A process for the treatment of 1,3-propane sultone distillation still bottoms

Abstract

The present application relates to the technical field of chemical production, and particularly relates to a 1,3-propane sulfone lactone distillation kettle residue treatment process.The present application comprises the following steps: (1) adding water to 1,3-propane sulfone lactone distillation residue liquid, refluxing and hydrolyzing to obtain a hydrolyzed solution; (2) performing precision filtration on the hydrolyzed solution to remove insoluble substances and obtain a filtrate; (3) performing ion exchange on the filtrate by using an anion exchange resin, so that 3-hydroxy propane sulfonic acid is adsorbed by the anion exchange resin; (4) using a strong alkali solution to elute the anion exchange resin to obtain a 3-hydroxy propane sulfonic acid sodium solution.The process of the present application only uses water, an anion exchange resin and a strong alkali solution, does not need to use a low flash point solvent or a strong acid / strong alkali to directly react, and only comprises four steps of hydrolyzing, filtering, anion exchange resin adsorbing and alkali washing desorbing, so that the process flow is simplified, the process time is short, the operation is simple, the safety is high, and the purity of the obtained product reaches more than 97%.

Description

Technical Field

[0001] This invention relates to the field of chemical production technology, specifically to a process for treating residues from the distillation vessel of 1,3-propanesulfonate lactone. Background Technology

[0002] 1,3-Propanesulfonate lactone (1,3-PS) is a key sulfonylating agent and organic synthesis intermediate, widely used in pharmaceutical chemistry (such as the synthesis of antiviral drug intermediates), electroplating additives (to improve coating uniformity), and high-performance inks (to regulate resin dispersibility). Its sulfonate lactone ring structure endows it with high reactivity, but at the same time, it requires stringent purity requirements (≥99%); even trace impurities can lead to failure in downstream applications.

[0003] Currently, 1,3-PS is synthesized industrially from 3-hydroxypropanesulfonic acid via high-temperature dehydration esterification (180–220℃), and purified by multi-stage vacuum distillation. This process has significant drawbacks: 1. Residual liquid treatment problem: During distillation, approximately 15–25% of the raw material is converted into a black, viscous residual liquid, mainly containing polysulfonates (40–60%), tarred carbonaceous impurities (20–30%), and unreacted 1,3-PS (10–15%). Due to its sulfur-containing organic matter (total sulfur content ≥5%) and complex components, the residual liquid is classified as hazardous waste (HW06 category), with outsourced treatment costs reaching 8,000–12,000 RMB / ton. 2. Resource waste: The residual 1,3-PS in the residual liquid leads to an 8–12% decrease in the overall product yield, resulting in annual losses exceeding 10 million RMB for companies with an annual production capacity of tens of thousands of tons.

[0004] The yield of distillation purification is limited by equipment design: to avoid carbonization of the material, the distillation vessel must retain at least 10% liquid phase residue to ensure fluidity, which further exacerbates the loss of 1,3-PS. In addition, high-temperature and long-term operation can easily trigger side reactions, such as the condensation of sulfonates to form oligomers that are difficult to separate (n=3–5), which further reduces the recyclability of the residue.

[0005] Patent CN107954975 A discloses a method for obtaining liquid 3-hydroxypropanesulfonic acid from the distillation residue of 1,3-propanesulfonate lactone through alkaline hydrolysis, concentration, and acidification. This method fails to consider the separation of highly water-soluble or non-alkaline-hydrolyzable substances from the product, resulting in low purity of the obtained liquid 3-hydroxypropanesulfonic acid. Furthermore, this method introduces alcohols such as ethanol and acidic hazardous chemicals such as hydrochloric acid and sulfuric acid, increasing the process hazard.

[0006] Therefore, it is urgent to develop a method for treating distillation residues that is safe, environmentally friendly, low-cost, and has a high recovery rate of 1,3-propanesulfonate lactone. Summary of the Invention

[0007] The purpose of this invention is to overcome the shortcomings of the prior art and provide a process for treating the residue of 1,3-propanesulfonate distillation kettle. This process is characterized by simple steps, short processing time, and high safety. The obtained sodium 3-hydroxypropanesulfonate solution can be directly recycled for the preparation of 1,3-propanesulfonate, which can reduce costs and the amount of hazardous waste.

[0008] This invention provides a process for treating residues from the distillation vessel of 1,3-propanesulfonate lactone, comprising the following steps:

[0009] (1) Add water to the distillation residue of 1,3-propanesulfonate lactone, reflux and hydrolyze to obtain the hydrolyzed solution;

[0010] (2) The hydrolyzed solution is precisely filtered to remove insoluble substances and obtain filtrate;

[0011] (3) Anion exchange resin is used to perform ion exchange on the filtrate, so that 3-hydroxypropanesulfonic acid is adsorbed by the anion exchange resin.

[0012] (4) The anion exchange resin was eluted with a strong alkaline solution to obtain a sodium 3-hydroxypropanesulfonate solution.

[0013] The reactions involved in this invention are shown in equations (I) to (III) as follows:

[0014]

[0015] In some embodiments of the present invention, the water in step (1) is pure water.

[0016] In some embodiments of the present invention, the mass of water added in step (1) is 1.0 to 10 times the mass of 1,3-propanesulfonate lactone in the distillation residue, preferably 3.0 to 5.0 times.

[0017] In some embodiments of the present invention, the hydrolysis temperature in step (1) is 60-100°C and the hydrolysis time is 1-5 hours; preferably, the hydrolysis temperature is 90°C and the hydrolysis time is 3 hours.

[0018] In some embodiments of the present invention, the filtration accuracy of the precision filter in step (2) is 0.1 to 50 micrometers, preferably 5 to 10 micrometers.

[0019] In some embodiments of the present invention, the anion exchange resin in step (3) is selected from any one of strong basic anion exchange resin and weak basic anion exchange resin, preferably a strong basic anion exchange resin.

[0020] In some embodiments of the present invention, the anion exchange resin described in step (3) needs to be cleaned before use, and the cleaning includes alkaline washing and water washing.

[0021] In some embodiments of the present invention, the temperature of the anion exchange in step (3) is 10-50°C and the time is 1-6 hours; preferably, the temperature of the anion exchange is 30°C and the time is 4 hours.

[0022] In some embodiments of the present invention, the strong alkaline solution in step (4) is an aqueous solution of an alkali metal hydroxide, wherein the alkali metal hydroxide is selected from sodium hydroxide, potassium hydroxide or lithium hydroxide.

[0023] In some embodiments of the present invention, the mass fraction of the strong alkali solution in step (4) is 3% to 10%, preferably 5% to 7%.

[0024] In some embodiments of the present invention, the elution temperature in step (4) is 10-60°C and the elution time is 2-6 hours. Preferably, the elution temperature is 30°C and the elution time is 4 hours.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] 1. The 1,3-propanesulfonate lactone distillation kettle residue treatment process provided by this invention recovers the residual liquid from hazardous waste treatment, obtains usable products, reduces costs, and reduces the amount of hazardous waste, thus having good environmental and economic benefits.

[0027] 2. The 1,3-propanesulfonate lactone distillation residue treatment process provided by this invention does not require the use of flammable or corrosive reagents, has high process safety, and only requires hydrolysis, filtration, anion exchange resin adsorption, and alkaline washing desorption. The process steps are simple, the processing time is short, and it is suitable for industrial promotion. Since no other solvents are used as auxiliary materials, the obtained pure sodium 3-hydroxypropanesulfonate solution can be directly recycled for the preparation of 1,3-propanesulfonate lactone, and the anion exchange resin can be recycled. Compared with the acid-base treatment process, the amount of hazardous waste is reduced by more than 80%, and the overall treatment cost is reduced by about 30%.

[0028] 3. The 1,3-propanesulfonate distillation residue treatment process provided by this invention separates the 3-hydroxypropanesulfonate ion from other impurities through ion adsorption, resulting in a product purity of over 97% and a recovery rate of over 90%. Both the product purity and recovery rate are significantly improved compared to the acid-base treatment process. Attached Figure Description

[0029] Figure 1 This is a schematic diagram of the process for treating the residue from the distillation vessel of 1,3-propanesulfonate lactone according to an embodiment of the present invention. Detailed Implementation

[0030] The following details a process for treating residues from the distillation vessel of 1,3-propanesulfonate lactone according to the present invention.

[0031] This invention provides a process for treating residues from the distillation vessel of 1,3-propanesulfonate lactone, comprising the following steps:

[0032] (1) Add water to the distillation residue of 1,3-propanesulfonate lactone, reflux and hydrolyze to obtain the hydrolyzed solution;

[0033] (2) The hydrolyzed solution is precisely filtered to remove insoluble substances and obtain filtrate;

[0034] (3) Anion exchange resin is used to perform ion exchange on the filtrate, so that 3-hydroxypropanesulfonic acid is adsorbed by the anion exchange resin.

[0035] (4) The anion exchange resin was eluted with a strong alkaline solution to obtain a sodium 3-hydroxypropanesulfonate solution.

[0036] The process of this invention uses only water, anion exchange resin, and strong alkaline solution, without the need for low flash point solvents or direct reactions of strong acids / bases. It consists of only four steps: hydrolysis, filtration, anion exchange resin adsorption, and alkaline washing desorption. The process is simplified, and through selective adsorption of the resin, 3-hydroxypropanesulfonate can be accurately separated, avoiding salt contamination introduced by acid-base neutralization in traditional acid-base processes and reducing raw material waste.

[0037] In some embodiments of the present invention, the water in step (1) is pure water. By adding pure water for reflux hydrolysis, compared with the acid-base method, the neutralization process is reduced, the operation process is simplified, the process safety is improved, and the generation of by-products is reduced, thereby improving the purity of the product.

[0038] In some embodiments of the present invention, the mass of water added in step (1) is 1.0 to 10 times the mass of 1,3-propanesulfonic acid lactone in the distillation residue, which can be 1.0 to 2.0 times, 2.0 to 3.0 times, 3.0 to 4.0 times, 4.0 to 5.0 times, 5.0 to 6.0 times, 6.0 to 7.0 times, 7.0 to 8.0 times, 8.0 to 9.0 times, or 9.0 to 10 times, preferably 3.0 to 5.0 times. An appropriate excess of water can make the hydrolysis product propanesulfonic acid dissolve better in the solution, which is convenient for subsequent separation and purification operations.

[0039] In some embodiments of the present invention, the hydrolysis temperature in step (1) is 60-100°C, which can be 60-70°C, 70-80°C, 80-90°C, or 90-100°C, and the hydrolysis time is 1-5h, which can be 1-2h, 2-3h, 3-4h, or 4-5h; preferably, the hydrolysis temperature is 90°C and the hydrolysis time is 3h.

[0040] In some embodiments of the present invention, the filtration accuracy of the precision filter in step (2) is 0.1 to 50 micrometers, which can be 0.1 to 0.5 micrometers, 0.5 to 1 micrometer, 1 to 5 micrometers, 5 to 10 micrometers, 10 to 20 micrometers, 20 to 30 micrometers, 30 to 40 micrometers, or 40 to 50 micrometers, preferably 5 to 10 micrometers.

[0041] In some embodiments of the present invention, the anion exchange resin in step (3) is selected from any one of strong basic anion exchange resin and weak basic anion exchange resin, preferably a strong basic anion exchange resin, such as Mitsubishi DIAION SA10A or DuPont AmberLite HPR550 OH.

[0042] In some embodiments of the present invention, the anion exchange resin described in step (3) needs to be cleaned before use. The cleaning includes alkaline washing and water washing. Alkaline washing can remove impurity ions and organic matter. Then, water washing is performed to remove residual alkaline solution and further remove impurities.

[0043] In some embodiments of the present invention, the temperature of the anion exchange in step (3) is 10-50°C, which can be 10-20°C, 20-30°C, 30-40°C, or 40-50°C, and the time is 1-6h, which can be 1-2h, 2-3h, 3-4h, 4-5h, or 5-6h; preferably, the temperature of the anion exchange is 30°C and the time is 4h.

[0044] In some embodiments of the present invention, the strong alkaline solution in step (4) is an aqueous solution of an alkali metal hydroxide, wherein the alkali metal hydroxide is selected from sodium hydroxide, potassium hydroxide or lithium hydroxide.

[0045] In some embodiments of the present invention, the mass fraction of the strong alkali solution in step (4) is 3% to 10%, which can be 3% to 4%, 4% to 5%, 5% to 6%, 6% to 7%, 7% to 8%, 8% to 9%, or 9% to 10%, preferably 5% to 7%.

[0046] In some embodiments of the present invention, the elution temperature in step (4) is 10-60°C, which can be 10-20°C, 20-30°C, 30-40°C, 40-50°C, or 50-60°C, and the elution time is 2-6 hours, which can be 2-3 hours, 3-4 hours, 4-5 hours, or 5-6 hours; preferably, the elution temperature is 30°C and the elution time is 4 hours.

[0047] The technical solution of the present invention is illustrated below through specific examples. It should be understood that the one or more method steps mentioned in the present invention do not preclude the existence of other method steps before or after the combined steps, or the insertion of other method steps between these explicitly mentioned steps; it should also be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, unless otherwise stated, the numbering of each method step is merely a convenient tool for identifying each method step, and not for limiting the order of the method steps or defining the scope of the present invention. Changes or adjustments to their relative relationships, without substantially altering the technical content, should also be considered within the scope of the present invention.

[0048] Example 1

[0049] The process for treating the residue from the distillation vessel of 1,3-propanesulfonate lactone in this embodiment is as follows: Figure 1 As shown, it includes the following steps:

[0050] (1) Add 200g of black 1,3-propanesulfonate lactone distillation residue (1,3-propanesulfonate lactone content is 45.3%) to a 500ml 3-necked flask, then add 66.80g of pure water, heat to an internal temperature of 90℃ and reflux for 3h to obtain the hydrolyzed solution.

[0051] (2) The hydrolyzed solution was filtered through 5-micron filter paper to obtain a black liquid without solid impurities;

[0052] (3) The black liquid was circulated and adsorbed for 4 hours between a tower and a flask containing 0.5 kg of DuPont AmberLite HPR550 OH strong base anion exchange resin via a peristaltic pump. After the adsorption was completed, the content of 3-hydroxypropane sulfonate in the remaining liquid was measured to be 1.1%. The resin was washed twice with pure water and no impurities were washed out.

[0053] (4) Using a peristaltic pump, 1000g of a solution containing 3.5% sodium hydroxide was circulated to the resin for desorption for 4 hours to obtain 1082.2g of liquid with a 3-hydroxypropanesulfonate content of 7.8% (equivalent to a recovery rate of 93.17%) and a purity of 98.3%.

[0054] Example 2

[0055] The process for treating the residue from the distillation vessel of 1,3-propanesulfonate lactone in this embodiment is as follows: Figure 1 As shown, it includes the following steps:

[0056] (1) Add 503g of black 1,3-propanesulfonate lactone distillation residue (1,3-propanesulfonate lactone content is 44.6%) to a 1000ml 3-necked flask, then add 232g of pure water, heat to an internal temperature of 80℃ and reflux for 3h to obtain the hydrolyzed solution.

[0057] (2) The hydrolyzed solution was filtered through 5-micron filter paper to obtain a black liquid without solid impurities;

[0058] (3) The black liquid was circulated and adsorbed for 4 hours between a tower and a flask containing 0.9 kg of DuPont AmberLite HPR550 OH strong base anion exchange resin via a peristaltic pump. After the adsorption was completed, the content of 3-hydroxypropane sulfonate in the remaining liquid was measured to be 1.3%. The resin was washed twice with pure water and no impurities were washed out.

[0059] (4) Using a peristaltic pump, 2000g of a solution containing 5.2% sodium hydroxide was circulated to the resin for desorption for 3h to obtain 2203.1g of liquid with a 3-hydroxypropanesulfonate content of 9.4% (equivalent to a recovery rate of 92.32%) and a purity of 98.8%.

[0060] Example 3

[0061] The process for treating the residue from the distillation vessel of 1,3-propanesulfonate lactone in this embodiment is as follows: Figure 1 As shown, it includes the following steps:

[0062] (1) Add 206g of black 1,3-propanesulfonate lactone distillation residue (1,3-propanesulfonate lactone content is 46.1%) to a 500ml 3-necked flask, then add 68.34g of pure water, heat to an internal temperature of 90℃ and reflux for 3h to obtain the hydrolyzed solution.

[0063] (2) The hydrolyzed solution was filtered through 5-micron filter paper to obtain a black liquid without solid impurities;

[0064] (3) The black liquid was circulated and adsorbed for 4 hours between a tower and a flask containing 1.2 kg of DuPont AmberLite HPR550 OH strong base anion exchange resin via a peristaltic pump. After the adsorption was completed, the content of 3-hydroxypropane sulfonate in the remaining liquid was measured to be 1.4%. The resin was washed twice with pure water and no impurities were washed out.

[0065] (4) Using a peristaltic pump, 500g of a solution containing 7.1% sodium hydroxide was circulated to the resin for desorption for 4 hours to obtain 584.4g of liquid with a 3-hydroxypropanesulfonate content of 14.82% (equivalent to a recovery rate of 90.21%) and a purity of 97.6%.

[0066] Comparative Example 1

[0067] The residue treatment of 1,3-propanesulfonate lactone distillation vessel in this comparative example adopted an acid-base method, including the following steps:

[0068] (1) Add 201.2g of anhydrous ethanol to a 500ml three-necked flask, then add 4.01g of deionized water, stir well, then add 21.01g of potassium hydroxide solid, heat the solution in a water bath and stir at 60℃ until the solid is completely dissolved.

[0069] (2) While stirring, add 102.57g of the distillation residue of 1,3-propanesulfonate lactone (1,3-propanesulfonate lactone content is 44.9%) dropwise using a dropping funnel at the temperature. After the addition is completed, raise the temperature to 75℃ and reflux for 10h.

[0070] (3) After reflux, the liquid was transferred to a 500ml single-necked bottle using a sand filter to filter out some undissolved substances. Then, it was placed on a rotary evaporator for vacuum concentration to obtain a mixture containing potassium 3-hydroxypropanesulfonate, potassium hydroxide, and impurities.

[0071] (4) Slowly add 37.2g of 37% hydrochloric acid solution to the mixture (the temperature is controlled below 30℃ during the addition). After the addition is completed, stir for 2 hours and let stand. Use a rotary evaporator at 70℃ to evaporate the excess water under reduced pressure to obtain 56.01g of a mixture containing 3-hydroxypropanesulfonic acid (content is 80.46%). The content and purity were tested and the yield was 85.3% and the purity was 83.5%.

[0072] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.

Claims

1. A 1,3-propane sultone still pot residue treatment process characterized by, The method comprises the following steps: (1) adding water to the distillation residue of 1,3-propane sultone, refluxing and hydrolyzing to obtain a hydrolyzed solution; the hydrolysis temperature is 60-100 ℃, the hydrolysis time is 1-5 h, and the mass of the added water is 1.0-10 times the mass of 1,3-propane sultone in the distillation residue; (2) performing precision filtration on the hydrolyzed solution to remove insoluble substances and obtain a filtrate; the precision filtration has a filtration accuracy of 0.1-50 microns; (3) performing ion exchange on the filtrate by using an anion exchange resin, so that 3-hydroxypropane sulfonic acid is adsorbed by the anion exchange resin; (4) eluting the anion exchange resin by using a strong alkali solution to obtain a 3-hydroxypropane sulfonic acid sodium solution; the mass fraction of the strong alkali solution is 3%-10%.

2. The 1,3-propane sultone still pot residue treatment process of claim 1, wherein, In step (1), the water is pure water; and / or the mass of the added water is 3.0-5.0 times the mass of 1,3-propane sultone in the distillation residue.

3. The 1,3-propane sultone still pot residue treatment process of claim 1, wherein, In step (1), the hydrolysis temperature is 90 ℃, and the hydrolysis time is 3 h.

4. The 1,3-propane sultone still pot residue treatment process of claim 1, wherein, In step (2), the precision filtration has a filtration accuracy of 5-10 microns.

5. The 1,3-propane sultone still pot residue treatment process of claim 1, wherein, In step (3), the anion exchange resin is selected from any one of a strong basic anion exchange resin and a weak basic anion exchange resin.

6. The 1,3-propane sultone still pot residue treatment process of claim 1, wherein, In step (3), the anion exchange resin needs to be cleaned before use, and the cleaning comprises alkali cleaning and water cleaning.

7. The 1,3-propane sultone still pot residue treatment process of claim 1, wherein, In step (3), the ion exchange temperature is 10-50 ℃, and the ion exchange time is 1-6 h.

8. The 1,3-propane sultone still pot residue treatment process of claim 1, wherein, In step (4), the strong alkali solution is an aqueous alkali metal hydroxide solution, and the alkali metal hydroxide is selected from sodium hydroxide, potassium hydroxide or lithium hydroxide.

9. The 1,3-propane sultone still pot residue treatment process of claim 1, wherein, In step (4), the mass fraction of the strong alkali solution is 5-7%.

10. The 1,3-propane sultone still pot residue treatment process of claim 1, wherein, In step (4), the elution temperature is 10-60 ℃, and the elution time is 2-6 h.

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