A microporous aluminum-based MOF material and application of an adsorbent prepared from the same in SO2 adsorption and removal

Abstract

The application belongs to the technical field of MOF materials and sulfur dioxide separation, and particularly relates to a microporous aluminum-based MOF material and application of an adsorbent prepared from the microporous aluminum-based MOF material in SO2 adsorption and removal. The microporous aluminum-based MOF material benefits from rich amino functional groups and enhanced hydrogen bond action, and exhibits trace SO2 capture performance. Although the material has high affinity for SO2, the adsorption isosteric heat of the material still remains at a relatively moderate level, indicating that the material has the potential of energy-saving regeneration. Based on these excellent adsorption characteristics, the application further develops a scalable and environmentally friendly synthesis route, and successfully prepares 1.06 kg of the material through a simple one-pot reaction, and the adsorption performance of the material remains unchanged.

Description

Technical Field

[0001] This invention belongs to the field of MOF materials and sulfur dioxide separation technology, and specifically relates to the application of a microporous aluminum-based MOF material and the adsorbent prepared therefrom in SO2 adsorption and removal. Background Technology

[0002] Industrial development requires substantial energy support. While the use of fossil fuels brings convenience to production and daily life, the flue gas produced by burning fuels such as coal and oil inevitably contains a certain amount of SO2. SO2 is not only harmful to human health and the environment, but is also one of the main components of air pollution and is highly corrosive. Therefore, desulfurization treatment must be carried out on the flue gas before it is emitted. In addition, SO2 can form sulfites and / or sulfates with precious metals, leading to the poisoning and deactivation of catalysts (especially supported precious metal catalysts). Current desulfurization technologies mainly use alkaline absorbents such as sodium hydroxide aqueous solution and limestone. Although traditional flue gas desulfurization processes can remove most of the SO2 produced by fossil fuel combustion, trace amounts of SO2 are still difficult to completely absorb. These residual SO2 not only cause environmental pollution and health hazards, but also react with organic amine absorbents during CO2 capture, leading to the permanent loss of amine activity and reducing CO2 capture efficiency. Desulfurization technology based on physical adsorption has become an effective method for SO2 removal due to its advantages such as low-temperature operation, low energy consumption, and no secondary pollution.

[0003] Metal-organic frameworks (MOFs) are novel porous materials formed by the coordination of metal ions / clusters with organic ligands. Leveraging the diversity of organic linkers, MOFs can be structurally designed through precise control of pore size and functional groups, thus exhibiting excellent SO2 adsorption performance. However, the application of MOF materials in industrial desulfurization (especially low partial pressure SO2 adsorption) still faces challenges such as high regeneration energy consumption, demanding synthesis conditions, and high economic costs. Furthermore, the strong corrosiveness and coordination ability of SO2 can lead to the formation of irreversible metal-sulfur bonds (especially under aqueous conditions), disrupting the metal-ligand coordination structure and ultimately causing MOF material degradation. Therefore, developing precisely designed and functionalized stable MOFs for SO2 adsorption and elucidating the role of functional groups in enhancing the selective recognition and binding of SO2 molecules remains of great significance. Summary of the Invention

[0004] To address the problems existing in the prior art, this invention provides a microporous aluminum-based MOF material and the application of the adsorbent prepared therefrom in SO2 adsorption and removal.

[0005] This invention is achieved through the following technical solution: An application of a microporous aluminum-based MOF material in SO2 adsorption and removal is disclosed. The microporous aluminum-based MOF material is prepared by a solvothermal reaction of Al2(SO4)3·18H2O and 5-aminoisophthalic acid. The microporous aluminum-based MOF material has one-dimensional square channels with exposed oxygen atoms, nitrogen atoms, and aromatic rings distributed on the channel surface. The aluminum metal nodes are in a fully coordinated mode. The microporous aluminum-based MOF material is named BJUT-4.

[0006] The preparation method of BJUT-4 includes the following steps: Al2(SO4)3·18H2O and 5-aminoisophthalic acid were dissolved in a mixed solvent of DMF and H2O. After thorough stirring, the mixture was heated to react. After cooling to room temperature, the product was separated by centrifugation, washed ten times alternately with water and DMF, and then soaked in methanol for 2 days to obtain the target product.

[0007] Furthermore, the molar ratio of Al2(SO4)3·18H2O to 5-aminoisophthalic acid is (0.5-1):1.

[0008] Furthermore, the volume ratio of DMF to H2O is 1:4, with each 3.33 mmol ligand corresponding to a 10 mL mixing volume.

[0009] Furthermore, the conditions for the heating reaction are: reaction temperature of 120-130℃, reaction time of 12 hours.

[0010] The present invention also provides a method for large-scale synthesis of BJUT-4, comprising the following steps: S1. Dissolve 5-aminoisophthalic acid in an aqueous solution of NaOH to prepare a Na2IPA-NH2 solution; S2. Na2IPA-NH2 solution, Al2(SO4)3·18H2O solution, and NaOH solution are added sequentially to the reaction vessel. The reaction system is stirred and reacted at 100℃-120℃ for 3-7 hours. After centrifugation, the product is washed with water and activated under vacuum at 393 K for 12 hours to finally obtain the target product.

[0011] Furthermore, the molar ratio of 5-aminoisophthalic acid to NaOH in S1 is 1:2, and the concentration of the Na2IPA-NH2 solution is 1.5 mol / L. -1 .

[0012] Furthermore, the molar ratio of Al2(SO4)3·18H2O to Na2IPA-NH2 in S2 is 1:2, and the molar ratio of Al2(SO4)3·18H2O to NaOH is 1:2.

[0013] Furthermore, under conditions of 298 K and 100 kPa, the SO2 / CO2 selectivity of the microporous aluminum-based MOF material is 152.29.

[0014] Furthermore, the microporous aluminum-based MOF material exhibits an adsorption capacity of 1.8 mmol / g at 0.01 bar and 3.12 mmol / g at 0.1 bar.

[0015] Furthermore, in a dynamic penetration experiment with a mixed gas containing 2500 ppm SO2, 15% CO2, and N2 as a balance, the SO2 penetration time of the microporous aluminum-based MOF material was 430 minutes, and the SO2 treatment capacity was 21.3 cm³. 3 g -1 .

[0016] Furthermore, the microporous aluminum-based MOF material can be regenerated and recycled.

[0017] This invention also provides an adsorbent comprising a microporous aluminum-based MOF material and a binder, wherein the binder is one of methylcellulose, PVA, or PVB. After the microporous aluminum-based MOF material is washed with water, it does not require drying; the binder is directly added, and after thorough kneading, it is processed into shape in an automatic granulator to obtain the adsorbent.

[0018] The beneficial technical effects of this invention are as follows: This invention synthesizes a microporous aluminum-based MOF material, BJUT-4, which exhibits excellent trace SO2 capture performance thanks to its abundant amino functional groups and enhanced hydrogen bonding. Despite BJUT-4's high affinity for SO2, its adsorption isotherm remains at a relatively moderate level, indicating the material's potential for energy-saving regeneration. Based on these excellent adsorption characteristics, this invention further develops a scalable and environmentally friendly synthetic route, successfully preparing 1.06 kg of the material via a simple one-pot reaction while maintaining its adsorption performance. Attached Figure Description

[0019] Figure 1 Schematic diagram of the structure, the microporous environment of Al-MOF, and the CO2 adsorption-desorption isotherm measured at 195 K.

[0020] Figure 2 Powder XRD patterns of the materials in Example 1 and Comparative Example 1.

[0021] Figure 3(a)-(b) Adsorption isotherms of SO2, CO2 and N2 at 298 K for the materials of Example 1 and Comparative Example 1; (c) Comparison of SO2 adsorption capacity at 0.01 bar, 0.1 bar and 1 bar at 298 K; (d) Comparison of IAST and SO2 adsorption heat in porous materials.

[0022] Figure 4 Example 1: IAST SO2 / CO2 adsorption selectivity of the material at 273 K and 298 K in a mixed gas containing 2500 ppm SO2 and 15% CO2.

[0023] Figure 5 Example 1: IAST SO2 / CO2 adsorption selectivity of the material at 273 K and 298 K in a mixed gas containing 2500 ppm SO2 and 15% CO2.

[0024] Figure 6 The heat of adsorption of SO2 and CO2 by the material of Example 1 was calculated using adsorption isotherms at 273 K and 298 K.

[0025] Figure 7 The heat of adsorption of SO2 and CO2 by the material of Example 1 was calculated using adsorption isotherms at 273 K and 298 K.

[0026] Figure 8 Schematic diagram of the dynamic penetration experimental setup.

[0027] Figure 9 (a) Dynamic breakthrough curves of the materials of Example 1 and Comparative Example 1 against a mixture of 0.25% SO2, 15% CO2, and 84.75% N2; (b) Three-cycle adsorption-breakthrough experiment of the material in Example 1; (c) Magnified powder XRD patterns at different reaction times during synthesis; (d) SO2 and CO2 adsorption isotherms at 298 K for the material of Example 1 and the material synthesized on a large scale; (e) SO2 adsorption kinetics curves of the material in Example 1 and the material synthesized on a large scale at 305 K; (f) Comparison of dynamic penetration curves of the material in Example 1 and the material synthesized on a large scale.

[0028] Figure 10 Simulation calculations of SO2 adsorption in the materials of Example 1 and Comparative Example 1.

[0029] Figure 11 Powder X-ray diffraction pattern of BJUT-4 synthesized on a large scale.

[0030] Figure 12 Schematic diagram of a large-scale synthesis apparatus in a 10-liter jacketed glass reactor.

[0031] Figure 13 A physical image of BJUT-4 synthesized on a large scale.

[0032] Figure 14 Nitrogen adsorption-desorption isotherm of BJUT-4 synthesized on a large scale at 77 K.

[0033] Figure 15 Comparison of IAST selectivity and ligand price for porous materials used in SO2 adsorption. Detailed Implementation

[0034] Example 1 Al2(SO4)3·18H2O (3.33 mmol) and 5-aminoisophthalic acid (3.33 mmol) were dissolved in a mixed solvent of 2 mL DMF and 8 mL H2O. After thorough stirring, the mixture was reacted at 120 °C for 12 hours. After cooling to room temperature, the product was separated by centrifugation, washed ten times alternately with water and DMF, and then soaked in methanol for 2 days.

[0035] Comparative Example 1 Al₂(SO₄)₃·18H₂O (1.65 mmol) and 5-methylisophthalic acid (3.33 mmol) were dissolved in a mixed solvent of 2 mL DMF and 8 mL H₂O. After thorough stirring, the mixture was reacted at 130 °C for 12 hours. After cooling to room temperature, the product was centrifuged, washed ten times alternately with water and DMF, and then soaked in methanol for 2 days.

[0036] (1) Structural characterization: such as Figure 2 As shown, the experimental PXRD patterns of the materials in Example 1 and Comparative Example 1 are consistent with the simulation results of single crystal data, indicating that the obtained samples are pure phases.

[0037] (2) Gas adsorption and selectivity calculations The samples obtained in Examples 1 and 2 were activated by drying in a vacuum degassing station at 393 K for 24 hours. The treated samples were used for gas adsorption tests: CO2 adsorption isotherms of the materials in Example 1 and Comparative Example 1 were measured at 195 K; adsorption isotherms of single-component gases (N2, CO2, SO2) of the two MOFs were measured at 273 K and 298 K.

[0038] The permanent porosity of the material was evaluated using CO2 adsorption at 195 K. Figure 1 The BET specific surface areas of the materials in Example 1 and Comparative Example 1 were 452.98 m². 2 / g and 459.36 m2 / g.

[0039] like Figure 3 As shown in a and b, both the materials of Example 1 and Comparative Example 1 exhibit type I adsorption isotherms for SO2, showing a sharp increase in adsorption capacity in the low partial pressure region. However, compared to the material of Comparative Example 1, the adsorption curve of the amino-functionalized material rises more steeply, which is attributed to the high affinity of the amino-functionalized channels for SO2. Further comparison of the SO2 adsorption capacity of the two materials ( Figure 3 (c) It was found that although there was no significant difference in adsorption capacity between the two at 1 bar, BJUT-4 achieved adsorption capacities of 1.8 mmol / g and 3.12 mmol / g at low pressures (0.01 bar and 0.1 bar), respectively, which were significantly better than the materials prepared in the comparative example. Compared with reported MOFs, BJUT-4 showed a relative advantage in SO2 adsorption capacity at 0.01 bar and 0.1 bar. Figure 3 (d) Given the trace nature of SO2 in industrial flue gas, the adsorption performance of materials in the low-pressure region is crucial. This study confirms that the high adsorption capacity of BJUT-4 in the low-pressure region is beneficial for the removal of low-concentration SO2 from actual flue gas.

[0040] The significant difference in SO2 / CO2 adsorption capacity prompted us to calculate their separation selectivity. The adsorption selectivity at 273 K and 298 K was evaluated using the Ideal Adsorption Solution Theory (IAST). Figure 4-5 At 298 K and 100 kPa, the SO2 / CO2 selectivity of BJUT-4 was approximately 152.29, significantly higher than that of Comparative Example 1 (21.76). The results indicate that, compared to methyl groups, amino functional groups can more effectively optimize the pore environment and enhance SO2 adsorption, thus significantly improving adsorption separation selectivity. The host-guest interaction was quantified by calculating the adsorption isotherm (Qst) under low coverage. Figure 6-7 The heat of SO2 adsorption of BJUT-4 near zero coverage is approximately 30.0 kJ / mol. -1 Comparative Example 1 is 28.8 kJ mol. -1 The higher Qst value of CAU-10-NH2 indicates a stronger binding effect with SO2, consistent with the results of static adsorption experiments. Notably, BJUT-4 exhibits a significantly lower Qst value compared to other benchmark materials (Table 1), which may stem from the structural flexibility of its organic linkers, which helps reduce heat accumulation during adsorption. A lower Qst value facilitates adsorbent regeneration and significantly reduces energy consumption.

[0041] Table 1. Comparison of adsorption capacity of MOF materials

[0042]

[0043] (3) Dynamic penetration experiments were conducted using the apparatus shown in Figure 8. Approximately 100 mg of the powder sample from Example 1 or Comparative Example 1 was filled into a custom-made quartz column (6 mm outer diameter, 2 mm inner diameter, 60 mm length), with cotton filling the gaps at both ends. The temperature was controlled by a heating jacket, and the gas flow rate was regulated by a mass flow controller (MFC). After activation at 393 K for 12 hours, the sample was introduced into a mixed gas at a flow rate of 10 mL / min. The components of the outlet gas were analyzed using a continuous sampling mass spectrometer (MS, HidenHPR-20). After the penetration experiment, the sample was regenerated in a helium flow at 393 K for repeated testing.

[0044] Dynamic penetration experiment results: To verify the actual separation performance of the powder samples in Example 1 or Comparative Example 1, a fixed-bed dynamic breakthrough experiment was conducted using a mixed gas containing 2500 ppm SO2, 15% CO2, and N2 as a balance gas. The material's high adsorption capacity and good selectivity for SO2 in the low-pressure region are beneficial for SO2 / CO2 separation.

[0045] like Figure 9 As shown in ab, CO2 rapidly penetrated the chromatographic column, while the breakthrough time of SO2 in the powder sample of Example 1 was approximately 430 minutes, with an SO2 processing capacity of 21.3 cm⁻¹. 3 g -1 In contrast, the SO2 processing capacity of the powder sample in Example 1 was only 3.4 cm³. 3 g -1 The results showed that BJUT-4 remained a highly efficient adsorbent even for trace amounts of SO2. SO2 is corrosive, therefore the stability of the MOF was crucial. Cyclic breakthrough experiments were conducted to investigate the stability of BJUT-4 during multiple adsorption-desorption cycles. Figure 9 (b) BJUT-4 did not show significant degradation in separation performance during three cycles, demonstrating good regeneration ability and stable SO2 adsorption capacity.

[0046] (4) Theoretical Simulation: To gain a deeper understanding of the adsorption behavior of CO2 and SO2 on the powder samples of Example 1 or Comparative Example 1, we performed DFT calculations. The calculated binding sites of SO2 and CO2 are as follows: Figure 10 As shown, for the BJUT-4 sample, SO2 adsorption mainly originated from the multiple weak interactions of N-Hδ⁺···δ⁻OS (2.7507 Å-2.9784 Å) in the amino group; while for the sample of Comparative Example 1, SO2 adsorption mainly came from the multiple weak interactions of C-Hδ⁺···δ⁻OS (2.7557 Å and 2.7825 Å) in the methyl group.

[0047] Simulation calculations show that the static binding energies of SO2 for the powder samples of Example 1 and Comparative Example 1 are 47.59 kJ / mol and 42.80 kJ / mol, respectively. These results differ from the higher Qst values ​​calculated using the adsorption isotherms. The simulation results indicate that the higher binding energy of the BJUT-4 sample gives it a stronger SO2 adsorption capacity. Overall, amino groups promote favorable SO2 adsorption through hydrogen bonding. The DFT calculations not only support our experimental data but also reveal the molecular-level mechanism of the difference in SO2 adsorption between the two MOFs.

[0048] Example 3 Green Synthesis Method: First, 22.5 mmol of 5-aminoisophthalic acid (IPA-NH2) was dissolved in an aqueous solution containing 45 mmol of NaOH to prepare 15 mL of Na2IPA-NH2 solution (1.5 mol L). -1 , 22.5 mmol). Then, in a round-bottom flask, 22.5 mL of Al2(SO4)3·18H2O solution (0.5 mol L) was added. -1 Add Na2IPA-NH2 solution (11.25 mmol) under stirring, followed by 2.5 mL of NaOH solution (9 mol L). -1 , 22.5 mmol). The reaction system was refluxed for 6 hours, with samples taken at specific time points (1, 2, 3, 4, 5, and 6 hours). The product was centrifuged, washed three times with water (200 mL each time), and activated under vacuum at 393 K for 12 hours, finally yielding 4.69 g of yellowish-white powder (93% yield based on Na2IPA-NH2).

[0049] Example 4: 10-liter scale synthesis of BJUT-4 First, 4.95 mol of 5-aminoisophthalic acid (IPA-NH2) was dissolved in an aqueous solution containing 9.9 mol of NaOH to prepare a Na2IPA-NH2 solution (1.5 mol L). -1 ,4.95 mol); Add 3300 mL of Na2IPA-NH2 (1.5 mol L -1 , 4.95 mol), 4950 mL Al2(SO4)3·18H2O (0.5 mol L -1 2.475 mol) and 550 mL NaOH (9 mol L) -1A 4.95 mol solution was sequentially added to a 10-liter reactor equipped with a condenser, and the mixture was refluxed at 400 rpm for 5 hours with mechanical stirring. The product was centrifuged, washed three times with water (2 L each time), and dried under vacuum at 393 K for 12 hours, finally yielding 1.06 kg of product BJUT-4-L (yield 95.6%), with a space-time yield of 578 kg m³. -3 day -1 .

[0050] Factors limiting the industrial application of MOFs include poor stability, high manufacturing costs, and difficulty in large-scale production. Therefore, this embodiment attempts to prepare BJUT-4 using a green and environmentally friendly method. To obtain a higher space-time yield (STY), this invention optimizes the process by adjusting the synthesis time under higher reaction concentration conditions. For example... Figure 9 As shown in (c), no significant changes were observed in the PXRD spectrum after 5 hours, thus the optimal synthesis time was determined to be 5 hours. The reaction was scaled up to a 10-liter scale, with each starting material scaled up proportionally. The PXRD of the sample prepared by this method is shown below. Figure 11 As shown, after vacuum drying, 1.06 kg (95.6% yield) was obtained, with a space-time yield of 578 kg m³. - 3 day -1 ( Figure 12-13 ).

[0051] Comparison of SO2 adsorption isotherms between BJUT-4 and BJUT-4-L shows that, at 1 bar, the adsorption capacity of BJUT-4-L is 4.92 mmol / g, slightly higher than that of BJUT-4. SO2 adsorption kinetics were tested at 305 K. Figure 9 (e) shows that both samples rapidly adsorbed SO2 within the first 10 minutes, with BJUT-4-L exhibiting a slightly higher adsorption capacity and rate. Subsequently, BJUT-4-L gradually reached adsorption saturation (approximately 0.6 mmol / g), a result consistent with the SO2 adsorption capacity at a partial pressure of 0.25 kPa (2500 ppm). BJUT-4-L had a slower adsorption rate and took significantly longer to reach saturation. Therefore, despite its relatively lower adsorption capacity, BJUT-4-L's rapid kinetics remain advantageous in dynamic adsorption processes.

[0052] Dynamic penetration test results ( Figure 9 (f) indicates that the SO2 adsorption capacity of BJUT-4-L decreased in the breakthrough experiment, which is consistent with the adsorption isotherm and kinetic results at the corresponding partial pressure. However, it is noteworthy that the SO2 breakthrough time in BJUT-4-L remained stable, which may be due to the presence of more structural defects (verified by 77K N2 adsorption: BJUT-4 hardly adsorbs N2, while BJUT-4-L can be characterized for N2 adsorption, see...). Figure 14 Calculations show that the BET specific surface areas of BJUT-4 and CAU-10-NH2-L are 452.98 m². 2 g -1 and 516.37 m 2 g -1 The pore volumes are 0.202 cm³. 3 g -1 and 0.326 cm 3 g -1 The increase in specific surface area and pore volume may be due to the presence of numerous defects in BJUT-4-L, which promote the rapid diffusion and entry of SO2 into the pores, thereby enhancing its SO2 adsorption capacity.

[0053] Cost is a key factor in practical applications. BJUT-4-L has a significant price advantage among reported SO2 adsorbents. Figure 15 Its ligand cost is lower than that of most MOF-based SO2 adsorbents. BJUT-4, with its multiple advantages including high selectivity, low cost, and low heat of adsorption, demonstrates greater potential for industrial applications.

[0054] Furthermore, after washing the material obtained in Example 1 with water, without drying, 31.8 g of binder was directly added, and after thorough kneading, it was processed into shape in an automatic granulator to obtain an adsorbent containing BJUT-4. This adsorbent has been verified to have adsorption and removal performance that is not significantly different from that of the raw material, demonstrating the commercialization potential of this adsorbent. Conclusion: This invention demonstrates, by comparing the SO2 adsorption performance of different functional groups, that amino-functionalized channels in aluminum-based MOFs can significantly enhance the selectivity and adsorption capacity of SO2 under low pressure. Based on its excellent adsorption and separation performance and low Qst value, we developed an environmentally friendly and economically feasible atmospheric pressure synthesis route, effectively replacing the traditional high-energy-consuming and polluting solvothermal method. This innovative method achieves kilogram-scale preparation of BJUT-4. The obtained BJUT-4-L not only maintains the adsorption and separation performance consistent with the basic research, but also exhibits excellent adsorption kinetics and dynamic separation performance. This study provides important insights for designing SO2 adsorbents with enhanced low-pressure performance and also provides efficient and economically feasible MOF-based adsorbents for industrial deep desulfurization applications.

Claims

1. An application of a microporous aluminum-based MOF material in SO2 adsorption and removal, characterized in that: The microporous aluminum-based MOF material is prepared by a solvothermal reaction of Al2(SO4)3·18H2O and 5-aminoisophthalic acid. The microporous aluminum-based MOF material has a one-dimensional square channel, and the surface of the channel is covered with exposed oxygen atoms, nitrogen atoms and aromatic rings. The aluminum metal nodes adopt a fully coordinated mode. The microporous aluminum-based MOF material is prepared by any of the following methods: Small-scale synthesis methods: Al2(SO4)3·18H2O and 5-aminoisophthalic acid were dissolved in a mixed solvent of DMF and H2O with a volume ratio of 1:

4. After stirring thoroughly, the mixture was heated to 120-130℃ for 12 hours. After cooling to room temperature, the product was separated by centrifugation, washed ten times alternately with water and DMF, and then soaked in methanol for 2 days to obtain the target product. The molar ratio of Al2(SO4)3·18H2O to 5-aminoisophthalic acid is (0.5-1):1, and each 3.33 mmol of 5-aminoisophthalic acid corresponds to 10 mL of mixed solution; Large-scale synthesis methods: S1. Dissolve 5-aminoisophthalic acid in an aqueous solution of NaOH to prepare a Na2IPA-NH2 solution; S2. Na2IPA-NH2 solution, Al2(SO4)3·18H2O solution and NaOH solution are added to the reaction vessel in sequence. The reaction system is stirred and reacted at 100℃-120℃ for 3-7 hours. The product is separated by centrifugation, washed with water, and activated under vacuum at 393 K for 12 hours to finally obtain the target product. The molar ratio of 5-aminoisophthalic acid to NaOH is 1:2, and the concentration of the Na2IPA-NH2 solution is 1.5 mol / L. -1 ; The molar ratio of Al2(SO4)3·18H2O to Na2IPA-NH2 in S2 is 1:2, and the molar ratio of Al2(SO4)3·18H2O to NaOH is 1:

2.

2. The application of the microporous aluminum-based MOF material according to claim 1 in SO2 adsorption and removal, characterized in that: The SO2 / CO2 selectivity of the microporous aluminum-based MOF material is 152.29 under the conditions of 298 K and 100 kPa.

3. The application of the microporous aluminum-based MOF material according to claim 1 in SO2 adsorption and removal, characterized in that: The microporous aluminum-based MOF material exhibits an adsorption capacity of 1.8 mmol / g at 0.01 bar and 3.12 mmol / g at 0.1 bar.

4. The application of the microporous aluminum-based MOF material according to claim 1 in SO2 adsorption and removal, characterized in that: In a dynamic penetration experiment with a mixed gas containing 2500 ppm SO2, 15% CO2, and N2 as a balance, the SO2 penetration time of the microporous aluminum-based MOF material was 430 minutes, and the SO2 treatment capacity was 21.3 cm³. 3 g -1 .

5. The application of the microporous aluminum-based MOF material according to claim 1 in SO2 adsorption and removal, characterized in that: The microporous aluminum-based MOF material can be regenerated and recycled.

6. An adsorbent, characterized in that: The adsorbent is composed of the microporous aluminum-based MOF material of claim 1 and a binder, wherein the binder is one of methylcellulose, PVA or PVB.

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