Solid catalyst and its preparation of natural oil fatty amido acid salt and its application

Abstract

The application discloses a solid catalyst and a natural oil fatty amido acid salt prepared by the solid catalyst and application, and belongs to the field of daily necessities. The product is prepared by taking active zinc as a catalytic component and gamma-Al2O3 as a carrier. When the natural oil fatty amido acid salt is directly synthesized by catalysis, the condition is mild, the natural oil cannot be damaged, the catalytic degree is high, the prepared product is far superior to similar products in use as an amino acid surfactant, and the product still has high catalytic activity after recovery, can be repeatedly used, and has high economic efficiency.

Description

Technical Field

[0001] This invention relates to the field of daily necessities, specifically to a solid catalyst, the natural oily acyl amino acid salt prepared therefrom, and its applications. Background Technology

[0002] Compared with traditional ionic surfactants, amino acid surfactants have advantages such as wide availability of raw materials, low toxicity of synthetic products, and good biodegradability. They are widely used in daily chemical products as active ingredients such as foaming agents, dispersants, and emulsifiers.

[0003] However, existing methods for preparing amino acid surfactants, especially natural oil acyl amino acid salt surfactants, involve the fatty acyl chloride acylation method. This method involves the Schotton-Baumann condensation reaction of amino acids and fatty acyl chlorides under alkaline conditions. However, this method has overly harsh reaction conditions and uses highly irritating and difficult-to-preserve acyl chloride reagents, making it difficult to mass-produce in conventional factories. There are also technologies that use catalysts to directly synthesize amino acid surfactants from natural oils. However, in this process, products prepared with some mild solid catalysts do not perform well and have insufficient catalytic activity. While using highly active catalysts such as strong bases can ensure a high degree of catalysis, these catalysts can cause irreversible damage to the unsaponifiable matter in natural oils, affecting the quality of the product. Furthermore, the catalytic synthesis process is accompanied by the production of irritating gases such as ammonia, which may be reabsorbed by the product during synthesis, resulting in an off-odor. This makes the product unsuitable for use in daily necessities such as cosmetics where a high level of sensory experience is required. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a solid catalyst. This product uses active zinc as the catalytic component in combination with γ-Al2O3 as the support. When catalyzing the direct synthesis of natural oil acyl amino acid salts, the conditions are mild and do not damage the unsoapable substances in natural oils. At the same time, the catalytic degree is high, and the prepared product is far superior to existing similar products when used as an amino acid surfactant. In addition, the product still has high catalytic activity after recycling, can be reused, and has a high cost-performance ratio.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] A solid catalyst comprising a γ-Al2O3 support and a zinc active catalytic component supported on the support.

[0007] The preparation method of the solid catalyst includes the following preparation steps:

[0008] (1) Prepare an aqueous solution of soluble zinc source, then add γ-Al2O3 powder, mix and disperse evenly, and sonicate. Separate the solid and liquid, and dry to obtain an intermediate solid.

[0009] (2) The intermediate solid is calcined in air at 200-500°C for 3-5 hours to obtain the solid catalyst.

[0010] Compared to the traditional fatty acid acyl chloride acylation method, the catalytic direct synthesis of amino acid surfactants from natural oils requires lower operating, time, and equipment costs, and offers higher production efficiency and greater safety. However, the use of catalysts is crucial in the catalytic direct synthesis process of natural oils. Currently, the main catalysts used for the synthesis of amino acid surfactants fall into two categories: one is strong acid or strong base liquid catalysts, specifically highly active chemical reagents such as sulfuric acid, potassium hydroxide, or sodium hydroxide. While these catalysts have high catalytic activity, they can also damage some non-soapable active substances in natural oil raw materials. Furthermore, when natural oil-based amino acid surfactants are used in daily chemical products, especially cosmetics, some of the non-soapable active substances they contain can not only assist the active amino acids in the components... Amino acid salts enhance the foaming, dispersing, and emulsifying effects when used as surfactants, and can also achieve skincare effects such as moisturizing and hydrating. If these non-soapable active ingredients are destroyed, the functionality of the component will be greatly reduced, even to the point of being inferior to some common ionic surfactants. Another type of milder catalyst is a solid catalyst with active metal components. These catalysts generally do not destroy the non-soapable active ingredients in natural oil raw materials. However, due to the complex composition of natural oils, the degree of catalytic synthesis of amino acid salts is not high without acid-base reactions. The basic performance of the prepared amino acid surfactants is weak. Furthermore, the current catalysts have a high deactivation rate, and the yield of products that can be catalyzed again after recycling is greatly reduced, often requiring single-use preparation. Therefore, in this invention, targeting natural oils as a catalytic raw material, the inventors used highly catalytically active zinc as the catalytic component, combined with highly compatible γ-Al₂O₃ powder as a carrier. Due to the spherical morphology of γ-Al₂O₃ powder, it exhibits high dispersibility after being introduced into natural oils. Furthermore, after specific calcination loading and crystal form control treatments, the resulting composite solid catalyst loaded with active zinc demonstrates high catalytic selectivity and activity for saponifiable active substances in natural oils, effectively catalyzing the preparation of natural oil acyl amino acid salts. When this product is used in daily chemical products, especially cosmetics, the active components and the non-saponifiable active substances retained in natural oils can work synergistically, resulting in ideal foaming, stabilizing, and skin-care effects. Moreover, this solid catalytic catalyst exhibits strong structural and catalytic activity stability, allowing for repeated recycling and reuse, making it highly suitable for large-scale industrial production.

[0011] However, the temperature range for calcination loading and crystal form control is particularly important during the preparation process. If the temperature is too low or too high, the catalytic activity during catalytic synthesis cannot be guaranteed, resulting in insufficient product yield. At the same time, if the catalytic active component and support of the solid catalyst are replaced with other similar components (or even if the crystal form of the support is changed), the same effect cannot be achieved. Therefore, specific selection is required to achieve the expected results.

[0012] Preferably, the calcination temperature in step (2) is one or any two of the following: 200℃, 250℃, 300℃, 350℃, 400℃, 450℃, and 500℃.

[0013] More preferably, the calcination temperature in step (2) is 250–350°C.

[0014] Since calcination involves the combination and dispersion of the carrier and the loaded material, as well as the crystal structure of both, especially the zinc active catalytic component, it affects the catalytic activity and structural stability of the resulting product. Therefore, the performance of the product prepared at different temperatures will naturally vary. After screening, when the calcination temperature is preferably within the above-mentioned range, the performance of the resulting product is better.

[0015] Preferably, the average particle size of the γ-Al2O3 powder is 3-5 mm.

[0016] When loading zinc-active catalytic components, using the resulting solid catalyst for the subsequent catalytic synthesis of natural oleic acid amino acid salts, and even separating the solid catalyst after catalytic synthesis, the size of the γ-Al2O3 powder used as the support will affect the product performance at these stages. If the support size is selected solely based on existing similar solid catalysts, it may lead to differences in the product yield during catalytic synthesis and the performance of subsequent products. Optimally, when the average particle size of the γ-Al2O3 powder used in the preparation of the solid catalyst is in the range of 3–5 mm, the solid catalyst exhibits superior performance.

[0017] Preferably, the soluble zinc source includes at least one of zinc chloride, zinc nitrate, and zinc sulfate.

[0018] More preferably, the soluble zinc source is zinc nitrate.

[0019] Preferably, in step (1), the concentration of the soluble zinc source in the prepared aqueous solution is 5-20% w / v (g / 100g);

[0020] More preferably, the concentration of the soluble zinc source in the prepared aqueous solution is 10-15% w / v.

[0021] In the scheme described in this invention, as the concentration of soluble zinc source increases, the zinc concentration loaded after the introduction of γ-Al2O3 powder will also be higher. However, this leads to a certain degree of decrease in the uniformity of active zinc loading, resulting in a decrease in the catalytic activity of the solid catalyst obtained after subsequent calcination due to the decrease in the uniformity of active zinc dispersion. Therefore, after optimization, when the concentration of soluble zinc source is within 10-15% w / v during the preparation of the aqueous solution, the loading effect of active zinc is better, and the prepared solid catalyst has higher catalytic activity.

[0022] Preferably, in step (1), the volume ratio of the aqueous solution to the γ-Al2O3 powder is 1:(0.8-1.2).

[0023] Preferably, in step (1), the power of the ultrasonic treatment is 40-60W and the time is 1-3h.

[0024] Before calcination, ultrasonic treatment can effectively disperse γ-Al2O3 powder, preventing the particles from agglomerating and accumulating, so that active zinc is only loaded on the surface of the large particles formed after agglomeration.

[0025] Preferably, in step (1), the drying temperature is 100-150°C and the drying time is 2-4 hours.

[0026] Another object of the present invention is to provide the application of the solid catalyst in the preparation of natural oleic acid salts.

[0027] Another object of the present invention is to provide a method for preparing a natural oleoyl acyl amino acid surfactant, comprising the following steps:

[0028] (1) Mix natural oils, glycerol, amino acid salts and the solid catalyst described in this invention, then heat under reduced pressure under a protective atmosphere and cool to obtain a viscous mixture;

[0029] (2) Dilute the viscous mixture with water and separate the solid catalyst to obtain the natural lipoic acid surfactant containing natural lipoic acid salt.

[0030] The solid catalyst of this invention has high catalytic activity and mild properties. Therefore, it can be directly mixed with raw materials such as natural oils and fats, and high-yield, high-activity natural oil acyl amino acid surfactants containing natural oil acyl amino acid salts can be prepared under conventional reduced pressure and high temperature conditions. At the same time, the solid catalyst has a stable structure, can be easily recycled and reused, and has a high production cost-effectiveness.

[0031] Preferably, in step (1), the natural oil includes at least one of coconut oil, avocado oil, corn oil, rapeseed oil, and camellia oil.

[0032] The solid catalyst described in this invention has universal applicability to the catalytic synthesis of natural oil acyl amino acid surfactants from various natural oils. Based on the component combination and efficacy requirements of daily necessities, especially cosmetics / skincare / cleansing products, those skilled in the art can use natural oils, including but not limited to the types mentioned above, as raw materials to prepare products (for example, to enhance the anti-aging effect of cosmetics / skincare / cleansing products, those skilled in the art can introduce a certain amount of avocado oil into the product components, and based on component compatibility matching, avocado oil can be used as a raw material to prepare avocado oil acyl amino acid salts as active ingredients for amino acid surfactants; as well as to avoid easily oxidized impurities that may exist in corn oil and rapeseed oil, and to ensure the low odor of the product, those skilled in the art can choose coconut oil with a lower content of volatile impurities as a natural oil to prepare products).

[0033] Preferably, in step (1), the natural oleoyl amino acid surfactant comprises the following raw materials in parts by weight:

[0034] 100 parts natural oils, 40-60 parts glycerin, 40-60 parts amino acid salts, and 1-5 parts solid catalyst.

[0035] More preferably, the amino acid salt is at least one selected from sodium glycine, sodium methyl taurate, sodium sarcosinate, and sodium alanine.

[0036] More preferably, the solid catalyst is in the range of one or any two of the following weight parts: 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, and 5 parts.

[0037] The amount of solid catalyst added can affect the rate of catalytic synthesis and the recovery efficiency of the solid catalyst after the synthesis product within a certain range. Those skilled in the art can select the appropriate amount of catalyst to add based on the actual preference.

[0038] Preferably, in step (1), the pressure during medium-pressure heating is -0.01 to -0.1 MPa, the temperature is 100 to 130°C, and the time is 4 to 6 hours.

[0039] Another object of the present invention is to provide a natural oleoyl acyl amino acid surfactant prepared by the preparation method described above.

[0040] The solid catalyst described in this invention directly catalyzes the synthesis of natural oil acyl amino acid surfactants containing natural oil acyl amino acid salts and unsaponifiable active ingredients. These surfactants have a wide variety of effective components. When used in daily chemical products, especially skin care cosmetics and cleansing products with skin care effects, they can not only fully exert the inherent emulsifying and foaming effects of surfactants, but also have a significant skin care effect. The prepared products can effectively improve skin hydration and moisturize after use. It is difficult to achieve the same effect using traditional surfactants or amino acid salt surfactants.

[0041] Another object of the present invention is to provide a skin care and cleansing product, comprising the natural oleoyl amino acid surfactant described in the present invention.

[0042] Preferably, the dosage form of the skin care and cleansing product includes cream, serum, and essential oil.

[0043] More preferably, the skincare cleansing product is a facial cleanser, comprising the following components in parts by weight per 100 parts:

[0044] The present invention comprises 10-40 parts of natural oleoyl amino acid surfactant, 5-20 parts of auxiliary surfactant, 0.1-5 parts of thickener, 5-20 parts of humectant, 0.1-5 parts of pH adjuster, 0.1-3 parts of preservative, 0.0005-0.01 parts of fragrance, and the balance being water by weight.

[0045] Preferably, the auxiliary surfactant includes at least one of sodium methylcocoyl taurate, sodium lauroyl aspartate, and cocamidopropyl betaine.

[0046] Preferably, the thickener includes at least one of acrylate copolymers and modified corn starch.

[0047] Preferably, the moisturizer includes at least one of glycerin, sorbitol, and propylene glycol.

[0048] Preferably, the pH adjuster includes at least one of citric acid and capryloylglycine.

[0049] Preferably, the preservative includes at least one of phenoxyethanol.

[0050] More preferably, the facial cleanser, per 100 parts, comprises the following components in parts by weight:

[0051] The present invention comprises 10-40 parts of natural oleoyl amino acid surfactant, 2-4 parts of sodium methyl cocoyl taurate, 4-6 parts of sodium lauroyl aspartate, 5-8 parts of cocamidopropyl betaine, 1-2 parts of acrylic (ester) copolymer, 0.5-1.5 parts of modified corn starch, 5-20 parts of glycerol, 0.5-1.5 parts of citric acid, 0.1-0.5 parts of capryloyl glycine, 0.5-1.5 parts of preservative, 0.0005-0.01 parts of fragrance, and the balance being water by weight.

[0052] The facial cleanser prepared based on the natural oleoyl amino acid surfactant described in this invention can fully exert the ideal cleansing effect, has good foaming effect during use, and can effectively increase the skin's moisture content during cleansing, resulting in improved skin hydration after cleansing; the product has high stability and can be transported and stored for a long time.

[0053] The beneficial effects of this invention are that it provides a solid catalyst, which uses active zinc as the catalytic component and γ-Al2O3 as the support. When catalyzing the direct synthesis of natural oil acyl amino acid salts, the conditions are mild and will not damage the unsoapable substances in natural oils. At the same time, the catalytic degree is high, and the prepared product is far superior to existing similar products when used as an amino acid surfactant. In addition, the product still has high catalytic activity after recycling, can be reused, and has a high cost-performance ratio. Detailed Implementation

[0054] To better illustrate the purpose, technical solution, and advantages of this invention, the invention will be further described below with reference to specific embodiments and comparative examples. The purpose of this description is to provide a detailed understanding of the invention, not to limit its scope. All other embodiments obtained by those skilled in the art without creative effort are within the protection scope of this invention. Unless otherwise specified, the experimental reagents and instruments involved in the implementation of this invention are commonly used reagents and instruments. The coconut oil used in the embodiments and comparative examples of this invention is food-grade coconut oil produced by Yihai Kerry; the avocado oil is food-grade avocado oil produced by Henri Germany; sodium methyl cocoyl taurate, sodium lauroyl aspartate, cocamidopropyl betaine, acrylate copolymers, and capryloyl glycine are all commercially available products; the modified corn starch is edible-grade corn starch produced by Dongmei; the preservative is Euxyl PE9010 produced by Schumacher Germany; and the flavoring is flavoring produced by Firmenich.

[0055] Example 1

[0056] This invention relates to an embodiment of a solid catalyst, the natural oleic acid salt prepared therefrom, and their applications. The preparation method of the solid catalyst includes the following steps:

[0057] (1) 5g of soluble zinc source Zn(NO3)2 was prepared into an aqueous solution with a concentration of 5% w / v using 100g of deionized water. Then, γ-Al2O3 powder (Henghuan New Material) with an average particle size of 3.5mm after sieving was placed in the same volume ratio as the aqueous solution and mixed and dispersed evenly. The mixture was then ultrasonically treated at 50W power for 2h, and the solid and liquid were separated. The mixture was dried at 140℃ for 4h to obtain an intermediate solid.

[0058] (2) The intermediate solid was calcined at 300°C for 4 hours in air atmosphere to obtain the solid catalyst.

[0059] Example 2

[0060] The embodiment of the solid catalyst described in this invention, the natural oleic acid salt prepared therefrom, and its application differs from Example 1 only in that the amount of soluble zinc source added is 10g, and the concentration of the aqueous solution is 10% w / v.

[0061] Example 3

[0062] The embodiment of the solid catalyst described in this invention, the natural oleic acid salt prepared therefrom, and its application differs from Example 1 only in that the amount of soluble zinc source added is 15g, and the concentration of the aqueous solution is 15% w / v.

[0063] Example 4

[0064] The embodiment of the solid catalyst described in this invention, the natural oleic acid salt prepared therefrom, and its application differs from Example 1 only in that the amount of soluble zinc source added is 20g, and the concentration of the aqueous solution is 20% w / v.

[0065] Example 5

[0066] The embodiment of the solid catalyst described in this invention and the natural oleic acid salt prepared therefrom and its application differs from Example 2 only in that the calcination temperature is 250°C.

[0067] Example 6

[0068] The embodiment of the solid catalyst described in this invention and the natural oleic acid salt prepared therefrom and its application differs from Example 2 only in that the calcination temperature is 350°C.

[0069] Example 7

[0070] The embodiment of the solid catalyst described in this invention and the natural oleic acid salt prepared therefrom and its application differs from Example 2 only in that the calcination temperature is 200°C.

[0071] Example 8

[0072] The embodiment of the solid catalyst described in this invention, the natural oleic acid salt prepared therefrom, and its application differs from Example 2 only in that the calcination temperature is 400°C.

[0073] Example 9

[0074] The embodiment of the solid catalyst described in this invention and the natural oleic acid salt prepared therefrom and its application differs from Example 2 only in that the calcination temperature is 450°C.

[0075] Example 10

[0076] The embodiment of the solid catalyst described in this invention and the natural oleic acid salt prepared therefrom and its application differs from Example 2 only in that the average particle size of the γ-Al2O3 powder after screening is 4.5 mm.

[0077] Example 11

[0078] The embodiment of the solid catalyst described in this invention and the natural oleic acid salt prepared therefrom and its application differs from Example 2 only in that the average particle size of the γ-Al2O3 powder after screening is 2.5 mm.

[0079] Example 12

[0080] The embodiment of the solid catalyst described in this invention, the natural oleic acid salt prepared therefrom, and its application differs from Example 2 only in that the average particle size of the γ-Al2O3 powder after screening is 6 mm.

[0081] Comparative Example 1

[0082] An example of a solid catalyst and its preparation of natural oleic acid salts and their applications differs from Example 2 only in that the calcination treatment temperature is 100°C.

[0083] Comparative Example 2

[0084] An example of a solid catalyst and its preparation of a natural oleic acid salt and its application is described, differing from Example 2 only in that the γ-Al2O3 powder is replaced with commercially available MgO powder with an average particle size of 5 mm after screening.

[0085] Comparative Example 3

[0086] A solid catalyst is commercially available MgO powder with an average particle size of 5 mm.

[0087] Comparative Example 4

[0088] A solid catalyst, specifically the γ-Al₂O₃ powder used in Example 1.

[0089] Example 1

[0090] To verify the effect of the concentration of the soluble zinc source in the preparation process of the solid catalyst described in this invention on the performance of the prepared product, the products obtained in Examples 1-4 and Comparative Example 4 were used to prepare natural oleoyl acyl amino acid surfactants. The specific methods are as follows:

[0091] (1) Mix 100g of commercially available coconut oil, 50g of glycerol, 50g of sodium glycine and 4g of the above solid catalyst, then reduce the pressure to 0.03-0.1MPa under a protective atmosphere and heat at 110°C for 5h. After heating, cool for 30min to obtain a viscous mixture.

[0092] (2) Dilute the viscous mixture with 300g of pure water, separate the solid catalyst, and obtain the natural lipoic acid surfactant containing natural lipoic acid salt.

[0093] Subsequently, the yield (%) of the prepared product was calculated as follows: 100% * (product quality * chromatographic purity) / theoretical yield.

[0094] Meanwhile, the obtained product was subjected to APHA colorimetry testing, specifically according to GB / T 3143-82, the method for determining the color of liquid chemical products.

[0095] The test results are shown in Table 1.

[0096] Table 1

[0097] product Comparative Example 4 Example 1 Example 2 Example 3 Example 4 Yield (%) No response 92.34 98.56 95.43 91.28 APHA colorimetry / 60 60 60 60

[0098] The test results show that the concentration of zinc active component introduced during the preparation of solid catalysts directly affects the catalytic effect of the prepared product. When preparing zinc-containing aqueous solutions, both too low and too high concentrations will affect the final catalytic efficiency and be reflected in the product yield. When the concentration of the solution is in the range of 10-15% w / v, the product yield can reach more than 95%.

[0099] Example 2

[0100] To verify the effect of calcination temperature on the product prepared by the solid catalyst described in this invention, the products obtained in Examples 5-9 and Comparative Example 1 were prepared using the same natural oleoyl acyl amino acid surfactant as in Effect Example 1, and the yield and APHA color of the products were statistically analyzed. The test results are shown in Table 2.

[0101] Table 2

[0102]

[0103] The test results clearly show that the calcination treatment has a significant impact on the final catalytic effect of the solid catalyst described in this invention during the preparation process. At lower temperatures, soluble zinc cannot form catalytically active zinc, so the product cannot be used as a catalyst. Under these conditions, natural oleic acid amino acid surfactants cannot be synthesized. As the calcination temperature increases, active zinc is gradually generated, and the catalytic degree also improves. However, the temperature during calcination also affects the loading effect and dispersion degree of the solid catalyst. When the calcination temperature is further increased, the product yield decreases. In conclusion, the synthesized product has the best effect when the calcination temperature is preferably between 250 and 350°C.

[0104] Example 3

[0105] To verify the effect of the support particle size on the product during the preparation of the solid catalyst described in this invention, the products obtained in Examples 10-12 were prepared using the same natural oleoyl acyl amino acid surfactant as in Effect Example 1, and the yield and APHA color of the products were statistically analyzed. The test results are shown in Table 3.

[0106] Table 3

[0107] product Example 11 Example 2 Example 10 Example 12 Yield (%) 96.95 98.56 98.21 95.37 APHA colorimetry 60 60 60 60

[0108] As can be seen from Table 3, when preparing solid catalysts, the specific surface area of ​​the γ-Al2O3 powder used as the support varies due to differences in particle size. The loading effect of active zinc and the uniformity of the overall solid catalyst also vary. These differences directly affect the catalytic efficiency during use. Particle size that is too large or too small will ultimately lead to a decrease in the yield of the product synthesized by the solid catalyst. Therefore, γ-Al2O3 powder with a particle size of 3-5 mm has the best effect.

[0109] Example of effect 4

[0110] To verify the catalytic effect of the natural oleoyl acyl amino acid salt obtained by the solid catalyst described in this invention, the catalysts described in Examples 1 / 2 / 4 / 7 / 9 and Comparative Examples 2 / 3 were used to prepare natural oleoyl acyl amino acid surfactants according to the method described in Effect Example 1, and then facial cleansers were prepared according to the formulations described in Table 4.

[0111] The specific preparation method is as follows:

[0112] (1) Mix natural oleoyl amino acid surfactant, sodium methyl cocoyl taurate, glycerol and some water, and then stir and dissolve in a water bath at 93°C to obtain mixture A;

[0113] (2) Add water-dispersed modified corn starch to mixture A, keep warm and stir for 30 min, add water-dispersed acrylic (ester) copolymer, keep warm and stir for 10 min, then add cocamidopropyl betaine, stir for 5 min, stop heating, add water-dispersed capryloyl glycine and citric acid, and a suitable amount of water, while stirring and cooling.

[0114] (3) When the mixture cools down to 45°C, add preservatives and flavorings and adjust the speed to 100 rpm. Continue stirring until the mixture turns white and thickens. Continue stirring for 30 minutes and then discharge the mixture.

[0115] Table 4

[0116] Components Servings by weight (out of 100) Natural lipoyl amino acid surfactants 30 Sodium methylcocoyl taurate 3 Sodium lauroyl aspartate 5 Cocamidopropyl Betaine 7.5 Acrylic (ester) copolymers 1.5 Modified corn starch 1 glycerin 15 Citric acid 1.1 Capryloylglycine 0.5 preservative 1 essence 0.001 water Remaining stock up to 100 servings

[0117] Meanwhile, a control group for products prepared using traditional processes and a control group for commercially available products were set up. The preparation method for products prepared using traditional processes is as follows:

[0118] (1) Mix 100g of commercially available coconut oil, 50g of glycerin, 50g of sodium glycine and 2g of sodium hydroxide, then reduce the pressure to 0.03-0.1MPa under a protective atmosphere and heat at 110°C for 5 hours. After heating, cool for 30 minutes to obtain a viscous mixture.

[0119] (2) Dilute the viscous mixture with 300g of pure water, and add citric acid to adjust the pH to neutral to obtain the natural oleic acid surfactant prepared by the traditional process.

[0120] During the preparation process, a relatively high concentration of irritating odor was still generated under ventilated conditions, requiring production personnel to wear additional protective masks.

[0121] Prepare facial cleanser according to the same formula;

[0122] A facial cleanser was prepared using commercially available sodium cocoyl glycinate (CAS: 90387-74-9) according to the same formula. The facial cleanser was then subjected to the following tests:

[0123] (1) Product stability test: Multiple environmental tests were conducted: Parallel samples were placed at 48±2℃ for 30 days (1.1); at 0±2℃ for 60 days (1.2); at room temperature under normal fluorescent light for 30 days (3); and under extreme conditions, 48±2℃ for 1 day, room temperature for 1 day, and -18±2℃ for 1 day were set as one cycle, and repeated 7 times. If no situation occurred, it was recorded as normal; otherwise, the specific situation was recorded.

[0124] (3) Product foaming effect test and product usage test: Ninety female volunteers aged 20-40 years with no history of facial skin diseases and low average skin moisture content on their cheeks and foreheads after cleansing and before the test (skin moisture content of residents in South China in July summer is greater than 20% but less than 30%) were randomly divided into 9 groups of 10 people each (the average skin moisture content within each group must be maintained between 24.0% and 26.0%, otherwise re-screening was required). Each group was given the product of the example group, the comparative group, and the control group to cleanse their cheeks and foreheads. After 1 hour of cleansing, the average skin moisture content was measured using an SK-III skin moisture meter. The average value of the data of all volunteers in each group was statistically analyzed. At the same time, the user experience was rated, and the specific scores are as follows:

[0125] Total score 5 points, 5 points: No irritation during use, and leaves skin moisturized and comfortable after use;

[0126] 4 stars: It is non-irritating when used, and leaves the skin feeling comfortable and moisturized after use;

[0127] 3 stars: No irritation during use, and no obvious sensory changes on the skin after use;

[0128] 2 points: No irritation during use, but dryness, tightness or other unpleasant sensory changes may occur on the skin after use;

[0129] 1 point: It has obvious irritation when or after use.

[0130] The final calculation for each group is the average score of all volunteers within the group.

[0131] At the same time, the same operation should be used when using it, that is, wet the area to be cleaned, then place a product the size of a thumbnail on the area to be cleaned, and then rub clockwise until foam is generated. After rubbing for 3 minutes, observe the degree of foaming and evaluate it on a scale of 1 to 5, where 5 is rich foam and 1 is almost no foam. The average score of all volunteers in each group is finally calculated.

[0132] The test results are shown in Table 5.

[0133] Table 5

[0134]

[0135]

[0136] The test results show that the natural oleoyl amino acid surfactant prepared by the solid catalyst of this invention differs from products prepared by traditional processes or similar commercially available products in terms of product stability, foaming effect, and skin-benefiting effect when used to prepare facial cleansers. This is mainly attributed to the difference in the active content of natural oleoyl amino acid salts and the retention content of unsaponifiable active substances in natural oils. It can be seen that the product obtained in Example 2 of this invention, after preparing a facial cleanser, not only has good stability and can fully exert the role of surfactant, with good foaming effect, but also has a more obvious skin-benefiting effect. After use, the skin is highly moisturized, and the skin's water content is improved, resulting in excellent overall performance. At the same time, even when using similar solid catalysts, the effects of the products obtained are different. Comparative Examples 2 and 3 used magnesium oxide, which has the same catalytic activity, as a catalyst alone or as a carrier to construct the catalyst. It can be seen that the facial cleanser prepared after the catalytic synthesis of natural oleoyl amino acid surfactant by the product is comparable to the traditional process preparation group or the commercially available group in terms of stability and foaming effect. However, although the skin-benefiting effect and sensory experience are better, they are still not as good as the product in Example 2.

[0137] Furthermore, a comparison of the products in each example group also shows that the loading and crystallization process of zinc active ingredients during the preparation process will also affect the composition of the final product. In addition to affecting the purity and yield of the product, the stability, foaming effect and use effect of the product will also be different due to the different composition and ratio of amino acid salt and unsaponifiable matter. However, compared with existing products, the stability levels of each example are basically the same, and even the product of Example 2 can still maintain the non-stratification effect under extreme cycling, and its stability is better than that of existing products.

[0138] Example 5

[0139] To verify the recyclability of the solid catalyst described in this invention, the solid catalyst of Example 2 separated in Effect Example 1 was recovered, washed and dried with deionized water, and then the same steps as in Effect Example 1 were repeated to prepare the natural oleic acid amino acid surfactant and the results were statistically analyzed. The recovery was repeated 3 times and the same operation was performed. The test results are shown in Table 6.

[0140] Table 6

[0141] product 1 recycling Recycled twice Recycled 3 times 4 recyclings Yield (%) 97.33 96.47 94.31 92.68 APHA colorimetry 60 60 60 60

[0142] It can be seen that the solid catalyst described in this invention is recyclable, and the purity of the product will not be affected after multiple recycling and reuse. Moreover, after 4 recyclings, the yield of the catalyst is reduced by less than 6% compared to the new product (98.56%). Furthermore, the same test was conducted on the existing solid catalyst product similar to that described in Comparative Example 3, and the same level could not be achieved.

[0143] Example 6

[0144] To verify the catalytic universality of the solid catalyst described in this invention, 100g of coconut oil used in the preparation of natural oleoyl acyl amino acid surfactants in Example 2 of Effect 1 was replaced with 120g of commercially available avocado oil, and the same operation was performed. The yield of the obtained product reached 98.22%, which was comparable to that of the product in Example 2. This product was also used in the preparation of facial cleanser in Example 4, and its stability and foaming effect were tested. The results are shown in Table 7.

[0145] Table 7

[0146] product Avocado oil group stability normal Foam effect 4.7

[0147] It can be seen that the product also has ideal performance, indicating that the solid catalyst is suitable for a variety of natural oils. Furthermore, the inventors used the same method to verify the applicability to corn oil, rapeseed oil, and camellia oil, with results similar to those of the avocado oil group, all achieving the expected results.

[0148] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. The application of a solid catalyst in the preparation of natural oleic acid salts, characterized in that, The solid catalyst comprises a γ-Al₂O₃ support and a zinc-active catalytic component supported on the support. The raw materials for preparing the natural oleic acid acyl amino acid salt include natural oils and amino acid salts. The preparation method of the solid catalyst includes the following steps: (1) Prepare an aqueous solution of a soluble zinc source, then add γ-Al2O3 powder, mix and disperse evenly, and sonicate. Separate the solid and liquid, and dry to obtain an intermediate solid. The soluble zinc source includes at least one of zinc chloride and zinc nitrate. (2) The intermediate solid is calcined in air at 200-500°C for 3-5 hours to obtain the solid catalyst.

2. The application as described in claim 1, characterized in that, The calcination temperature in step (2) is 250~350℃.

3. The application as described in claim 1, characterized in that, The average particle size of the γ-Al2O3 powder is 3~5mm.

4. The application as described in claim 1, characterized in that, In step (1), the concentration of the soluble zinc source in the prepared aqueous solution is 5~20%w / v.

5. A natural oleic acid surfactant, characterized in that, The preparation raw materials include the following parts by weight: 100 parts of natural oils, 40-60 parts of glycerol, 40-60 parts of amino acid salts, and 1-5 parts of the solid catalyst used in the application according to any one of claims 1-4; the natural oils include at least one selected from coconut oil, avocado oil, corn oil, rapeseed oil, and camellia oil; the method for preparing the natural oil acyl amino acid surfactant is characterized by comprising the following steps: (1) Mix natural oils, glycerol, amino acid salts and the solid catalyst, then heat under reduced pressure under a protective atmosphere and cool to obtain a viscous mixture; (2) Dilute the viscous mixture with water and separate the solid catalyst to obtain the natural lipoic acid surfactant containing natural lipoic acid salt.

6. A skin care and cleansing product, characterized in that, Includes the natural oleoyl amino acid surfactant described in claim 5.

7. The skin care and cleansing product as described in claim 6, characterized in that, Based on 100 parts, it includes the following components by weight: The ingredients include 10-40 parts of natural oleoyl amino acid surfactant, 5-20 parts of auxiliary surfactant, 0.1-5 parts of thickener, 5-20 parts of humectant, 0.1-5 parts of pH adjuster, 0.1-3 parts of preservative, 0.0005-0.01 parts of fragrance, and the balance being water by weight.

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