CN108893138B - Method for removing thiophene sulfides from fuel oil by using Ag2O/SiO2-ZrO2 composite aerogel as adsorbent - Google Patents

Abstract

The invention discloses a method for removing thiophene sulfides in fuel oil by using Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel as an adsorbent. The method uses Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel as an adsorbent , filled into a fixed bed adsorption device, and at a temperature of 0~100 °C, a simulated gasoline containing thiophene sulfur was passed at a space velocity of 1~10 h ^-1 , and a simulated gasoline with a sulfur concentration below 1 ppm was obtained after adsorption. In the Ag ₂ O/SiO ₂ ‑ZrO ₂ composite aerogel of the present invention, Zr ⁴⁺ is introduced into the silicon skeleton structure of the aerogel to generate L acid, the lone pair of electrons on the S atom in the thiophene compound has basicity, and the gas The L acid center in the gel matrix Ag ₂ O/SiO ₂ ‑ZrO ₂ can adsorb thiophene sulfur compounds through acid-base interaction, and the synergistic effect of π complexation and acid-base interaction can further improve its adsorption to thiophene sulfides performance; the adsorption reaction of the present invention is carried out under normal pressure, the adsorption conditions are mild, the requirements for adsorption equipment are low, the operation is convenient, and the adsorption effect of thiophene compounds is good.

Description

Ag2O/SiO2-ZrO2 composite aerogel as adsorbent for removal of thiophene sulfur in fuel oil chemical method

technical field

The invention belongs to the technical field of fuel oil processing, in particular to a method for removing thiophene sulfides in fuel oil by using Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel as an adsorbent.

Background technique

With the vigorous development of the automobile industry, the massive emission of sulfides in automobile exhaust not only makes the problem of environmental pollution more and more serious, but also threatens the health of human beings. Fuel cells also have very high requirements on the sulfur content in fuel oil. The presence of organic sulfides will poison the catalysts in the fuel cell electrodes, so that the fuel cells cannot effectively convert the chemical energy in diesel gasoline into electrical energy. Therefore, the deep desulfurization of fuel oil has become the focus of global attention.

At present, the desulfurization technology of fuel oil mainly includes hydrodesulfurization technology, alkylation desulfurization technology, biological desulfurization technology, extraction desulfurization technology, oxidative desulfurization technology, adsorption desulfurization technology, etc. In the current industrial production, the main process of desulfurization is still the traditional hydrodesulfurization, but it has disadvantages such as high operating cost, large hydrogen consumption, harsh operating conditions, and reducing the octane number in gasoline. Moreover, hydrodesulfurization only has a good effect on mercaptans, sulfides, inorganic sulfur, etc., and has a poor desulfurization effect on thiophene sulfides with extremely high thermal stability. Adsorption desulfurization has low cost, mild operating conditions, good desulfurization effect, and does not pollute the environment. Among them, π complex adsorption desulfurization is selective relative to physical adsorption desulfurization, and it is easier to desorb and regenerate for chemical adsorption desulfurization. Prospective desulfurization methods.

The key to π complex adsorption desulfurization is to prepare an efficient π complex adsorbent. Metal ions commonly used in the preparation of π complex desulfurization adsorbents include Cu ²⁺ , Ag ⁺ , Ni ²⁺ , Co ²⁺ and so on. To prepare π complex desulfurization adsorbents, these metal ions must be dispersed on a carrier with high specific surface area. According to different carriers, π complex desulfurization adsorbents can be divided into molecular sieves, activated carbons, and metal oxides.

π complex desulfurization adsorbent with molecular sieve as carrier. Chinese patent CN 103170305 A uses 13X molecular sieve loaded with Ag ions as desulfurization adsorbent, which is used to deeply remove thiophene and its derivatives and benzothiophene in gasoline. Among them, the element content of silver accounts for 3% to 5% of the total weight of the adsorbent, and the silver element is in an ionic state. Chinese patent CN 1511629 A prepares a molecular sieve adsorbent for deep removal of sulfide, which is composed of Y-type molecular sieve loaded with metal salts. This kind of π complex adsorbent has the advantages of low carrier price, simple preparation method and cyclic regeneration. However, the number of transition metal ions exchanged by the microporous molecular sieve desulfurization adsorbent is limited, the adsorption capacity of sulfide is not large, and the microporous structure of the microporous molecular sieve itself, the macromolecular thiophene sulfide cannot enter the pores due to the molecular size effect. Form π complexation with metal ions, that is, deep desulfurization cannot be achieved.

π complex desulfurization adsorbent with activated carbon as carrier. Chinese patent CN 103143322 A prepares an activated carbon adsorbent loaded with Fe ions, which has large adsorption capacity and selectivity for thiophene and its derivatives in gasoline, and has a simple preparation method, easy regeneration and long service life of the adsorbent . Chinese patent CN 104549143 A uses salts containing Al, Zn, Ni and other metals and H ₃ PO ₄ as auxiliary agents to modify the activated carbon, which better solves the problem that a single adsorbent cannot simultaneously Effective removal of various sulfides, low sulfur removal rate and low penetration sulfur capacity of desulfurizers. However, the pore structure of activated carbon is dominated by micropores, and the adsorption capacity of modified activated carbon for thiophene macromolecular sulfides is still very small, which is difficult to meet the requirements of industrial production.

A π complex desulfurization adsorbent based on metal oxides. Chinese patent CN 10300787 A contacts sulfur-containing fuel oil with copper-doped mesoporous γ-Al ₂ O ₃ , and uses an adsorption method to achieve desulfurization, with low operating cost, large adsorption capacity, and convenient regeneration. Chinese patent CN 10161923 A prepares a desulfurization adsorbent, the adsorbent comprises alumina as a binder, zinc oxide as a carrier, contacting with a complexing agent solution, and then supporting a metal promoter. It is used for desulfurization of fuel oil, with high activity and large capacity for adsorbing sulfur. However, during the preparation process, metal ions easily block the pores of metal oxides, resulting in the accumulation of supported active components on the surface, unable to enter the pores to provide active sites, reducing the adsorption desulfurization performance, and this method is difficult to apply to industrial production.

SUMMARY OF THE INVENTION

Aiming at the above-mentioned problems existing in the existing π complex adsorbents in the removal of thiophene sulfides in fuel oil, the purpose of the present invention is to provide a Ag ₂ O/SiO ₂ -ZrO ₂ compound with large adsorption capacity and easy regeneration. Aerogel is used as adsorbent to remove thiophene sulfides in fuel oil through the synergistic effect of π complex adsorption and acid-base effect.

The Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel is a method for removing thiophene sulfides in fuel oil as an adsorbent, which is characterized in that the Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel is used as an adsorbent Filled into a fixed-bed adsorption device, at a temperature of 0~100 °C, the simulated gasoline containing thiophene sulfur was passed into the simulated gasoline at a space velocity of 1~10 h ^-1 , and the simulated gasoline with a sulfur concentration of less than 1 ppm was obtained after adsorption. , the thiophene sulfide is thiophene or benzothiophene.

The Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel is a method for removing thiophene sulfides in fuel oil as an adsorbent, and is characterized in that the Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel uses a silver source , silicon source and zirconium source as raw materials, prepared by sol-gel-atmospheric pressure drying method.

The Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel is an adsorbent for removing thiophene sulfides in fuel oil, and is characterized in that the Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel adsorbent is prepared The silver source is silver acetate or silver nitrate, the silicon source is methyl orthosilicate, ethyl orthosilicate, silica sol or water glass, and the zirconium source is zirconium oxynitrate.

The Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel is an adsorbent for removing thiophene sulfides in fuel oil, and it is characterized in that the Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel adsorbent contains The molar ratio of silicon and zirconium is 1~150:1.

The Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel is an adsorbent for removing thiophene sulfides in fuel oil, and it is characterized in that the Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel adsorbent contains The molar ratio of silicon and silver is 10~50:1.

The Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel is a method for removing thiophene sulfides in fuel oil as an adsorbent, and is characterized in that the space velocity of the simulated gasoline containing thiophene or benzothiophene is 1 ~5 h ^-1 .

The Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel is an adsorbent method for removing thiophene sulfides in fuel oil, and is characterized in that the adsorption temperature is 0-60°C.

The Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel is an adsorbent for removing thiophene sulfides in fuel oil, and is characterized in that the concentration of thiophene or benzothiophene sulfur in simulated gasoline is 0.1 mgS/g ~ 10mgS/g.

The Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel is an adsorbent method for removing thiophene sulfides in fuel oil, which is characterized in that the Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel adsorbs after adsorption The agent is regenerated by solvent elution, and the solvent is cyclohexene, diethyl ether, benzene or toluene.

By adopting the above-mentioned technology, compared with the prior art, the beneficial effects of the present invention are as follows:

(1) The Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel of the present invention has typical mesoporous characteristic pore size (5~20 nm), high porosity (85~99%), high specific surface area (600~1500 m ² /g) and other unique physical and chemical properties, so thiophene sulfides can enter the aerogel pores unhindered, and the active components and sulfides can fully contact;

(2) Compared with other π complex adsorbents, the Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel of the present invention is used as a π complex desulfurization adsorbent. The active components can be fully exposed. During the synthesis process of the aerogel, transition metal salts with π complexation can be added to it, so the amount of the active components can be adjusted;

(3) The Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel of the present invention, compared with the Ag ₂ O/SiO ₂ aerogel, introduces Zr ⁴⁺ into the silicon skeleton structure of the aerogel to generate L acid , the lone pair of electrons on the S atom in thiophene compounds has basicity, the L acid center in the aerogel matrix Ag ₂ O/SiO ₂ -ZrO ₂ can adsorb thiophene sulfur compounds through acid-base interaction, π complexation and The synergistic effect of acid-base action can further improve its adsorption performance for thiophene sulfides; the thermal stability and mechanical strength of aerogel matrix SiO ₂ -ZrO ₂ are relatively high.

(4) The Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel adsorbent of the present invention has good adsorption performance for thiophene sulfides, can be regenerated by solvent washing, and still has good adsorption performance after regeneration;

(5) The adsorption reaction of the present invention is carried out under normal pressure, the adsorption conditions are mild, the requirements for adsorption equipment are low, the operation is convenient, and the adsorption effect on thiophene compounds is good.

Detailed ways

The present invention is further described below in conjunction with specific embodiment:

Preparation of Ag ₂ O/SiO _{2 -ZrO 2} Composite _{Aerogel Adsorbent} Taking the gel adsorbent as an example, its preparation method is as follows:

Dissolve 0.12 g of silver nitrate in beaker A containing 1 mL of H ₂ O, then add 20 mL of EtOH and 8 mL of TEOS, respectively, with slow stirring. Dissolve 0.33 g of zirconium oxynitrate in beaker B containing 2 mL of H ₂ O; then slowly drop the zirconium oxynitrate solution in beaker B (1 drop of zirconium oxynitrate solution every 2 seconds) into beaker A for 2 hours After adding ammonia water to adjust the pH value to 6.5, and standing at room temperature for about 15 min to obtain Ag ₂ O/SiO ₂ -ZrO ₂ gel, and then aging for 16h in absolute ethanol/orthosilicon acetate with a volume ratio of 25:15 , in order to strengthen the skeleton structure of the gel, and then replace the gel with n-hexane, and replace the solvent twice within 24 h to remove ethanol, water, acid and other organic molecules in the gel; After drying under low temperature for 2 h, an Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel with a molar ratio of silicon and silver of 50:1 and a molar ratio of silicon and zirconium of 25:1 was obtained.

Examples 1-5: Adsorption performance of Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogels with different silicon and silver sources on thiophene sulfides in simulated gasoline

In the Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel with a molar ratio of silicon to silver of 50:1 and a molar ratio of silicon to zirconium of 25:1 prepared by sol-gel method, the silicon source used is methyl orthosilicate. Ester, ethyl orthosilicate, silica sol, silver source is silver nitrate, silver acetate, zirconium source is zirconium oxynitrate. The prepared Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel was subjected to penetration adsorption desulfurization experiments. The specific operations were as follows: in the fixed bed reactor, the bottom layer was filled with an appropriate amount of absorbent cotton, and then filled with 1 g of Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel with appropriate amount of quartz sand. The packed adsorbent was fully wetted with n-heptane before the adsorption experiment was started. Simulated gasoline (0.5 mgS/g) was introduced at 25°C, and the space velocity was 3 h ^-1 . The adsorbed simulated gasoline was collected at the outlet at the lower end of the reactor for chromatographic analysis. When the sulfur concentration in the effluent was 0.005 mgS /g is set as the penetration point. The breakthrough adsorption capacity results of the obtained thiophene and benzothiophene are shown in Tables 1 and 2.

Table 1 Adsorption properties of Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogels with different silicon sources for thiophene sulfides in simulated gasoline

Table 2 Adsorption properties of Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogels with different silver sources for thiophene sulfides in simulated gasoline

It can be seen from Table 1 and Table 2 that the silicon source and silver source used in synthesizing Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel, when the silicon source is selected from ethyl orthosilicate, and the silver source is selected from silver nitrate. The synthesized Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel has the largest penetration adsorption capacity for thiophene and benzothiophene in the penetration adsorption experiment. Therefore, the preferred silicon source is ethyl orthosilicate, and the silver source is Silver nitrate.

Examples 6-10: Adsorption performance of Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogels with different molar ratios of silicon to zirconium on thiophene sulfides in simulated gasoline

The molar ratio of silicon and silver is 50:1, and the molar ratio of silicon and zirconium is 15, 25, 50, 100, and 150, respectively. Other conditions are the same as the Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel prepared in Example 2. The breakthrough adsorption experiment of thiophene sulfides in gasoline. Its penetration adsorption experiment operation is the same as that of Examples 1~5, and the adsorption results are shown in Table 3.

Table 3 Adsorption properties of Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogels with different molar ratios of silicon to zirconium for thiophene sulfides in simulated gasoline

It can be seen from Table 3 that the molar ratio of silicon and silver is 50:1, and the Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogels with different molar ratios of silicon and zirconium decrease the molar ratio of silicon and zirconium, that is, the content of zirconium increases. With increasing, the penetration adsorption capacity of thiophene and benzothiophene increased first and then decreased. When the molar ratio of silicon to zirconium is 25:1, the penetration adsorption capacity of thiophene and benzothiophene reaches the maximum, so the Ag ₂ O/SiO ₂ -ZrO ₂ composite gas condensate with the molar ratio of silicon to zirconium of 15~50:1 is preferred. glue.

Examples 11-14: Adsorption performance of Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogels with different molar ratios of silicon to silver on thiophene sulfides in simulated gasoline

The molar ratio of silicon and zirconium is 25:1, and the molar ratio of silicon and silver is 10, 20, 50, and 100, respectively. Other conditions are the same as the Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel prepared in Example 2. Thiophene sulfides were subjected to breakthrough adsorption experiments. Its penetration adsorption experiment operation is the same as that of Examples 1~5, and the adsorption results are shown in Table 4.

Table 4 Adsorption properties of Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogels with different molar ratios of silicon to silver on thiophene sulfides in simulated gasoline

It can be seen from Table 4 that the molar ratio of silicon to zirconium is 25:1, and the Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel decreases with the decrease of the molar ratio of silicon and silver, that is, the increase of silver content, and the difference between thiophene and benzothiophene The breakthrough adsorption capacity first increased and then decreased. When the molar ratio of silicon and silver is 50:1, the penetration adsorption capacity of thiophene and benzothiophene reaches the maximum, so the Ag ₂ O/SiO ₂ -ZrO ₂ composite gas with the molar ratio of silicon and silver of 20~50:1 is preferred. gel.

Example 15~19: Adsorption performance of Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel for thiophene sulfides in simulated gasoline at different space velocities

The molar ratio of silicon and silver is 50:1, the molar ratio of silicon and zirconium is 25:1, and other conditions are the same as the Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel prepared in Example 2. The breakthrough adsorption experiments of thiophene sulfides in simulated gasoline were carried out at space velocities of 1 h ^-1 , 3 h ^-1 , 5 h ^-1 , 8 h ^-1 , and 10 h ^-1 . Its penetration adsorption experiment operation is the same as that of Examples 1~5, and the adsorption results are shown in Table 5.

Table 5 Adsorption properties of Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogels for thiophene sulfides in simulated gasoline at different space velocities

It can be seen from Table 5 that with the decrease of space velocity, the penetration adsorption capacity of thiophene and benzothiophene will gradually increase. When the space velocity decreases to 5 h ^-1 , the penetration adsorption of thiophene sulfides The capacity does not change much, so the preferred space velocity is 1 to 5 h ^-1 .

Example 20~24: Adsorption performance of Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel for thiophene sulfides in simulated gasoline at different adsorption temperatures

The molar ratio of silicon and silver is 50:1, the molar ratio of silicon and zirconium is 25:1, and other conditions are the same as the Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel prepared in Example 2. The adsorption temperatures were selected as 0°C, 25°C, 40°C, 80°C, and 100°C, respectively, and the breakthrough adsorption experiment was carried out on thiophene sulfides in simulated gasoline. The penetration adsorption experimental operation is the same as that of Examples 1 to 5, and the adsorption results are shown in Table 6.

Table 6 Adsorption properties of Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogels for thiophene sulfides in simulated gasoline at different adsorption temperatures

It can be seen from Table 6 that with the increase of the adsorption temperature, the breakthrough adsorption capacity of thiophene and benzothiophene gradually decreases. After 80 °C, the adsorption breakthrough capacity of thiophene and benzothiophene is very small, indicating that the At the temperature, the thiophene and benzothiophene adsorbed by Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel have been desorbed. Therefore, the preferential adsorption temperature is 0~40℃.

Example 25~36: Adsorption performance of Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogels for thiophene sulfides under different sulfur concentrations in simulated gasoline

The molar ratio of silicon and silver is 50:1, the molar ratio of silicon and zirconium is 25:1, and other conditions are the same as the Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel prepared in Example 2. The sulfur concentrations of thiophene or benzothiophene in simulated gasoline were 0.1 mgS/g, 0.5 mgS/g, 1 mgS/g, 2 mgS/g, 5 mgS/g, and 10 mgS/g, respectively, for breakthrough adsorption experiments. The penetration adsorption operation is the same as that of Examples 1 to 5, and the adsorption results are shown in Table 7.

Table 7 Adsorption performance of Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogels for thiophene sulfides under different sulfur concentrations in simulated gasoline

It can be seen from Table 7 that with the increase of the thiophene or benzothiophene sulfur concentration in the simulated gasoline, the penetration adsorption capacity of Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogels for thiophene and benzothiophene decreased. Therefore, it is preferable that the sulfur concentration of thiophene or benzothiophene in simulated gasoline is 0.1-5 mgS/g.

Example 31~34: Regeneration and adsorption performance of Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogels with different regeneration solvents for thiophene sulfides in simulated gasoline

The Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel adsorbent prepared by the method of Example 2 was selected; firstly, the Ag ₂ O/SiO ₂ -ZrO ₂ composite gas after use was treated with cyclohexene, ether, benzene and toluene respectively. The thiophene sulfides in the gel were eluted, and then the regeneration solvent in the Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel was eluted with n-heptane, and then the thiophene sulfides in the simulated gasoline were penetrated Adsorption experiments. The penetration adsorption experiment operation is the same as that of Examples 1 to 5, and the adsorption results are shown in Table 8.

Table 8 Adsorption properties of Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogels for thiophene sulfides in simulated gasoline with different regeneration solvents

It can be seen from Table 8 that the solvents used for the regeneration of Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogels include cyclohexene, ether, benzene and toluene. When benzene is selected, Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel has the best regeneration effect on thiophene and benzothiophene. It is therefore preferred that the regeneration solvent is benzene.

Claims (2)

1. Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel is a method for removing thiophene sulfides in fuel oil as an adsorbent, characterized in that the Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel is an adsorbent , filled into a fixed bed adsorption device, and at a temperature of 0~100 °C, a simulated gasoline containing thiophene sulfur is introduced, and after adsorption, a simulated gasoline with a sulfur concentration of less than 1 ppm is obtained, and the thiophene sulfide is thiophene or benzene. thiophene; Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel is prepared from silver source, silicon source and zirconium source by sol-gel-atmospheric pressure drying method; Ag ₂ O/SiO ₂ -ZrO ₂ The molar ratio of silicon and zirconium in the composite aerogel adsorbent is 25 to 50:1; the molar ratio of silicon and silver in the Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel adsorbent is 50: 1, and the adsorption temperature is 25~40℃; the silver source is silver acetate or silver nitrate, the silicon source is methyl orthosilicate, ethyl orthosilicate, silica sol or water glass, and the zirconium source is zirconium oxynitrate; The space velocity of the simulated gasoline containing thiophene or benzothiophene is 1~5 h ^-1 ; The concentration of thiophene or benzothiophene sulfur in simulated gasoline is 0.1-5 mgS/g. 2. Ag ₂ O/SiO ₂ -ZrO ₂ composite aerogel according to claim 1 is a method for adsorbent to remove thiophene sulfides in fuel oil, characterized in that after adsorption, Ag ₂ O/SiO ₂ -ZrO _2. The composite aerogel adsorbent is regenerated by solvent elution, and the solvent is cyclohexene, diethyl ether, benzene or toluene.