Fatty alcohol polyoxyethylene ether sodium sulfate and cardanol polyoxyethylene ether sodium sulfate compound and preparation method thereof
By combining sodium fatty alcohol polyoxyethylene ether sulfate and sodium cashew phenolate polyoxyethylene ether sulfate, the problems of product flowability and detergency under high active ingredient content were solved, realizing efficient continuous production and transportation, and improving detergency performance.
Patent Information
- Application Number
- CN202511272380.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-08
- Publication Date
- 2025-12-16
AI Technical Summary
Sodium fatty alcohol polyoxyethylene ether sulfate and sodium cashew phenol polyoxyethylene ether sulfate tend to form hard gels at high active ingredient content, which affects the continuous production and transportation of products, and their detergency performance is limited when used alone.
By employing a compounding method of sodium fatty alcohol polyoxyethylene ether sulfate and sodium cashew phenol polyoxyethylene ether sulfate, and by controlling the sulfonation reaction conditions and neutralization process, the product maintains flowability at high active ingredient content, and enhances detergency performance through structural similarity.
It achieves improved product flowability and detergency with high active ingredient content, making it suitable for continuous production and transportation, and its detergency performance is superior to that of the components when used alone.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the field of fine chemical technology, and particularly relates to a fatty alcohol polyoxyethylene ether sodium sulfate and cashew phenol polyoxyethylene ether sodium sulfate compound and a preparation method thereof. BACKGROUND
[0002] Fatty alcohol sulfates have poor resistance to hard water, and if 2-3 ethylene oxides are added to the fatty alcohol molecules before sulfation and neutralization, the product has greatly increased resistance to hard water. Fatty alcohol polyoxyethylene ether sulfates are the most important and largest yield among modified fatty alcohol products, and are widely used in shampoo, bath products, shaving cream and other hygiene products due to their excellent solubility, hard water resistance, foaming, wetting force and low irritation.
[0003] Fatty alcohol polyoxyethylene ether can be sulfonated and neutralized with alkali to form active fatty alcohol polyoxyethylene ether sodium sulfate. Since the mass fraction of fatty alcohol polyoxyethylene ether sodium sulfate (AES) is between 30-53%, a gel phase is formed and it does not have flowability. In order to ensure that the product has a certain flowability and is convenient for production and transportation, only two products with contents of 27-30% and 70% are available in industry. Due to the structural characteristics, AES can only be produced in the above two content specifications, and the rest is inorganic salt (produced by neutralization), un-sulfated substance and most water. The lower the content, the higher the proportion of water in the product, resulting in increased product transportation and use costs.
[0004] Cashew phenol is a byproduct of cashew production, and cashew phenol and its derivatives are the main components of cashew shell liquid. Due to its unique structure of phenolic and aliphatic groups, it can replace petroleum phenol to synthesize surfactants. In recent years, the research on cashew phenol surfactants has become a focus of many manufacturers. Cashew phenol can also be subjected to polyethoxylation reaction to form cashew phenol polyoxyethylene ether by adding ethylene oxide, which is similar to the polyether synthesized from fatty alcohols. However, due to the natural and renewable raw material, it has a certain price advantage and excellent degradability. Similarly, cashew phenol polyoxyethylene ether sodium sulfate (CES) has good foaming and foam stability, significantly improves the solubilizing capacity of inorganic salts, and reduces the irritation to human skin, which can gradually replace petroleum-based synthetic alkyl phenol polyoxyethylene ether sulfates.
[0005] The monomer phase structure of CES and AES is similar, and with the continuous increase of active content, the phase structure gradually changes from clear liquid to hard gel, flowable gel to solid phase, i.e. at high active concentration, only under high temperature conditions, it has certain flowability or no flowability, which affects the continuous production of the product and the transportation of the product. SUMMARY
[0006] To solve the above problems, considering that AES and CES both have alcohol ether ethoxylated sulfate structure, according to the principle of similarity, the two theoretically have good compounding performance, can effectively cross the sol-gel interval of the product, that is, still has good fluidity under the condition of high active substance content, facilitates the continuous production and transportation of the product, and the surface activity of the two can be superimposed and expanded after the superposition of the surface performance, enriches the use performance of the product, and improves the decontamination power of the product.
[0007] The present application aims to provide a preparation method of a fatty alcohol polyoxyethylene ether sodium sulfate and cardanol polyoxyethylene ether sodium sulfate compound; the present application also aims to provide a fatty alcohol polyoxyethylene ether sodium sulfate and cardanol polyoxyethylene ether sodium sulfate compound with high active substance content, fluidity and strong decontamination power.
[0008] The present application discloses a preparation method of a fatty alcohol polyoxyethylene ether sodium sulfate and cardanol polyoxyethylene ether sodium sulfate compound, comprising the following steps:
[0009] S1 sulfonation reaction: a mixture of SO3 and air is reacted with fatty alcohol polyoxyethylene ether to obtain fatty alcohol polyoxyethylene ether sulfate; a mixture of SO3 and air is reacted with cardanol polyoxyethylene ether to obtain cardanol polyoxyethylene ether sulfate;
[0010] S2 neutralization reaction: fatty alcohol polyoxyethylene ether sulfate, cardanol polyoxyethylene ether sulfate, liquid caustic, hydrogen peroxide and water are mixed and subjected to neutralization reaction to obtain a fatty alcohol polyoxyethylene ether sodium sulfate and cardanol polyoxyethylene ether sodium sulfate compound.
[0011] Hydrogen peroxide is mainly used for product color removal.
[0012] In the sulfonation reaction, sulfur trioxide is used as a sulfonating agent, and the molar ratio of sulfur trioxide to fatty alcohol polyoxyethylene ether directly affects the degree of reaction and the properties of the product. If SO3 is excessive, it may cause over-sulfonation, causing side reactions or producing unnecessary by-products; if SO3 is insufficient, it may cause incomplete reaction, affecting the yield.
[0013] Temperature has a significant impact on the selectivity and yield of the reaction. Higher temperatures can accelerate the reaction rate, but may also promote the occurrence of side reactions, such as over-sulfonation or other decomposition reactions. Conversely, lower temperatures, while reducing side reactions, may slow down the reaction rate and prolong the production cycle. Temperature also affects the quality of the final product, including physical and chemical properties such as color, purity, etc. Therefore, in actual production, it is necessary to find an optimal temperature range that can ensure efficient production and ensure product quality.
[0014] Further, in step S1, the volume concentration of SO3 gas in the mixed gas used for the sulfonation reaction with the fatty alcohol polyoxyethylene ether is ≤3%; the molar ratio of SO3 to the fatty alcohol polyoxyethylene ether in the sulfonation reaction is 1.01-1.02:1; and the sulfonation reaction temperature is controlled to be ≤32℃.
[0015] The AES sulfonation reaction needs to use circulating cooling water to quickly remove the reaction heat, and the sulfonation reaction temperature is controlled to be ≤32℃.
[0016] Further, in step S1, the volume concentration of SO3 gas in the mixed gas used for the sulfonation reaction with the cardanol polyoxyethylene ether is 4-7%; the molar ratio of SO3 to the cardanol polyoxyethylene ether in the sulfonation reaction is 1.2-1.4:1; and the sulfonation reaction temperature is controlled to be 50-100℃.
[0017] The CES sulfonation reaction needs to use hot water or steam to heat the reaction, and the sulfonation reaction temperature is controlled to be 50-100℃.
[0018] Further, in step S1, the cardanol polyoxyethylene ether has a solid content >99%, a moisture content <0.1%, and a structural formula (I), and an iodine value of 75-79 g / 100g.
[0019] The structural formula (I) is: wherein n is 0, 2, 4, or 6, and m is 2-25.
[0020] Further, in step S2, the fatty alcohol polyoxyethylene ether sulfate, the cardanol polyoxyethylene ether sulfate, the liquid caustic, the hydrogen peroxide, and the water are fully mixed by a homogenizing mixing pump; and then are conveyed to a vacuum neutralizer for degassing treatment.
[0021] The homogenizing mixing pump is a device specially designed for efficient mixing and homogenization of liquid materials. It usually uses a high-speed rotating rotor and stator system to generate strong shear force, impact force, and high-frequency vibration, thereby effectively dispersing, emulsifying, and mixing the materials. The materials experience strong mechanical action when passing through narrow gaps, which helps to break up liquid droplets or solid particles and promote their full contact.
[0022] The vacuum neutralizer is a special device for neutralization reaction in a vacuum environment, mainly used in chemical production (such as the neutralization process after sulfonation reaction). Its core function is to optimize reaction efficiency, reduce side reactions, and remove volatile substances under vacuum conditions. The vacuum neutralizer solves the problems of high temperature, many by-products, and large air content in traditional neutralization reactions through the coordinated design of vacuum environment and mechanical structure.
[0023] Further, the vacuum degree of the vacuum neutralizer is controlled to be -95 to -70 KPa, and the material inlet temperature is controlled to be 50±5℃.
[0024] Further, in the step S2, the mass ratio of the fatty alcohol polyoxyethylene ether sulfate and the cardanol polyoxyethylene ether sulfate is controlled to be 1~1.5.
[0025] Further, in the step S2, the liquid alkali is added to control the pH value of the product to be 10~11, and the amount of the hydrogen peroxide added is 0.3~0.5% of the total amount of the acid ester.
[0026] Further, the amount of the water added is controlled to make the solid content of the total product to be between 70~80%.
[0027] The application further discloses a fatty alcohol polyoxyethylene ether sodium sulfate and cardanol polyoxyethylene ether sodium sulfate compound prepared by the preparation method.
[0028] The application provides a preparation method of a fatty alcohol polyoxyethylene ether sodium sulfate (AES) and cardanol polyoxyethylene ether sodium sulfate (CES) compound, which utilizes the structural similarity of CES and AES, and produces the two by compounding, uses the cardanol polyoxyethylene ether prepared from natural cardanol to replace the petroleum-based alkylphenol polyoxyethylene ether, has good cost advantage, and the CES raw material is renewable, has high natural degradation rate, and has good environmental protection. The compounding production of CES and AES utilizes the flowable gel phase characteristics of AES at an active matter content of about 70%, mixes the CES acid ester and the AES acid ester together and then neutralizes and processes, utilizes the structural similarity to relieve the hard gel phase characteristics of CES at a high active matter content, makes the compounded product have good flowability, and is convenient for production and transportation. The CES and the AES are structurally similar, and the compounded product has good detergency. DETAILED DESCRIPTION
[0029] In order to make the technical scheme of the application clearer, the application is further described in detail below in combination with specific examples.
[0030] In the embodiment part of the application, the cardanol polyoxyethylene ether raw material is obtained by adding and reacting cardanol extracted from natural cashew nut shell and ethylene oxide through ethoxylation, and the cardanol polyoxyethylene ether sulfate sodium salt obtained by sulfonation and neutralization, and the structural formula is as follows:
[0031] m=2~25.
[0032] Example 1
[0033] S1 sulfonation reaction:
[0034] Sulfonation reaction of the fatty alcohol polyoxyethylene ether:
[0035] Sulfur of 250 kg / h and process air with dew point below -60℃ after freeze drying were fully combusted in a sulfur furnace to generate SO2 dilution gas, which was then catalytically oxidized to SO3 dilution gas in a conversion tower. The SO3 dilution gas was cooled, diluted again, and filtered to obtain SO3 / air dilution gas with a volume fraction of 3%, which was then introduced into the head of a multi-tube falling film sulfonation reactor. The sulfonation reaction was carried out in the multi-tube falling film sulfonation reactor with AEO2 of 2130 kg / h. The sulfonation reactor used circulating cooling water to control the reaction temperature at 30-32℃. After the liquid material fell down the sulfonation reaction tube, gas-liquid separation was performed to obtain fatty alcohol polyoxyethylene ether sulfate.
[0036] Sulfonation reaction of cardanol polyoxyethylene ether:
[0037] Sulfur of 58 kg / h and process air with dew point below -60℃ after freeze drying were fully combusted in a sulfur furnace to generate SO2 dilution gas, which was then catalytically oxidized to SO3 dilution gas in a conversion tower. The SO3 dilution gas was cooled, diluted again, and filtered to obtain SO3 / air dilution gas with a volume fraction of 5%, which was then introduced into the head of a multi-tube falling film sulfonation reactor. The sulfonation reaction was carried out in the multi-tube falling film sulfonation reactor with cardanol polyoxyethylene ether of 885 kg / h. The sulfonation reactor used hot water to control the sulfonation reaction temperature at 78℃. After the liquid material fell down the sulfonation reaction tube, gas-liquid separation was performed to obtain cardanol polyoxyethylene ether sulfate.
[0038] The multi-tube falling film sulfonation reactor solves the problems of high heat release, strong corrosion, and multiple side reactions in sulfonation reactions through the design of multi-tube falling film + counterflow contact + high-efficiency cooling, becoming the mainstream equipment for modern sulfonation processes. The technical core lies in balancing mass transfer, heat transfer, and reaction kinetics, making it suitable for industrial scenarios with high requirements for product purity, energy consumption, and continuous operation.
[0039] S2 neutralization reaction:
[0040] The fatty alcohol polyoxyethylene ether sulfate was transported to a homogenizing mixer at a flow rate of 1000 kg / h, and the cardanol polyoxyethylene ether sulfate was transported at a flow rate of about 1000 kg / h. Process water (400 kg / h), 32wt% sodium hydroxide aqueous solution (560 kg / h), and 27.5wt% hydrogen peroxide (10 kg / h) were added to the homogenizing mixer. After sufficient mixing in the homogenizing mixer, the mixture was introduced into a vacuum degasser to obtain an AES / CES complex product after neutralization treatment.
[0041] The obtained AES / CES complex product was detected, and the results are shown in Table 1.
[0042] Table 1 Detection results of the AES / CES complex product obtained in Example 1
[0043]
[0044] Comparative Example 1
[0045] Sulfonation reaction of fatty alcohol polyoxyethylene ether:
[0046] 250 kg / h of sulfur was fully combusted with process air with a dew point of below -60°C after freeze drying in a sulfur combustion furnace to generate SO2 dilution gas, which was then catalytically oxidized to SO3 dilution gas in a conversion tower. After cooling, secondary dilution and filtration, SO3 / air dilution gas with a volume fraction of 3% was obtained, which entered the head of the sulfonation reactor and reacted with 2130 kg / h of fatty alcohol polyoxyethylene ether (AEO2) in the sulfonation reactor. The sulfonation reactor used circulating cooling water to control the reaction temperature at 30-32°C. After the liquid material fell down along the sulfonation reaction tube, gas-liquid separation was performed to obtain fatty alcohol polyoxyethylene ether sulfate.
[0047] Neutralization reaction:
[0048] The fatty alcohol polyoxyethylene ether sulfate was transported to a homogenizing pump at a flow rate of 1000 kg / h using a flow meter and regulating valve, and process water (258 kg / h), 32wt% liquid caustic (360 kg / h) and 27.5wt% hydrogen peroxide (5 kg / h) were added and fully mixed in the homogenizing pump, and then entered a vacuum degasser to obtain sodium fatty alcohol polyoxyethylene ether sulfate (AES) through neutralization treatment.
[0049] Table 2 Test results of AES product obtained in Comparative Example 1
[0050]
[0051] As can be seen from Tables 1-2, by compounding a quantitative flow of AES acid ester and CES acid ester and then jointly neutralizing, degassing and bleaching, the active matter content of the compounded product obtained exceeds the range of active matter that can be produced by the two alone, and the compounded product has the same flowability as AES at room temperature under the conditions, and the compounded product perfectly crosses the gel interval of CES with high active matter and has good flowability at room temperature, which can be continuously produced.
[0052] The AES / CES was compounded in different mass ratios, and the flowability of the compounded product obtained is shown in Table 3.
[0053] Table 3 Flowability of AES / CES compounded product with different mass ratios
[0054]
[0055] From Table 3, it can be seen that due to the low molecular weight of AES, under different mass ratios of acid ester, when the proportion of AES is low, the compounded product still shows a gel state at room temperature and does not have fluidity; when the proportion of AES is more than 50%, the compounded product restores fluidity.
[0056] The decontamination ability of AES, CES and the AES / CES compounded product obtained in Example 1 was tested, the soiled cloth and soiled liquid and the test method were carried out according to GB / T 13174-2021, and the decontamination ability of the commercially available standard laundry detergent was compared, and the obtained decontamination ability test data are shown in Table 4.
[0057] Table 4 Test results of decontamination ability
[0058]
[0059] From Table 4, it can be seen that the comparison of the decontamination ability test data of the three can show that the decontamination performance of CES on carbon black and protein is better than that of AES, but the decontamination performance test on sebum is weaker than that of AES, but is better than the decontamination ability of the currently commercially available laundry detergent; after the AES and CES are compounded, due to the similar structure of the two, part of the performance is strengthened, and from the decontamination performance, the decontamination performance of the compounded product on carbon black and protein is better than that of the single component, and the decontamination performance on sebum is obviously improved, and the overall decontamination performance is strengthened.
[0060] The above-described examples only express several embodiments of the present application, and the description is more specific and detailed, but it should not be understood as limiting the scope of the patent of the present application. It should be pointed out that for ordinary skilled persons in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application should be subject to the appended claims.
Claims
1. A method for preparing a compound of sodium fatty alcohol polyoxyethylene ether sulfate and sodium cashew phenol polyoxyethylene ether sulfate, characterized in that, Includes the following steps: S1 sulfonation reaction: A mixture of SO3 and air is sulfonated with fatty alcohol polyoxyethylene ether to obtain fatty alcohol polyoxyethylene ether sulfate; A mixture of SO3 and air is sulfonated with cashew nut phenol polyoxyethylene ether to obtain cashew nut phenol polyoxyethylene ether sulfate. S2 Neutralization reaction: Fatty alcohol polyoxyethylene ether sulfate, cashew nut phenol polyoxyethylene ether sulfate, liquid alkali, hydrogen peroxide and water are mixed and neutralized to obtain a compound of fatty alcohol polyoxyethylene ether sulfate and cashew nut phenol polyoxyethylene ether sulfate.
2. The method for preparing a compound of sodium fatty alcohol polyoxyethylene ether sulfate and sodium cashew phenol polyoxyethylene ether sulfate according to claim 1, characterized in that, In step S1, the volume concentration of SO3 gas in the mixed gas used for the sulfonation reaction with fatty alcohol polyoxyethylene ether is ≤3%; the molar ratio of SO3 to fatty alcohol polyoxyethylene ether in the sulfonation reaction is 1.01~1.02:1; and the sulfonation reaction temperature is controlled to be ≤32℃.
3. The method for preparing a compound of sodium fatty alcohol polyoxyethylene ether sulfate and sodium cashew phenol polyoxyethylene ether sulfate according to claim 1, characterized in that, In step S1, the volume concentration of SO3 gas in the mixed gas used for the sulfonation reaction with cashew phenol polyoxyethylene ether is 4-7%; the molar ratio of SO3 to cashew phenol polyoxyethylene ether in the sulfonation reaction is 1.2-1.4:1; and the sulfonation reaction temperature is controlled at 50-100℃.
4. The method for preparing a compound of sodium fatty alcohol polyoxyethylene ether sulfate and sodium cashew phenol polyoxyethylene ether sulfate according to claim 1, characterized in that, In step S1, the cashew phenol polyoxyethylene ether has a solid content >99%, a moisture content <0.1%, has structural formula (Ⅰ), and an iodine value of 75~79 g / 100g; Structural formula (Ⅰ): , where n is 0, 2, 4, 6, and m is 2~25.
5. The method for preparing a compound of sodium fatty alcohol polyoxyethylene ether sulfate and sodium cashew phenol polyoxyethylene ether sulfate according to claim 1, characterized in that, In step S2, the fatty alcohol polyoxyethylene ether sulfate, cashew phenol polyoxyethylene ether sulfate, liquid alkali, hydrogen peroxide and water are thoroughly mixed by a homogenizing pump and then transported to a vacuum neutralizer for degassing.
6. The method for preparing a compound of sodium fatty alcohol polyoxyethylene ether sulfate and sodium cashew phenol polyoxyethylene ether sulfate according to claim 5, characterized in that, The vacuum level of the vacuum neutralizer is controlled between -95 and -70 kPa, and the material inlet temperature is controlled at 50 ± 5 °C.
7. The method for preparing a compound of sodium fatty alcohol polyoxyethylene ether sulfate and sodium cashew phenol polyoxyethylene ether sulfate according to claim 5, characterized in that, In step S2, the mass ratio of fatty alcohol polyoxyethylene ether sulfate and cashew phenol polyoxyethylene ether sulfate is controlled at 1~1.
5.
8. The method for preparing a compound of sodium fatty alcohol polyoxyethylene ether sulfate and sodium cashew phenol polyoxyethylene ether sulfate according to claim 5, characterized in that, In step S2, the pH value of the product is controlled to be between 10 and 11 when the liquid alkali is added, and the amount of hydrogen peroxide added is 0.3 to 0.5% of the total ester content.
9. The method for preparing a compound of sodium fatty alcohol polyoxyethylene ether sulfate and sodium cashew phenol polyoxyethylene ether sulfate according to claim 5, characterized in that, The amount of water added is controlled so that the solid content of the total product is between 70% and 80%.
10. A compound of sodium fatty alcohol polyoxyethylene ether sulfate and sodium cashew phenol polyoxyethylene ether sulfate, characterized in that, It is prepared by the preparation method according to any one of claims 1-9.