Preparation method of functional component in surfactant and product thereof

Abstract

The invention discloses a preparation method of a functional component in a surfactant and a product of the functional component, and belongs to the technical field of sulfonation processes. The preparation method comprises the following steps: introducing glycerol and SO3 into a falling-film sulfonation device for sulfonation reaction to obtain a mixture; sequentially carrying out aging and neutralization treatment on the mixture to obtain the functional component used in the surfactant, wherein the molar ratio of glycerol to SO3 is 1.0: (0.8-1). The SO3 falling-film sulfonation process provided by the invention realizes the advantages of high conversion rate, few side reactions, light color and continuous production in the process of preparing sodium glycerosulfate, is suitable for green chemical industry and large-scale production of surfactants, and has good application prospects and popularization values.

Description

Technical Field

[0001] The invention belongs to the technical field of sulfonation processes, and in particular relates to a preparation method for a functional component in a surfactant and a product thereof. Background Art

[0002] Glycerol is a simple triol compound. Due to its excellent hydrophilicity, biocompatibility, and chemical stability, it is widely used in food, cosmetics, and daily chemical products. Its industrial production primarily utilizes natural oils and fats as raw materials. Natural glycerol offers advantages such as a wide range of sources, high yields, and low costs. This aligns with the development trend of green, renewable raw materials, thus giving glycerol a significant role.

[0003] In recent years, the application of glycerol in the field of surfactants has gradually gained attention. In terms of product development, glycerol is expanding from traditional functional materials such as moisturizers and solvents to functional, high-value-added products. Sulfonation modification of glycerol molecules through molecular functionalization can introduce sulfate groups (-OSO3H) while retaining their original hydrophilic backbone, significantly enhancing their polarity and ionicity, giving them strong anionic surface activity, and further expanding their application potential in emulsifiers, detergents, dispersants, etc. In addition, sulfonated glycerol products can be compounded with other types of surfactants, effectively reducing the overall cost of the compounded system while improving system performance, expanding their application space in the fields of green daily chemicals and functional cleaning.

[0004] However, traditional glycerol sulfonation methods, which mostly utilize kettle reactors and use fuming sulfuric acid or sulfur trioxide / solvent systems as the sulfonating agent, suffer from harsh reaction conditions (high temperature and high acidity), complex side reaction products (multiple sulfonated impurities and dehydration byproducts), long sulfonation times, poor selectivity, dark product color, and cumbersome post-processing procedures. These issues severely impact the purity and performance stability of sulfonated glycerol, limiting its widespread application on an industrial scale. Summary of the Invention

[0005] In response to the above technical problems, the present invention proposes a method for preparing a functional component in a surfactant and a product thereof.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] One of the technical solutions of the present invention:

[0008] A method for preparing a functional component for a surfactant comprises the following steps:

[0009] Glycerol and SO3 are introduced into a falling film sulfonation device for sulfonation reaction to obtain a mixture;

[0010] The mixture is subjected to aging and neutralization treatments in sequence to obtain the functional component used in the surfactant;

[0011] Wherein, the molar ratio of glycerol to SO3 is 1.0:0.8~1.

[0012] Beneficial effects: The present invention precisely controls the molar ratio, that is, by limiting the molar ratio of glycerol to SO3 to 1.0:0.8-1, it ensures the full sulfonation of glycerol, reduces the residual unreacted glycerol, and improves the purity of the product (i.e., the content of active sulfate).

[0013] Optionally, the feed temperature of the glycerol is 35-40° C., and the feed speed is 15-20 r / min.

[0014] Optionally, the SO3 gas concentration is 7 vol% to 10 vol%, with the remainder being dry air.

[0015] Beneficial effect: The present invention controls the SO3 concentration to 7% to 10%, which can ensure sufficient reaction activity and avoid the risk of violent side reactions caused by excessively high concentrations.

[0016] Optionally, the conditions during the sulfonation reaction are:

[0017] The sulfonation temperature is 45-50°C; after the raw materials and SO3 are introduced, the reaction products will flow into the collection tank. The acid value of the product in the test tank is tested. When the theoretical acid value is reached, the reaction is confirmed to be complete; then the next stage is entered.

[0018] The theoretical acid value is the acid value that the reaction product should have, calculated based on stoichiometry. The acid value is defined as the number of milligrams of potassium hydroxide (KOH) required to neutralize 1 gram of sample.

[0019] Beneficial effects: The present invention adopts a falling film sulfonation tube, which allows glycerol to form a thin film flow on the tube wall, increases the gas-liquid contact area, significantly improves the mass transfer efficiency, and thus accelerates the sulfonation reaction rate; and by controlling the reaction temperature to maintain at 45-50°C, it not only ensures the gas-liquid mass transfer rate of SO3, but also prevents the occurrence of side reactions caused by excessively high temperature, thereby ensuring the high quality of the product.

[0020] Optionally, the conditions during the aging process are:

[0021] The aging temperature is 80-90°C; the aging time is 60 minutes.

[0022] Beneficial effect: The present invention limits the aging treatment temperature to 80-90°C, which helps to further improve the uniformity and stability of the product and ensure the quality consistency of the final product.

[0023] Optionally, the conditions during the neutralization process are:

[0024] The concentration of NaOH used for neutralization is 20-30 wt.%, the neutralization temperature is 45-50 DEG C, and the pH value after neutralization is controlled at 7-8.

[0025] The second technical solution of the present invention:

[0026] A functional component used in a surfactant is prepared by the above preparation method.

[0027] The third technical solution of the present invention:

[0028] A surfactant used in the fields of green daily chemicals and functional cleaning comprises the above-mentioned functional components.

[0029] Compared with the prior art, the present invention has the following advantages and technical effects:

[0030] The glycerol sulfonation process provided by the present invention achieves an efficient, mild, and controllable preparation process for sodium glycerol sulfate by systematically optimizing reaction conditions. Specifically, the present invention provides an SO3 falling-film sulfonation process that achieves the advantages of high purity, minimal side reactions, light color, and continuous production. It is suitable for green chemical industry and large-scale surfactant production, and has excellent application prospects and promotional value. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] The accompanying drawings, which constitute part of the present invention, are provided to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are provided to explain the present invention and do not constitute an undue limitation of the present invention. In the accompanying drawings:

[0032] Figure 1 This is a diagram of the product prepared in Example 1 of the present invention.

[0033] Figure 2 This is the ESI-MS spectrum of the product prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0034] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0035] It should be understood that the terms described herein are intended only to describe particular embodiments and are not intended to limit the present invention. In addition, for numerical ranges herein, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each smaller range between any intermediate value within a stated value or stated range and any other stated value or intermediate value within the stated range is also encompassed by the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded within the scope.

[0036] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of any conflict with any incorporated document, the contents of this specification shall prevail.

[0037] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the invention. The description and examples are intended to be exemplary only.

[0038] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0039] The present invention discloses a method for preparing a functional component used in a surfactant, comprising the following steps:

[0040] (1) Using glycerol as raw material, a continuous and uniform liquid film is formed in the wall of a falling film sulfonation tube, and sulfurizing agent SO3 gas is introduced to carry out the sulfonation reaction;

[0041] (2) transferring the mixed product obtained in step (1) into a water bath equipped with a magnetic stirring device for aging treatment;

[0042] (3) neutralizing the product after aging treatment in step (2) with NaOH to generate a sodium glycerol sulfate mixture.

[0043] In some optional embodiments, in step (1), the glycerol feed rate is 15 to 20 r / min.

[0044] In some optional embodiments, in step (1), the glycerol feed temperature is 35-40°C.

[0045] In some optional embodiments, in step (1), the temperature of the falling film sulfonation tube is set to 45-50°C.

[0046] In some optional embodiments, in step (1), the SO3 gas concentration is 7% to 10%.

[0047] In some optional embodiments, in step (1), the molar ratio of glycerol to SO3 is 1.0:0.8-1.

[0048] In some optional embodiments, in step (2), the aging temperature is 80-90°C.

[0049] In some optional embodiments, in step (2), the total residence time of the aging reaction system is 60 minutes.

[0050] In some optional embodiments, in step (3), the concentration of NaOH in the neutralization reaction is 20-30%.

[0051] In some optional embodiments, in step (3), the neutralization reaction temperature is controlled at 45-50°C.

[0052] In some optional embodiments, in step (3), the neutralization sequence is to slowly add NaOH to the aged product.

[0053] In some optional embodiments, in step (3), the pH value after neutralization is controlled at 7-8.

[0054] In the glycerol sulfonation process, reaction temperature is a key factor influencing reaction rate and product quality. If the reaction temperature is too low, the gas-liquid mass transfer rate of SO₃ is slowed, the sulfonation reaction rate decreases, and incomplete glycerol sulfonation can occur. If the reaction temperature is too high, side reactions can be exacerbated. As a sulfonating agent, SO₃ concentration has a direct impact on reaction efficiency and product quality. Too low a concentration will result in incomplete glycerol sulfonation, leaving a large amount of unreacted glycerol in the product, affecting performance. Too high a concentration can cause localized SO₃ accumulation, triggering a violent reaction. The molar ratio of glycerol to SO₃ directly influences the degree of sulfonation and the proportion of byproducts. If the SO₃ dosage is too low, some glycerol will not participate in the reaction, affecting conversion. If the molar ratio is too high, excess SO₃ can easily cause side reactions and product degradation.

[0055] To ensure a stable SO3 supply and proper reaction progress, the system is equipped with a gas mass flow meter and temperature sensor for real-time monitoring of the SO3 flow rate and reactor wall temperature. If incomplete SO3 absorption or a darkening of the product color is detected during the reaction, the gas-liquid ratio, SO3 gas concentration, or feed temperature can be adjusted to optimize the reaction.

[0056] In summary, the present invention adopts the above method to set the feed temperature and feed rate of glycerol, and the falling film sulfonation tube to uniformly contact SO3 with glycerol within the set temperature range, regulate the gas concentration of SO3 and the molar ratio of glycerol to SO3, generate a glycerol sulfate mixture, and then perform aging treatment. The product is neutralized with NaOH solution to obtain a sodium glycerol sulfate mixture.

[0057] All raw materials used in the present invention were purchased commercially. Glycerol was industrial grade and sourced from Taiyuan Fuyuxin Chemical Co., Ltd.; sodium hydroxide was analytical grade and sourced from Tianjin Kemiou Chemical Reagent Co., Ltd.; and a falling film sulfonation unit was purchased from the China Daily Chemical Industry Research Institute, model FJEE.

[0058] The technical solution of the present invention is further illustrated by the following examples. The content of sulfate ester salt and inorganic sulfate in the products of the following examples was tested, and the testing method was as follows:

[0059] The analytical method for sulfate esters in a mixture comprises the following steps:

[0060] (1) Weigh the sample, add 0.5 mol / L sulfuric acid, install a condenser and heat for 60 min;

[0061] (2) Add a few drops of phenolphthalein and titrate with NaOH standard solution until the end point shows color.

[0062] The method for determining the content of inorganic sulfate in the mixture is based on GB / T 6366-2012 and includes the following steps:

[0063] (1) Weigh the sample, dissolve it in water to volume, and then add dithizone solution; if the solution turns green, gradually add NaOH until red appears, and then add HNO3 dropwise until green appears;

[0064] (2) Add ammonium dichloroacetate buffer and acetone and shake well to mix;

[0065] Titrate with standard lead nitrate solution until the green color disappears, turns into dark red and remains stable for 15 seconds, which is the end point.

[0066] Example 1

[0067] A method for preparing a functional component for a surfactant comprises the following steps:

[0068] Preheat 500g of glycerol to 36°C, pass it into a falling film sulfonation tube at a flow rate of 15.5r / min and cover the tube wall with glycerol. Set the parameters so that the molar ratio of glycerol to SO3 is 1.0:0.8, the SO3 concentration is controlled at 7% (volume concentration, the same below), and the reaction temperature is maintained at 45°C. The obtained glycerol sulfate mixture is transferred to a water bath with a magnetic stirring device and aged at 80°C for 60min. Finally, 20% NaOH is gradually added dropwise to the treated product at a neutralization temperature of 45°C until the pH value of the solution stabilizes at 7-8.

[0069] After testing: the inorganic sulfate content in the product is 5.26%, and the sulfate ester content is 25.39%.

[0070] Figure 1 This is a picture of the product prepared in Example 1 of the present invention. It can be seen from the picture that the product is light in color and transparent.

[0071] Figure 2 This is the ESI-MS spectrum of the product prepared in Example 1 of the present invention; Figure 2 As shown, in negative ion mode, the main characteristic ion peak was detected at m / z = 170.9954, corresponding to the [M-Na]- ion of sodium monoglycerol sulfate (C3H7O6SNa, molecular weight 194.14), with a theoretical value of m / z = 171.1501. These results indicate that the target compound, sodium monoglycerol sulfate, was generated in the reaction product.

[0072] Example 2

[0073] A method for preparing a functional component for a surfactant comprises the following steps:

[0074] Preheat 500g of glycerol to 37°C, pass it into a falling film sulfonation tube at a flow rate of 16r / min and cover the tube wall with glycerol. Set the parameters so that the molar ratio of glycerol to SO3 is 1.0:0.9, the SO3 concentration is controlled at 8%, and the reaction temperature is maintained at 46°C. The obtained glycerol sulfate mixture is transferred to a water bath with a magnetic stirring device and aged at 85°C for 60min. Finally, 25% NaOH is gradually added dropwise to the treated product at a neutralization temperature of 46°C until the pH value of the solution stabilizes at 7-8.

[0075] After testing: the inorganic sulfate content in the product is 5.14%, and the sulfate ester content is 25.19%.

[0076] Example 3

[0077] A method for preparing a functional component for a surfactant comprises the following steps:

[0078] Preheat 500g of glycerol to 35°C and introduce it into a falling-film sulfonation tube at a flow rate of 16.5 rpm until the glycerol covers the entire tube wall. The reaction parameters were set to a glycerol to SO₃ molar ratio of 1.0:1.0, a SO₃ concentration of 9%, and a reaction temperature of 47°C. The resulting glycerol sulfate mixture was transferred to a water bath equipped with a magnetic stirrer and aged at 90°C for 60 minutes. Finally, 30% NaOH was gradually added dropwise to the treated product at a neutralization temperature of 47°C until the solution stabilized at a pH of 7-8.

[0079] After testing: the inorganic sulfate content in the product is 5.22%, and the sulfate ester content is 25.27%.

[0080] Comparative Example 1

[0081] The only difference from Example 1 is that the SO3 gas concentration is increased to 11%.

[0082] After testing: the inorganic sulfate content in the product is 38.26%, and the sulfate ester content is 12.39%.

[0083] Comparative Example 2

[0084] The difference from Example 2 is that the molar ratio of the raw material to SO3 is replaced with 1.0:2.0.

[0085] The increase in the molar ratio leads to uncontrollable reaction temperature, excessive sulfonation in the tube, and the formation of charred matter.

[0086] After testing: the inorganic sulfate content in the product is 39.16%, and the sulfate ester content is 10.69%.

[0087] Comparative Example 3

[0088] The difference from Example 3 is that the sulfonation reaction temperature is increased to 70°C.

[0089] As the reaction temperature increases, the glycerol sulfate content decreases, affecting the yield and purity of the target product.

[0090] After testing: the inorganic sulfate content in the product is 40.02%, and the sulfate ester content is 10.08%.

[0091] Comparative Example 4

[0092] 250g of glycerol was sulfated in a constant temperature water bath with a magnetic stirring device at a reaction temperature of 45°C. 50% fuming sulfuric acid (i.e., sulfuric acid solution of sulfur trioxide) was used as the vulcanizing agent. Fuming sulfuric acid was added dropwise while stirring. The amount of fuming sulfuric acid was 5ml.

[0093] Glycerin will carbonize, resulting in dark brown or tar-like deposits.

[0094] After testing: the inorganic sulfate content in the product is 39.66%, and the sulfate ester content is 11.75%.

[0095] Summary: The present invention provides a sulfonation method for glycerol, which adopts SO3 and glycerol in a falling film sulfonation device. The process conditions are mild and controllable, with high purity. It can be compounded with other surfactants to optimize performance and reduce costs. It is suitable for green chemical industry and large-scale surfactant production, and has good application prospects and promotion value.

[0096] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the present invention should be included in the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection of the claims.

Claims

1. A method for preparing a functional component for a surfactant, characterized in that: The following steps are involved: Glycerol and SO3 are introduced into a falling film sulfonation device for sulfonation reaction to obtain a mixture; The mixture is subjected to aging and neutralization treatments in sequence to obtain the functional component used in the surfactant; Wherein, the molar ratio of glycerol to SO3 is 1.0:0.8~1.

2. The method for preparing a functional component for a surfactant according to claim 1, wherein: The feeding temperature of the glycerol is 35-40° C., and the feeding speed is 15-20 r / min.

3. The method for preparing a functional component for a surfactant according to claim 1, wherein: The SO3 concentration is 7 vol% to 10 vol%.

4. The method for preparing a functional component for a surfactant according to claim 1, wherein: The conditions during the sulfonation reaction are: The sulfonation temperature is 45-50°C.

5. The method for preparing a functional component for a surfactant according to claim 1, wherein: The conditions during the aging process are: The aging temperature is 80-90°C; the aging time is 60 minutes.

6. The method for preparing a functional component for a surfactant according to claim 1, characterized in that: The conditions in the neutralization process are: The neutralization temperature is 45-50°C, and the pH value after neutralization is controlled at 7-8.

7. A functional component for a surfactant, characterized in that: The invention is prepared by the preparation method according to any one of claims 1 to 6.

8. A surfactant for daily chemical or functional cleaning, characterized in that: The invention comprises the functional component according to claim 7.

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