Novel ''clover'' configuration alkyl long-chain hybrid polyacid functionalized non-aqueous liquid phase desulfurization technology suitable for hydrogen sulfide removal

Abstract

The invention discloses a novel alkyl long-chain hybrid polyacid functionalized non-aqueous liquid phase desulfurization technology suitable for hydrogen sulfide removal, and comprises a preparation method and desulfurization application of an alkyl long-chain hybrid polyacid functionalized non-aqueous liquid phase desulfurizer. Polyoxometallate and alkyl long-chain ionic liquid are combined and then dissolved in an ionic liquid-based eutectic solvent, and desulfurization regeneration application is achieved through a matched hydrogen sulfide bubbling absorption device. The novel alkyl long-chain hybridized polyacid functionalized non-aqueous liquid phase desulfurizer with clover configuration solves the technical bottlenecks of poor stability, equipment corrosion, high-temperature work limitation and the like of the traditional water-phase wet oxidation desulfurization process, is simple in process, convenient to operate and green and pollution-free in regeneration process, and has practical application prospects in the industrial field.

Description

Technical Field

[0001] The present invention relates to a preparation method and desulfurization application of a novel "clover" configuration alkyl long-chain hybrid polyacid functionalized non-aqueous liquid phase desulfurizer, belonging to the technical field of air pollutant control. Background Art

[0002] Hydrogen sulfide (H2S) is considered a colorless, toxic, and corrosive gas, usually present in industrial processes such as oil extraction and natural gas purification. It is harmful to human health and forms sulfur dioxide after combustion, leading to acid rain and other disastrous weather. Considering environmental protection and human health and safety, H2S is still an important regulated pollutant in most countries. Wet oxidation desulfurization processes such as ADA and HPF methods have received extensive attention due to their high sulfur loading and desulfurization rate. However, traditional wet oxidation desulfurization generally uses aqueous solutions, so there are inevitably problems such as poor desulfurizer stability, equipment corrosion, and high-temperature operation limitations.

[0003] Based on this, many non-aqueous solvents have been developed. Ionic liquids (ILs) are room-temperature molten salts composed of organic cations and organic or inorganic anions. They possess unique physical and chemical properties, such as designability, ultra-low volatility, non-flammability, high thermal stability, and chemical stability. Deep eutectic solvents (DES) are multi-component eutectic solvents formed by hydrogen bond donors and acceptors through hydrogen bond interactions, usually in a liquid state at room temperature. Deep eutectic solvents not only retain many functions of ionic liquids but also provide a more direct way to adjust functions and eliminate some limitations, such as lower viscosity, simplicity of synthesis, and low cost. These non-aqueous solvents, as green media, are used to prepare non-aqueous liquid phase desulfurizers to solve the dilemmas faced by traditional wet desulfurization processes. Therefore, the development of a high-performance and high-potential non-aqueous liquid phase desulfurization technology for treating H2S has become a current research hotspot. Summary of the Invention

[0004] Aiming at the deficiencies of the above-mentioned prior art, the present invention provides a preparation method of a novel "clover" configuration alkyl long-chain hybrid polyacid functionalized non-aqueous liquid phase desulfurizer and its corresponding desulfurization application technology. This technology can have excellent desulfurization performance in the medium and high temperature range, and the preparation conditions are mild, and the process operation is simple.

[0005] The present invention is achieved through the following technical solutions:

[0006] Preparation method of a novel "clover" configuration alkyl long-chain hybrid polyacid functionalized non-aqueous liquid phase desulfurizer, which includes preparing alkyl long-chain hybrid polyacid by combining polyoxometalate with alkyl long-chain ionic liquid, and then dissolving it in an ionic liquid-based deep eutectic solvent. The appearance color of this desulfurizer is clear and uniform. Hydrogen sulfide removal is carried out through a supporting bubbling absorption device, and subsequent regeneration of the desulfurizer is achieved by adding H2O2 and stirring with air.

[0007] The preparation method of the novel "clover" configuration alkyl long-chain hybrid polyacid functionalized non-aqueous liquid phase desulfurizer is as follows:

[0008] Phosphomolybdic acids with different central atoms and coordination atoms are combined with ionic liquids with different alkyl long-chain lengths (1-butyl-3-methylimidazolium chloride, 1-benzyl-3-methylimidazolium chloride, 1,3-didodecyl-2-methylimidazolium chloride, 1-dodecyl-3-methylimidazolium chloride, 1-tetradecyl-3-methylimidazolium chloride, 1-hexadecyl-3-methylimidazolium chloride, etc.) in a molar ratio of 1:1 to 1:6 to prepare alkyl long-chain hybrid polyacid. At the same time, an ionic liquid-based deep eutectic solvent is prepared by heating and stirring an ionic liquid (1-butyl-3-methylimidazolium chloride) and azole derivatives (imidazole, 1-methylimidazole, 4-methylimidazole, etc.) in a ratio of 3:1 to 1:3. Weigh a certain mass of alkyl long-chain hybrid polyacid and add it to the ionic liquid-based deep eutectic solvent, stir and dissolve to prepare a novel alkyl long-chain hybrid polyacid functionalized non-aqueous liquid phase desulfurizer for use in H2S removal experiments.

[0009] The application technology of the novel alkyl long-chain hybrid polyacid functionalized non-aqueous liquid phase desulfurization is as follows:

[0010] The alkyl long-chain hybrid polyacid functionalized non-aqueous liquid phase desulfurization device is as Figure 1 shown. Place a certain volume of alkyl long-chain hybrid polyacid functionalized non-aqueous liquid phase desulfurizer in a bubbling absorber, and carry out the removal of H2S gas through bubbling absorption. The temperature is controlled by a constant temperature oil bath. Pass a certain flow rate of H2S-containing gas, and use a H2S gas analyzer to dynamically detect the concentration of H2S gas in the tail gas. The tail gas is absorbed and treated with NaOH solution. After absorption for a period of time, the color of the desulfurizer turns brownish red, and the concentration of hydrogen sulfide gas in the tail gas increases. After exceeding a certain value, stop ventilation. After desulfurization is completed, add a small amount of H2O2 solution to the desulfurizer, and stir it by air bubbling until the color of the desulfurizer returns from brownish red to light blue. After heating and drying, the desulfurizer can completely recover its original desulfurization performance.

[0011] The volume of the novel alkyl long-chain hybrid polyacid functionalized non-aqueous liquid phase desulfurizer is 4 - 5 mL.

[0012] The absorber is a standard glass bubbling absorber.

[0013] The hydrogen sulfide-containing gas carrier gas is N2 or air, with a flow rate of 200 mL / min and a hydrogen sulfide concentration of 500 - 2000 mg / m 3 , and the air flow rate is 200 mL / min.

[0014] The absorption temperature is 25°C to 200°C, and the regeneration temperature is room temperature 25°C.

[0015] The concentration of the H2O2 solution is 30%, and the addition amount is 5 - 10% of the mass of the desulfurizer.

[0016] The regeneration time is 1 - 2 h.

[0017] The drying temperature is 40 - 80°C, and the drying time is 2 - 4 h. Description of the Drawings

[0018] Figure 1 Schematic diagram of the application device for the alkyl long-chain hybrid polyacid functionalized non-aqueous liquid phase desulfurization technology of the present invention

[0019] Figure 2 Scanning electron microscope pictures of the alkyl long-chain hybrid polyacid of the present invention before (a) and after (b) adding the ionic liquid-based deep eutectic solvent.

[0020] Figure 3 Desulfurization performance (a) of the alkyl long-chain hybrid polyacid functionalized non-aqueous liquid phase desulfurizer with different alkyl long-chain types of the present invention at 25°C and PCDES@3C 14 -2Im desulfurizer at different temperatures (b)

[0021] Figure 4 For Comparative Example 1 and 2 (a) of the present invention, Comparative Example 3 and 4 (b) and PCDES@3C of the present invention 14 -2Im desulfurization performance comparison

[0022] The desulfurization principle of the present invention is:

[0023] The alkyl long-chain hybrid polyacid can change from the original disordered core-shell structure wrapped to an ordered "clover" conformation through the entanglement and crosslinking of the alkyl long-chains in the ionic liquid-based deep eutectic solvent. Its microstructure is observed by scanning electron microscope to change from the molten waxy layer state of the core-shell structure (such as Figure 2 a) to an ordered layered structure (such as Figure 2b). This conformational change not only exposes more active sites for polyoxometalate desulfurization, but also expands the capture range of polyoxometalate for H2S by the stretching of long chains. In addition, the charge chain transfer behavior from the alkyl long-chain ionic liquid cation to the polyoxometalate anion significantly enhances the H2S capture performance of polyoxometalate. Then, the removal effect of H2S is finally achieved by replacing the oxygen element on the surface of polyoxometalate with elemental sulfur. Benefiting from the multiple H2S capture enhancement effects, the novel "clover" configuration of alkyl long-chain hybrid polyoxometalate functionalized non-aqueous liquid phase desulfurizer exhibits excellent desulfurization performance.

[0024] The novel alkyl long-chain hybrid polyoxometalate functionalized non-aqueous liquid phase desulfurizer of the present invention is simply configured, has excellent desulfurization effect, wide temperature window, wide applicable conditions, simple and easy regeneration without pollution, and has certain industrial application value.

[0025] The beneficial effects of the present invention are as follows: The present invention combines the ionic liquid hybrid polyoxometalate system commonly used in oil desulfurization and the deep eutectic solvent with an ionic liquid background and applies them to the field of gas purification research. The novel alkyl long-chain hybrid polyoxometalate functionalized non-aqueous liquid phase desulfurizer is simply configured, and its desulfurization effect is significantly better than that of the same type of non-aqueous solvent. As Figure 3 shown in a and b, the optimal desulfurizer PCDES@3C 14 -2Im can maintain 100% desulfurization efficiency for nearly 150 minutes and can maintain stable desulfurization efficiency within a wide temperature window range of 25°C - 200°C. The expected results are expected to solve the problems of weak desulfurization performance of single ionic liquid / / deep eutectic solvent, low applicable temperature of traditional aqueous wet oxidation desulfurization, unsatisfactory desulfurizer stability, large consumption of water and subsequent wastewater treatment. The desulfurization technology has a wide temperature window for use, simple process, convenient operation, novel method, and is easy to be popularized industrially. Detailed implementation manners

[0026] The present invention will be further described below in conjunction with examples and comparative examples.

[0027] Example 1 Preparation method of novel alkyl long-chain hybrid polyoxometalate functionalized non-aqueous liquid phase desulfurizer

[0028] (I) Preparation method of 0.01mol / L 1-dodecyl-3-methylimidazole hybrid polyoxometalate functionalized non-aqueous liquid phase desulfurizer

[0029] Weigh 0.09 g (0.05 mmol) of Keggin-structured phosphomolybdic acid (H3PMo 12 O 40 ·13H2O) and dissolve it in 50 ml of distilled water, and then add 1-dodecyl-3-methylimidazole chloride (C 12 mimCl) and H3PMo 12 O 40Dissolve in 50 mL of distilled water according to a molar ratio of 1:1 to 1:6, mix the two solutions, a large amount of yellow-green precipitate is produced, stir at room temperature and then filter and dry to obtain a yellow-green solid. The prepared yellow-green solid is labeled as [C 12 mim] x H 3-x PMo 12 O 40 , where x is the molar ratio of C 12 mimCl to H3PMo 12 O 40 . Weigh 10 g of 1-butyl-3-methylimidazolium chloride (BmimCl) and add it to a 50 ml round-bottom flask, then add imidazole (Im) according to a molar ratio of 3:1 to 1:3 at the same time, mix, heat and stir until a clear and homogeneous solution is formed, and then take it out and put it in a drying oven for standby. The sample is labeled as BmimCl / Im(1:n), where n represents the molar ratio of Im to BmimCl. Weigh 0.05 mmol of 1-dodecyl-3-methylimidazolium hybrid polyoxometalate [C 12 mim] x H 3-x PMo 12 O 40 and add it to the ionic liquid-based deep eutectic solvent BmimCl / Im (5 ml), stir and dissolve at room temperature until a light blue clear solution is obtained. The prepared solution is labeled as PCDES@xC 12 -nIm, where x is the molar ratio of C 12 mim to H3PMo 12 O 40 .

[0030] (II) Preparation method of 1-tetradecyl-3-methylimidazolium hybrid polyoxometalate functionalized non-aqueous liquid phase desulfurizer with a concentration of 0.01 mol / L

[0031] Weigh 0.09 g (0.05 mmol) of Keggin structure phosphomolybdic acid (H3PMo 12 O 40 ·13H2O) and dissolve it in 50 ml of distilled water, then dissolve 1-tetradecyl-3-methylimidazolium chloride (C 14 mimCl) and H3PMo 12 O 40 according to a molar ratio of 1:1 to 1:6 in 50 mL of distilled water, mix the two solutions, a large amount of yellow-green precipitate is produced, stir at room temperature and then filter and dry to obtain a yellow-green solid. The prepared yellow-green solid is labeled as [C 14 mim] x H 3-x PMo 12 O 40, where x is the molar ratio of [C 14 mim]Cl to H3PMo 12 O 40 . Weigh 10 g of 1-butyl-3-methylimidazolium chloride (BmimCl) and add it to a 50 ml round-bottom flask. Then add imidazole (Im) at a molar ratio of 3:1 to 1:3 simultaneously, mix, heat, and stir until a clear and homogeneous solution is formed. Then take it out and place it in a drying oven for standby. The sample is labeled as BmimCl / Im(1:n), where n represents the molar ratio of Im to BmimCl. Weigh 0.05 mmol of 1-tetradecyl-3-methylimidazolium hybrid polyacid [C 14 mim] x H 3-x PMo 12 O 40 and add it to the ionic liquid-based deep eutectic solvent BmimCl / Im (5 ml). Stir and dissolve it at room temperature until a light blue clear solution is obtained. The prepared solution is labeled as PCDES@xC 14 -nIm, where x is the molar ratio of C 14 mim to H3PMo 12 O 40 , and n is the molar ratio of Im to BmimCl.

[0032] (III) Preparation method of 1-hexadecyl-3-methylimidazolium hybrid polyacid functionalized non-aqueous liquid desulfurizer with a concentration of 0.01 mol / L

[0033] Weigh 0.09 g (0.05 mmol) of Keggin-structured phosphomolybdic acid (H3PMo 12 O 40 ·13H2O) and dissolve it in 50 ml of distilled water. Then dissolve 1-hexadecyl-3-methylimidazolium chloride (C 16 mimCl) and H3PMo 12 O 40 at a molar ratio of 1:1 to 1:6 in 50 mL of distilled water. Mix the two solutions, and a large amount of yellow-green precipitate will be produced. Stir at room temperature and then filter and dry to obtain a yellow-green solid. The prepared yellow-green solid is labeled as [C 16 mim] x H 3-x PMo 12 O 40 , where x is the molar ratio of [C 16 mim]Cl to H3PMo 12 O 40Molar ratio. Weigh 10 g of 1-butyl-3-methylimidazolium chloride (BmimCl) and add it to a 50 ml round-bottom flask. Then add imidazole (Im) at a molar ratio of 3:1 to 1:3 simultaneously, mix, heat, and stir until a clear and homogeneous solution is formed. Then take it out and place it in a drying oven for standby. The sample is labeled as BmimCl / Im(1:n), where n represents the molar ratio of Im to BmimCl. Weigh 0.05 mmol of 1-hexadecyl-3-methylimidazolium heteropolyacid 16 mim] x H 3-x PMo 12 O 40 Add it to the ionic liquid-based deep eutectic solvent BmimCl / Im (5 ml), stir and dissolve at room temperature until a light blue clear solution is obtained. The prepared solution is labeled as PCDES@xC 16 -nIm, where x is the molar ratio of C 16 mim to H3PMo 12 O 40 , and n is the molar ratio of Im to BmimCl.

[0034] (IV) Preparation method of 0.01 mol / L 1-butyl-3-methylimidazolium heteropolyacid functionalized non-aqueous liquid desulfurizer

[0035] Weigh 0.09 g (0.05 mmol) of Keggin structure phosphomolybdic acid (H3PMo 12 O 40 ·13H2O) and dissolve it in 50 ml of distilled water. Then dissolve 1-butyl-3-methylimidazolium chloride (BmimCl) and H3PMo 12 O 40 at a molar ratio of 1:1 to 1:6 in 50 mL of distilled water. Mix the two solutions, and a large amount of yellow-green precipitate is produced. Stir at room temperature and then filter and dry to obtain a yellow-green solid. The prepared yellow-green solid is labeled as [Bmim] x H 3-x PMo 12 O 40 , where x is the molar ratio of [Bmim]Cl to H3PMo 12 O 40 . Weigh 10 g of 1-butyl-3-methylimidazolium chloride (BmimCl) and add it to a 50 ml round-bottom flask. Then add imidazole (Im) at a molar ratio of 3:1 to 1:3 simultaneously, mix, heat, and stir until a clear and homogeneous solution is formed. Then take it out and place it in a drying oven for standby. The sample is labeled as BmimCl / Im(1:n), where n represents the molar ratio of Im to BmimCl. Weigh 0.05 mmol of 1-butyl-3-methylimidazolium heteropolyacid [Bmim] xH 3-x PMo 12 O 40 Add it to the ionic liquid-based deep eutectic solvent BmimCl / Im (5 ml), stir and dissolve it at room temperature until a light blue clear solution is obtained. The prepared solution is labeled as PCDES@xC4-nIm, where x is the molar ratio of Bmim to H3PMo 12 O 40 and n is the molar ratio of Im to BmimCl.

[0036] (V) Preparation method of 1-benzyl-3-methylimidazole hybrid polyacid functionalized non-aqueous liquid phase desulfurizer with a concentration of 0.01 mol / L

[0037] Weigh 0.09 g (0.05 mmol) of Keggin-structured phosphomolybdic acid (H3PMo 12 O 40 ·13H2O) and dissolve it in 50 ml of distilled water. Then dissolve 1-benzyl-3-methylimidazole chloride (BzmimCl) and H3PMo 12 O 40 in 50 mL of distilled water according to the molar ratio of 1:1 to 1:6. Mix the two solutions, a large amount of yellow-green precipitate will be produced. Stir at room temperature and then filter and dry to obtain a yellow-green solid. The prepared yellow-green solid is labeled as [Bzmim] x H 3-x PMo 12 O 40 , where x is the molar ratio of [Bzmim]Cl to H3PMo 12 O 40 . Weigh 10 g of 1-butyl-3-methylimidazole chloride (BmimCl) and add it to a 50 ml round-bottom flask. Then add imidazole (Im) according to the molar ratio of 3:1 to 1:3 at the same time. Mix, heat and stir until a clear and homogeneous solution is formed. Then take it out and put it in a drying oven for standby. The sample is labeled as BmimCl / Im(1:n), where n represents the molar ratio of Im to BmimCl. Weigh 0.05 mmol of 1-benzyl-3-methylimidazole hybrid polyacid [Bzmim] x H 3-x PMo 12 O 40 Add it to the ionic liquid-based deep eutectic solvent BmimCl / Im (5 ml), stir and dissolve it at room temperature until a light blue clear solution is obtained. The prepared solution is labeled as PCDES@xBz-nIm, where x is the molar ratio of Bzmim to H3PMo 12 O 40 and n is the molar ratio of Im to BmimCl.

[0038] (6) Preparation method of 1,3-didodecyl-2-methylimidazole hybrid polyacid functionalized non-aqueous liquid phase desulfurizer with a concentration of 0.01 mol / L

[0039] Weigh 0.09 g (0.05 mmol) of Keggin structure phosphomolybdic acid (H3PMo 12 O 40 ·13H2O) and dissolve it in 50 ml of distilled water. Then dissolve 1,3-didodecyl-3-methylimidazole chloride (C 12 C 12 mimCl) and H3PMo 12 O 40 in 50 mL of distilled water according to a molar ratio of 1:1 to 1:6. Mix the two solutions, and a large amount of yellow-green precipitate will be produced. Stir at room temperature and then filter and dry to obtain a yellow-green solid. The prepared yellow-green solid is labeled as [C 12 C 12 mim] x H 3-x PMo 12 O 40 , where x is the molar ratio of [C 12 C 12 mim]Cl to H3PMo 12 O 40 . Weigh 10 g of 1-butyl-3-methylimidazole chloride (BmimCl) and add it to a 50 ml round-bottom flask. Then add imidazole (Im) according to a molar ratio of 3:1 to 1:3 at the same time, mix, heat and stir until a clear and homogeneous solution is formed. Then take it out and put it in a drying oven for standby. The sample is labeled as BmimCl / Im(1:n), where n represents the molar ratio of Im to BmimCl. Weigh 0.05 mmol of 1,3-didodecyl-3-methylimidazole hybrid polyacid [C 12 C 12 mim] x H 3-x PMo 12 O 40 and add it to the ionic liquid-based deep eutectic solvent BmimCl / Im (5 ml). Stir and dissolve at room temperature until a light blue clear solution is obtained. The prepared solution is labeled as PCDES@xC 12 C 12 -nIm, where x is the molar ratio of C 12 C 12 mim to H3PMo 12 O 40 , and n is the molar ratio of Im to BmimCl.

[0040] Example 2 Application of 1-dodecyl-3-methylimidazole hybrid polyacid functionalized non-aqueous liquid phase desulfurization technology

[0041] Put 5 mL of 0.01 mol / L dodecyl-3-methylimidazole hybrid polyacid-functionalized non-aqueous liquid-phase desulfurizer PCDES@3C 12 -2Im into the H2S bubbling absorption device at a temperature of 25 °C. Pass H2S gas with a concentration of 1000 mg / m 3 through at a rate of 200 mL / min. Use an H2S gas analyzer to dynamically detect the concentration of H2S gas in the tail gas. The tail gas is absorbed and treated with NaOH solution. As Figure 3 shown in a, PCDES@3C 12 -2Im maintains a hydrogen sulfide removal efficiency of over 80% within 120 minutes.

[0042] Example 3 Application of tetradecyl-3-methylimidazole hybrid polyacid-functionalized non-aqueous liquid-phase desulfurization technology

[0043] Put 5 mL of 0.01 mol / L tetradecyl-3-methylimidazole hybrid polyacid-functionalized non-aqueous liquid-phase desulfurizer PCDES@3C 14 -2Im into the H2S bubbling absorption device at a temperature of 25 °C. Pass H2S gas with a concentration of 1000 mg / m 3 through at a rate of 200 mL / min. Use an H2S gas analyzer to dynamically detect the concentration of H2S gas in the tail gas. The tail gas is absorbed and treated with NaOH solution. As Figure 3 shown in a, it can maintain a hydrogen sulfide removal efficiency of 100% for nearly 150 minutes. And as Figure 3 shown in b, PCDES@3C 14 -2Im can maintain a stable desulfurization efficiency within a wide temperature window range of 25 °C - 200 °C.

[0044] Example 4 Application of hexadecyl-3-methylimidazole hybrid polyacid-functionalized non-aqueous liquid-phase desulfurization technology

[0045] Put 5 mL of 0.01 mol / L hexadecyl-3-methylimidazole hybrid polyacid-functionalized non-aqueous liquid-phase desulfurizer PCDES@3C 16 -2Im into the H2S bubbling absorption device at a temperature of 25 °C. Pass H2S gas with a concentration of 1000 mg / m 3 through at a rate of 200 mL / min. Use an H2S gas analyzer to dynamically detect the concentration of H2S gas in the tail gas. The tail gas is absorbed and treated with NaOH solution. As Figure 3 shown in a, PCDES@3C 16 -2Im maintains a hydrogen sulfide removal efficiency of 100% within 120 minutes.

[0046] Example 5 Application of 1-butyl-3-methylimidazole hybrid polyacid functionalized non-aqueous liquid phase desulfurization technology

[0047] 5 mL of 0.01 mol / L 1-butyl-3-methylimidazole hybrid polyacid functionalized non-aqueous liquid phase desulfurizer PCDES@3C4-2Im was placed in a H2S bubbling absorption device at a temperature of 25 °C. A H2S gas with a concentration of 1000 mg / m 3 was passed through at a rate of 200 mL / min. The concentration of H2S gas in the tail gas was dynamically detected using a H2S gas analyzer. The tail gas was absorbed and treated with NaOH solution. As Figure 3 shown in a, the H2S removal efficiency of PCDES@3C4-2Im remained above 60% within 120 minutes.

[0048] Example 6 Application of 1-benzyl-3-methylimidazole hybrid polyacid functionalized non-aqueous liquid phase desulfurization technology

[0049] 5 mL of 0.01 mol / L 1-benzyl-3-methylimidazole hybrid polyacid functionalized non-aqueous liquid phase desulfurizer PCDES@3Bz-2Im was placed in a H2S bubbling absorption device at a temperature of 25 °C. A H2S gas with a concentration of 1000 mg / m 3 was passed through at a rate of 200 mL / min. The concentration of H2S gas in the tail gas was dynamically detected using a H2S gas analyzer. The tail gas was absorbed and treated with NaOH solution. As Figure 3 shown in a, the H2S removal efficiency of PCDES@3Bz-2Im remained above 40% within 120 minutes.

[0050] Example 7 Application of 1,3-didodecyl-3-methylimidazole hybrid polyacid functionalized non-aqueous liquid phase desulfurization technology

[0051] 5 mL of 0.01 mol / L 1,3-didodecyl-3-methylimidazole hybrid polyacid functionalized non-aqueous liquid phase desulfurizer PCDES@3C 12 C 12 -2Im was placed in a H2S bubbling absorption device at a temperature of 25 °C. A H2S gas with a concentration of 1000 mg / m 3 was passed through at a rate of 200 mL / min. The concentration of H2S gas in the tail gas was dynamically detected using a H2S gas analyzer. The tail gas was absorbed and treated with NaOH solution. As Figure 3 shown in a, the H2S removal efficiency of PCDES@3C 12 C 12 -2Im remained above 90% within 120 minutes.

[0052] Example 8 Regeneration application of 1-tetradecyl-3-methylimidazole hybrid polyacid functionalized non-aqueous liquid phase desulfurizer

[0053] The 1-tetradecyl-3-methylimidazole hybrid polyoxometalate-functionalized non-aqueous liquid-phase desulfurizer PCDES@3C 14 -2Im after desulfurization is completed is added with a 30% H2O2 solution with a mass of 10% of the desulfurizer, and air is bubbled and stirred at 200 mL / min at room temperature for 1 h until the desulfurizer returns to its original light blue clear solution. After drying at 60 °C for 2 h, the regeneration is completed. After regeneration, the desulfurization performance of PCDES@3C 14 -2Im can be completely restored, the hydrogen sulfide removal efficiency remains at 100% within 120 minutes, and it can be recycled multiple times.

[0054] The application of the functionalized non-aqueous liquid-phase desulfurization technology in Comparative Example 1 only adding 1-tetradecyl-3-methylimidazole without adding polyoxometalate

[0055] Weigh 10 g of BmimCl and add it to a 50 ml round-bottom flask, then add Im at a molar ratio of 1:2 at the same time, mix, heat and stir until a clear and homogeneous solution BmimCl / Im(1:2) is formed, and then take it out and put it in a drying oven for standby. Weigh 0.15 mmol C 14 mimCl is added to the ionic liquid-based deep eutectic solvent BmimCl / Im(5 ml), and stirred and dissolved at room temperature until a clear solution is obtained. The prepared solution is labeled as C 14 mimCl + BmimCl / Im(1:2). Place 5 mL of 0.01 mol / L C 14 mimCl + BmimCl / Im(1:2) in a H2S bubbling absorption device at a temperature of 25 °C. Pass a H2S gas with a concentration of 1000 mg / m 3 through at 200 mL / min, and use a H2S gas analyzer to dynamically detect the concentration of H2S gas in the tail gas. The tail gas is absorbed and treated with a NaOH solution. As Figure 4 shown in a, the hydrogen sulfide removal efficiency is reduced to less than 30% within 20 minutes, and the desulfurization performance is much lower than that in Examples 2-8 of the present invention.

[0056] The application of the functionalized non-aqueous liquid-phase desulfurization technology in Comparative Example 2 only adding polyoxometalate without adding 1-tetradecyl-3-methylimidazole

[0057] Weigh 10 g of BmimCl and add it to a 50 ml round-bottom flask, then add Im at a molar ratio of 1:2 at the same time, mix, heat and stir until a clear and homogeneous solution BmimCl / Im(1:2) is formed, and then take it out and put it in a drying oven for standby. Weigh 0.05 mmol H3PMo 12 O 40It was added to the ionic liquid-based deep eutectic solvent BmimCl / Im (5 ml) and stirred at room temperature until dissolved to obtain a clear solution. The prepared solution was labeled as PMo 12 +BmimCl / Im (1:2). 5 mL of 0.01 mol / L PMo 12 +BmimCl / Im (1:2) was placed in a H2S bubbling absorption device at a temperature of 25 °C. Through H2S gas with a concentration of 1000 mg / m 3 at a flow rate of 200 mL / min, the concentration of H2S gas in the tail gas was dynamically detected using a H2S gas analyzer. The tail gas was absorbed and treated with NaOH solution. As Figure 4 shown in a, the desulfurization efficiency of hydrogen sulfide decreased to less than 50% within 80 minutes, and the desulfurization performance was much lower than that of Example 3 in the present invention.

[0058] For Comparative Example 3, a functionalized non-aqueous liquid-phase desulfurization technology that only adds heteropolyacid and does not add 1-tetradecyl-3-methylimidazole was applied

[0059] In this comparative example, 0.5Cu-DES-NFs disclosed in the Chinese invention patent with patent application number 202010802965.8 and publication number CN111888891A was used. Ethylene glycol and choline chloride were placed in a flask according to a molar ratio of 2:1 and heated at 80 °C for 2 hours. After cooling, a clear and transparent liquid was obtained, and 20% ethanolamine by mass was added thereto, and bubbling and mixing were carried out to prepare a deep eutectic solvent. 0.5% nanometer copper powder by mass was weighed and added to the deep eutectic solvent, and magnetic stirring was carried out for 30 minutes, and intermittent ultrasonic treatment was carried out for 1 h to obtain it. As Figure 4 shown in b and Table 1, it could only maintain 100% desulfurization performance for 80 minutes at 25 °C, and the desulfurization performance was lower than that of Example 3 in the present invention.

[0060] Table 1 shows the comparison of desulfurization performance between PCDES@3C 14 -2Im and different non-aqueous liquid-phase desulfurization systems

[0061] Types of desulfurizers Breakthrough time Applicable temperature window Desulfurization efficiency <![CDATA[PCDES@3C 14 -2Im]]> 150 minutes 25-200℃ 100％ 0.5Cu-DES-NFs 80 minutes 25℃ 100％ Fe-5MEA-ILs 40 minutes 80℃ 100％ <![CDATA[NP@SiO2-0.5%]]> 60 minutes 80℃ 100％

[0062] For Comparative Example 4, a functionalized non-aqueous liquid-phase desulfurization technology that only adds heteropolyacid and does not add 1-tetradecyl-3-methylimidazole was applied

[0063] This comparative example uses Fe-5MEA-ILs and NP@SiO2-0.5% disclosed in a Chinese invention patent with a patent application number of 202110237216.X and a publication number of CN113019091A. Add 1% iron chloride by mass ratio and ethanolamine (MEA) with a molar ratio of 1:5 to the BmimCl ionic liquid, and mix well by magnetic stirring, denoted as Fe-5MEA-ILs. Add 0.5% silica nanoparticles by mass ratio to Fe-5MEA-ILs, stir magnetically for 30 minutes, and intermittently sonicate for 1 h to obtain an ionic liquid-based complex iron-silica nanofluid desulfurizer (NP@SiO2-0.5%) with a nanoparticle mass fraction of 0.5%. As Figure 4 As shown in b and Table 1, Fe-5MEA-ILs can only maintain 100% desulfurization performance for 40 minutes at 80 °C, and NP@SiO2-0.5% can only maintain 100% desulfurization performance for 60 minutes at 80 °C. The desulfurization performance is lower than that of Example 3 in the present invention.

[0064] The above embodiments are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described by referring to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than limiting words. Those skilled in the art should understand that based on the technical solution of the present invention, various modifications or deformations that can be made by those skilled in the art without creative efforts are still within the protection scope of the present invention.

Claims

1. A novel "cloverleaf" configuration alkyl long-chain hybrid polyacid functionalized non-aqueous liquid phase desulfurizer suitable for hydrogen sulfide removal, characterized in that: The novel "cloverleaf" structured alkyl long-chain hybrid polyacid functionalized non-aqueous liquid phase desulfurizer is prepared by combining polyoxometalate with alkyl long-chain ionic liquid and then dissolving it in an ionic liquid-based low eutectic solvent, wherein the polyoxometalate is phosphomolybdic acid with different central atoms and coordination atoms; the alkyl long-chain ionic liquid is 1-butyl-3-methylimidazolium chloride or 1-benzyl-3-methylimidazolium chloride or 1,3-didodecyl-2-methylimidazolium chloride or 1-dodecyl-3-methylimidazolium chloride or 1-tetradecyl-3-methylimidazolium chloride or 1-hexadecyl-3-methylimidazolium chloride; and the ionic liquid-based low eutectic solvent is prepared by ionic liquid and azole derivatives.

2. The novel "cloverleaf" configuration alkyl long-chain hybrid polyacid functionalized non-aqueous liquid phase desulfurizer suitable for hydrogen sulfide removal according to claim 1, characterized in that: The ionic liquid is 1-butyl-3-methylimidazole chloride, and the azole derivative is imidazole or 1-methylimidazole or 4-methylimidazole.

3. The application method of the novel "cloverleaf" configuration alkyl long-chain hybrid polyacid functionalized non-aqueous liquid phase desulfurizer suitable for hydrogen sulfide removal according to any one of claims 1-2, characterized in that: Place in a glass bubbling absorber, control the absorption temperature in a constant temperature oil bath to 25-200°C, flow rate to 50-200mL / min, concentration to 500-2000mg / m 3 The hydrogen sulfide gas is absorbed by NaOH solution. The best desulfurizer PCDES@3C 14 -2Im can maintain 100% desulfurization efficiency for nearly 150 minutes and can maintain stable desulfurization efficiency in a wide temperature window range of 25℃-200℃.

4. A method for regenerating a novel "cloverleaf" configuration alkyl long-chain hybrid polyacid functionalized non-aqueous liquid phase desulfurizer suitable for hydrogen sulfide removal according to any one of claims 1-2, characterized in that: The regeneration method is to add 30% H2O2 solution with a mass of 5%-10% of the desulfurizer, and then introduce air bubbling and stirring at a flow rate of 200mL / min. The regeneration temperature is room temperature 25°C and the regeneration time is 1-2h.

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