Production method of alkyl sulfate triethanolamine salt product

Abstract

The present invention aims to solve the problem that the preservative effect of the preservative in aqueous alkyl sulfate triethanolamine salt is not long-lasting. The technical solution is: a method for producing an alkyl sulfate triethanolamine salt surfactant product, comprising: (1) obtaining an alkyl sulfate ester; (2) neutralizing the alkyl sulfate ester with an aqueous triethanolamine solution to obtain an alkyl sulfate triethanolamine salt intermediate material I; and (3) mixing the alkyl sulfate triethanolamine salt intermediate material I with the following components: (i) ketone, (ii) hydrogen peroxide, and (iii) EDTA or its salt; and the method can be used in the production of the alkyl sulfate triethanolamine salt surfactant product.

Description

[0001] This application is a divisional application of the patent application with application number 202210797818.5, application date July 6, 2022, and invention name “Method for producing alkyl sulfate triethanolamine salt products”. Background Art

[0002] Triethanolamine alkyl sulfate is produced by the sequential sulfation of fatty alcohols with SO₃ followed by neutralization with triethanolamine. In the toiletries industry, triethanolamine alkyl sulfate is widely used in various shampoos and bath products, serving as an excellent base active ingredient. It is particularly well-suited for use in high-quality, concentrated, low-viscosity shampoos. Its excellent solubility properties can effectively lower the product's cloud point, thereby improving formulation quality.

[0003] During storage and transportation, especially in hot summer weather, aqueous alkyl sulfate triethanolamine salt liquid or paste products are prone to bacterial growth and may even cause serious product spoilage, affecting product quality. To overcome the problem of bacterial growth, antibacterial biocides or preservatives are usually required.

[0004] Kasong (also known as Kasong) is a well-known antimicrobial biocide widely used as a preservative in various fields. Kasong's active ingredients are isothiazolinone derivatives, including 5-chloro-2-methyl-4-isothiazolin-3-one (CIT) and 2-methyl-4-isothiazolin-3-one (MIT). However, the preservative effect of Kasong in aqueous triethanolamine alkyl sulfate is not long-lasting. Summary of the Invention

[0005] One of the technical problems to be solved by the present invention is the defect that the antiseptic effect of the preservative in aqueous alkyl sulfate triethanolamine salt is not long-lasting enough. A new production method of alkyl sulfate triethanolamine salt product is provided. The method has the characteristic that the antiseptic effect of the produced alkyl sulfate triethanolamine salt product is longer-lasting.

[0006] In order to solve one of the above technical problems, the technical solution of the present invention is as follows:

[0007] The production method of the alkyl sulfate triethanolamine salt surfactant product comprises:

[0008] (1) Obtaining alkyl sulfonates;

[0009] (2) neutralizing the alkyl sulfate with a triethanolamine aqueous solution to obtain an alkyl sulfate triethanolamine salt intermediate material I;

[0010] (3) mixing the alkyl sulfate triethanolamine salt intermediate material I with Kaisong and Kaisong auxiliary agent;

[0011] The Kaisong auxiliary agent includes hydrogen peroxide.

[0012] We found that when Kaisong was used as an intermediate for the inhibition of bacteria and corruption in triethanolamine alkyl sulfate salts, it was very unstable. However, when hydrogen peroxide was used as a Kaisong adjuvant along with Kaisong in the intermediate, its stability was greatly improved. We compared Kaisong and found that when Kaisong was used as an intermediate for the inhibition of bacteria and corruption in sodium alkyl sulfate, it did not exhibit such instability. We believe that an unknown side reaction may have occurred during the neutralization of the alkyl sulfate with the triethanolamine aqueous solution, affecting Kaisong's stability. The use of the Kaisong adjuvant reduced or even eliminated the negative impact of this unknown side reaction on Kaisong's stability.

[0013] In the above technical solution, as long as the step of neutralizing the alkyl sulfate with an aqueous triethanolamine solution is adopted, the source and method of obtaining the alkyl sulfate are not particularly limited. For example, but not limited to, the alkyl sulfate is obtained by using a fatty alcohol as an organic raw material and performing a sulfation process with SO3.

[0014] As a non-limiting example of the process conditions for obtaining alkyl sulfate by using fatty alcohol as an organic raw material and performing sulfation with SO3, the SO3 is used in the form of being diluted with a gaseous diluent.

[0015] As a non-limiting example of the process conditions for obtaining alkyl sulfate by using fatty alcohol as an organic raw material and performing sulfation with SO3, the gaseous diluent is air or nitrogen.

[0016] As a non-limiting example of the process conditions for obtaining alkyl sulfate esters by using fatty alcohol as the organic raw material and sulfation with SO3, by weight, SO3 accounts for 0.1 to 10% of the total weight of SO3 and the gaseous diluent. As a further non-limiting example, SO3 accounts for 0.5%, 1%, 1.5%, 2.0%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, etc. of the total weight of SO3 and the gaseous diluent.

[0017] As a non-limiting example of the process conditions for obtaining alkyl sulfate by using fatty alcohol as an organic raw material and performing sulfation with SO3, the molar ratio of SO3 to the organic material is 1.02 to 1.03.

[0018] As a non-limiting example of the process conditions for obtaining alkyl sulfate by sulfation using fatty alcohol as an organic raw material with SO3, the temperature of the sulfation reaction is 35-45°C.

[0019] In the above technical solution, the alkyl group is preferably a C8-C18 alkyl group, such as but not limited to a C9 alkyl group, a C10 alkyl group, a C11 alkyl group, a C12 alkyl group, a C13 alkyl group, a C14 alkyl group, a C15 alkyl group, a C16 alkyl group, a C17 alkyl group, etc. For comparison purposes only, the embodiments and comparative examples are all C12-14 alkyl groups.

[0020] In the above technical solution, the pH of the intermediate material I in step (2) is preferably 6.0-8.0. For example, but not limited to, the pH is 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, etc., and more preferably the pH is 6.0-7.5.

[0021] In the above technical solution, the neutralization temperature in step (2) is preferably 55-65° C., for example but not limited to 56° C., 57° C., 58° C., 59° C., 60° C., 61° C., 62° C., 63° C., 64° C., etc.

[0022] In the above technical solution, the weight concentration of triethanolamine in the triethanolamine solution in step (2) is preferably 10-23%, for example but not limited to 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23% and the like.

[0023] In the above technical solution, the mixing temperature in step (3) is not particularly limited, and those skilled in the art can reasonably select it without inventive effort. For example, the mixing temperature in step (3) can be 10 to 45° C., such as but not limited to 15° C., 20° C., 25° C., 30° C., 35° C., 40° C., etc.

[0024] In the above technical solution, the mixing time in step (3) is preferably at least 30 minutes. For example, but not limited to, the mixing time is 45 minutes, 60 minutes, 75 minutes, 90 minutes, 105 minutes, 120 minutes, 135 minutes, 150 minutes, 165 minutes, 180 minutes, 195 minutes, 210 minutes, 225 minutes, 240 minutes, 270 minutes, 300 minutes, 330 minutes, 360 minutes, etc.

[0025] In the above technical solution, there is no particular limitation on the mixing method of the alkyl sulfate triethanolamine salt intermediate material I with the Kaisong and Kaisong auxiliary agent in step (3). For example, the mixing in step (3) can be achieved in the following three ways:

[0026] Method 3.1

[0027] include:

[0028] Step 3.1.1, mixing the intermediate material I of the alkyl sulfate triethanolamine salt with kaison to obtain the intermediate material II;

[0029] Step 3.1.2: Mix the intermediate material II with the Kaisong additive.

[0030] Method 3.2

[0031] Mixing the alkyl sulfate triethanolamine salt intermediate material I, the Kaisong auxiliary agent, and the Kaisong at the same time (for example, adding the Kaisong auxiliary agent and the Kaisong to the alkyl sulfate triethanolamine salt intermediate material I at the same time to mix);

[0032] Method 3.3

[0033] include:

[0034] Step 3.3.1, mixing the intermediate material I of the alkyl sulfate triethanolamine salt with the Kaisong auxiliary agent to obtain the intermediate material II;

[0035] Step 3.3.2: Mix the intermediate material II with Kaisong.

[0036] We found that method 3.3 is significantly better than method 3.2 in improving the stability of the Kaisong, and method 3.2 is also significantly better than method 3.1.

[0037] In the above technical solution, the mixing temperature of step 3.1.1 and step 3.1.2 can independently be 10 to 45°C, for example but not limited to 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, etc.

[0038] In the above technical solution, the mixing time in step 3.1.1 is preferably at least 30 minutes. For example, but not limited to, the mixing time is 45 minutes, 60 minutes, 75 minutes, 90 minutes, 105 minutes, 120 minutes, 135 minutes, 150 minutes, 165 minutes, 180 minutes, 195 minutes, 210 minutes, 225 minutes, 240 minutes, 270 minutes, 300 minutes, 330 minutes, 360 minutes, etc.

[0039] In the above technical solution, there is no limit to the mixing time in step 3.1.2. The longer the mixing time, the more complete the mixing. For example, the mixing time in step 3.1.2 is more than 30 minutes, such as but not limited to 30 minutes, 45 minutes, 60 minutes, 75 minutes, 90 minutes, 105 minutes, 120 minutes, 135 minutes, 150 minutes, 165 minutes, 180 minutes, 195 minutes, 210 minutes, 225 minutes, 240 minutes, 270 minutes, 300 minutes, 330 minutes, 360 minutes, etc.

[0040] In the above technical solution, the mixing temperature of step 3.3.1 and step 3.3.2 can independently be 10 to 45°C, for example but not limited to 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, etc.

[0041] In the above technical solution, the mixing time in step 3.3.1 is preferably at least 30 minutes. For example, but not limited to, the mixing time is 45 minutes, 60 minutes, 75 minutes, 90 minutes, 105 minutes, 120 minutes, 135 minutes, 150 minutes, 165 minutes, 180 minutes, 195 minutes, 210 minutes, 225 minutes, 240 minutes, 270 minutes, 300 minutes, 330 minutes, 360 minutes, etc.

[0042] In the above technical solution, there is no limit to the mixing time in step 3.3.2. The longer the mixing time, the more complete the mixing. For example, the mixing time in step 3.3.2 is more than 30 minutes, such as but not limited to 30 minutes, 45 minutes, 60 minutes, 75 minutes, 90 minutes, 105 minutes, 120 minutes, 135 minutes, 150 minutes, 165 minutes, 180 minutes, 195 minutes, 210 minutes, 225 minutes, 240 minutes, 270 minutes, 300 minutes, 330 minutes, 360 minutes, etc.

[0043] However, we found that when the amount of hydrogen peroxide is higher than a certain value, the chromaticity of the product will be significantly increased, which comprehensively improves the stability of the product without significantly affecting the chromaticity of the product. Preferably, the amount of hydrogen peroxide is calculated as H2O2, accounting for 0-100ppm by weight of the alkyl sulfate triethanolamine salt intermediate material I, for example, but not limited to 1ppm, 2ppm, 3ppm, 4ppm, 5ppm, 6ppm, 7ppm, 8ppm, 9ppm, 10ppm, 11ppm, 12ppm, 13ppm, 14ppm, 15ppm, 16ppm, 17ppm, 18ppm, 19ppm, 20ppm, 21ppm, 22ppm, 23ppm, 24ppm, 25ppm, 26ppm, 27ppm, 28ppm, 29ppm, 35ppm, 40ppm, 50ppm, 60ppm, 70ppm, 80ppm, 90ppm, etc., more preferably 10-100ppm.

[0044] We know that commercially available Kesong products are usually provided in the form of solutions, and the active ingredients are 5-chloro-2-methyl-4-isothiazolin-3-one (abbreviated as CIT) and 2-methyl-4-isothiazolin-3-one (abbreviated as MIT). The molar ratio of CIT to MIT can be 2.5 to 4. The active ingredient content in Kesong products (calculated as a percentage of the total weight of CIT and MIT) has different specifications (as non-limiting examples, such as 1.5%, 2.5%, 14%, etc.), all of which can be used in the present invention and can achieve comparable technical effects. For comparison purposes only, the Kesong used in the specific embodiment of the present invention is a 1.5% solution. In the present invention, the amount of Kesong used is calculated based on the total amount of CIT and MIT.

[0045] It is clear to those skilled in the art that when used for the antibacterial and anti-corruption purposes of the alkyl sulfate triethanolamine salt intermediate material I, the amount of Kaisong is not particularly limited and can be reasonably selected based on factors such as the length of time the product needs to be stored and transported, the storage season, etc., without the need for creative work.

[0046] As a non-limiting example only, the amount of Kaisong can be greater than 0ppm and less than 500ppm of the weight of the fatty alcohol sulfate triethanolamine salt intermediate material I. More specific non-limiting examples of the point value of the dosage can be 2ppm, 4ppm, 6ppm, 8ppm, 10ppm, 12ppm, 14ppm, 16ppm, 18ppm, 20ppm, 25ppm, 30ppm, 35ppm, 40ppm, 45ppm, 50ppm, 55ppm, 60ppm, 65ppm, 70ppm, 75ppm, 80ppm, 85ppm, 90ppm, 95ppm, 100ppm, 150ppm, 200ppm, 250ppm, 300ppm, 350ppm, 400ppm, 450ppm and the like.

[0047] In the above technical solution, when step (3) does not use hydrogen peroxide as the ketone auxiliary agent but uses EDTA or its salt instead, the effect on stabilizing ketone is not very obvious, if any. However, when step (3) uses both hydrogen peroxide and EDTA or its salt as the ketone auxiliary agent, EDTA or its salt significantly enhances the stabilizing effect of hydrogen peroxide on ketone.

[0048] As a non-limiting example, when the Kaisong auxiliary agent includes hydrogen peroxide and EDTA or its salt, EDTA or its salt is calculated as ethylenediaminetetraacetic acid, and the amount used is more than 0% and less than 2% by weight of the alkyl sulfate triethanolamine salt intermediate material I, for example but not limited to 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9% and the like.

[0049] In the above technical solution, when the Kaisong auxiliary agent in step (3) uses both hydrogen peroxide and EDTA or its salt, the mixing mode in step 3.3.1 can be:

[0050] Mode 3.3.1.1

[0051] Step 3.3.1.1.1, mixing the alkyl sulfate triethanolamine salt intermediate material I with hydrogen peroxide to obtain intermediate material Ia;

[0052] Step 3.3.1.1.2: Mix the intermediate material Ia with EDTA or its salt to obtain the intermediate material II.

[0053] Mode 3.3.1.2

[0054] The alkyl sulfate triethanolamine salt intermediate material I is mixed with hydrogen peroxide and EDTA (or its salt) at the same time (for example, hydrogen peroxide and EDTA (or its salt) are added to the alkyl sulfate triethanolamine salt intermediate material I at the same time and mixed) to obtain material II.

[0055] Mode 3.3.1.3

[0056] Step 3.3.1.3.1, mixing the alkyl sulfate triethanolamine salt intermediate material I with EDTA or its salt to obtain intermediate material Ib;

[0057] Step 3.3.1.3.2: Mix the intermediate material Ib with hydrogen peroxide to obtain the intermediate material II.

[0058] We found that mode 3.3.1.3 is significantly better than modes 3.3.1.2 and 3.3.1.1 in improving Kaison stability, while mode 3.3.1.2 is comparable to mode 3.3.1.1.

[0059] In the above technical solution, the mixing temperature of step 3.3.1.1.1 and step 3.3.1.1.2 can independently be 10 to 45°C, for example but not limited to, the mixing temperature of step 3.3.1.1.1 and step 3.3.1.1.2 is 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, etc.

[0060] In the above technical solution, it is preferred that the mixing time of step 3.3.1.1.1 and step 3.3.1.1.2 is independently at least 30 minutes. For example, but not limited to, the mixing time of step 3.3.1.1.1 and step 3.3.1.1.2 is independently 45 minutes, 60 minutes, 75 minutes, 90 minutes, 105 minutes, 120 minutes, 135 minutes, 150 minutes, 165 minutes, 180 minutes, 195 minutes, 210 minutes, 225 minutes, 240 minutes, 270 minutes, 300 minutes, 330 minutes, 360 minutes, etc.

[0061] In the above technical solution, the mixing temperature of step 3.3.1.3.1 and step 3.3.1.3.2 can independently be 10 to 45°C, for example but not limited to, the mixing temperature of step 3.3.1.3.1 and step 3.3.1.3.2 is 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, etc.

[0062] In the above technical solution, it is preferred that the mixing time of step 3.3.1.3.1 and step 3.3.1.3.2 is independently at least 30 minutes. For example, but not limited to, the mixing time of step 3.3.1.3.1 and step 3.3.1.3.2 is independently 45 minutes, 60 minutes, 75 minutes, 90 minutes, 105 minutes, 120 minutes, 135 minutes, 150 minutes, 165 minutes, 180 minutes, 195 minutes, 210 minutes, 225 minutes, 240 minutes, 270 minutes, 300 minutes, 330 minutes, 360 minutes, etc.

[0063] In the above technical solution, the weight content of the anionic active matter of the alkyl sulfate triethanolamine salt in the product is preferably 30-43%, for example but not limited to 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43% and the like.

[0064] The second technical problem to be solved by the present invention is to provide an alkyl sulfate triethanolamine salt surfactant product.

[0065] To solve the second of the above technical problems, the technical solution of the present invention is as follows:

[0066] The alkyl sulfate triethanolamine salt surfactant product is obtained by the production method described in any one of the technical solutions to one of the above technical problems.

[0067] The third technical problem to be solved by the present invention is the application of an alkyl sulfate triethanolamine salt surfactant product as a storage and transportation form of the alkyl sulfate triethanolamine salt surfactant.

[0068] To solve the third of the above technical problems, the technical solution of the present invention is as follows:

[0069] The use of the alkyl sulfate triethanolamine salt surfactant product described in the technical solution of the second technical problem or the product obtained by the production method described in any one of the technical solutions of one of the technical problems as a storage and transportation form of the alkyl sulfate triethanolamine salt surfactant.

[0070] Determination of anionic active matter content in surfactant materials

[0071] In the present invention, the content of anionic active matter in all materials containing alkyl sulfate triethanolamine salt or alkyl sulfate sodium salt is determined according to the standard method (GB / T 5173-2018 Determination of anionic active matter content of surfactant detergents - Direct two-phase titration method).

[0072] pH determination method

[0073] In the present invention, the pH value of the product is measured according to the standard method (GB / T 6368-2008 Determination of pH value of aqueous surfactant solution - Potentiometric method).

[0074] Evaluation method of Kaison stability

[0075] (1) Determination of the content of Kaisong in new products

[0076] (2) 150 g of the new product was placed in a 250 ml glass conical flask, the bottle mouth was sealed with a rubber stopper, and the bottle was placed in a constant temperature box at 40 ± 0.5 ° C for 168 hours. Then the content of Kaisong in the sample after constant temperature treatment was determined.

[0077] (3) Calculation of Kaison loss rate

[0078] The loss rate of Kesong = ((the original amount of Kesong added to the product - the amount of Kesong in the product after constant temperature storage for 168 hours) / the original amount of Kesong added to the product) × 100%.

[0079] Determination of the content of Kaisong:

[0080] This method is suitable for the determination of the content of kaison in surfactants.

[0081] 1. Principle

[0082] After treatment, the samples were separated by high performance liquid chromatography, detected by ultraviolet detector and quantified by external standard method.

[0083] 2. Reagents

[0084] Methanol: HPLC grade

[0085] Kesong standard: 1.5% Kesong solution from Rohm and Haas, containing 0.35% 2-methyl-4-isothiazolin-3-one (MIT) and 1.15% 5-chloro-2-methyl-isothiazolin-3-one (CIT).

[0086] 3. Mobile phase solution

[0087] Solution A: filtered methanol, Solution B: filtered distilled water

[0088] Measure 350 mL of solution A and place it in a 1000 mL volumetric flask. Dilute it to the mark with solution B, shake well, pour it into a clean plastic bottle, and place it in an ultrasonic cleaner for degassing for 30 minutes.

[0089] 4. Instruments

[0090] Liquid chromatograph: with UV detector

[0091] 5. Steps

[0092] 5.1. Instrument parameter settings

[0093] Chromatographic column: C18 column

[0094] Detector: UV (272nm)

[0095] Mobile phase: 35% methanol solution

[0096] Flow rate: 1.0ml / min

[0097] Column temperature: 40°C

[0098] Run time: 10 minutes

[0099] 5.2 Preparation of Kaisong Standard Solution

[0100] 5.2.1. Kesong stock solution (30ppm Kesong active ingredient)

[0101] Weigh 0.18-0.22 g (accurate to ±0.0002 g) of the Kesong standard into a 100 ml volumetric flask and dilute to the mark with distilled water to prepare the Kesong stock solution.

[0102] 5.2.2 Kaisong Standard Solution

[0103] Pipette 8.0 ml of the Kesong stock solution into a 25 ml volumetric flask and dilute to volume with distilled water. This solution contains approximately 10 ppm of Kesong active ingredient.

[0104] 5.3 Sample Preparation

[0105] Weigh 10g of the sample to be analyzed and dilute it twice with water

[0106] Filter 5 ml of the aqueous layer using a 0.45 μm microporous filter into a 10 ml vial and label the vial "S". If more than one sample is to be tested, label them S-1 and S-2.

[0107] 5.4 Detection

[0108] Use an injection needle to draw an appropriate amount of 10 ppm Kaisong standard solution and inject it into the chromatograph as a reference sample, and record the peak areas of 2-methyl-4-isothiazolin-3-one (MIT) and 5-chloro-2-methyl-isothiazolin-3-one (CIT).

[0109] The filtered sample was injected into a chromatograph for analysis, and the peak areas of 2-methyl-4-isothiazolin-3-one (MIT) and 5-chloro-2-methyl-isothiazolin-3-one (CIT) were recorded.

[0110] 5.5 Calculation

[0111] 5.5.1. Calculate the contents (ppm) of 2-methyl-4-isothiazolin-3-one (MIT) and 5-chloro-2-methyl-isothiazolin-3-one (CIT) in a 10 ppm Kayson standard solution.

[0112] The content of MIT in the standard solution M T (ppm):

[0113] M T =32×standard product weight×0.35

[0114] CIT content in the standard solution T (ppm):

[0115] C T =32×standard product weight×1.15

[0116] The “weight of the standard product” in the formula is the weight actually weighed in Section 5.2.1 above.

[0117] 5.5.2. Calculate the content of 2-methyl-4-isothiazolin-3-one (MIT) and 5-chloro-2-methyl-isothiazolin-3-one (CIT) in the sample in ppm and the total content of active ingredients in the sample.

[0118] The content of MIT in the sample M S (ppm):

[0119] M S =(sample peak area / standard solution peak area)×M T × the dilution factor of the sample CIT content in the sample C S (ppm):

[0120] Cs = (sample peak area / standard solution peak area) × CT × dilution factor of the sample

[0121] Total content of Kaisong active ingredients in the sample (ppm):

[0122] The total content of active ingredients in the sample = the content of MIT in the sample M S + CIT content in the sample Cs.

[0123] 5.6. Cleaning of chromatographic column

[0124] After all samples have been analyzed, flush the column with mobile phase.

[0125] The present invention is described in detail below through specific embodiments. DETAILED DESCRIPTION

[0126] 1. Method for obtaining fatty alcohol sulfate triethanolamine salt intermediate material I in a specific embodiment 1

[0127] Step 1: Acquisition of organic materials

[0128] Fatty alcohol is directly used as the organic material for the sulfation in the following step 2, and the fatty alcohol is C12-14 fatty alcohol.

[0129] Step 2: Sulfation in sulfonation reactor

[0130] The organic material and a sulfur trioxide-dry air mixture with a sulfur trioxide content of 4% were introduced from the top of the sulfonation reactor at a feed rate of 1130 kg / hour. The molar ratio of sulfur trioxide to the organic material was 1.03. The sulfation reaction temperature was 45°C. After the sulfation reaction was completed, the sulfated product was obtained in the form of a sulfate ester. Then, the following was carried out:

[0131] Step 3: Neutralization of sulfate

[0132] The sulfated product in the form of a sulfate ester is neutralized with a 20% by weight aqueous solution of triethanolamine at a neutralization temperature of 55° C. to obtain an alkyl sulfate triethanolamine salt. The mixture is then adjusted in pH by adding water and a pH adjuster, and stirred to obtain an alkyl sulfate triethanolamine salt intermediate material I having an anionic active matter weight content of 40.39% and a pH of 7.03.

[0133] 2. Method for Obtaining the Dilution Material of the Fatty Alcohol Sulfate Triethanolamine Salt Intermediate Material I in a Specific Implementation

[0134] Take the above-mentioned alkyl sulfate triethanolamine salt intermediate material I, add water to adjust the active matter content, stir evenly, and finally obtain a diluted material of the alkyl sulfate triethanolamine salt intermediate material I, with an anionic active matter content of 29.87% and a pH of 7.02.

[0135] 3. Method for obtaining sodium alkyl sulfate diluent in a specific embodiment

[0136] The method for obtaining the sodium alkyl sulfate diluent in Comparative Example 3 is as follows:

[0137] Step 1: Acquisition of organic materials

[0138] The C12-14 fatty alcohol is directly used as the organic material for the sulfation described in the following step 2.

[0139] Step 2: Sulfation in sulfonation reactor

[0140] The organic material and a sulfur trioxide-dry air mixture with a sulfur trioxide content of 4% were introduced from the top of the sulfonation reactor at a feed rate of 1740 kg / hour. The molar ratio of sulfur trioxide to the organic material was 1.03. The sulfation reaction temperature was 40°C. After the sulfation reaction was completed, the sulfated product was obtained in the form of a sulfate ester. Then, the following was carried out:

[0141] Step 3: Neutralization of sulfate

[0142] The sulfated product in the form of sulfate ester was neutralized with a sodium hydroxide aqueous solution having a weight concentration of 32% at a temperature of 60° C. to obtain an alkyl sulfate sodium salt material having an anionic active matter weight content of 70.89% and a pH of 8.56.

[0143] Step 4: Preparation of 30% aqueous sodium alkyl sulfate

[0144] The alkyl sulfate sodium salt material with an anionic active matter weight content of 70.89% was diluted and adjusted to finally obtain a fatty alcohol sodium sulfate diluted material with an anionic active matter weight content of 29.67% and a pH of 7.04.

[0145] 4. The Kaisong solution used in the specific embodiment

[0146] The Kesong solution used in the Examples and Comparative Examples has a commercially available concentration of 1.5% by weight. Measurements before use revealed a 2-methyl-4-isothiazolin-3-one concentration of 0.35% by weight, a 5-chloro-2-methyl-isothiazolin-3-one concentration of 1.16% by weight, and a total active ingredient content of 1.51% in the Kesong solution. Testing was performed according to the standard (GB / T 29666-2013 Cosmetic Preservatives: Mixtures of Methylchloroisothiazolinone and Methylisothiazolinone with Magnesium Chloride and Magnesium Nitrate).

[0147] [Example 1]

[0148] Add Kaisong and hydrogen peroxide together into the fatty alcohol sulfate triethanolammonium salt intermediate material I, specifically:

[0149] Take 10.0 kg of fatty alcohol sulfate triethanolamine salt intermediate material I (the weight content of anionic active matter in intermediate material I is 40.39%, and the pH is 7.03), add 1.45 g of hydrogen peroxide with a weight concentration of 27.5% (that is, H2O2 is equivalent to 40 ppm by weight of intermediate material I) and 6.662 g of Kaisong solution with a weight concentration of 1.51% (the amount is equivalent to 10 ppm by weight of intermediate material I), stir at 40°C for 300 minutes to obtain the product.

[0150] 150 g of the above product was placed in a 250 ml glass conical flask, the bottle mouth was sealed with a rubber stopper, and the bottle was placed in a constant temperature box at 40±0.5°C for 168 hours. The content of kaison was measured by sampling and the content was 9.33 ppm.

[0151] Kaison loss rate = ((10-9.33) / 10) × 100% = 6.7%.

[0152] For comparison purposes, the experimental results are listed in Table 1.

[0153] [Example 2]

[0154] First, add hydrogen peroxide to the fatty alcohol sulfate triethanolammonium salt intermediate material I, and then add Kaisong, specifically:

[0155] Take 10.0 kg of fatty alcohol sulfate triethanolamine salt intermediate material I (the weight content of anionic active matter in intermediate material I is 40.39%, and the pH is 7.03), add 1.45 g of hydrogen peroxide with a weight concentration of 27.5% (that is, H2O2 is equivalent to 40 ppm by weight of intermediate material I), and stir at 40°C for 60 minutes; then add 6.662 g of Kaisong solution with a weight concentration of 1.51% (the amount is equivalent to 10 ppm by weight of intermediate material I), and stir at 40°C for 300 minutes to obtain the product.

[0156] 150 g of the above product was placed in a 250 ml glass conical flask, the bottle mouth was sealed with a rubber stopper, and the bottle was placed in a constant temperature box at 40±0.5°C for 168 hours. The content of kaison was measured by sampling and the content was 9.79 ppm.

[0157] Kaison loss rate = ((10-9.79) / 10) × 100% = 2.1%.

[0158] For comparison purposes, the experimental results are listed in Table 1.

[0159] [Example 3]

[0160] First, add Kaisong to the fatty alcohol sulfate triethanolammonium salt intermediate material I, and then add hydrogen peroxide, specifically:

[0161] Take 10.0 kg of fatty alcohol sulfate triethanolamine salt intermediate material I (the weight content of anionic active matter in intermediate material I is 40.39%, and the pH is 7.03), add 6.662 g of 1.51% weight concentration of Kaisong solution (the amount is equivalent to 10 ppm by weight of intermediate material I), and stir at 40 ° C for 60 minutes; then add 1.45 g of hydrogen peroxide with a weight concentration of 27.5% (that is, H2O2 is equivalent to 40 ppm by weight of intermediate material I), and stir at 40 ° C for 300 minutes to obtain the product.

[0162] 150 g of the above product was placed in a 250 ml glass conical flask, the bottle mouth was sealed with a rubber stopper, and the bottle was placed in a constant temperature box at 40±0.5°C for 168 hours. The content of kaison was measured by sampling and the content was 7.35 ppm.

[0163] Kaison loss rate = ((10-7.35) / 10) × 100% = 26.5%.

[0164] For comparison purposes, the experimental results are listed in Table 1.

[0165] [Example 4]

[0166] Add Kaisong, hydrogen peroxide and EDTA-4Na together into the fatty alcohol sulfate triethanolammonium salt intermediate material I, specifically:

[0167] Take 10.0 kg of fatty alcohol sulfate triethanolamine salt intermediate material I (the weight content of anionic active matter in intermediate material I is 40.39%, and the pH is 7.03), add 1.45 g of hydrogen peroxide with a weight concentration of 27.5% (that is, H2O2 is equivalent to 40 ppm by weight of intermediate material I), 6.662 g of Kaisong solution with a weight concentration of 1.51% (the amount is equivalent to 10 ppm by weight of intermediate material I) and 10 g of EDTA-4Na (calculated as EDTA) (equivalent to 0.1% by weight of intermediate material I), and stir at 40°C for 300 minutes to obtain the product.

[0168] 150 g of the above product was placed in a 250 ml glass conical flask, the bottle mouth was sealed with a rubber stopper, and the bottle was placed in a constant temperature box at 40±0.5°C for 168 hours. The content of kaison was measured by sampling and the content was 9.45 ppm.

[0169] Kaison loss rate = ((10-9.45) / 10) × 100% = 5.5%.

[0170] For comparison purposes, the experimental results are listed in Table 1.

[0171] [Example 5]

[0172] First, add hydrogen peroxide and EDTA-4Na to the fatty alcohol sulfate triethanolammonium salt intermediate material I, and then add Kaisong, specifically:

[0173] Take 10.0 kg of fatty alcohol sulfate triethanolamine salt intermediate material I (the weight content of anionic active matter in intermediate material I is 40.39%, and the pH is 7.03), add 1.45 g of hydrogen peroxide with a weight concentration of 27.5% (that is, H2O2 is equivalent to 40 ppm by weight of intermediate material I) and 10 g of EDTA-4Na (calculated as EDTA) (equivalent to 0.1% by weight of intermediate material I), and stir at 40°C for 60 minutes; then add 6.662 g of Kaisong solution with a weight concentration of 1.51% (the amount is equivalent to 10 ppm by weight of intermediate material I), and stir at 40°C for 300 minutes to obtain the product.

[0174] 150 g of the above product was placed in a 250 ml glass conical flask, the bottle mouth was sealed with a rubber stopper, and the bottle was placed in a constant temperature box at 40±0.5°C for 168 hours. The content of kaison was measured by sampling and the content was 9.86 ppm.

[0175] Kaison loss rate = ((10-9.86) / 10) × 100% = 1.4%.

[0176] For comparison purposes, the experimental results are listed in Table 1.

[0177] [Example 6]

[0178] First, add hydrogen peroxide to the fatty alcohol sulfate triethanolammonium salt intermediate material I, then add EDTA-4Na, and finally add Kaisong, specifically:

[0179] Take 10.0 kg of fatty alcohol sulfate triethanolamine salt intermediate material I (the weight content of anionic active matter in intermediate material I is 40.39%, and the pH is 7.03), add 1.45 g of hydrogen peroxide with a weight concentration of 27.5% (that is, H2O2 is equivalent to 40 ppm by weight of intermediate material I), and stir at 40°C for 60 minutes; then, add 10 g of EDTA-4Na (calculated as EDTA) (equivalent to 0.1% by weight of intermediate material I) and stir at 40°C for 60 minutes; finally, add 6.662 g of Kaisong solution with a weight concentration of 1.51% (the amount is equivalent to 10 ppm by weight of intermediate material I) and stir at 40°C for 300 minutes to obtain the product.

[0180] 150 g of the above product was placed in a 250 ml glass conical flask, the bottle mouth was sealed with a rubber stopper, and the bottle was placed in a constant temperature box at 40±0.5°C for 168 hours. The content of kaison was measured by sampling and the content was 9.84 ppm.

[0181] Kaison loss rate = ((10-9.84) / 10) × 100% = 1.6%.

[0182] For comparison purposes, the experimental results are listed in Table 1.

[0183] [Example 7]

[0184] First, add EDTA-4Na to the fatty alcohol sulfate triethanolammonium salt intermediate material I, then add hydrogen peroxide, and finally add Kaisong, specifically:

[0185] Take 10.0 kg of fatty alcohol sulfate triethanolamine salt intermediate material I (the weight content of anionic active matter in intermediate material I is 40.39%, and the pH is 7.03), add 10 g of EDTA-4Na (calculated as EDTA) (equivalent to 0.1% by weight of intermediate material I), and stir at 40°C for 60 minutes; then, add 1.45 g of hydrogen peroxide with a weight concentration of 27.5% (that is, H2O2 equivalent to 40 ppm by weight of intermediate material I), and stir at 40°C for 60 minutes; finally, add 6.662 g of Kaisong solution with a weight concentration of 1.51% (the amount is equivalent to 10 ppm by weight of intermediate material I), and stir at 40°C for 300 minutes to obtain the product.

[0186] 150 g of the above product was placed in a 250 ml glass conical flask, the bottle mouth was sealed with a rubber stopper, and the bottle was placed in a constant temperature box at 40±0.5°C for 168 hours. The content of kaison was measured by sampling and the content was 9.94 ppm.

[0187] Kaison loss rate = ((10-9.94) / 10) × 100% = 0.6%.

[0188] For comparison purposes, the experimental results are listed in Table 1.

[0189] [Example 8]

[0190] Add Kaisong and EDTA-4a together to the fatty alcohol sulfate triethanolamine salt intermediate material I and add it, specifically:

[0191] Take 10.0 kg of fatty alcohol sulfate triethanolamine salt intermediate material I (the weight content of anionic active matter in intermediate material I is 40.39%, and the pH is 7.03), 6.662 g of Kaisong solution with a weight concentration of 1.51% (equivalent to 10 ppm by weight of intermediate material I) and 10 g of EDTA-4Na (calculated as EDTA) (equivalent to 0.1% by weight of intermediate material I), and stir at 40°C for 300 minutes to obtain the product.

[0192] 150 g of the above product was placed in a 250 ml glass conical flask, the flask mouth was sealed with a rubber stopper, and the flask was placed in a constant temperature box at 40±0.5°C for 168 hours. The content of kaison was measured by sampling and the content was 2.91 ppm.

[0193] Kaison loss rate = ((10-2.91) / 10) × 100% = 70.9%.

[0194] For comparison purposes, the experimental results are listed in Table 1.

[0195] [Comparative Example 1]

[0196] Take 10.0 kg of fatty alcohol sulfate triethanolamine salt intermediate material I (the weight content of anionic active matter in intermediate material I is 40.39%, and the pH is 7.03), add 6.662 g of Kaisong solution with a weight concentration of 1.51% (equivalent to 10 ppm by weight of intermediate material I), and stir at 40°C for 300 minutes to obtain the product.

[0197] Take 150g of the above product and place it in a 250ml glass conical flask, plug the bottle mouth with a rubber stopper, and place it in a constant temperature box at 40±0.5℃. After storing for 168 hours, take a sample and measure the content of kaison to find that it is 2.68ppm.

[0198] Kaison loss rate = ((10-2.68) / 10)×100% = 73.2%.

[0199] For comparison purposes, the experimental results are listed in Table 1.

[0200] [Comparative Example 2]

[0201] Take 10.0 kg of the diluted material of the intermediate material I of the alkyl sulfate triethanolamine salt (anion active matter content of 29.87%, pH of 7.02), add 6.662 g of a 1.51% weight concentration of Kaisong solution (equivalent to 10 ppm by weight of the intermediate material I), and stir at 40°C for 300 minutes to obtain the product.

[0202] Take 150g of the above product and put it into a 250ml glass conical flask, plug the bottle mouth with a rubber stopper, and place it in a constant temperature box at 40±0.5℃. After storing for 168 hours, take a sample and measure the content of kaison to find that it is 3.19ppm.

[0203] Kaison loss rate = ((10-3.19) / 10) × 100% = 68.1%.

[0204] For comparison purposes, the experimental results are listed in Table 1.

[0205] [Comparative Example 3]

[0206] Take 10.0 kg of sodium fatty alcohol sulfate diluent (the weight content of anionic active matter in the sodium fatty alcohol sulfate diluent is 29.67%, and the pH is 7.04), add 6.662 g of Kaisong solution with a weight concentration of 1.51% (equivalent to 10 ppm by weight of the sodium fatty alcohol sulfate diluent), and stir at 40°C for 300 minutes to obtain the product.

[0207] Take 150g of the above product and put it into a 250ml glass conical flask, plug the bottle mouth with a rubber stopper, and place it in a constant temperature box at 40±0.5℃. After storing for 168 hours, take a sample and measure the content of kaisonite, which is 9.71ppm.

[0208] Kaison loss rate = ((10-9.81) / 10) × 100% = 1.9%.

[0209] For comparison purposes, the experimental results are listed in Table 1.

[0210] Compared with Comparative Examples 1 and 2, it can be seen that there is no obvious instability in the content of kaison in the production of sodium alkyl sulfate.

[0211] Table 1

[0212]

[0213] *: Sodium fatty alcohol sulfate diluent is used instead of fatty alcohol sulfate triethanolamine salt intermediate material I.

Claims

1. A method for producing an alkyl sulfate triethanolamine salt surfactant product, comprising: (1) Obtaining alkyl sulfate; (2) neutralizing the alkyl sulfate with a triethanolamine aqueous solution to obtain an alkyl sulfate triethanolamine salt intermediate material I; (3) The intermediate material I of the alkyl sulfate triethanolamine salt is mixed with the following components: (i) Kaison, (ii) hydrogen peroxide, (iii) EDTA or its salts; The amount of Kaisong is greater than 0ppm and less than 500ppm based on the weight of the fatty alcohol sulfate triethanolamine salt intermediate material I; The amount of hydrogen peroxide used is calculated as H2O2, accounting for 1 to 100 ppm by weight of the alkyl sulfate triethanolamine salt intermediate material I; EDTA or its salts are calculated as ethylenediaminetetraacetic acid, and the amount used is not less than 0% and not more than 2% by weight of the alkyl sulfate triethanolamine salt intermediate material I; The weight content of anionic active matter of alkyl sulfate triethanolamine salt in the product is 30-43%.

2. The production method according to claim 1, wherein The alkyl sulfate is obtained by using fatty alcohol as an organic raw material and performing a sulfation process using SO3.

3. The production method according to claim 1, wherein The alkyl group is a C8-C18 alkyl group.

4. The production method according to claim 1, wherein The pH of the intermediate material I in step (2) is 6.0-8.

0.

5. The production method according to claim 1, wherein The temperature of the neutralization in step (2) is 55-65°C.

6. The production method according to claim 1, wherein The weight concentration of triethanolamine in the triethanolamine aqueous solution in step (2) is 10-23%.

7. The production method according to claim 1, wherein The mixing temperature in step (3) is 10-45°C.

8. The production method according to claim 1 or 7, characterized in that The mixing time in step (3) is at least 30 minutes.

9. The alkyl sulfate triethanolamine salt surfactant product obtained by the production method according to any one of claims 1 to 8.

10. Use of the alkyl sulfate triethanolamine salt surfactant product according to claim 9 as a storage and transportation form of the alkyl sulfate triethanolamine salt surfactant.

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