Synthesis method and application of diselenide coupled gemini sodium sulfonate compound

Abstract

The invention provides a synthesis method of a diselenide coupled gemini sodium sulfonate compound and acid-base induced recovery and regeneration recycling of the diselenide coupled gemini sodium sulfonate compound. The obtained diselenide coupled gemini sodium sulfonate compound is good in water solubility, high in surface activity and good in emulsifying and solubilizing capacity, acid-base induced recovery and regeneration cyclic utilization reaction conditions of the diselenide coupled gemini sodium sulfonate compound established by the method are mild, controllability is good, the yield is not lower than 99.5%, and the method is suitable for industrial production. The recovery rate of the surfactant in the wastewater obtained by washing the oil-containing sand by using the diselenide coupled gemini sodium sulfonate compound aqueous solution obtained by the invention is not less than 96.7%, the recovery rate of oil is not less than 98.3%, and the chemical oxygen demand of the residual wastewater treated by activated carbon and anion exchange resin is not more than 31.2 mg O2 / L.

Description

Technical Field

[0001] The invention relates to a synthesis method of a sodium gemini sulfonate compound and its acid-base induced recovery and regeneration recycling, in particular to a method for synthesizing a sodium sulfonate surfactant compound by coupling with diselenide and its acid-base induced recovery and regeneration recycling, belonging to the technical field of sustainable fine organic chemicals. Background Art

[0002] In recent years, the switch control of surfactants has attracted widespread attention from chemists, which has led to various types of switch surfactants becoming a research hotspot in the field of sustainable fine organic chemical technology. Gemini surfactants are a type of fine chemicals with good water solubility, hard water resistance and surface activity, but they also bring a problem: it is extremely difficult to recover this type of gemini surfactant from the aqueous solution after use. To solve this problem, the present invention synthesizes a diselenide-coupled sodium gemini sulfonate compound using a diselenide group as a connecting structure, and the product is a water-soluble solid at room temperature with excellent surface activity; due to its unique diselenide connecting structure characteristics, the diselenide bond can be oxidatively broken and reductively connected under the induction of alkali and acid, respectively, so that the water-soluble sodium gemini sulfonate compound can be reversibly converted into a water-soluble monosodium selenide sulfonate compound, thereby achieving high-efficiency recovery and regeneration and recycling of the diselenide-coupled sodium gemini sulfonate compound. There have been reports of a gemini sodium cysteine ​​compound with a disulfide bond as a connecting structure (Journal of Colloid and Interface Science, 2008, 321, 227-234). However, the molecular structure and chemical properties of the compound are essentially different from the diselenide coupled gemini sodium sulfonate compound described in the present invention. The most important difference is that the disulfide bond oxidation and reduction reported in the literature are respectively carried out by hydrogen peroxide and dithiothreitol as an oxidant and a reducing agent. In fact, oxygen in the air can also break the disulfide bond, while the breaking of the diselenide connecting structure described in the present invention must be achieved by iodine as an oxidant under the induction of alkali. The oxidation process is extremely controllable, and oxygen in the air cannot achieve the oxidative breaking of the diselenide bond. Similarly, the reduction process is achieved by using sodium iodide obtained by the above iodine reduction as a reducing agent under the induction of acid. The reduction process is also well controllable, and any reducing agent other than sodium iodide cannot reduce and generate a diselenide bond linking structure. In addition, the above document does not involve the content of recovering surfactants from aqueous solutions. The beneficial effects brought by the present invention are that, in addition to the good controllability of the alkali-induced oxidative breakage and acid-induced reduction formation process of the diselenide connection structure, the diselenide coupled sodium geminisulfonate compound obtained by the present invention is used to prepare a washing liquid, which is used to treat the soil contaminated by hydrophobic organic matter to obtain a washing waste liquid, and then the diselenide connection structure is broken by alkali-induced oxidative breakage to convert the water-soluble diselenide coupled sodium geminisulfonate compound into a monosodium selenide sulfonate that is insoluble in water and in common organic solvents, and can be recovered from the washing aqueous waste liquid and emulsion at a ratio of not less than 96.7%, and then the diselenide connection structure is produced by acid-induced reduction to achieve the regeneration of the diselenide coupled sodium geminisulfonate compound, and the regeneration ratio is not less than 99%. The structural formula of the diselenide coupled sodium geminisulfonate compound is as follows: Summary of the invention

[0003] The purpose of the present invention is to provide a synthesis method of a diselenide coupled gemini sulfonate sodium compound and its acid-base induced recovery and regeneration recycling utilization in view of the current shortage of recovery of switch gemini surfactants.

[0004] A method for synthesizing a diselenide-coupled sodium geminisulfonate compound, wherein 2-octyltetrahydrofuran is first reacted with a mixture of sodium sulfite and sodium bisulfite to obtain sodium 3-hydroxyundecylsulfonate, then sodium 3-hydroxyundecylsulfonate is reacted with phosphorus tribromide to obtain sodium 3-bromondecylsulfonate, and finally sodium 3-bromondecylsulfonate is reacted with Se2Na2 to obtain a diselenide-coupled sodium geminisulfonate compound. Reaction formulas (1) to (3) are shown below: .

[0005] Furthermore, the temperature for the reaction of 2-octyltetrahydrofuran with the mixture of sodium sulfite and sodium bisulfite is room temperature, the reaction medium is deionized water, the molar ratio of sodium sulfite to sodium bisulfite is 1:1, the molar ratio of 2-octyltetrahydrofuran to the mixture of sodium sulfite and sodium bisulfite is 1:1.1-1.5, and the reaction time is 1-3 hours.

[0006] Furthermore, the temperature of the reaction of sodium 3-hydroxyundecyl sulfonate and phosphorus tribromide is 0 to 15 degrees, the reaction medium is dichloromethane, the molar ratio of sodium 3-hydroxyundecyl sulfonate to phosphorus tribromide is 1:0.3 to 0.5, and the reaction time is 0.5 to 2.5 hours.

[0007] Further, the temperature of the reaction of 3-bromondecyl sodium sulfonate and Se2Na2 is 0 to 25 degrees, the reaction medium is deionized water, the molar ratio of 3-bromondecyl sodium sulfonate to Se2Na2 is 1:0.51 to 0.55, and the reaction time is 1.5 to 5.5 hours. The above-synthesized product is detected by two-phase titration, indicating that it is a diselenide-coupled gemini sodium sulfonate compound with a purity of ≥98.1%, and the yield of the diselenide-coupled gemini sodium sulfonate compound is not less than 47.6%.

[0008] A diselenide coupled sodium geminisulfonate compound is acid-base induced recovery and regeneration and recycling. First, the diselenide connection structure is oxidatively broken by base-induced cleavage to obtain 3-sodium selenite-undecyl sodium sulfonate. 3-sodium selenite-undecyl sodium sulfonate is insoluble in water and common organic solvents. Then, 3-sodium selenite-undecyl sodium sulfonate is reduced to diselenide coupled sodium geminisulfonate compound under acid induction, so as to realize the recovery and recycling of diselenide coupled sodium geminisulfonate compound. Its reaction formulas (4) to (5) are shown as follows: Furthermore, the reaction temperature for alkali-induced oxidative cleavage of the diselenide linking structure to obtain 3-sodium selenite-undecyl sodium sulfonate is room temperature, the reaction medium is deionized water, the alkali is sodium carbonate, iodine is the oxidant, the molar ratio of 3-sodium selenite-undecyl sodium sulfonate to iodine is 1:3-3.2, the reaction time is 0.5-1 hour, and during the reaction, sodium carbonate is used to control the pH of the reaction system to be greater than or equal to 7.5, and the yield of 3-sodium selenite-undecyl sodium sulfonate is not less than 96.7%.

[0009] Furthermore, the sodium 3-selenite-undecylsulfonate is poorly soluble in common organic solvents including saturated alkanes, benzene, toluene, xylene, chlorobenzene and nitrobenzene.

[0010] Furthermore, the reaction temperature for reducing 3-sodium selenite-undecyl sodium sulfonate to a diselenide-coupled sodium geminisulfonate compound under acid induction is room temperature, the reaction medium is deionized water, the acid is hydrochloric acid, sodium iodide is a reducing agent, the molar ratio of 3-sodium selenite-undecyl sodium sulfonate to sodium iodide is 1:3-3.5, the reaction time is 0.5-1 hour, and during the reaction, hydrochloric acid is used to control the pH of the reaction system to be less than or equal to 6.5, and the yield of the diselenide-coupled sodium geminisulfonate compound is not less than 99.5%.

[0011] The method of the present invention has the following advantages over the prior art: 1. The diselenide-coupled sodium gemisyl sulfonate compound obtained by the present invention has good water solubility, high surface activity and good emulsification and solubilization ability; 2. The acid-base induced recovery and regeneration recycling reaction conditions of the diselenide coupled sodium gemisolate compound established by the present invention are mild, controllable, and the yield is not less than 99.5%.

[0012] 3. The recovery rate of surfactant in wastewater obtained by washing oil-containing sand with the aqueous solution of diselenide coupled sodium geminisulfonate compound obtained by the present invention is not less than 96.7%, and the recovery rate of oil is not less than 98.3%. The chemical oxygen demand of the remaining wastewater after treatment with activated carbon and anion exchange resin does not exceed 31.2 mg O2 / L. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the diselenide coupled sodium gemisolate compound synthesized in Example 1 of the present invention.

[0014] Figure 2 This is the selenium nuclear magnetic resonance spectrum of the diselenide-coupled sodium gemisolate compound synthesized in Example 1 of the present invention. DETAILED DESCRIPTION

[0015] The process for synthesizing the diselenide coupled sodium gemisolate compound of the present invention and its acid-base induced recovery and regeneration recycling are further described below by means of specific examples.

[0016] Example 1: Synthesis of Diselenide-Coupled Sodium Gemini Sulfonate 27.6 g of 2-octyltetrahydrofuran (0.15 mol) was added to a 500 mL round-bottom flask, and 24.75 g of a mixture of sodium sulfite and sodium bisulfite (0.165 mol) was added, and then 100 mL of deionized water was added and stirred at 25 degrees Celsius for 1 hour. Filter under normal pressure, and then wash the filter cake repeatedly with a saturated saline solution, and finally wash with deionized water until there is no chloride ion in the washing liquid after silver nitrate test. After drying the filter cake in an oven at 105 degrees Celsius, the intermediate product (light yellow solid) sodium 3-hydroxyundecane sulfonate can be obtained, and the yield is 91.3%.

[0017] Take 14.4 g of sodium 3-hydroxyundecanesulfonate (0.05 mol) and add it to a 250 mL round-bottom flask, then add 110 mL of dichloromethane, and then take 4.07 g of phosphorus tribromide (0.015 mol) and dissolve it in 50 mL of dichloromethane in advance, and add the phosphorus tribromide-dichloromethane solution dropwise at 0 degrees Celsius while stirring, and react for 0.5 hours after the addition is complete. After the solvent dichloromethane is removed under reduced pressure, the residue is repeatedly washed with a saturated saline solution, and finally washed with deionized water until there is no chloride ion in the washing liquid after silver nitrate test, and after drying in a vacuum drying oven at 65 degrees Celsius, it is recrystallized three times with anhydrous methanol, and after removing methanol, the intermediate product (white solid) sodium 3-bromondecanesulfonate can be obtained, and the yield is 49.6%.

[0018] Add 1.04 g of Se2Na2 (5.1 mmol) to a 250 mL round-bottom flask, then add 50 mL of an aqueous solution pre-dissolved with sodium borohydride, and then add 3.52 g of sodium 3-bromondecylsulfonate (0.01 mol), and stir at 0-5 degrees Celsius for 1.5 hours. After removing water under reduced pressure, the residue is first washed three times with an aqueous sodium bisulfite solution, dried in a vacuum oven at 65 degrees Celsius, and then desalted by hot dissolution with anhydrous methanol. After removing methanol, the product (white solid) diselenide coupled geminisulfonate sodium is obtained, with a yield of 71.1%. The purity of the two-phase titration analysis is about 98.8%.

[0019] The hydrogen nuclear magnetic resonance data and analysis of the product diselenide coupled with sodium gemisyl sulfonate: Figure 1It can be seen that the signal of methyl group H is near 0.88 ppm, the signal of methylene group and methine group H is near 1.25-1.32 ppm, the signal of methylene group H is near 1.72 ppm, and the signal of methylene group H is near 3.03 ppm, which is not close to the sulfonic acid group. The integral ratio of the above signal areas is 3:17.1:1.9:2, which is very close to the theoretical value of the separation structure of diselenide coupled sodium geminisulfonate. Figure 2 It can be seen that the signal near 155.4 ppm is selenium. The H NMR and Se NMR spectra of the products are shown in Figure 1 and Figure 2 .

[0020] Example 2: Synthesis of Diselenide-Coupled Sodium Gemini Sulfonate 9.2 g of 2-octyltetrahydrofuran (0.05 mol) was added to a 250 mL round-bottom flask, and 11.25 g of a mixture of sodium sulfite and sodium bisulfite (0.075 mol) was added, and then 100 mL of deionized water was added and stirred at 20 degrees Celsius for 3 hours. Filter under normal pressure, and then wash the filter cake repeatedly with a saturated saline solution, and finally wash with deionized water until there is no chloride ion in the washing liquid after silver nitrate test. After drying the filter cake in an oven at 105 degrees Celsius, the intermediate product (white solid) sodium 3-hydroxyundecane sulfonate can be obtained, and the yield is 92.7%.

[0021] Take 8.64 g of sodium 3-hydroxyundecanesulfonate (0.03 mol) and add it to a 250 mL round-bottom flask, then add 75 mL of dichloromethane, and then take 4.07 g of phosphorus tribromide (0.015 mol) and dissolve it in 80 mL of dichloromethane in advance, control the temperature in the range of 0-5 degrees Celsius, add phosphorus tribromide-dichloromethane solution dropwise while stirring, and react for 2.5 hours after the addition is complete. After the solvent dichloromethane is removed under reduced pressure, the residue is repeatedly washed with a saturated saline solution, and finally washed with deionized water until there is no chloride ion in the washing liquid after silver nitrate test, and after drying in a vacuum drying oven at 68 degrees Celsius, it is recrystallized three times with anhydrous methanol, and after removing methanol, the intermediate product (light yellow solid) sodium 3-bromondecanesulfonate can be obtained, and its yield is 49.1%.

[0022] Add 2.02 g of Se2Na2 (9.9 mmol) to a 250 mL round-bottom flask, then add 75 mL of an aqueous solution pre-dissolved with sodium borohydride, and then add 6.32 g of sodium 3-bromondecylsulfonate (0.018 mol), and stir the reaction at a temperature of 5-15 degrees Celsius for 5.5 hours. After removing water under reduced pressure, the residue was first washed three times with an aqueous sodium bisulfite solution, dried in a vacuum oven at 55 degrees Celsius, and then desalted by hot dissolution with anhydrous methanol. After removing methanol, the product (white solid) diselenide coupled geminisulfonate sodium was obtained, with a yield of 77.3%. The purity of the two-phase titration analysis was about 98.7%.

[0023] The H NMR and Se NMR spectra of the product were respectively the same as those obtained in Example 1. Figure 1 and Figure 2 same.

[0024] Example 3: Synthesis of Diselenide-Coupled Sodium Gemini Sulfonate 184 g of 2-octyltetrahydrofuran (1 mol) was added to a 2.5 L glass reactor, and 195 g of a mixture of sodium sulfite and sodium bisulfite (1.3 mol) was added, and then 1 L of deionized water was added and stirred at 25 degrees Celsius for 2.1 hours. The filter cake was repeatedly washed with a saturated salt solution using a 3-layer 200-mesh polypropylene fiber filter cloth under normal pressure, and finally washed with deionized water until there was no chloride ion in the washing liquid after silver nitrate test. After the filter cake was dried in an oven at 105 degrees Celsius, the intermediate product (white solid) sodium 3-hydroxyundecyl sulfonate was obtained, and the yield was 82.7%.

[0025] Take 288 grams of sodium 3-hydroxyundecanesulfonate (1 mol) and add it to a 2.5L glass reactor, then add 1.2L of dichloromethane, and then take 108.4 grams of phosphorus tribromide (0.4 mol) and dissolve it in 1.8L of dichloromethane in advance, control the temperature within the range of 5-15 degrees Celsius, add phosphorus tribromide-dichloromethane solution dropwise while stirring, and react for 1.8 hours after the addition is complete. After the solvent dichloromethane is removed under reduced pressure, the residue is repeatedly washed with a saturated saline solution, and finally washed with deionized water until there is no chloride ion in the washing liquid after silver nitrate test, and after drying in a vacuum drying oven at 65 degrees Celsius, recrystallize three times with anhydrous methanol, and remove methanol to obtain the intermediate product (light yellow solid) sodium 3-bromondecanesulfonate, with a yield of 36.1%.

[0026] Add 106.1 g of Se2Na2 (0.52 mol) to a 2.5 L glass reactor, then add 1.75 L of an aqueous solution pre-dissolved with sodium borohydride, and then add 351 g of sodium 3-bromondecylsulfonate (1 mol), and stir the reaction at a temperature of 15-25 degrees Celsius for 4.5 hours. After removing water under reduced pressure, the residue is first washed three times with an aqueous sodium bisulfite solution, dried in a vacuum oven at 55 degrees Celsius, and then desalted by hot dissolution with anhydrous methanol. After removing methanol, the product (white solid) diselenide coupled geminisulfonate sodium is obtained, with a yield of 47.6%. The purity of the two-phase titration analysis is about 98.1%.

[0027] The H NMR and Se NMR spectra of the product were respectively the same as those obtained in Example 1. Figure 1 and Figure 2 same.

[0028] Example 4: Recovery of Diselenide-Coupled Sodium Gemini Sulfonate In this embodiment, the washing waste liquid obtained by washing quartz sand contaminated by tetradecane with the micellar aqueous solution of diselenide-coupled sodium geminisulfonate is used as an example, and diselenide-coupled sodium geminisulfonate is recovered in the form of 3-sodium selenite-undecyl sodium sulfonate. In a 2.5L stainless steel reactor, 1.5L of a 1.1% diselenide-coupled sodium geminisulfonate aqueous solution is added, and then 0.5 kg of an oil sand mixture with a mass ratio of tetradecane to quartz sand of 0.5:1 is added, and stirred at room temperature for 2.5 hours at a stirring speed of 100 rpm. The washing waste liquid is discharged from the discharge port of the reactor, and the sand is rinsed with a small amount of deionized water. The washing waste water is merged into the previously obtained waste liquid, and the total waste liquid mass is about 1.8 kg. When sodium carbonate is added to the waste liquid to adjust the pH to 8.5, 17.95 grams of elemental iodine are added, and the reaction is stirred at room temperature for 1 hour. During the reaction, sodium carbonate is added as needed to ensure that the pH of the system is not less than 7.5. Then, the upper oil phase and the lower water phase were separated after standing for stratification. The upper oil phase was clear and transparent. The recovery rate of tetradecane in the oil phase was 99.1% after weighing. There was solid precipitation in the lower water phase. The precipitation was separated from the water by filtration, dehydrated and dried, and weighed. The recovery rate of 3-sodium selenite-undecylsulfonate was 96.7%. The wastewater obtained by filtration was slightly turbid. After being treated with ion exchange resin and activated carbon, its chemical oxygen demand was determined to be 31.2 mg O2 / L.

[0029] Example 5: Recovery of Diselenide-Coupled Sodium Gemini Sulfonate In this embodiment, the washing waste liquid obtained by washing quartz sand contaminated by toluene with the micellar aqueous solution of diselenide-coupled twin sodium sulfonate is used as an example, and diselenide-coupled twin sodium sulfonate is recovered in the form of 3-sodium selenite-undecyl sodium sulfonate. In a 100 mL beaker, 50 mL of a 1% diselenide-coupled twin sodium sulfonate aqueous solution is added, and then 50 g of an oil sand mixture with a mass ratio of toluene to quartz sand of 0.5:1 is added, and stirred at room temperature for 2 hours at a stirring speed of 60 rpm. Pour out the washing waste liquid, rinse the sand with a small amount of deionized water, and merge the washing waste water into the previously obtained waste liquid, with a total waste liquid mass of about 81 grams. When sodium carbonate is added to the waste liquid to adjust the pH to 8.0, 0.54 grams of elemental iodine is added, and the reaction is stirred at room temperature for 0.5 hours. During the reaction, sodium carbonate is added as needed to ensure that the pH of the system is not less than 7.5. Then, the upper oil phase and the lower water phase were separated by standing. The upper oil phase was clear and transparent. The recovery rate of toluene in the oil phase was 98.3% by weight. There was solid precipitation in the lower water phase. The precipitation was separated from the water by filtration, dehydrated and dried, and weighed. The recovery rate of 3-sodium selenite-undecylsulfonate was 97.9%. The wastewater obtained by filtration was slightly turbid. After treatment with ion exchange resin and activated carbon, its chemical oxygen demand was determined to be 27.6 mg O2 / L.

[0030] Example 6: Regeneration of diselenide coupled sodium gemisolate In this example, 3-sodium selenite-undecyl sodium sulfonate obtained in Example 4 and Example 5 was used as the starting material to investigate its effect in the alkali-induced sodium iodide reduction regeneration to form diselenide-coupled sodium geminisulfonate. Take 0.4 g of 3-sodium selenite-undecyl sodium sulfonate obtained in Example 4 and put it into a 50 mL beaker, then add 15 mL of deionized water, and then add 0.52 g of sodium iodide. Adjust the pH of the system with dilute hydrochloric acid and keep the pH not more than 6.5, stir at room temperature for 1 hour, and stir at 50 rpm. After the reaction is completed, remove the solvent water under reduced pressure, and then wash the residue repeatedly with a small amount of ethyl acetate until the washing liquid is checked for the typical starch blueing phenomenon. The obtained residue is then desalted with anhydrous methanol and dried, and the yield of diselenide-coupled sodium geminisulfonate is calculated by weighing to be 99.9%. The purity of the two-phase titration analysis is 99.8%. Its hydrogen nuclear magnetic resonance spectrum and selenium nuclear magnetic resonance spectrum are the same as the results obtained in Example 1 Figure 1 and Figure 2 Exactly the same.

[0031] Take 0.4 g of 3-sodium selenite-undecyl sodium sulfonate obtained in Example 5 and put it in a 50 mL beaker, then add 15 mL of deionized water, and then add 0.44 g of sodium iodide, adjust the pH of the system with dilute hydrochloric acid and keep the pH not more than 6.5, stir at room temperature for 0.5 hours, and stir at 50 rpm. After the reaction is completed, remove the solvent water under reduced pressure, and then wash the residue repeatedly with a small amount of ethyl acetate until the washing liquid is tested for the typical starch blueing phenomenon. The obtained residue is then desalted with anhydrous methanol and dried, and the yield of diselenide coupled gemini sodium sulfonate is calculated by weighing to be 99.9%. The purity of the two-phase titration analysis is 99.9%. Its hydrogen nuclear magnetic resonance spectrum and selenium nuclear magnetic resonance spectrum are the same as the results obtained in Example 1 Figure 1 and Figure 2 Exactly the same.

[0032] Example 7: Recycling of regenerated diselenide coupled sodium gemisyl sulfonate In this example, the regenerated diselenide coupled sodium geminisulfonate obtained in Example 6 was used as the starting material to investigate the effect of washing quartz sand contaminated by chlorobenzene with its micellar aqueous solution, and the effect of recovering diselenide coupled sodium geminisulfonate in the form of 3-sodium selenite-undecyl sodium sulfonate, and the chemical oxygen demand value of the wastewater obtained after recovering chlorobenzene and 3-sodium selenite-undecyl sodium sulfonate respectively after ion exchange resin and activated carbon treatment. In a 100 mL beaker, 50 mL of a 1% regenerated diselenide coupled sodium geminisulfonate aqueous solution was added, and then 25 g of an oil sand mixture with a mass ratio of chlorobenzene to quartz sand of 0.5:1 was added, and stirred at room temperature for 2 hours at a stirring speed of 60 rpm. The washing waste liquid was poured out, and the sand was rinsed with a small amount of deionized water, and the washing waste water was merged into the previously obtained waste liquid, with a total waste liquid mass of about 60.8 grams. Sodium carbonate was added to the waste liquid to adjust the pH to 8.0, and then 0.54 g of elemental iodine was added. The reaction was stirred at room temperature for 0.5 hours. During the reaction, sodium carbonate was added as needed to ensure that the pH of the system was not less than 7.5. Then the stratification was allowed to stand, and the upper oil phase and the lower water phase were separated. The upper oil phase was clear and transparent, and the recovery rate of chlorobenzene in the oil phase was 98.9% by weighing. There was a solid precipitate in the lower water phase. The precipitate was separated from the water by filtration, dehydrated and dried, and weighed. The recovery rate of 3-sodium selenite-undecylsulfonate was calculated to be 98.5%. The filtered wastewater was colorless and transparent. After treatment with ion exchange resin and activated carbon, its chemical oxygen demand was determined to be 18.3 mg O2 / L.

[0033] The above embodiments are only used to illustrate the present invention and are not intended to limit the technical solutions described in the present invention. Any person familiar with the present invention can easily change or replace the components after the present invention is disclosed, and all technical improvements that do not depart from the present invention should be included in the scope of the claims of the present invention.

Claims

1. A method for synthesizing a diselenide-coupled sodium gemisolate compound, characterized in that: First, 2-octyltetrahydrofuran is reacted with a mixture of sodium sulfite and sodium bisulfite to obtain sodium 3-hydroxyundecyl sulfonate, then sodium 3-hydroxyundecyl sulfonate is reacted with phosphorus tribromide to obtain sodium 3-bromodecaneyl sulfonate, and finally sodium 3-bromodecaneyl sulfonate is reacted with Se2Na2 to obtain a diselenide-coupled sodium gemini sulfonate compound.

2. The method for synthesizing the diselenide coupled sodium gemisolate compound according to claim 1, characterized in that: The structural formula of the diselenide coupled sodium gemisolate compound is as follows: 。 3. The method for synthesizing the diselenide coupled sodium gemisolate compound according to claim 1, characterized in that: The temperature for the reaction of 2-octyltetrahydrofuran with the mixture of sodium sulfite and sodium bisulfite is room temperature, the reaction medium is deionized water, the molar ratio of sodium sulfite to sodium bisulfite is 1:1, the molar ratio of 2-octyltetrahydrofuran to the mixture of sodium sulfite and sodium bisulfite is 1:1.1-1.5, and the reaction time is 1-3 hours.

4. The method for synthesizing the diselenide-coupled sodium gemisolate compound according to claim 1, characterized in that: The temperature of the reaction of sodium 3-hydroxyundecyl sulfonate and phosphorus tribromide is 0 degrees Celsius to 15 degrees Celsius, the reaction medium is dichloromethane, the molar ratio of sodium 3-hydroxyundecyl sulfonate to phosphorus tribromide is 1:0.3-0.5, and the reaction time is 0.5-2.5 hours.

5. The method for synthesizing the diselenide coupled sodium gemisolate compound according to claim 1, characterized in that: The temperature of the reaction of sodium 3-bromodecanesulfonate and Se2Na2 is 0 degrees Celsius to 25 degrees Celsius, the reaction medium is deionized water, the molar ratio of sodium 3-bromodecanesulfonate to Se2Na2 is 1:0.51-0.55, and the reaction time is 1.5-5.5 hours.

6. A method for acid-base induced recovery and regeneration of a diselenide-coupled sodium gemisolate compound, characterized in that: First, alkali is used to induce oxidative cleavage of the diselenide linking structure to obtain 3-sodium selenite-undecylsulfonate, which is difficult to dissolve in water and common organic solvents. Then, under acid induction, 3-sodium selenite-undecylsulfonate is reduced to a diselenide-coupled sodium geminisulfonate compound, thereby realizing the recovery and recycling of the diselenide-coupled sodium geminisulfonate compound.

7. The acid-base induced recovery and regeneration cycle of the diselenide coupled sodium gemisolate compound according to claim 6, characterized in that: The reaction temperature for obtaining sodium 3-selenite-undecyl sodium sulfonate by oxidative cleavage of the base-induced diselenide linking structure is room temperature, the reaction medium is deionized water, the base is sodium carbonate, iodine is an oxidant, the molar ratio of sodium 3-selenite-undecyl sodium sulfonate to iodine is 1:3-3.2, the reaction time is 0.5-1 hour, and during the reaction, sodium carbonate is used to control the pH of the reaction system to be greater than or equal to 7.5, and the yield of sodium 3-selenite-undecyl sodium sulfonate is not less than 96.7%.

8. The acid-base induced recovery and regeneration cycle of the diselenide coupled sodium gemisolate compound according to claim 6, characterized in that: The sodium 3-selenite-undecylsulfonate is poorly soluble in common organic solvents including saturated alkanes, benzene, toluene, xylene, chlorobenzene and nitrobenzene.

9. The acid-base induced recovery and regeneration cycle of the diselenide coupled sodium gemisolate compound according to claim 6, characterized in that: The reaction temperature for reducing 3-sodium selenite-undecyl sodium sulfonate to a diselenide-coupled sodium geminisulfonate compound under acid induction is room temperature, the reaction medium is deionized water, the acid is hydrochloric acid, sodium iodide is a reducing agent, the molar ratio of 3-sodium selenite-undecyl sodium sulfonate to sodium iodide is 1:3-3.5, the reaction time is 0.5-1 hour, hydrochloric acid is used to control the pH of the reaction system to be less than or equal to 6.5 during the reaction, and the yield of the diselenide-coupled sodium geminisulfonate compound is not less than 99.5%.

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