A porous liquid extractant based on nickel-based MOF-74 and its preparation method and application

Abstract

The present invention provides a porous liquid extractant based on nickel-based MOF-74 and its preparation method and application, belonging to the field of desulfurization technology. The present invention reacts by heating after mixing 2,5-dihydroxy terephthalic acid solution and nickel acetate solution to obtain MOF-74 (Ni); 1-bromo-6-chlorohexane solution and imidazole derivative solution are reacted after mixing to obtain an intermediate product, and then a bis(trifluoromethane)sulfonamide lithium salt solution and an aqueous solution of the intermediate product are mixed to carry out a secondary reaction to obtain an ionic liquid; finally, MOF-74 (Ni) is reacted after mixing with the ionic liquid to obtain a porous liquid extractant. The porous liquid extractant prepared by the present invention not only retains the porosity of MOF-74 (Ni), but also combines the mobility of the ionic liquid, thereby improving the desulfurization performance of the extractant.

Description

Technical Field

[0001] The present invention relates to the technical field of desulfurization, and in particular to a porous liquid extractant based on nickel-based MOF-74, and a preparation method and application thereof. Background Art

[0002] With the acceleration of industrialization, the problem of air pollution is becoming increasingly serious, among which sulfur oxides (SO x ) is one of the main air pollutants, and its emission mainly comes from the combustion of sulfur compounds in transportation fuels. In order to reduce SO x To address emissions, governments around the world have implemented stringent sulfur content standards for fuel oil. Against this backdrop, hydrodesulfurization, a commonly used desulfurization method in the oil refining industry, while highly effective in removing most sulfides, is significantly less effective when treating aromatic sulfur compounds with stable molecular structures, such as thiophene, becoming a key factor limiting desulfurization efficiency.

[0003] To overcome this limitation of hydrodesulfurization technology, a variety of alternative desulfurization methods are currently available, including adsorption desulfurization and extractive desulfurization. These new methods have demonstrated significant advantages in reducing the need for complex equipment and lowering operating conditions, providing new ideas for innovation in desulfurization technology. However, these methods currently face numerous challenges in practical application, such as poor adsorbent selectivity, low adsorption efficiency, high volatility of extractants, and insufficient stability. This makes it difficult to achieve satisfactory desulfurization results with a single method.

[0004] Based on this, there is an urgent need for a more efficient, stable, and porous liquid extractant that can effectively remove stubborn pollutants such as aromatic sulfur compounds. Summary of the Invention

[0005] The purpose of the present invention is to provide a porous liquid extractant based on nickel-based MOF-74, a preparation method and application thereof, so as to solve the technical problems of poor selectivity of the adsorbent, low adsorption efficiency, high volatility and insufficient stability of the extractant in the existing single method.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] The present invention provides a method for preparing a porous liquid extractant based on nickel-based MOF-74, comprising the following steps:

[0008] (1) mixing a 2,5-dihydroxyterephthalic acid solution and a nickel acetate solution and heating them to react to obtain MOF-74(Ni);

[0009] (2) mixing a 1-bromo-6-chlorohexane solution and an imidazole derivative solution and reacting them to obtain an intermediate product, and then mixing a bis(trifluoromethane)sulfonamide lithium salt solution and an aqueous solution of the intermediate product and performing a secondary reaction to obtain an ionic liquid;

[0010] (3) MOF-74(Ni) is mixed with an ionic liquid and reacted to obtain a porous liquid extractant.

[0011] Furthermore, the mass concentration of the 2,5-dihydroxyterephthalic acid solution is 1-3%, and the mass concentration of the nickel acetate solution is 2-7%;

[0012] The mass ratio of 2,5-dihydroxyterephthalic acid in the 2,5-dihydroxyterephthalic acid solution to nickel acetate in the nickel acetate solution is 0.522:1-2.

[0013] Furthermore, in the step (1), the mixing time is 20 to 40 minutes;

[0014] The temperature of the heating reaction is 100-120° C., and the time of the heating reaction is 24-36 hours.

[0015] Furthermore, in step (2), the molar concentration of the 1-bromo-6-chlorohexane solution is 0.5 to 0.8 mmol / mL, the molar concentration of the imidazole derivative solution is 1 to 2 mmol / mL, the molar concentration of the bis(trifluoromethane)sulfonamide lithium salt solution is 0.5 to 1 mmol / mL, and the molar concentration of the aqueous solution of the intermediate product is 0.4 to 0.6 mmol / mL;

[0016] The molar ratio of 1-bromo-6-chlorohexane in the 1-bromo-6-chlorohexane solution, imidazole derivative in the imidazole derivative solution, bis(trifluoromethane)sulfonamide lithium salt in the bis(trifluoromethane)sulfonamide lithium salt solution and the intermediate product is 15:20-40:10-30:5-15.

[0017] Furthermore, in step (2), the reaction temperature is 50-70° C., and the reaction time is 8-12 h;

[0018] The temperature of the secondary reaction is 20-30° C., and the time of the secondary reaction is 6-10 hours.

[0019] Furthermore, in the step (2), the imidazole derivative comprises butyl imidazole, octyl imidazole or benzyl imidazole;

[0020] The structural formula of the ionic liquid is:

[0021]

[0022] Wherein, R is butyl, octyl or benzyl.

[0023] Furthermore, in step (3), the mass of MOF-74(Ni) is 1 to 13 wt % of the total mass of MOF-74(Ni) and the ionic liquid.

[0024] Furthermore, in step (3), the reaction temperature is 20-40° C., and the reaction time is 3-5 h.

[0025] The present application provides a porous liquid extractant prepared by the preparation method of the porous liquid extractant based on nickel-based MOF-74.

[0026] The present application also provides an application of a porous liquid extractant in extracting sulfur compounds from fuel oil, wherein the porous liquid extractant and fuel oil are mixed and reacted;

[0027] The volume ratio of the porous liquid extractant to the fuel is 1:1 to 3, wherein the sulfur content of the fuel is 50 to 1000 ppm;

[0028] The mixing speed is 400-600 rpm, the reaction temperature is 30-60° C., and the reaction time is 40-80 min.

[0029] Beneficial effects of the present invention:

[0030] (1) The porous liquid extractant prepared by the present invention not only retains the porosity of MOF-74(Ni), but also combines the fluidity of the ionic liquid, thereby achieving the performance of MOF-74(Ni) in adsorbing sulfides and the performance of the ionic liquid in extracting sulfides, and significantly improving the desulfurization performance of the porous liquid extractant;

[0031] (2) The porous liquid extractant based on MOF-74 (Ni) of the present invention has mild conditions and simple operation in the extraction desulfurization process, and can achieve the purpose of deep desulfurization without adding any solvent or oxidant. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 XRD pattern of MOF-74(Ni) in the porous liquid extractant prepared in Example 2;

[0033] Figure 2 A line graph showing viscosity-temperature curves of the porous liquid extractants prepared in Examples 2 to 4 at different temperatures;

[0034] Figure 3 The line graphs are modulus-temperature curves of the porous liquid extractants prepared in Examples 2 to 4 at different temperatures;

[0035] Figure 4 These are photos of the porous liquid extractants prepared in Examples 2 to 6;

[0036] Figure 5 A bar graph showing the desulfurization rates of the ionic liquid and the porous liquid extractants prepared in Examples 2 to 6 in fuel oil;

[0037] Figure 6 This is a bar graph showing the desulfurization rates of the porous liquid extractant prepared in Example 4 in fuels of different concentrations;

[0038] Figure 7 This is a bar graph showing the desulfurization rates of the porous liquid extractant prepared in Example 4 in different fuels;

[0039] Figure 8 This is a bar graph showing the desulfurization rate of the porous liquid extractant prepared in Example 4 after being regenerated and reused for different times. DETAILED DESCRIPTION

[0040] The present invention provides a method for preparing a porous liquid extractant based on nickel-based MOF-74, comprising the following steps:

[0041] (1) mixing a 2,5-dihydroxyterephthalic acid solution and a nickel acetate solution and heating them to react to obtain MOF-74(Ni);

[0042] (2) mixing a 1-bromo-6-chlorohexane solution and an imidazole derivative solution and reacting them to obtain an intermediate product, and then mixing a bis(trifluoromethane)sulfonamide lithium salt solution and an aqueous solution of the intermediate product and performing a secondary reaction to obtain an ionic liquid;

[0043] (3) MOF-74(Ni) is mixed with an ionic liquid and reacted to obtain a porous liquid extractant.

[0044] In the present invention, the mass concentration of the 2,5-dihydroxyterephthalic acid solution is 1 to 3%, preferably 1.2 to 2.8%, and more preferably 1.5 to 2.5%; the mass concentration of the nickel acetate solution is 2 to 7%, preferably 2.3 to 6.5%, and more preferably 2.5 to 6.1%;

[0045] The mass ratio of 2,5-dihydroxyterephthalic acid in the 2,5-dihydroxyterephthalic acid solution to nickel acetate in the nickel acetate solution is 0.522:1-2, preferably 0.522:1.2-1.8, and more preferably 0.522:1.3-1.5.

[0046] In the present invention, in step (1), the mixing time is 20 to 40 minutes, preferably 25 to 35 minutes, and more preferably 30 minutes;

[0047] The temperature of the heating reaction is 100-120° C., preferably 105-115° C., more preferably 110° C.; the time of the heating reaction is 24-36 h, preferably 26-34 h, more preferably 28-32 h.

[0048] In the present invention, in step (2), the molar concentration of the 1-bromo-6-chlorohexane solution is 0.5 to 0.8 mmol / mL, preferably 0.55 to 0.75 mmol / mL, and more preferably 0.6 to 0.7 mmol / mL; the molar concentration of the imidazole derivative solution is 1 to 2 mmol / mL, preferably 1.2 to 1.8 mmol / mL, and more preferably 1.4 to 1.6 mmol / mL; the molar concentration of the bis(trifluoromethane)sulfonamide lithium salt solution is 0.5 to 1 mmol / mL, preferably 0.55 to 0.8 mmol / mL, and more preferably 0.6 to 0.7 mmol / mL; the molar concentration of the aqueous solution of the intermediate product is 0.4 to 0.6 mmol / mL, preferably 0.45 to 0.55 mmol / mL, and more preferably 0.5 mmol / mL;

[0049] The molar ratio of 1-bromo-6-chlorohexane in the 1-bromo-6-chlorohexane solution, the imidazole derivative in the imidazole derivative solution, the bis(trifluoromethane)sulfonamide lithium salt in the bis(trifluoromethane)sulfonamide lithium salt solution, and the intermediate product is 15:20-40:10-30:5-15, preferably 15:25-35:15-25:7-12, and more preferably 15:30:20:10.

[0050] In the present invention, in step (2), the reaction temperature is 50-70°C, preferably 55-65°C, more preferably 60°C; the reaction time is 8-12h, preferably 9-11h, more preferably 10h.

[0051] In the present invention, after the reaction is completed, it is preferred to wash with ethyl acetate 6 times to remove unreacted products, then remove the solvent at 70° C., and finally dry in a vacuum oven at 60° C. for 12 hours to obtain an intermediate product.

[0052] In the present invention, the temperature of the secondary reaction is 20-30° C., preferably 22-28° C., more preferably 25° C.; the time of the secondary reaction is 6-10 h, preferably 7-9 h, more preferably 8 h.

[0053] In the present invention, after the secondary reaction is completed, the layers are separated, and the lower layer product is preferably washed 5 times with deionized water and dried at 80° C. for 24 h to obtain an ionic liquid.

[0054] In the present invention, in the step (2), the imidazole derivative comprises butyl imidazole, octyl imidazole or benzyl imidazole, preferably butyl imidazole or benzyl imidazole, more preferably butyl imidazole;

[0055] The structural formula of the ionic liquid is:

[0056]

[0057] Among them, R is butyl, octyl or benzyl, preferably butyl or benzyl, more preferably butyl.

[0058] In the present invention, in step (3), the mass of MOF-74(Ni) is 1 to 13 wt %, preferably 2 to 10 wt %, and more preferably 3 to 7 wt % of the total mass of MOF-74(Ni) and the ionic liquid.

[0059] In the present invention, in step (3), the reaction temperature is 20-40°C, preferably 25-35°C, more preferably 30°C; the reaction time is 3-5h, preferably 3.5-4.5h, more preferably 4h.

[0060] In the present invention, the synthesis path of the porous liquid extractant is:

[0061]

[0062] The present application provides a porous liquid extractant prepared by the preparation method of the porous liquid extractant based on nickel-based MOF-74.

[0063] The present application also provides an application of a porous liquid extractant in extracting sulfur compounds from fuel oil, wherein the porous liquid extractant and fuel oil are mixed and reacted.

[0064] In the present invention, the volume ratio of the porous liquid extractant to the fuel is 1:1-3, preferably 1:1-2.5, and more preferably 1:1-2; wherein the sulfur content of the fuel is 50-1000ppm, preferably 100-900ppm, and more preferably 150-800ppm.

[0065] In the present invention, the mixing speed is 400-600 rpm, preferably 450-550 rpm, more preferably 500 rpm; the reaction temperature is 30-60°C, preferably 35-55°C, more preferably 40-50°C; the reaction time is 40-80 min, preferably 50-70 min, more preferably 60 min.

[0066] The technical solutions provided by the present invention are described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0067] Example 1

[0068] 0.522 g of 2,5-dihydroxyterephthalic acid was dissolved in 30 mL of tetrahydrofuran to obtain a 2,5-dihydroxyterephthalic acid solution, and 1.306 g of nickel acetate was dissolved in 30 mL of deionized water to obtain a nickel acetate solution. The 2,5-dihydroxyterephthalic acid solution and the nickel acetate solution were mixed for 30 minutes, and then heated at 110° C. for 24 hours to obtain MOF-74(Ni).

[0069] 15mmol 1-bromo-6-chlorohexane, 30mmol N-n-butylimidazole was dissolved in 20 mL of ethyl acetate solution to obtain 1-bromo-6-chlorohexane solution and N-n-butylimidazole solution, and the 1-bromo-6-chlorohexane solution and the imidazole derivative solution were mixed, and then reacted at 60°C for 10 hours. After the reaction, the unreacted product was removed by washing with ethyl acetate 6 times, and then the solvent was removed at 70°C. Finally, it was dried in a vacuum oven at 60°C for 12 hours to obtain an intermediate product; 20 mmol of bis(trifluoromethane)sulfonamide lithium salt (LiNTf2) was dissolved in 30 mL of water to obtain a bis(trifluoromethane)sulfonamide lithium salt solution, 10 mmol of the intermediate product was dissolved in 20 mL of water to obtain an aqueous solution of the intermediate product, the bis(trifluoromethane)sulfonamide lithium salt solution and the aqueous solution of the intermediate product were mixed, and a secondary reaction was carried out at 25°C for 8 hours. After the reaction, the lower layer product was washed 5 times with deionized water and dried at 80°C for 24 hours to obtain an ionic liquid;

[0070] MOF-74(Ni) was mixed with an ionic liquid, with the mass of MOF-74(Ni) being 2 wt % of the total mass of MOF-74(Ni) and the ionic liquid, and then reacted at 30° C. for 4 h to obtain a porous liquid extractant.

[0071] Example 2

[0072] Compared with Example 1, the only difference is that the imidazole derivative used in Example 2 is benzyl imidazole.

[0073] The porous liquid extractant prepared in Example 2 was tested, and the test results are as follows: Figure 1 shown. Figure 1 The XRD pattern of MOF-74 (Ni) in the porous liquid extractant prepared in Example 2. Figure 1It can be seen that MOF-74(Ni) has two main peaks (2θ=6.8° and 11.8°), which are attributed to the characteristic diffraction peaks of MOF-74 material, indicating that MOF-74(Ni) material has been successfully synthesized in the porous liquid extractant.

[0074] Example 3

[0075] Compared with Example 2, the only difference is that in Example 3, the mass of MOF-74(Ni) is 3 wt % of the total mass of MOF-74(Ni) and the ionic liquid.

[0076] Example 4

[0077] Compared with Example 2, the only difference is that in Example 4, the mass of MOF-74(Ni) is 5 wt % of the total mass of MOF-74(Ni) and the ionic liquid.

[0078] The porous liquid extractants prepared in Examples 2 to 4 were tested, and the test results are as follows: Figures 2-3 shown. Figure 2 A line graph showing viscosity-temperature curves of the porous liquid extractants prepared in Examples 2 to 4 at different temperatures; Figure 3 The following is a broken line graph of the modulus-temperature curve of the porous liquid extractant prepared in Examples 2 to 4 at different temperatures. Figures 2-3 It can be seen that at 25°C, the viscosities of the porous liquid extractants prepared in Examples 2-4 were 1763, 1785, and 1805 mPa·s, respectively. The viscosity of the porous liquid extractants decreased sharply with increasing temperature and increased with increasing MOF-74(Ni) loading. At 50°C, the viscosities of the 2%, 3%, and 5% porous liquid extractants were 388, 396.3, and 416 mPa·s, respectively, indicating relatively low viscosities. Over the entire temperature range tested, the loss modulus G" was greater than the storage modulus G', and the results of the modulus variation with temperature indicate that the porous liquid extractants possess stable fluid properties. Therefore, due to the excellent fluidity and stability of the porous liquid extractants, the practical applications of MOF-74(Ni) porous liquid extractants have been expanded.

[0079] Example 5

[0080] Compared with Example 2, the only difference is that in Example 5, the mass of MOF-74(Ni) is 7 wt % of the total mass of MOF-74(Ni) and the ionic liquid.

[0081] Example 6

[0082] Compared with Example 2, the only difference is that in Example 6, the mass of MOF-74(Ni) is 10 wt % of the total mass of MOF-74(Ni) and the ionic liquid.

[0083] Figure 4 The following are photos of the porous liquid extractants prepared in Examples 2 to 6. Figure 4 It can be seen that it is a homogeneous and stable liquid.

[0084] The desulfurization performance of the porous liquid extractants prepared in Examples 2 to 6 was tested. The test method was as follows: 5 mL of ionic liquid and the porous liquid extractants prepared in Examples 2 to 6 were respectively taken and mixed with 5 mL of fuel at a speed of 500 rpm. The fuel was prepared by a weight method based on sulfur content. Formula (1) shows the relationship between C(S) sulfur concentration and organic sulfur mass, molar mass, simulated oil volume, and sulfur atomic molar mass. The sulfur content of the fuel was calculated using Formula (1).

[0085]

[0086] After mixing, the mixture was reacted at 50°C for 60 minutes. After the reaction was completed, the upper layer of oil sample was taken and the sulfur content of the fuel was determined by gas chromatography. Combined with the standard curves of different sulfides, the sulfide content before and after the treatment of the oil product can be measured by gas chromatography, and the desulfurization rate can be calculated according to formula (2). The results are shown in Figure 5 .

[0087]

[0088] C0 is the sulfur content in the simulated oil before treatment, C t It is the sulfur content in the simulated oil after treatment, in ppm.

[0089] 5 mL of thiophene fuel with an initial sulfur content of 50 to 1000 ppm and 5 mL of the porous liquid extractant prepared in Example 4 were mixed at a speed of 500 rpm. After mixing, the mixture was reacted at 50°C for 60 minutes. After the reaction was completed, the upper oil sample was taken and the sulfur content of the fuel was determined by gas chromatography. The desulfurization rate was calculated. The results are shown in FIG. Figure 6 .

[0090] 5 mL of thiophene, benzothiophene and dibenzothiophene fuel with an initial sulfur content of 500 ppm and 5 mL of the porous liquid extractant prepared in Example 4 were mixed at a speed of 500 rpm. After mixing, the mixture was reacted at 50°C for 60 minutes. After the reaction was completed, the upper oil sample was taken and the sulfur content of the fuel was determined by gas chromatography. The desulfurization rate was calculated. The results are shown in FIG. Figure 7 .

[0091] The regeneration and reuse of the porous liquid extractant prepared in Example 4 were tested. The test method was as follows: 5 mL of thiophene with an initial sulfur content of 500 ppm and 5 mL of the porous liquid extractant prepared in Example 4 were mixed at a rotation speed of 500 rpm, and reacted at 50°C for 60 minutes after mixing. After the reaction, the mixed solution after removing thiophene was allowed to stand, the upper oil phase was removed, cyclohexane was added as a stripping agent, stirred for 15 minutes, and then the upper cyclohexane phase was poured out. The above operation was repeated and washed repeatedly with cyclohexane 4 times. During the stripping washing process, the structure of the porous liquid remained stable and always remained in one phase, so no loss was caused during the stripping washing process; finally, it was placed in a vacuum drying oven at 60°C to remove the low-boiling point stripping agent cyclohexane. The test results are as follows Figure 8 shown. Figure 8 The desulfurization rates of the porous liquid extractant prepared in Example 4 after being regenerated and reused for different times.

[0092] Depend on Figures 5 to 8 It can be seen that the porous liquid extractant prepared by the present invention has an excellent desulfurization effect and can be applied to fuel desulfurization.

[0093] As can be seen from the above embodiments, the present invention provides a porous liquid extractant based on nickel-based MOF-74, its preparation method and application, wherein a 2,5-dihydroxyterephthalic acid solution and a nickel acetate solution are mixed and heated to react to obtain MOF-74 (Ni); a 1-bromo-6-chlorohexane solution and an imidazole derivative solution are mixed and reacted to obtain an intermediate product, and then a bis(trifluoromethane)sulfonamide lithium salt solution and an aqueous solution of the intermediate product are mixed and reacted to obtain an ionic liquid; finally, MOF-74 (Ni) is mixed with the ionic liquid and reacted to obtain a porous liquid extractant. The porous liquid extractant prepared by the present invention retains the porosity of MOF-74 (Ni) and combines the fluidity of the ionic liquid, thereby improving the desulfurization performance of the extractant.

[0094] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A method for preparing a porous liquid extractant based on nickel-based MOF-74, characterized in that: The following steps are involved: (1) Mixing a 2,5-dihydroxyterephthalic acid solution and a nickel acetate solution and heating them to react, thereby obtaining MOF-74(Ni); (2) mixing a 1-bromo-6-chlorohexane solution and an imidazole derivative solution and reacting them to obtain an intermediate product, and then mixing a bis(trifluoromethane)sulfonamide lithium salt solution and an aqueous solution of the intermediate product and performing a secondary reaction to obtain an ionic liquid; (3) MOF-74(Ni) is mixed with an ionic liquid and reacted to obtain a porous liquid extractant; In the step (2), the imidazole derivative comprises butyl imidazole, octyl imidazole or benzyl imidazole; The structural formula of the ionic liquid is: ， Wherein, R is butyl, octyl or benzyl.

2. The method for preparing a porous liquid extractant based on nickel-based MOF-74 according to claim 1, characterized in that: The mass concentration of the 2,5-dihydroxyterephthalic acid solution is 1-3%, and the mass concentration of the nickel acetate solution is 2-7%; The mass ratio of 2,5-dihydroxyterephthalic acid in the 2,5-dihydroxyterephthalic acid solution to nickel acetate in the nickel acetate solution is 0.522:1-2.

3. The method for preparing a porous liquid extractant based on nickel-based MOF-74 according to claim 1 or 2, characterized in that: In the step (1), the mixing time is 20 to 40 minutes; The temperature of the heating reaction is 100-120° C., and the time of the heating reaction is 24-36 hours.

4. The method for preparing a porous liquid extractant based on nickel-based MOF-74 according to claim 3, characterized in that: In the step (2), the molar concentration of the 1-bromo-6-chlorohexane solution is 0.5-0.8 mmol / mL, the molar concentration of the imidazole derivative solution is 1-2 mmol / mL, the molar concentration of the bis(trifluoromethane)sulfonamide lithium salt solution is 0.5-1 mmol / mL, and the molar concentration of the aqueous solution of the intermediate product is 0.4-0.6 mmol / mL; The molar ratio of 1-bromo-6-chlorohexane in the 1-bromo-6-chlorohexane solution, imidazole derivative in the imidazole derivative solution, bis(trifluoromethane)sulfonamide lithium salt in the bis(trifluoromethane)sulfonamide lithium salt solution, and the intermediate product is 15:20-40:10-30:5-15.

5. The method for preparing a porous liquid extractant based on nickel-based MOF-74 according to claim 4, characterized in that: In step (2), the reaction temperature is 50-70°C and the reaction time is 8-12 hours; The temperature of the secondary reaction is 20-30° C., and the time of the secondary reaction is 6-10 hours.

6. The method for preparing a porous liquid extractant based on nickel-based MOF-74 according to claim 5, characterized in that: In the step (3), the mass of MOF-74(Ni) is 1 to 13 wt % of the total mass of MOF-74(Ni) and the ionic liquid.

7. The method for preparing a porous liquid extractant based on nickel-based MOF-74 according to claim 6, characterized in that: In the step (3), the reaction temperature is 20-40° C., and the reaction time is 3-5 h.

8. A porous liquid extractant prepared by the method for preparing a porous liquid extractant based on nickel-based MOF-74 according to any one of claims 1 to 7.

9. Use of the porous liquid extractant according to claim 8 in extracting sulfur compounds from fuel oil, characterized in that: mixing the porous liquid extractant and fuel and reacting them; The volume ratio of the porous liquid extractant to the fuel is 1:1-3, wherein the sulfur content of the fuel is 50-1000 ppm; The mixing speed is 400-600 rpm, the reaction temperature is 30-60° C., and the reaction time is 40-80 min.

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