90°C, with a speed of 400r / min and a stirring time of 4h until a gel is formed. Subsequently, the obtained gel is placed in a blast drying oven, dried at a temperature of 120°C for 12h, and then ground to obtain gel powder;

[0122] 3) 100 g of the acid-treated ZSM-5 molecular sieve obtained in step 1), 200 g of the acid-treated attapulgite obtained in step 1), 200 g of the gel powder obtained in step 2), and 500 g of activated alumina were mixed, 60 g of water was added, and the mixture was rolled into balls. The mixture was cured in a closed environment at 60°C for 12 h, then dried, and then calcined at 500°C for 2 h to obtain the oxygen-containing compound removing agent.

[0123] Comparative Example 6

[0124] This comparative example provides a method for preparing an oxygen-containing compound removing agent, comprising the following steps:

[0125] 1) Weigh 800 ml of 1 mol / L hydrochloric acid, add 400 g of ZSM-5 molecular sieve, transfer to a stainless steel reactor, heat treat at 150° C. for 8 h, filter and dry to obtain an acid-treated ZSM-5 molecular sieve; weigh 1200 ml of 1 mol / L hydrochloric acid, add 600 g of attapulgite, transfer to a stainless steel reactor, heat treat at 150° C. for 8 h, filter and dry to obtain an acid-treated attapulgite;

[0126] 2) Take citric acid, zinc nitrate hexahydrate and gallium nitrate nonahydrate, and dissolve them in 1L of deionized water to form a mixed solution. The total molar concentration of gallium ions and zinc ions in the mixed solution is 0.6 mol / L, the molar ratio of citric acid to the total molar amount of zinc ions in zinc nitrate hexahydrate and gallium ions in gallium nitrate nonahydrate is 1:1, and the molar ratio of zinc ions in zinc nitrate hexahydrate and gallium ions in gallium nitrate nonahydrate is 1:1. Subsequently, the mixed solution is vigorously stirred in a water bath at 90°C at a speed of 400r / min for 4 hours until a gel is formed. Subsequently, the obtained gel is placed in a blast drying oven, dried at a temperature of 120°C for 12 hours, and then ground to obtain gel powder;

[0127] 3) 100 g of the acid-treated ZSM-5 molecular sieve obtained in step 1), 200 g of the acid-treated attapulgite obtained in step 1), 200 g of the gel powder obtained in step 2), and 500 g of activated alumina were mixed, 60 g of water was added, and the mixture was rolled into balls. The mixture was cured in a closed environment at 60°C for 12 h, then dried, and then calcined at 500°C for 2 h to obtain the oxygen-containing compound removing agent.

[0128] Test Example 1

[0129] The desulfurizers prepared in the examples and comparative examples were all tested for specific surface area, pore volume, and average pore size using a physical adsorption instrument (model ASAP2460, purchased from Micromeritics Instruments, Inc., USA) to investigate the changes in specific surface area and pore distribution of the desulfurizers. The results are shown in Table 1.

[0130] Table 1

[0131]

[0132]

[0133] Test Example 2

[0134] The desorbents prepared in the examples and comparative examples were subjected to a desorbent particle strength test according to GB / T 44750-2024 “Measurement of compressive strength of particles”. The results are shown in Table 2.

[0135] Table 2

[0136]

[0137]

[0138] Test Example 3

[0139] Activity evaluation of the removal agent: The removal agents prepared in the examples and comparative examples were tested for activity in a self-made fixed-bed glass reactor. The packing column was charged with 2 mL of the removal agents prepared in the examples and comparative examples, respectively. The specific composition of the feed gas is shown in Table 3. The space velocity through the packing column was 1000-5000 h -1 , packing column pressure: 1-4MPa, packing column temperature: room temperature, the gas chromatograph model used is Agilent 7890B gas chromatograph (purchased from Agilent Technologies Co., Ltd.) to detect the gas after the raw gas passes through the packing column reaction. When dimethyl ether gas is detected, it is breakthrough, and the breakthrough capacity of dimethyl ether is calculated. The calculation formula is: Where E: penetration capacity / %; h -1 : space velocity; V: amount of remover loaded / ml; t: dimethyl ether breakthrough time / h; C: mass concentration of dimethyl ether in the feed gas / %; m: mass of remover / g. The calculated results are shown in Table 4. The reaction was terminated after 5 hours. Based on the total content of methanol, dimethyl ether, and MTBE detected in the reaction, the total removal rate of methanol, dimethyl ether, and MTBE was calculated. The calculated results are shown in Table 4.

[0140] Table 3

[0141]

[0142] Table 4

[0143] Penetration capacity% Total removal rate% Example 1 6.21 96.21 Example 2 7.69 97.69 Example 3 8.04 100 Example 4 7.21 97.21 Example 5 7.65 97.65 Example 6 6.74 96.74 Example 7 7.62 97.62 Example 8 6.25 96.25 Example 9 6.19 95.19 Example 10 6.02 90.87 Comparative Example 1 4.91 89.3 Comparative Example 2 4.85 84.97 Comparative Example 3 5.03 83.85 Comparative Example 4 5.24 88.24 Comparative Example 5 5.15 84.15 Comparative Example 6 5.38 85.38

[0144] Breakthrough capacity refers to the mass ratio of the total amount of target substance adsorbed by an adsorbent or catalyst to the amount of adsorbent or catalyst when the concentration of methanol, dimethyl ether, or dimethyl ether in the effluent reaches breakthrough during a fixed-bed adsorption or catalytic reaction. This emphasizes the actual processing capacity or loading capacity of the adsorbent / catalyst.

[0145] As can be seen from Tables 1, 2, and 4, the removers obtained using the preparation method of the present invention in the examples have high specific surface area, pore volume, pore diameter, high penetration capacity, and high mechanical strength. Among them, all the operating parameters and raw material ratios used in Example 3 are optimal values, and the obtained remover has the best performance. However, compared with Example 1, the penetration capacity and total removal rate of the products obtained in Comparative Example 1, in which the molecular sieve and the attapulgite are not acid-treated, Comparative Example 2, in which the molecular sieve and the attapulgite are not formed with other raw materials, Comparative Example 3, in which the gel powder is not formed with other raw materials, Comparative Example 4, in which no gallium salt is added, Comparative Example 5, in which no zinc salt is added, and Comparative Example 6, in which no strontium salt is added, are far inferior to those of the remover obtained in Example 1.

[0146] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will readily appreciate that other variations or modifications based on the above descriptions are possible. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

Claims

1. An oxygen-containing compound removing agent, characterized in that The oxygen-containing compound removing agent includes an acid-treated molecular sieve, an acid-treated attapulgite and a metal compound; The metal oxides include gallium metal compounds, zinc metal compounds and strontium metal compounds.

2. The oxygen-containing compound removing agent according to claim 1, characterized in that The specific surface area of ​​the oxygen-containing compound removal agent is 238-403m 2 / g, pore volume 0.32-0.43cm 3 / g, average pore size 7-11nm; Preferably, the specific surface area of ​​the oxygen-containing compound removing agent is 264-403m 2 / g, pore volume 0.36-0.43cm 3 / g, average pore diameter 8-11nm.

3. A method for preparing the oxygen-containing compound removing agent according to claim 1 or 2, characterized in that: The steps include: 1) treating the molecular sieve and the attapulgite with acid to obtain the acid-treated molecular sieve and the acid-treated attapulgite; 2) mixing the template, gallium salt, zinc salt, strontium salt and water to form a mixed solution, heating and stirring to form a gel, and then drying and grinding to obtain a gel powder; 3) The acid-treated molecular sieve obtained in step 1), the acid-treated attapulgite, the gel powder obtained in step 2) and a molding aid are mixed, molded, cured, and then calcined to obtain the oxygen-containing compound removing agent.

4. The method for preparing the oxygen-containing compound removing agent according to claim 3, wherein: In step 1), the molecular sieve and the attapulgite are placed in an acid solution, respectively, and subjected to heat treatment to obtain the acid-treated molecular sieve and the acid-treated attapulgite.

5. The method for preparing the oxygen-containing compound removing agent according to claim 4, wherein: The concentration of the acid in the acid solution is 1-3 mol / L; The acid in the acid solution includes at least one of nitric acid, hydrochloric acid, and sulfuric acid; The molecular sieve and acid solution ratio is 1: (1-3), the unit is g / mL; The dosage ratio of the attapulgite to the acid solution is 1:(1-3), and the unit is g / mL.

6. The method for preparing the oxygen-containing compound removing agent according to claim 4 or 5, characterized in that: The molecular sieve includes at least one of aluminum phosphate molecular sieve, silicon aluminum phosphate molecular sieve, ZSM-5 molecular sieve, Y-type molecular sieve, X-type molecular sieve, and A-type molecular sieve; The heating temperature is 150-200°C and the heating time is 2-12h; Optionally, a drying step is further included after the heating treatment step is completed.

7. The method for preparing the oxygen-containing compound removing agent according to any one of claims 3 to 6, characterized in that: In step 2), the molar ratio of gallium ions in the gallium salt, zinc ions in the zinc salt, and strontium ions in the strontium salt is (0.5-3): (0.5-3): (0.5-3); The ratio of the total molar amount of gallium ions in the gallium salt, zinc ions in the zinc salt and strontium ions in the strontium salt to the molar amount of the template is 1:(1-3); The total molar content of gallium ions of the gallium salt, zinc ions of the zinc salt, and strontium ions of the strontium salt in the mixed solution is 0.6-1.8 mol / L; The heating and stirring temperature is 70-100°C, the heating and stirring speed is 200-500r / min, and the heating and stirring time is 3-6h; In step 2), the drying temperature is 100-120° C. and the drying time is 8-16 hours.

8. The method for preparing the oxygen-containing compound removing agent according to any one of claims 3 to 7, characterized in that: In step 2), the template comprises at least one of citric acid, tartaric acid, ethylenediaminetetraacetic acid, and gluconic acid; Preferably, the template is citric acid; The gallium salt includes at least one of gallium nitrate nonahydrate, gallium sulfate, gallium chloride, and gallium iodide; The zinc salt includes at least one of zinc nitrate hexahydrate, zinc sulfate, and zinc chloride; The strontium salt includes at least one of strontium nitrate tetrahydrate, strontium chloride, strontium acetate, and strontium hydroxide.

9. The method for preparing the oxygen-containing compound removing agent according to any one of claims 3 to 8, characterized in that: In step 3), the mass ratio of the acid-treated molecular sieve, the acid-treated attapulgite, the gel powder obtained in step 2), and the molding aid is (100-300): (200-500): (100-300): (300-500); The molding aid includes at least one of alumina, silica, magnesium oxide, and clay; In step 3), the curing temperature is 40-80°C and the curing time is 6-48h; The calcination temperature is 350-750°C and the calcination time is 2-6 hours; Optionally, after the health-preserving step is completed, a drying step is further included; Optionally, the forming includes water-added strip extrusion forming or water-added ball rolling forming.

10. Use of the oxygen-containing compound removing agent according to claim 1 or 2 or the oxygen-containing compound removing agent prepared by the preparation method according to any one of claims 3 to 9 in removing oxygen-containing compounds from hydrocarbon compounds; Optionally, the hydrocarbon compound includes a C3-C5 hydrocarbon compound; Optionally, the C3-C5 hydrocarbon compound includes C3-C5 alkane and / or C3-C5 olefin; Optionally, the oxygen-containing compound includes at least one of methanol, dimethyl ether, methyl ethyl ketone, butyraldehyde, and methyl tert-butyl ether.

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