A desulfurization adsorbent and a method for preparing the same

Abstract

The present application relates to the technical field of adsorbing material, in particular to a desulfurization adsorbent and a preparation method. The TiO2 / clay desulfurization adsorbent obtained by conventional calcination method or single alcohol impregnation method is prone to surface particle accumulation and adsorbent channel blockage, which leads to the decline of the adsorption performance of the desulfurization adsorbent to organic sulfides. In view of the above problems, the present application provides a desulfurization adsorbent, in the process of preparing the desulfurization adsorbent, the clay carrier and the active component are dispersed and dissolved in anhydrous ethanol under a nitrogen atmosphere, and then the two are blended under a nitrogen atmosphere, and after blending, atomization drying is carried out at high temperature. The operation mode, the adsorption effect of the obtained desulfurization adsorbent is good, and the desulfurization adsorbent has good adsorption to various organic sulfides in various organic solvents.

Description

Technical Field

[0001] This invention relates to the field of adsorption materials technology, specifically to a desulfurization adsorbent and its preparation method. Background Technology

[0002] Globally, approximately 80% of energy comes from fossil fuels, with crude oil accounting for 37%, contributing almost half of the energy from fossil fuels. Fuel oil, especially gasoline and diesel, is a crucial product of crude oil refining. Sulfides are the most common impurities in fuel oil, typically ranging from 0.1% to 5% by mass, existing as sulfides, mercaptans, thiophenes, and their derivatives. The combustion of sulfides in fuel oil forms sulfate oxides (SOx) and sulfate particles, causing a series of environmental problems. Simultaneously, SO2 emissions from combustion also harm human health, causing serious diseases such as upper respiratory tract infections, asthma, and lung cancer. Therefore, sulfur content is the most critical environmental indicator for fuel oil. Given the rapidly growing energy demand and increasingly serious environmental problems, achieving low-sulfur or zero-sulfur fuel oil is imperative. Deep desulfurization of fuel oil not only enhances the status of clean energy in the consumption structure but also promotes the comprehensive and coordinated development of the economy, society, and ecology, possessing significant practical strategic importance.

[0003] Traditional industrial desulfurization is mainly divided into two methods: hydrotreating and non-hydrotreating. Hydrotreating requires high-temperature and high-pressure operating conditions, posing significant challenges in energy consumption and safety. Furthermore, highly stable thiophene sulfides and their derivatives in oil products cannot be completely removed, making deep desulfurization extremely difficult. Non-hydrotreating methods mainly include extraction desulfurization, oxidative desulfurization, biological desulfurization, and adsorption desulfurization. Among these, adsorption desulfurization offers advantages such as mild conditions, simple operation, rapid desulfurization speed, low energy consumption, easy adsorbent regeneration, and no byproducts during the desulfurization process, making it a hot topic in deep fuel desulfurization technology research both domestically and internationally. The key to adsorption desulfurization is the adsorbent used; its desulfurization rate primarily depends on the material's texture. Advantageous characteristics include low cost and ease of preparation, good structural strength and stability, large specific surface area, multiple adsorption sites, and high activity. Natural clay, a hydrous mineral rich in magnesium, aluminum, and silicon, possesses inherent desulfurization properties. Due to its unique layered chain structure, high porosity, large specific surface area, and strong surface activity, it is commonly used as a base material for desulfurization adsorbents. TiO2, due to its green and non-toxic properties, stable characteristics, and high activity, is widely used as an active component in substrates. Furthermore, numerous studies have shown that TiO2 possesses various desulfurization active centers, allowing organic sulfides to form hydrogen bonds and π bonds with the acidic hydroxyl groups (-OH) on its surface and Ti, respectively, thus enabling selective adsorption and removal. Therefore, supported composite materials with clay as the substrate and TiO2 as the active component exhibit excellent performance in deep adsorption desulfurization.

[0004] There are three main methods for preparing TiO2 / clay-based desulfurization adsorbents: hydrothermal method, sol-gel method, and impregnation method. The hydrothermal method uses water as a solvent under high temperature and pressure to induce a chemical reaction in the raw materials. This method is highly dependent on production equipment and has a low safety factor. The sol-gel method involves multiple steps such as hydrolysis, condensation, aging, drying, and calcination, resulting in a long preparation time. While the impregnation method is simple to operate, requiring only the carrier to be immersed in the precursor solution for loading, uneven liquid-solid mixing is prone to occur, leading to low loading. Furthermore, regardless of the preparation method, organic compounds containing Ti, such as tetrabutyl titanate, are used as precursors. These organic precursors rapidly hydrolyze to form TiO2 particles in the presence of moisture. Therefore, loss of the Ti organic precursor is unavoidable during the above preparation processes. Simultaneously, the hydrolyzed TiO2 deposits on the carrier surface, hindering uniform adhesion of the precursor and causing particle accumulation and pore blockage. Finally, the organic precursor on the carrier surface needs to come into contact with air at high temperature to transform into the TiO2 active component. However, due to the limited contact area between the particles and air, incomplete transformation of the active component may occur. In summary, many problems in traditional preparation methods significantly reduce the desulfurization performance of TiO2-based composite adsorbents. Summary of the Invention

[0005] The existing technology has the problem that TiO2 / clay-based desulfurization adsorbents obtained by conventional calcination or monoalcohol impregnation methods are prone to surface particle accumulation and adsorbent pore blockage, leading to a decrease in their adsorption performance for organic sulfides. To address the above problems, this invention provides a desulfurization adsorbent, the preparation method of which includes the following steps:

[0006] (1) Preparation of inert carrier alcohol solution: First, disperse clay in hydrochloric acid aqueous solution with a concentration of 1-6 mol / L and stir at room temperature for 2-5 h. Then wash the mixed solution with deionized water until neutral. Then dry the acidified clay in an oven at 100-110℃ for 8-12 h to obtain carrier powder. Place anhydrous ethanol in a reaction vessel and disperse the carrier powder in anhydrous ethanol at room temperature. Then continuously blow N2 above the surface of anhydrous ethanol to remove air in the reaction vessel. The blowing direction is parallel to the surface of anhydrous ethanol. Keep the pressure in the reaction vessel constant and stir and disperse for 30-60 min to obtain inert carrier alcohol solution.

[0007] (2) Preparation of active component alcohol solution: Anhydrous ethanol is placed in the reaction vessel. N2 is continuously purged into the reaction vessel to remove air. The direction of nitrogen purging is parallel to the liquid surface of anhydrous ethanol. The pressure in the reaction vessel is constant. After N2 is continuously purged for 20-30 minutes, the organic precursor tetrabutyl titanate is added into the reaction vessel. The mixture is stirred and dissolved at room temperature for 3-5 minutes to obtain the active component alcohol solution.

[0008] (3) Preparation of diol mixture: At room temperature, under the condition of continuous N2 in the reactor of step (2), the inert carrier alcohol solution obtained in step (1) is added to the active component alcohol solution obtained in step (2), and the mixture is stirred continuously for 0.5-1h under N2 atmosphere to obtain diol mixture. After the reaction is completed, the condition of continuous N2 in the reactor is maintained.

[0009] (4) Preparation of desulfurization adsorbent by spray drying: The diol mixture obtained in step (3) is passed into an airflow atomizing device at a constant flow rate and dried by atomization using high temperature air. Finally, the dried solid is collected and passed through a 100-140 mesh sieve to obtain the product.

[0010] Preferably, the N2 purging flow rate is 300-400 cm⁻¹. 3 / min.

[0011] Preferably, the clay includes at least one of attapulgite, bentonite, and kaolin.

[0012] Preferably, the ratio of clay to hydrochloric acid aqueous solution is 0.5-1.2g:8-15mL.

[0013] Preferably, in step (1), the mass ratio of anhydrous ethanol to carrier powder is 10-20:1.

[0014] Preferably, in step (2), the molar ratio of anhydrous ethanol to tetrabutyl titanate is 70-100:1.

[0015] Preferably, in step (3), the mass ratio of the inert carrier alcohol solution to the active component alcohol solution is 0.3-1:1.

[0016] Preferably, the temperature for atomization drying in step (4) is 90-120℃.

[0017] The present invention has the following beneficial effects:

[0018] (1) In the process of preparing desulfurization adsorbent, the clay carrier and active components are first dispersed and dissolved in anhydrous ethanol under a nitrogen atmosphere, and then the two are mixed under a nitrogen atmosphere. After mixing, the mixture is then atomized and dried at high temperature. This operation method results in a better adsorption effect of the desulfurization adsorbent, which has good adsorption properties for a variety of organic sulfides in a variety of organic solvents.

[0019] (2) In this invention, the diol solutions formed by the clay carrier and the active component are mixed separately. Compared with adding the clay carrier to the monool solution formed by the active component and anhydrous ethanol, this significantly improves the adsorption performance of the obtained desulfurization adsorbent. The reason is:

[0020] Even after acidification and drying (e.g., drying at 105°C for 12 hours), the clay carrier still contains a small amount of free water. When some Ti organic precursors (e.g., tetrabutyl titanate) come into contact with the free water, they rapidly hydrolyze to form TiO2 particles, which easily deposit on the carrier surface. This not only hinders the uniform adhesion of the active components to the carrier surface, but the accumulation of TiO2 particles can also clog the pores of the carrier, resulting in a significant decrease in the adsorption performance of the obtained desulfurization adsorbent. In this invention, the acidified and dried clay carrier is first dispersed in anhydrous ethanol, and then mixed with the active component alcohol solution under a nitrogen atmosphere. In this way, the anhydrous ethanol can combine with the free water in the clay carrier structure to form a stable alcohol-water azeotropic structure, thereby avoiding the subsequent hydrolysis reaction between the free water and the Ti active components. Furthermore, when the carrier is dispersed in an alcohol solution, each particle of the carrier is suspended due to buoyancy. Compared with the state without alcohol solution, its dispersion is significantly improved, effectively avoiding particle accumulation. This makes the carrier of the desulfurization adsorbent obtained by the present invention less prone to problems such as hydrolysis and deactivation of active components, surface particle accumulation, and blockage of adsorbent pores.

[0021] (3) In the process of preparing the desulfurization adsorbent, steps (1)-(3) of this invention must be carried out under nitrogen protection to ensure that each step avoids the introduction of water as much as possible, so as to reduce the hydrolysis of Ti organic precursor and ultimately effectively solve the problem that Ti organic precursor is rapidly hydrolyzed to form TiO2 particles, which are easily deposited on the surface of the carrier or the particles accumulate and block the carrier pores. Attached image description:

[0022] Figure 1 Flowchart of the preparation process of the desulfurization adsorbent in Example 1.

[0023] Figure 2 The dynamic breakthrough curves of the desulfurization adsorbents obtained in Examples 1, 2, and 3 for the adsorption of different thiophene sulfides in oil products.

[0024] Figure 3 Dynamic breakthrough curves of the desulfurization adsorbents obtained in Examples 1, 4, and 5 for the adsorption of sulfides in different oil products.

[0025] Figure 4 Dynamic breakthrough curves of the desulfurization adsorbents obtained in Examples 1, 6, and 7 for the adsorption of different concentrations of sulfides in oil.

[0026] Figure 5 The dynamic breakthrough curves of desulfurization adsorbents obtained using different clay carriers for the adsorption of sulfides in oil products in Examples 1, 8, and 9 are shown. Detailed implementation method:

[0027] The present invention will be described in detail below with reference to embodiments. However, it should be understood that the following embodiments are merely illustrative examples of implementation of the present invention and are not intended to limit the scope of the present invention.

[0028] The attapulgite clay used in the following embodiments of the present invention is industrial grade and was purchased from Jiangsu Nanda Zijin Technology Group.

[0029] The bentonite used in the following embodiments of the present invention is industrial grade and was purchased from Changzhou Lehuan Trading Co., Ltd.

[0030] The kaolin used in the following embodiments of the present invention is industrial grade and was purchased from Changzhou Lehuan Trading Co., Ltd.

[0031] The nitrogen gas used in the following embodiments of the present invention is analytical grade, with a purity of 99.99%.

[0032] Example 1

[0033] (1) Preparation of inert carrier alcohol solution: First, 5g of attapulgite clay was dispersed in 50mL of 3mol / L hydrochloric acid aqueous solution, stirred at room temperature for 5h, and allowed to stand for 12h. Then, the mixed solution was washed with deionized water until neutral. Then, the acidified clay was placed in an oven at 105℃ and dried for 12h to obtain carrier powder. 49.28g of anhydrous ethanol was placed in a reaction vessel, and 3.5g of carrier powder was dispersed in anhydrous ethanol at room temperature. Then, N2 was continuously blown above the surface of the anhydrous ethanol to remove air in the reaction vessel. The blowing direction was parallel to the surface of the anhydrous ethanol. The pressure in the reaction vessel was kept constant. The mixture was stirred and dispersed for 30min to obtain the inert carrier alcohol solution.

[0034] (2) Preparation of active component alcohol solution: 7.57g of anhydrous ethanol was placed in the reaction vessel. N2 was continuously purged into the reaction vessel to remove air. The direction of nitrogen purging was parallel to the liquid surface of anhydrous ethanol. The pressure in the reaction vessel was constant. After N2 was continuously purged for 30min, 0.63g of tetrabutyl titanate was added into the reaction vessel. The mixture was stirred and dissolved at room temperature for 5min to obtain the active component alcohol solution.

[0035] (3) Preparation of diol mixture: At room temperature, under the condition of continuous N2 in the reactor of step (2), the inert carrier alcohol solution obtained in step (1) is added to the active component alcohol solution obtained in step (2), and the mixture is stirred continuously for 1 hour under N2 atmosphere to obtain diol mixture. After the reaction is completed, the condition of continuous N2 in the reactor is maintained.

[0036] (4) Preparation of desulfurization adsorbent by spray drying: The diol mixture obtained in step (3) is passed into an air spray dryer at a flow rate of 15 mL / min and dried by atomization using high-temperature air at a temperature of 100°C. Finally, the dried solid is collected and passed through a 100-mesh sieve to obtain the desulfurization adsorbent. The preparation flow chart of the desulfurization adsorbent in Example 1 is shown in the attached instruction manual. Figure 1 As shown. Figure 1 1 is a stirred reactor; 2 is a peristaltic pump; 3 is a small air spray dryer; 4 is a drying chamber; 5 is a collection chamber; 6 is an air heater; and 7 is an air filter.

[0037] Dynamic adsorption experiment

[0038] The desulfurization adsorbent obtained in Example 1 was placed in an adsorption column made of 300 series stainless steel, 10 cm long and 1.5 cm in diameter. The amount of desulfurization adsorbent in the adsorption column was 5 g. Both ends of the adsorption column were sealed with quartz wool, and the desulfurization adsorbent was sealed inside the adsorption column. At room temperature and pressure, fuel oil was pumped from the bottom to the top of the adsorption column at a rate of 0.48 mL / min using a peristaltic pump. Sampling was started from the first drop of liquid flowing out from the top of the adsorption column, and a sample was taken every 2 minutes to determine the sulfur content of the simulated oil after adsorption. A dynamic breakthrough curve was plotted, and the dynamic saturated sulfur capacity of the desulfurization adsorbent for desulfurizing organic sulfides in the oil was calculated. A mixture of n-octane and organic sulfides was used as the oil, wherein the organic sulfides were benzothiophene, and the content of organic sulfides in the fuel oil was 1000 mgS / L.

[0039] After the experiment, the dynamic saturated sulfur capacity of the desulfurization adsorbent for desulfurizing organic sulfides in oil was calculated to be 6.48 mg / g.

[0040] Example 2 is the same as Example 1, except that in Example 2, a mixture of n-octane and an organic sulfide is used as the oil product, wherein the organic sulfide is thiophene, and the content of the organic sulfide in the oil product is 1000 mgS / L. After the experiment, the dynamic saturated sulfur capacity of the desulfurization adsorbent for desulfurizing the organic sulfides in the oil product was calculated to be 2.40 mg / g.

[0041] Example 3 is the same as Example 1, except that in Example 3, a mixture of n-octane and an organic sulfide is used as the oil product, wherein the organic sulfide is dibenzothiophene, and the content of the organic sulfide in the oil product is 1000 mgS / L. After the experiment, the dynamic saturated sulfur capacity of the desulfurization adsorbent for desulfurizing the organic sulfides in the oil product was calculated to be 5.76 mg / g.

[0042] Example 4 is the same as Example 1, except that in Example 4, a mixture of n-octane and an organic sulfide is used as the oil product, wherein the organic sulfide is benzothiophene, and the content of the organic sulfide in the oil product is 500 mgS / L. After the experiment, the dynamic saturated sulfur capacity of the desulfurization adsorbent for desulfurizing the organic sulfides in the oil product was calculated to be 4.68 mg / g.

[0043] Example 5 is the same as Example 1, except that in Example 5, a mixture of n-octane and an organic sulfide is used as the oil product, wherein the organic sulfide is benzothiophene, and the content of the organic sulfide in the oil product is 200 mgS / L. After the experiment, the dynamic saturated sulfur capacity of the desulfurization adsorbent for desulfurizing the organic sulfides in the oil product was calculated to be 2.10 mg / g.

[0044] Example 6 is the same as Example 1, except that in Example 6, a mixture of n-heptane and an organic sulfide is used as the oil product, wherein the organic sulfide is benzothiophene, and the content of the organic sulfide in the oil product is 1000 mgS / L. After the experiment, the dynamic saturated sulfur capacity of the desulfurization adsorbent for desulfurizing the organic sulfides in the oil product was calculated to be 6.96 mg / g.

[0045] Example 7 is the same as Example 1, except that in Example 7, a mixture of n-hexane and an organic sulfide is used as the oil product, wherein the organic sulfide is benzothiophene, and the content of the organic sulfide in the oil product is 1000 mgS / L. After the experiment, the dynamic saturated sulfur capacity of the desulfurization adsorbent for desulfurizing the organic sulfides in the oil product was calculated to be 1.20 mg / g.

[0046] Example 8 is the same as Example 1, except that the same mass of bentonite is used in Example 8 to replace the attapulgite in Example 1. After the experiment, the dynamic saturated sulfur capacity of the desulfurization adsorbent for desulfurizing organic sulfides in oil was calculated to be 5.76 mg / g.

[0047] Example 9 is the same as Example 1, except that in Example 9, kaolin of the same mass is used to replace attapulgite in Example 1. After the experiment, the dynamic saturated sulfur capacity of the desulfurization adsorbent for desulfurizing organic sulfides in oil was calculated to be 1.20 mg / g.

[0048] Comparative Example 1 is the same as Example 1, except that the adsorbent in Comparative Example 1 is prepared according to the following steps:

[0049] (1) Preparation of inert carrier: First, 5g of attapulgite clay was dispersed in 50mL of 3mol / L hydrochloric acid aqueous solution, stirred at room temperature for 5h, and allowed to stand for 12h. Then, the mixed solution was washed with deionized water until neutral. Then, the acidified clay was placed in an oven at 105℃ and dried for 12h to obtain carrier powder.

[0050] (2) Preparation of alcohol solution of active component:

[0051] Place 7.57g of anhydrous ethanol into a reaction vessel. Continuously purge the reaction vessel with N2 to remove air. The direction of the nitrogen purging is parallel to the liquid surface of the anhydrous ethanol. Keep the pressure inside the reaction vessel constant. After continuously purging with N2 for 30 minutes, start adding 0.63g of tetrabutyl titanate into the reaction vessel. Stir and dissolve at room temperature for 5 minutes to obtain the active component alcohol solution.

[0052] (3) Preparation of monool mixture: At room temperature, under the condition of continuous N2 in the reactor of step (2), 3.5g of the carrier powder obtained in step (1) is added to the active component alcohol solution obtained in step (2), and stirred continuously for 1h under N2 atmosphere to obtain monool mixture. After the reaction is completed, the condition of continuous N2 in the reactor is maintained.

[0053] (4) Preparation of desulfurization adsorbent by spray drying: The mixture obtained in step (3) is passed into an air spray dryer at a flow rate of 15 mL / min and dried by atomization using high-temperature air at a temperature of 100℃. Finally, the dried solid is collected and passed through a 100-mesh sieve to obtain the desulfurization adsorbent. After the experiment, the dynamic saturated sulfur capacity of the desulfurization adsorbent for desulfurizing organic sulfides in oil was calculated to be 6.30 mg / g.

[0054] Comparative Example 2 is the same as Example 1, except that step (4) in Comparative Example 2 is as follows:

[0055] The diol mixture obtained in step (3) was allowed to stand for 1 hour, filtered, washed with deionized water until neutral, dried at 105°C, ground and sieved through a 100-mesh sieve, and finally calcined in a muffle furnace at 350°C for 5 hours to obtain the final product. After the experiment, the dynamic saturated sulfur capacity of the desulfurization adsorbent for desulfurizing organic sulfides in oil was calculated to be 6.28 mg / g.

[0056] Comparative Example 3 is the same as Example 1, except that the adsorbent in Comparative Example 3 is prepared using the following method:

[0057] (1) Preparation of inert carrier alcohol solution: First, 5g of attapulgite clay was dispersed in 50mL of 3mol / L hydrochloric acid aqueous solution, stirred at room temperature for 5h, and allowed to stand for 12h. Then, the mixed solution was washed with deionized water until neutral. Then, the acidified clay was placed in an oven at 105℃ and dried for 12h to obtain carrier powder. 49.28g of anhydrous ethanol was placed in a reaction vessel, and 3.5g of carrier powder was dispersed in anhydrous ethanol at room temperature and stirred for 30min to obtain inert carrier alcohol solution.

[0058] (2) Preparation of active component alcohol solution: Take 7.57g of anhydrous ethanol and place it in the reaction vessel. Add 0.63g of tetrabutyl titanate to the reaction vessel and stir to dissolve for 5min at room temperature to obtain active component alcohol solution.

[0059] (3) Preparation of diol mixture: At room temperature, the inert carrier alcohol solution obtained in step (1) is added to the active component alcohol solution obtained in step (2), and the mixture is stirred for 1 hour to obtain the diol mixture.

[0060] (4) Preparation of desulfurization adsorbent by spray drying: The diol mixture obtained in step (3) was passed into an air spray dryer at a flow rate of 15 mL / min and dried by atomization using high-temperature air at a temperature of 100℃. The dried solid was then collected and passed through a 100-mesh sieve. After the experiment, the dynamic saturated sulfur capacity of the desulfurization adsorbent for desulfurizing organic sulfides in oil was calculated to be 5.85 mg / g.

[0061] Comparative Example 4 is the same as Example 1, except that the adsorbent in Comparative Example 4 is prepared using the following method:

[0062] (1) Preparation of inert carrier alcohol solution: First, 5g of attapulgite clay was dispersed in 50mL of 3mol / L hydrochloric acid aqueous solution, stirred at room temperature for 5h, and allowed to stand for 12h. Then, the mixed solution was washed with deionized water until neutral. Then, the acidified clay was placed in an oven at 105℃ and dried for 12h to obtain carrier powder. 49.28g of anhydrous ethanol was placed in a reaction vessel, and 3.5g of carrier powder was dispersed in anhydrous ethanol at room temperature and stirred for 30min to obtain inert carrier alcohol solution.

[0063] (2) Preparation of active component alcohol solution: 7.57g of anhydrous ethanol was placed in the reaction vessel. N2 was continuously purged into the reaction vessel to remove air. The direction of nitrogen purging was parallel to the liquid surface of anhydrous ethanol. The pressure in the reaction vessel was constant. After N2 was continuously purged for 30min, 0.63g of tetrabutyl titanate was added into the reaction vessel. The mixture was stirred and dissolved at room temperature for 5min to obtain the active component alcohol solution.

[0064] (3) Preparation of diol mixture: At room temperature, under the condition of continuous N2 in the reactor of step (2), the inert carrier alcohol solution obtained in step (1) is added to the active component alcohol solution obtained in step (2), and the mixture is stirred continuously for 1 hour under N2 atmosphere to obtain diol mixture.

[0065] (4) Preparation of desulfurization adsorbent by spray drying: The diol mixture obtained in step (3) was passed into an air spray dryer at a flow rate of 15 mL / min and dried by atomization using high-temperature air at a temperature of 100℃. The dried solid was then collected and passed through a 100-mesh sieve. After the experiment, the dynamic saturated sulfur capacity of the desulfurization adsorbent for desulfurizing organic sulfides in oil was calculated to be 6.35 mg / g.

[0066] Comparative Example 5 is the same as Example 1, except that the adsorbent in Comparative Example 5 is prepared using the following method:

[0067] (1) Preparation of inert carrier alcohol solution: First, 5g of attapulgite clay was dispersed in 50mL of 3mol / L hydrochloric acid aqueous solution, stirred at room temperature for 5h, and allowed to stand for 12h. Then, the mixed solution was washed with deionized water until neutral. Then, the acidified clay was placed in an oven at 105℃ and dried for 12h to obtain carrier powder. 49.28g of anhydrous ethanol was placed in a reaction vessel, and 3.5g of carrier powder was dispersed in anhydrous ethanol at room temperature. Then, N2 was continuously blown above the surface of the anhydrous ethanol to remove air in the reaction vessel. The blowing direction was parallel to the surface of the anhydrous ethanol. The pressure in the reaction vessel was kept constant. The mixture was stirred and dispersed for 30min to obtain the inert carrier alcohol solution.

[0068] (2) Preparation of active component alcohol solution: Take 7.57g of anhydrous ethanol and place it in the reaction vessel. Add 0.63g of tetrabutyl titanate to the reaction vessel and stir to dissolve for 5min at room temperature to obtain active component alcohol solution.

[0069] (3) Preparation of diol mixture: At room temperature, the inert carrier alcohol solution obtained in step (1) is added to the active component alcohol solution obtained in step (2), and the mixture is stirred continuously for 1 hour under N2 atmosphere to obtain diol mixture.

[0070] (4) Preparation of desulfurization adsorbent by spray drying: The diol mixture obtained in step (3) was passed into an air spray dryer at a flow rate of 15 mL / min and dried by atomization using high-temperature air at a temperature of 100℃. Finally, the dried solid was collected and passed through a 100-mesh sieve to obtain the desulfurization adsorbent. After the experiment, the dynamic saturated sulfur capacity of the desulfurization adsorbent for desulfurizing organic sulfides in oil was calculated to be 6.17 mg / g.

[0071] Comparative Example 6 is the same as Example 1, except that the adsorbent in Comparative Example 6 is prepared using the following method:

[0072] (1) Preparation of inert carrier alcohol solution: First, 5g of attapulgite clay was dispersed in 50mL of 3mol / L hydrochloric acid aqueous solution, stirred at room temperature for 5h, and allowed to stand for 12h. Then, the mixed solution was washed with deionized water until neutral. Then, the acidified clay was placed in an oven at 105℃ and dried for 12h to obtain carrier powder. 49.28g of anhydrous ethanol was placed in a reaction vessel, and 3.5g of carrier powder was dispersed in anhydrous ethanol at room temperature. Then, N2 was continuously blown above the surface of the anhydrous ethanol to remove air in the reaction vessel. The blowing direction was parallel to the surface of the anhydrous ethanol. The pressure in the reaction vessel was kept constant. The mixture was stirred and dispersed for 30min to obtain the inert carrier alcohol solution.

[0073] (2) Preparation of active component alcohol solution: 7.57g of anhydrous ethanol was placed in the reaction vessel. N2 was continuously purged into the reaction vessel to remove air. The direction of nitrogen purging was parallel to the liquid surface of anhydrous ethanol. The pressure in the reaction vessel was constant. After N2 was continuously purged for 30min, 0.63g of tetrabutyl titanate was added into the reaction vessel. The mixture was stirred and dissolved at room temperature for 5min to obtain the active component alcohol solution.

[0074] (3) Preparation of diol mixture: At room temperature, the inert carrier alcohol solution obtained in step (1) is added to the active component alcohol solution obtained in step (2), and the mixture is stirred for 1 hour to obtain the diol mixture.

[0075] (4) Preparation of desulfurization adsorbent by spray drying: The diol mixture obtained in step (3) was passed into an air spray dryer at a flow rate of 15 mL / min and dried by atomization using high-temperature air at a temperature of 100℃. Finally, the dried solid was collected and passed through a 100-mesh sieve to obtain the desulfurization adsorbent. After the experiment, the dynamic saturated sulfur capacity of the desulfurization adsorbent for desulfurizing organic sulfides in oil was calculated to be 6.38 mg / g.

[0076] Instruction manual attached Figure 2 These are the dynamic breakthrough curves of the desulfurization adsorbents obtained in Examples 1, 2, and 3 for the adsorption of different thiophene sulfides in oil.

[0077] Instruction manual attached Figure 3 These are the dynamic breakthrough curves of the desulfurization adsorbents obtained in Examples 1, 4, and 5 for the adsorption of sulfides in different oil products;

[0078] Instruction manual attached Figure 4 These are the dynamic breakthrough curves of the desulfurization adsorbents obtained in Examples 1, 6, and 7 for the adsorption of different concentrations of sulfides in oil products;

[0079] Instruction manual attached Figure 5 These are the dynamic breakthrough curves of the desulfurization adsorbents obtained using different clay carriers in Examples 1, 8, and 9, showing their adsorption of sulfides in oil.

[0080] Based on the above-described preferred embodiments of the present invention, and through the foregoing description, those skilled in the art can make various changes and modifications without departing from the inventive concept. The technical scope of this invention is not limited to the contents of the specification, but must be determined according to the scope of the claims.

Claims

1. A desulfurization adsorbent, characterized in that, The preparation method of the desulfurization adsorbent includes the following steps: (1) Preparation of inert carrier alcohol solution: First, disperse clay in hydrochloric acid aqueous solution with a concentration of 1-6 mol / L, stir at room temperature for 2-5 h, let stand for 12-24 h, and then wash the mixed solution with deionized water until neutral; then put the acidified clay into an oven at 100-110℃ and dry for 8-12 h to obtain carrier powder; place anhydrous ethanol in a reaction vessel, and then disperse the carrier powder in anhydrous ethanol at room temperature. Then, continuously blow N2 above the surface of anhydrous ethanol to remove air in the reaction vessel. The blowing direction is parallel to the surface of anhydrous ethanol. The pressure in the reaction vessel is constant. Stir and disperse for 30-60 min to obtain inert carrier alcohol solution. (2) Preparation of active component alcohol solution: Anhydrous ethanol is placed in the reaction vessel. N2 is continuously purged into the reaction vessel to remove air. The direction of nitrogen purging is parallel to the liquid surface of anhydrous ethanol. The pressure in the reaction vessel is constant. After N2 is continuously purged for 20-30 minutes, the organic precursor tetrabutyl titanate is added into the reaction vessel. The mixture is stirred and dissolved at room temperature for 3-5 minutes to obtain the active component alcohol solution. (3) Preparation of diol mixture: At room temperature, under the condition of continuous N2 in the reactor of step (2), the inert carrier alcohol solution obtained in step (1) is added to the active component alcohol solution obtained in step (2), and the mixture is stirred continuously for 0.5-1h under N2 atmosphere to obtain diol mixture. After the reaction is completed, the condition of continuous N2 in the reactor is maintained. (4) Preparation of desulfurization adsorbent by spray drying: The diol mixture obtained in step (3) is passed into an airflow atomizing device at a constant flow rate and dried by atomization using high temperature air. Finally, the dried solid is collected and passed through a 100-140 mesh sieve to obtain the product.

2. The desulfurization adsorbent according to claim 1, characterized in that, The N2 purging flow rate is 300-400 cm⁻¹. 3 / min.

3. The desulfurization adsorbent according to claim 1, characterized in that, The clay includes at least one of attapulgite, bentonite, and kaolin.

4. The desulfurization adsorbent according to claim 1, characterized in that, The ratio of clay to hydrochloric acid aqueous solution is 0.5-1.2g: 8-15mL.

5. The desulfurization adsorbent according to claim 1, characterized in that, In step (1), the mass ratio of anhydrous ethanol to carrier powder is 10-20:

1.

6. The desulfurization adsorbent according to claim 1, characterized in that, In step (2), the molar ratio of anhydrous ethanol to tetrabutyl titanate is 70-100:

1.

7. The desulfurization adsorbent according to claim 1, characterized in that, In step (3), the mass ratio of the inert carrier alcohol solution to the active component alcohol solution is 0.3-1:

1.

8. The desulfurization adsorbent according to claim 1, characterized in that, The temperature for atomization drying in step (4) is 90-120℃.

9. An adsorption method for the physical adsorption of benzothiophene, thiophene, and dibenzothiophene in oil products, characterized in that, The desulfurization adsorbent according to any one of claims 1-8 is used, wherein the oil product includes one or more of n-octane, n-heptane, and n-hexane.

10. The adsorption method for physical adsorption of benzothiophene, thiophene, and dibenzothiophene in oil products according to claim 9, characterized in that, The oil is n-octane or n-heptane.

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