CN110317631A - The removal methods of thiophene sulphur in a kind of fuel oil - Google Patents

Abstract

A method for removing thiophene sulfur in fuel oil belongs to the technical field of fuel oil processing. The method uses ethyl orthosilicate as a silicon source, 3-aminopropyltriethoxysilane as an ammonia source, palladium chloride or palladium sulfate as a palladium source, and adopts a sol-gel-normal pressure drying method to prepare _SiO2 ‑APTES‑Pd composite airgel, quantitatively filling it in a fixed bed adsorption device, injecting simulated gasoline containing thiophene sulfides at a certain temperature and space velocity, and collecting the adsorbed gas at the outlet of the lower end of the reaction device Simulate gasoline for chromatographic analysis. The results show that SiO ₂ ‑APTES‑Pd composite airgel has good adsorption properties to thiophene sulfides, and the SiO ₂ ‑APTES‑Pd composite airgel of the present invention has good selectivity to thiophene sulfides, The preparation method of the SiO ₂ ‑APTES‑Pd composite airgel adsorbent in the present invention is simple and low in cost, the adsorbent can be used repeatedly, has high economic benefits, is environmentally friendly, has mild adsorption conditions, and has low requirements for adsorption equipment .

Description

A method for removing thiophene sulfur in fuel oil

technical field

The invention belongs to the technical field of fuel oil processing, and relates to a method for removing thiophene sulfur in fuel oil, in particular to a method for removing thiophene sulfur in fuel oil by using SiO ₂ -APTES-Pd composite airgel as an adsorbent.

Background technique

With the vigorous development of the automobile industry, the large amount of sulfide emissions from automobile exhaust not only makes environmental pollution more and more serious, but also threatens human health. Fuel cells also have very high requirements on the sulfur content in fuel oil. The presence of organic sulfides will poison the catalyst in the fuel cell electrodes, making the fuel cells unable to 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, oxidation desulfurization technology, adsorption desulfurization technology, etc. In current industrial production, the main process of desulfurization is still traditional hydrodesulfurization, but its operating cost is high, hydrogen consumption is large, operating conditions are harsh, and the octane number in gasoline is reduced, and hydrodesulfurization is only for sulfur Alcohols, sulfides, inorganic sulfur, etc. have good effects, but the desulfurization effect on thiophene sulfides with high thermal stability is poor; adsorption desulfurization has the advantages of low cost, mild operating conditions, good desulfurization effect, and no environmental pollution. , is currently the most promising desulfurization method.

The key to π-complex adsorption desulfurization lies in the preparation of an efficient π-complex adsorbent. Metal ions commonly used to prepare π-complex desulfurization adsorbents include Cu ²⁺ , Ag ⁺ , Ni ²⁺ , Co ²⁺ , Pd ²⁺ , etc. To prepare π-complex desulfurization adsorbents, these metal ions must be dispersed on a carrier with a 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 108949220 A prepared a mesoporous Si-based composite aerogel containing Pd ²⁺ by using a sol-gel method. While maintaining high porosity, high specific surface area, and sufficient exposure of the active components in the framework, by adding transition metal Pd ²⁺ with π complexation, it not only overcomes the pore wall effect and space of the microporous adsorbent. The problem of steric hindrance is solved, and the adsorption capacity of thiophene sulfides is improved through π complexation, thereby significantly improving the desulfurization efficiency. However, the π adsorbent prepared by this method has problems such as easy collapse of the Si skeleton structure, low doping amount of transition metal ions, and relatively simple adsorption mechanism, making it difficult to achieve the purpose of deep desulfurization and meet industrial production.

π-complex desulfurization adsorbent with activated carbon as the carrier. Shenyang University of Chemical Technology (publication number CN 103143322 A) prepared an activated carbon adsorbent loaded with Fe ions, which has a large adsorption capacity and selectivity for thiophene and its derivatives in gasoline, and the preparation method is simple and easy to regenerate. The adsorbent has a long service life. China Petroleum & Chemical Corporation (publication number CN 104549143 A) modified activated carbon by using salts containing Al, Zn, Ni and other metals and H ₃ PO ₄ as additives to solve the problem of gas raw material adsorption, purification and desulfurization. There are problems in the technology that a single adsorbent cannot effectively remove multiple sulfides at the same time, the sulfur removal rate is low, and the breakthrough sulfur capacity of the desulfurizer is low. 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.

π-complex desulfurization adsorbent with metal oxide as carrier. Nantong University (publication number CN 10300787 A) contacted mesoporous γ-Al ₂ O ₃ doped with copper elements with sulfur-containing fuel oil, and achieved desulfurization by adsorption method. The operation cost is low, the adsorption capacity is large, and regeneration is convenient. China Petroleum & Chemical Corporation (publication number CN 10161923 A) prepared a desulfurization adsorbent, which includes alumina as a binder and zinc oxide as a carrier, then contacts with a complexing agent solution, and then loads metals to promote agent. It is used for desulfurization of fuel oil, with high activity and large adsorption capacity of sulfur. However, during the preparation process, metal ions are easy to block the pores of metal oxides, resulting in the accumulation of loaded active components on the surface, which cannot enter the pores to provide active sites, reducing the adsorption and desulfurization performance, and this method is difficult to apply to industrial production.

Zhejiang University of Technology (publication number CN 201811557282) prepared a highly selective and highly reproducible SiO _{2 -APTES} hybrid airgel desulfurization adsorbent. By hybridizing and crosslinking SiO ₂ with APTES, the -NH ₂ Form hydrogen bonds with thiophene sulfides to improve the desulfurization adsorption performance. However, SiO ₂ -APTES airgel has the disadvantage of low adsorption capacity. Therefore, by coordinating the metal ion Pd ²⁺ with π-complex adsorption capacity with the amine group on the surface of SiO ₂ , hydrogen bonding is used to , π complexation and synergistic effect to improve the adsorption capacity of thiophene sulfides, but also solve the problems existing in the above-mentioned adsorbents because the carrier has no anchoring group, which leads to the agglomeration of the loaded metal particles and the decrease in dispersion, so as to improve the desulfurization The purpose of adsorption capacity and dispersion of metal ions.

Contents of the invention

The method for removing thiophene sulfur in fuel oil is characterized in that the SiO ₂ -APTES-Pd composite airgel adsorbent is prepared by a sol-gel-normal pressure drying method.

The method for removing thiophene-like sulfur in fuel oil is characterized in that the SiO ₂ -APTES-Pd composite airgel is used as the adsorbent, and the adsorbent is filled into a fixed bed adsorption device. At a temperature of ~100°C, the simulated gasoline containing thiophene sulfur was injected at a space velocity of 1-10 h ^-1 , and the simulated gasoline with a sulfur concentration below 1 ppm was obtained after adsorption.

The method for removing thiophene sulfur in fuel oil is characterized in that the adsorbed thiophene sulfur is thiophene, benzothiophene and dibenzothiophene.

The method for removing thiophene sulfur in fuel oil is characterized in that the SiO ₂ -APTES-Pd composite airgel adsorbent uses silicon source, ammonia source and palladium source as raw materials, adopts sol-gel-atmospheric pressure Prepared by drying method.

The method for removing thiophene sulfur in fuel oil is characterized in that the silicon source for preparing the SiO ₂ -APTES-Pd composite airgel adsorbent is ethyl orthosilicate, preferably ethyl orthosilicate; The ammonia source is 3-aminopropyltriethoxysilane; the palladium source is palladium chloride or palladium sulfate, preferably palladium chloride.

The method for removing thiophene sulfur in fuel oil is characterized in that the silicon-palladium molar ratio in the SiO ₂ -APTES-Pd composite airgel adsorbent is 508-2544:1, preferably 508:1, 636:1, 848:1, 1272:1 or 2544:1, the optimum is 848:1.

The method for removing thiophene-like sulfur in fuel oil is characterized in that the space velocity of the simulated gasoline containing thiophene-like sulfur is 1-5 h ^-1 .

The method for removing thiophene-like sulfur in fuel oil is characterized in that the adsorption temperature of SiO ₂ -APTES-Pd composite airgel to adsorb thiophene-like sulfur is 0-40°C.

The method for removing thiophene sulfur in fuel oil is characterized in that the concentration of thiophene sulfur in simulated gasoline is 0.1-10 mgS/g, preferably 0.1-5 mgS/g.

The method for removing thiophene-like sulfur in fuel oil is characterized in that 20wt% cyclohexene and 20wt% toluene are respectively mixed into simulated gasoline containing thiophene-like sulfur.

The method for removing thiophene sulfur in fuel oil is characterized in that the solvent used for regeneration after the SiO ₂ -APTES-Pd composite airgel absorbs thiophene sulfur is cyclohexene, ether, benzene, and toluene.

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

1) The SiO ₂ -APTES-Pd composite airgel of the present invention has a typical mesoporous characteristic pore size (5-20 nm), high porosity (85-99%), and high specific surface area (600-1500 m ² /g) and other unique physical and chemical properties, so thiophene sulfides can enter the airgel pores without hindrance, and be adsorbed after full contact;

2) The SiO ₂ -APTES-Pd composite airgel of the present invention coordinates the metal ion Pd ²⁺ with π complex adsorption capacity with the amine group on the surface of SiO ₂ , compared with the SiO ₂ aerogel, It introduces -NH ₂ into the airgel silicon skeleton structure, and -NH ₂ can form hydrogen bonds with S in thiophene, benzothiophene or dibenzothiophene, and at the same time, Pd ² anchored by -NH ₂ through coordination ⁺ can undergo π-complexation with thiophene sulfides, and use hydrogen bonds and π-complexation synergies to improve the adsorption capacity of thiophene sulfides, increase the doping amount and dispersion of metal ions Pd ²⁺ , and also solve the problem of The existing adsorbents have problems such as agglomeration of loaded metal particles and a decrease in dispersion because the carrier has no anchoring group, so as to achieve the purpose of improving the desulfurization adsorption capacity and the dispersion of metal ions;

3) Compared with other existing adsorbents, the SiO ₂ -APTES-Pd composite airgel of the present invention has a unique physical structure and a three-dimensional network-like mesoporous structure with high pore volume, so that the adsorption process is less affected by diffusion , and the π-complexation formed by thiophene and its derivatives and Pd ²⁺ is stronger than that formed by benzene or cyclohexene and Pd ²⁺ , also considering the unique hydrogen bond interaction due to coupling-NH2, Therefore, in the presence of aromatics and olefins, it still has high adsorption selectivity and adsorption capacity for thiophene sulfides in simulated gasoline;

4) The SiO ₂ -APTES-Pd composite airgel 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 thiophene compounds have a good adsorption effect.

Detailed ways

The present invention will be further described below in conjunction with specific examples, but the protection scope of the present invention is not limited thereto.

Example 1: Taking the SiO ₂ -APTES-Pd composite airgel adsorbent with a silicon-palladium molar ratio of 848:1 as an example, its preparation method is as follows:

Stir the mixed solution of 20mL EtOH, 8 mL TEOS, and 2 mL H ₂ O vigorously under acidic conditions and mix evenly, add ammonia water to adjust the pH value to 6.5, then slowly add 1mL APTES, and stand at room temperature for about 15 minutes to obtain SiO ₂ -APTES hybrid alcohol gel, then aged in absolute ethanol/orthosilicon acetate with a volume ratio of 25:15 for 16 hours to strengthen the gel skeleton structure, and then solvent-replaced the gel with n-hexane, 24 Replace the solvent twice within h to remove ethanol, water, acid and other organic molecules in the gel, and crush to obtain the airgel. Then 0.03g of PdCl ₂ was dissolved in 1 mL of deionized water, and the above PdCl ₂ solution was added dropwise to the crushed airgel, and placed in a water bath heating pot to keep stirring at 45°C for 4 hours (the solution color changed from brown to yellow to changes to pale yellow). Finally, the obtained pale yellow solution was dried at 120° C. for 4 hours to obtain a SiO ₂ -APTES-Pd composite airgel with a silicon-palladium molar ratio of 848:1.

Examples 1-2: Adsorption performance of SiO ₂ -APTES-Pd composite aerogels with different palladium sources on thiophene sulfides in simulated gasoline.

In the SiO ₂ -APTES-Pd composite airgel prepared by the sol-gel method, the silicon source used is ethyl orthosilicate, and the prepared SiO ₂ -APTES-Pd composite airgel was subjected to penetration adsorption The desulfurization experiment, the specific operation is as follows: In the fixed bed reactor, the bottom layer is filled with an appropriate amount of absorbent cotton, and then filled with 1 g of SiO ₂ -APTES-Pd composite airgel and an appropriate amount of quartz sand. Before the adsorption experiment started, the packed adsorbent was fully wetted with n-heptane. Feed simulated gasoline, collect the adsorbed simulated gasoline at the outlet of the lower end of the reactor, and carry out chromatographic analysis. When the sulfur concentration in the effluent is 0.005mgS/g, it is defined as the breakthrough point. The obtained breakthrough adsorption capacities of thiophene, benzothiophene and dibenzothiophene are shown in Table 1.

Table 1 Adsorption performance of SiO ₂ -APTES-Pd composite aerogels with different palladium sources on thiophene sulfides in simulated gasoline

It can be seen from Table 1 that the source of palladium should be palladium chloride, and the synthesized SiO ₂ -APTES-Pd composite airgel has a relatively large effect on thiophene, benzothiophene and dibenzothiophene in the penetration adsorption experiment. of adsorption capacity.

Examples 3-7: Adsorption performance of SiO ₂ -APTES-Pd composite aerogels with different silicon-palladium molar ratios on thiophene sulfides in simulated gasoline.

The SiO ₂ -APTES-Pd composite aerogels with silicon-palladium molar ratios of 2544, 1272, 848, 636 and 508 were selected to conduct breakthrough adsorption experiments on thiophene sulfides in simulated gasoline. The operation of the breakthrough adsorption experiment is the same as in Examples 1-2, and the adsorption results are shown in Table 2.

Table 2 Adsorption performance of SiO ₂ -APTES-Pd composite aerogels with different molar ratios of silicon to palladium on thiophene sulfides in simulated gasoline

It can be seen from Table 2 that for SiO ₂ -APTES-Pd composite aerogels with different silicon-palladium molar ratios, the breakthrough adsorption capacity of thiophene and benzothiophene increases first and then decreases with the decrease of silicon-palladium molar ratio. When the silicon-palladium molar ratio is 848:1, the breakthrough adsorption capacity of thiophene, benzothiophene and dibenzothiophene reaches the maximum, so the SiO ₂ -APTES-Pd composite airgel with a silicon-palladium molar ratio of 848:1 is preferred .

Implementation Cases 8~12: Adsorption performance of SiO ₂ -APTES-Pd composite aerogels for thiophene sulfides in simulated gasoline with different space velocities

The SiO ₂ -APTES-Pd composite airgel with a silicon-palladium molar ratio of 848:1 was selected. The breakthrough adsorption experiments were carried out on thiophene sulfides in simulated gasoline at space velocities of 1 h ^-1 , 3 h ^-1 , 5 h ^-1 , 8 h ^-1 , 10 h ^-1 . The operation of the breakthrough adsorption experiment is the same as in Examples 1-2, and the adsorption results are shown in Table 3.

Table 3 Adsorption properties of SiO ₂ -APTES-Pd composite aerogels for thiophene sulfides in simulated gasoline at different space velocities

It can be seen from Table 3 that the breakthrough adsorption capacity of ^thiophene , benzothiophene and dibenzothiophene will gradually increase with the decrease of space velocity. The breakthrough adsorption capacity does not change much, so the preferred space velocity is 1~3 h ^-1 .

Implementation cases 13~17: Adsorption performance of SiO ₂ -APTES-Pd composite aerogels for thiophene sulfides in simulated gasoline at different adsorption temperatures

The SiO ₂ -APTES-Pd composite airgel with a silicon-palladium molar ratio of 848:1 was selected. The adsorption temperature was selected as 0°C, 25°C, 40°C, 80°C, and 100°C, respectively, and the penetration adsorption experiments were carried out on thiophene sulfides in simulated gasoline. The operation of the breakthrough adsorption experiment was the same as in Examples 1-2, and the adsorption results are shown in Table 4.

Table 4 Adsorption performance of SiO ₂ -APTES-Pd composite aerogels for thiophene sulfides in simulated gasoline at different adsorption temperatures

It can be seen from Table 4 that with the increase of adsorption temperature, the breakthrough adsorption capacities of thiophene, benzothiophene and dibenzothiophene gradually decrease, and after 80 °C, the breakthrough adsorption capacities of thiophene, benzothiophene and dibenzothiophene The adsorption breakthrough capacity is very small, indicating that thiophene, benzothiophene and dibenzothiophene adsorbed by SiO ₂ -APTES-Pd composite airgel have been desorbed at this temperature. Therefore, the preferred adsorption temperature is 0~40°C.

Implementation Cases 18~23: Simulating the Adsorption Performance of SiO ₂ -APTES-Pd Composite Airgel on Thiophene Sulfides under Different Sulfur Concentrations in Gasoline

A SiO ₂ -APTES-Pd composite airgel with a silicon-palladium molar ratio of 848:1 was selected. The sulfur concentrations of thiophene, benzothiophene or dibenzothiophene 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. Permeation adsorption experiment. The breakthrough adsorption operation is the same as in Examples 1-2, and the adsorption results are shown in Table 5.

Table 5 Adsorption performance of SiO ₂ -APTES-Pd composite airgel on thiophene sulfides under different sulfur concentrations in simulated gasoline

It can be seen from Table 5 that the SiO ₂ -APTES-Pd composite aerogel has a greater effect on the penetration adsorption of thiophene, benzothiophene and dibenzothiophene as the sulfur concentration of simulated gasoline increases. The capacity tends to decrease, so it is preferable to simulate the sulfur concentration of thiophene or benzothiophene in gasoline at 0.1~2 mgS/g.

Implementation cases 24~25: Effects of different olefins on the adsorption performance of SiO ₂ -APTES-Pd composite airgel on thiophene sulfides in simulated gasoline.

The SiO ₂ -APTES-Pd composite airgel was used for breakthrough adsorption experiments on thiophene simulated gasoline containing 20wt% cyclohexene and 20wt% cyclopentene. The operation of the breakthrough adsorption experiment is the same as in Examples 1-2, and the adsorption results are shown in Table 6.

Table 6 Effect of competitive adsorption of olefins on desulfurization adsorption performance of SiO ₂ -APTES-Pd composite airgel

It can be seen from Table 6 that the incorporation of cyclohexene and cyclopentene in simulated gasoline has little effect on the desulfurization performance of SiO ₂ -APTES-Pd composite airgel.

Implementation cases 26~27: Effect of different aromatic hydrocarbons on the adsorption performance of SiO ₂ -APTES-Pd composite airgel on thiophene sulfides in simulated gasoline.

The SiO ₂ -APTES-Pd composite aerogel was used for breakthrough adsorption experiments on thiophene simulated gasoline containing 20wt% benzene and 20wt% toluene. The operation of the breakthrough adsorption experiment is the same as in Examples 1-2, and the adsorption results are shown in Table 7.

Table 7 Effect of competitive adsorption of aromatics on desulfurization adsorption performance of SiO ₂ -APTES-Pd composite airgel

It can be seen from Table 7 that the incorporation of benzene and toluene in simulated gasoline has little effect on the desulfurization performance of SiO ₂ -APTES-Pd composite airgel.

Implementation Cases 28~31: Regeneration Adsorption Performance of SiO ₂ -APTES-Pd Composite Airgel for Simulating Thiophene Sulfides in Gasoline with Different Regeneration Solvents

First use cyclohexene, ether, benzene, toluene to elute the thiophene sulfides in the used SiO ₂ -APTES-Pd composite airgel, and then use n-heptane to elute the SiO ₂ -APTES-Pd composite airgel The regeneration solvent in the rubber was eluted, and then the penetration adsorption experiment was carried out on the thiophene sulfides in the simulated gasoline. The operation of the breakthrough adsorption experiment was the same as in Examples 1-2, and the adsorption results are shown in Table 8.

Table 8 Adsorption properties of SiO ₂ -APTES-Pd composite aerogels for thiophene sulfides in simulated gasoline with different regeneration solvents

It can be seen from Table 8 that the solvents used to regenerate the SiO ₂ -APTES-Pd composite airgel include cyclohexene, ether, benzene, and toluene, all of which have good regeneration effects. When benzene is selected, SiO ₂ -APTES-Pd composite airgel has the best regeneration effect on thiophene, benzothiophene and dibenzothiophene. It is therefore preferred that the regeneration solvent is benzene.

Implementation Case 32-33: Comparison of Adsorption Performance of APTES-SiO2 Composite Airgel and APTES-SiO2-Pd Composite Airgel on Thiophene Sulfides in Simulated Gasoline

APTES-SiO2 composite aerogels and APTES-SiO2-Pd composite aerogels were used for breakthrough adsorption experiments on thiophene sulfides in simulated gasoline. The operation of the breakthrough adsorption experiment is the same as in Examples 1-2, and the adsorption results are shown in Table 9.

Table 9 Adsorption properties of APTES-SiO2 composite aerogel and APTES-SiO2-Pd composite aerogel for thiophene sulfides in simulated gasoline

It can be seen from Table 9 that compared with purely coupled APTES, the hydrogen bond interaction possessed by graft-NH2. The SiO2 airgel is first coupled with APTES, and then coordinated with Pd2+, and combined with the π complex interaction of Pd2+ while forming a hydrogen bond, it can significantly improve the adsorption capacity of Si-based airgel for thiophene sulfides. .

Claims (10)

1. the removal methods of thiophene sulphur in a kind of fuel oil, it is characterised in that with SiO₂- APTES-Pd composite aerogel is absorption Agent enters the absorbent filling in preventing fixed bed adsorber, at a temperature of 0 ~ 100 DEG C, with 1 ~ 10 h^-1Air speed be passed through containing The analog gasoline of thiophene sulphur obtains the analog gasoline of 1ppm or less sulphur concentration after adsorbing.

2. the removal methods of thiophene sulphur in a kind of fuel oil according to claim 1, it is characterised in that adsorbed thiophene Pheno class sulphur is thiophene, benzothiophene and dibenzothiophenes.

3. the removal methods of thiophene sulphur in a kind of fuel oil according to claim 1 or 2, it is characterised in that SiO₂- APTES-Pd composite aerogel adsorbent is using silicon source, ammonia source and palladium source as raw material, using collosol and gel-atmosphere pressure desiccation preparation ?.

4. the removal methods of thiophene sulphur in a kind of fuel oil according to claim 3, it is characterised in that preparation SiO₂- The silicon source of APTES-Pd composite aerogel adsorbent is ethyl orthosilicate, preferably ethyl orthosilicate；Ammonia source is 3- aminopropyl three Ethoxysilane；Palladium source is palladium chloride or palladium sulfate, preferably palladium chloride.

5. the removal methods of thiophene sulphur in a kind of fuel oil according to claim 3, it is characterised in that SiO₂-APTES- Silicon palladium molar ratio in Pd composite aerogel adsorbent is 508-2544:1, preferably 508:1,636:1,848:1,1272:1 or 2544:1, optimal is 848:1.

6. the removal methods of thiophene sulphur in a kind of fuel oil according to claim 1, it is characterised in that be passed through containing thiophene The air speed of the analog gasoline of pheno class sulphur is 1 ~ 5 h^-1。

7. the removal methods of thiophene sulphur in a kind of fuel oil according to claim 1, it is characterised in that SiO₂-APTES- The adsorption temp that Pd composite aerogel adsorbs thiophene sulphur is 0 ~ 40 DEG C.

8. the removal methods of thiophene sulphur in a kind of fuel oil according to claim 1, it is characterised in that in analog gasoline The concentration of thiophene sulphur is 0.1 ~ 10mgS/g, preferably 0.1 ~ 5 mgS/g.

9. the removal methods of thiophene sulphur in a kind of fuel oil according to claim 1, it is characterised in that contain thiophene-based 20wt% cyclohexene, 20wt% toluene are mixed in the analog gasoline of sulphur respectively.

10. the removal methods of thiophene sulphur in a kind of fuel oil according to claim 1, it is characterised in that SiO₂-APTES- Regenerating solvent used after Pd composite aerogel absorption thiophene sulphur is cyclohexene, ether, benzene, toluene.