Solid catalyst, natural oil acyl amino acid salt prepared from solid catalyst and application of natural oil acyl amino acid salt

Abstract

The invention discloses a solid catalyst, natural oil acylamino acid salt prepared from the solid catalyst and application, and belongs to the field of daily necessities, the product takes active zinc as a catalytic component and gamma-Al2O3 as a carrier, when the natural oil acylamino acid salt is directly synthesized through catalysis, the conditions are mild, and the cost is low. The prepared product does not cause damage to non-soapable substances in natural grease and has a high catalytic degree, and the effect of the prepared product is far better than that of existing similar products when the prepared product is used as an amino acid surfactant; in addition, the product still has high catalytic activity after being recycled, can be repeatedly used, and is high in economic cost performance.

Description

Technical Field

[0001] The invention relates to the field of daily necessities, and in particular to a solid catalyst and a natural oil acylamino acid salt prepared therefrom and applications thereof. Background Art

[0002] Compared with traditional ionic surfactants, amino acid surfactants have the advantages of a wide range of raw material sources, 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, the existing preparation methods of amino acid surfactants, especially natural oil acylamino acid salt surfactants, are fatty acid chloride acylation methods, which involve the Schotten-Baumann condensation reaction of amino acids and fatty acid chlorides in an alkaline environment. However, the reaction conditions of this method are too harsh, and it is accompanied by the use of acyl chloride reagents that are highly irritating and difficult to preserve, making it difficult to mass produce in conventional factories; there are also technologies that use catalysts to catalyze the direct synthesis of natural oils to prepare amino acid surfactants, but in this process, the use effect of some products prepared by mild solid catalysts is not ideal, and the catalytic degree is insufficient; and although the use of some highly active catalysts such as strong bases can ensure a high degree of catalysis, these catalysts will cause irreversible damage to the unsaponifiable matter in natural oils, affecting the quality of the product, and in the catalytic synthesis process, some irritating gases such as ammonia will be produced, and these gases may be reabsorbed by the product during the synthesis process, resulting in the product having an odor, and cannot be used in some daily necessities such as cosmetics that have high requirements for sensory experience. Summary of the invention

[0004] Based on the defects of the prior art, the present invention aims to provide a solid catalyst, which uses active zinc as a catalytic component and γ-Al 2 O 3 As a carrier, when catalyzing and directly synthesizing natural oil acylamino acid salts, not only are the conditions mild and will not damage the non-soap-containing substances in natural oils, but the catalytic degree is also high. The prepared product is much better than existing similar products when used as an amino acid surfactant. In addition, the product still has high catalytic activity after recovery, can be reused, and is economical and cost-effective.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is:

[0006] A solid catalyst comprising γ-Al 2 O 3 A carrier and a zinc active catalytic component loaded on the carrier.

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

[0008] (1) Prepare a soluble zinc source in aqueous solution and then place it in γ-Al 2 O 3 The powders are mixed and dispersed uniformly and ultrasonically treated, solid-liquid separated, and dried to obtain an intermediate solid;

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

[0010] Compared with the traditional fatty acid chloride acylation method, the catalytic natural oil direct synthesis method for preparing amino acid surfactants requires lower operation, time and equipment costs, higher production efficiency and greater safety. However, in the catalytic natural oil direct synthesis process, the use of catalysts is very critical. The existing main amino acid surfactant synthesis catalysts are mainly of two types. One type is a strong acid or strong base liquid catalyst, specifically sulfuric acid or highly active chemical reagents such as potassium hydroxide and sodium hydroxide. Although this catalyst has high catalytic activity, it will also cause damage to some non-soap active substances in the natural oil raw materials. When natural oil amino acid surfactants are used in daily chemical products, especially cosmetics, some of the non-soap active substances they contain can not only assist the active amino acids in the components, but also can effectively reduce the production cost of amino acid surfactants. The amino acid salts can enhance the foaming, dispersion and emulsification effects when used as surfactants, and can also achieve some skin care effects such as moisturizing and hydrating. If these non-soap active substances are destroyed, the use function of the component will be greatly reduced, and even worse than some ordinary ionic surfactants; another type of milder catalyst is a solid catalyst with active metal components. This type of catalyst basically does not destroy the non-soap active substances in the natural oil raw materials. However, due to the complex composition of natural oils, the degree of catalytic synthesis of amino acid salts by the catalyst is not high without acid-base reaction, and the basic use performance of the prepared amino acid surfactant is weak. In addition, the current catalysts have a high deactivation rate, and the yield of the product that continues to catalyze after recovery is greatly reduced, and it is often necessary to prepare it once. For this reason, in the technical solution of the present invention, for the catalytic raw material of natural oils, the inventor uses active zinc with specific high catalytic activity as the catalytic component, and at the same time matches it with γ-Al with high adaptability. 2 O 3 Powder as a carrier, due to γ-Al 2 O 3The powder has a spherical morphology and has high dispersibility after the introduction of natural oils. At the same time, after specific calcination loading and crystal form regulation treatment, the composite solid catalyst loaded with active zinc has high catalytic selectivity and catalytic activity for saponifiable active substances in natural oils, and can effectively catalyze the preparation of natural oil acylamino acid salts. At the same time, when the product is used in daily chemical products, especially cosmetics, the active components and the non-soap active substances retained in natural oils can fully synergize, so that the product has ideal foaming effect, stabilization effect and skin care activity effect. At the same time, the solid catalytic structure stability and catalytic activity stability are strong, and it can be recycled and reused many times, which is very suitable for factory-scale production.

[0011] However, during the preparation process, the temperature range for calcination loading and crystal form regulation is particularly important. 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 catalytically active components and carrier of the solid catalyst are replaced with other similar components (even the crystal form of the carrier is changed), the same effect cannot be achieved. Therefore, specific selection is required to achieve the desired effect.

[0012] Preferably, the temperature during the calcination treatment in step (2) is in the range of one or any two of 200°C, 250°C, 300°C, 350°C, 400°C, 450°C, and 500°C.

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

[0014] Since the calcination treatment involves the combined dispersion effect of the carrier and the load, as well as the crystal structure of the two, especially the zinc active catalytic component, which affects the catalytic activity and structural stability of the obtained product, the use effects of products prepared at different temperatures are naturally different. After screening, when the temperature during the calcination treatment is preferably within the above range, the use effect of the obtained product is better.

[0015] Preferably, the γ-Al 2 O 3 The average particle size of the powder is 3 to 5 mm.

[0016] When the zinc active catalytic component is loaded, the obtained solid catalyst is subsequently used for the catalytic synthesis of natural oil acylamino acid salts or even the solid catalyst is separated after the catalytic synthesis is completed, the γ-Al as a carrier 2 O 3 The size of the powder will affect the product effect at these stages. If the carrier size is selected based on existing similar solid catalysts, the yield of the product during catalytic synthesis and the use effect of subsequent products may be different. After optimization, when the γ-Al 2 O3 When the average particle size of the powder is within the range of 3 to 5 mm, the solid catalyst has a better use effect.

[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 to 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 the present invention, as the concentration of the soluble zinc source increases, the γ-Al 2 O 3 The zinc concentration loaded after the powder will also be higher, but this is accompanied by 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 treatment based on the decrease in the uniformity of active zinc dispersion. Therefore, after optimization, when the concentration of the soluble zinc source is within 10-15% w / v during the configuration of the aqueous solution, the loading effect of active zinc is better and the catalytic activity of the prepared solid catalyst is higher.

[0022] Preferably, in step (1), the aqueous solution and γ-Al 2 O 3 The volume ratio of the powder is 1:(0.8~1.2).

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

[0024] Before calcination, γ-Al can be effectively dispersed by ultrasonic treatment. 2 O 3 Powder, to avoid the agglomeration and accumulation of the particles of the substance, so that the 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 use of the solid catalyst in the preparation of natural oil acylamino acid salts.

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

[0028] (1) mixing natural oil, glycerol, amino acid salt and the solid catalyst of the present invention, then heating under reduced pressure in a protective atmosphere, and cooling to obtain a viscous mixture;

[0029] (2) diluting the viscous mixture with water and separating the solid catalyst to obtain the natural oil acylamino acid surfactant containing the natural oil acylamino acid salt.

[0030] The solid catalyst of the present invention has high catalytic activity and mild properties, so it can be directly mixed with raw materials such as natural oils and fats, and a high-yield and high-activity natural oil acylamino acid surfactant containing natural oil acylamino acid salt can be prepared under a conventional reduced pressure and high temperature environment. At the same time, the solid catalyst has a stable structure, can be easily recovered and reused, and has a high production cost-effectiveness.

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

[0032] The solid catalyst of the present invention has universal applicability to the process of catalyzing the synthesis of natural oil acylamino acid surfactants for various natural oils. Based on the component matching and efficacy requirements of daily necessities, especially cosmetics / skin care / cleaning products, to which the component is applied, those skilled in the art can use natural oils including but not limited to the above-mentioned types as raw materials to prepare products (for example, in order to enhance the anti-aging effect of cosmetics / skin care / cleaning products, those skilled in the art can introduce a certain amount of avocado oil into the product components, and based on the compatibility matching of the components, avocado oil acylamino acid salt can be prepared using avocado oil as a raw material as an amino acid surfactant active ingredient; for example, in order to avoid easily oxidizable impurities that may exist in corn oil and rapeseed oil and ensure the low odor of the product, those skilled in the art can choose coconut oil with a lower volatile impurity content as a natural oil to prepare the product).

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

[0034] 100 parts of natural oils and fats, 40-60 parts of glycerol, 40-60 parts of amino acid salts and 1-5 parts of solid catalysts.

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

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

[0037] The solid catalyst addition amount within a certain range will affect the rate of catalytic synthesis and the recovery efficiency of the solid catalyst after the synthesis product. Those skilled in the art can select a suitable catalyst addition amount according to actual preferences.

[0038] Preferably, in the step (1), the pressure during the reduced 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 oil acylamino acid surfactant prepared by the preparation method.

[0040] The natural oil acylamino acid surfactant containing natural oil acylamino acid salt and unsaponifiable active substances synthesized by direct catalysis of the solid catalyst of the present invention has a variety of effective ingredients. When used in daily chemical products, especially skin care cosmetics and skin cleaning products with skin care effects, it can not only give full play to the intrinsic emulsification effect and foaming effect of the surfactant, but also play an obvious care role on the skin. After use, the prepared product can effectively improve the moisture content of the skin and play a moisturizing function, while it is difficult to achieve the same effect when using traditional surfactants or amino acid salt active agents.

[0041] Another object of the present invention is to provide a skin care cleanser comprising the natural oil acylamino acid surfactant of the present invention.

[0042] Preferably, the dosage forms of the skin care cleansing product include cream, essence, and essence oil.

[0043] More preferably, the skin care cleaning product is a facial cleanser, which comprises the following components in parts by weight per 100 parts:

[0044] The invention comprises 10 to 40 parts of the natural oil acylamino acid surfactant, 5 to 20 parts of the auxiliary surfactant, 0.1 to 5 parts of the thickener, 5 to 20 parts of the moisturizer, 0.1 to 5 parts of the pH regulator, 0.1 to 3 parts of the preservative, 0.0005 to 0.01 parts of the flavor and the balance of water.

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

[0046] Preferably, the thickener includes at least one of acrylic acid (ester) copolymers and modified corn starch.

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

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

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

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

[0051] The invention comprises 10-40 parts of the natural oil acyl 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 acid (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 flavor and the balance of water.

[0052] The facial cleanser prepared based on the natural oil acylamino acid surfactant of the present invention can give full play to the ideal cleansing effect, has good foaming effect when used, and can effectively increase the moisture content of the skin during cleansing, and the moisturization of the skin is improved after cleansing; the product has high stability and can be transported and stored for a long time.

[0053] The beneficial effect of the present invention is that the present invention provides a solid catalyst, which uses active zinc as a catalytic component and γ-Al 2 O 3 As a carrier, when catalyzing and directly synthesizing natural oil acylamino acid salts, not only are the conditions mild and will not damage the non-soap-containing substances in natural oils, but the catalytic degree is also high. The prepared product is much better than existing similar products when used as an amino acid surfactant. In addition, the product still has high catalytic activity after recovery, can be reused, and is economical and cost-effective. DETAILED DESCRIPTION

[0054] In order to better illustrate the purpose, technical scheme and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments and comparative examples, the purpose of which is to understand the content of the present invention in detail, rather than to limit the present invention. All other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention. The experimental reagents and instruments involved in the implementation of the present invention are all commonly used ordinary reagents and instruments unless otherwise specified. The coconut oil used in each embodiment and comparative example of the present invention is food-grade coconut oil produced by Yihai Kerry; avocado oil is food-grade avocado oil produced by Henry, Germany; sodium methyl cocoyl taurate, sodium lauroyl aspartate, cocamidopropyl betaine, acrylic acid (ester) copolymer, and capryloyl glycine are all commercially available products; modified corn starch is edible corn starch produced by Dongmei; preservative is Euxyl PE9010 produced by Schumet, Germany; flavor is flavor produced by Firmenich.

[0055] Example 1

[0056] The present invention discloses a solid catalyst and a natural oil acylamino acid salt prepared therefrom and an embodiment of its application. The method for preparing the solid catalyst comprises the following steps:

[0057] (1) 5 g of soluble zinc source Zn(NO 3 ) 2 A 5% w / v aqueous solution was prepared with 100 g of deionized water, and then γ-Al with an average particle size of 3.5 mm after screening was placed in the same volume ratio of the aqueous solution. 2 O 3 The powder (Henghuan New Materials) was mixed and dispersed uniformly and ultrasonically treated at 50 W for 2 h, solid-liquid separation was performed, and dried at 140 °C for 4 h to obtain an intermediate solid;

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

[0059] Example 2

[0060] The embodiment of the solid catalyst, the natural oil acylamino acid salt prepared therefrom and the application thereof of the present invention is different from the embodiment 1 only in that the addition amount of the soluble zinc source is 10 g and the concentration of the aqueous solution is 10% w / v.

[0061] Example 3

[0062] The embodiment of the solid catalyst, the natural oil acylamino acid salt prepared therefrom and the application thereof of the present invention is different from the embodiment 1 only in that the addition amount of the soluble zinc source is 15 g and the concentration of the aqueous solution is 15% w / v.

[0063] Example 4

[0064] The embodiment of the solid catalyst, the natural oil acylamino acid salt prepared therefrom and the application thereof of the present invention is different from the embodiment 1 only in that the addition amount of the soluble zinc source is 20 g and the concentration of the aqueous solution is 20% w / v.

[0065] Example 5

[0066] The embodiment of the solid catalyst, the natural oil acylamino acid salt prepared therefrom and the application thereof described in the present invention is different from Example 2 only in that the temperature of the calcination treatment is 250°C.

[0067] Example 6

[0068] The embodiment of the solid catalyst, the natural oil acylamino acid salt prepared therefrom and the application thereof described in the present invention is different from the embodiment 2 only in that the temperature of the calcination treatment is 350°C.

[0069] Example 7

[0070] The embodiment of the solid catalyst, the natural oil acylamino acid salt prepared therefrom and the application thereof described in the present invention is different from Example 2 only in that the temperature of the calcination treatment is 200°C.

[0071] Example 8

[0072] The embodiment of the solid catalyst, the natural oil acylamino acid salt prepared therefrom and the application thereof described in the present invention is different from Example 2 only in that the temperature of the calcination treatment is 400°C.

[0073] Example 9

[0074] The embodiment of the solid catalyst, the natural oil acylamino acid salt prepared therefrom and the application thereof described in the present invention is different from Example 2 only in that the temperature of the calcination treatment is 450°C.

[0075] Example 10

[0076] The embodiment of the solid catalyst and the natural oil acylamino acid salt prepared therefrom and the application thereof of the present invention is different from the embodiment 2 only in that the γ-Al 2 O 3 The average particle size of the powder after screening is 4.5 mm.

[0077] Embodiment 11

[0078] The embodiment of the solid catalyst and the natural oil acylamino acid salt prepared therefrom and the application thereof of the present invention is different from the embodiment 2 only in that the γ-Al 2 O 3 The average particle size of the powder after screening is 2.5 mm.

[0079] Example 12

[0080] The embodiment of the solid catalyst and the natural oil acylamino acid salt prepared therefrom and the application thereof of the present invention is different from the embodiment 2 only in that the γ-Al 2 O 3 The average particle size of the powder after screening is 6 mm.

[0081] Comparative Example 1

[0082] The embodiment of a solid catalyst, a natural oil acylamino acid salt prepared therefrom, and its application is different from the embodiment 2 only in that the temperature of the calcination treatment is 100°C.

[0083] Comparative Example 2

[0084] A solid catalyst and a natural oil acylamino acid salt prepared therefrom and its application are provided in the embodiment, which differs from the embodiment 2 only in that the γ-Al 2 O 3 The powder was 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, the γ-Al used in Example 1 2 O 3 Powder

[0089] Effect Example 1

[0090] In order to verify the influence of the configuration concentration of the soluble zinc source in the preparation process of the solid catalyst of the present invention on the use effect of the prepared product, the products obtained in Examples 1 to 4 and the product of Comparative Example 4 were used to prepare a natural oil acylamino acid surfactant, and the specific method was as follows:

[0091] (1) 100 g of commercially available coconut oil, 50 g of glycerol, 50 g of sodium glycinate and 4 g of the above-mentioned solid catalyst were mixed, and then the pressure was reduced to 0.03-0.1 MPa under a protective atmosphere and heated at 110° C. for 5 h. After the heating was completed, the mixture was cooled for 30 min to obtain a viscous mixture;

[0092] (2) diluting the viscous mixture with 300 g of pure water and separating the solid catalyst to obtain the natural oil acylamino acid surfactant containing the natural oil acylamino acid salt.

[0093] Then the yield (%) of the prepared product is calculated as 100%*(product quality*chromatographic analysis purity) / theoretical calculated yield;

[0094] At the same time, the obtained product is subjected to APHA colorimetry test, and the specific test method is: GB / T 3143-82 Liquid Chemical Product Color Determination Method.

[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 Chroma / 60 60 60 60

[0098] It can be seen from the test results that when preparing solid catalysts, the concentration setting when introducing zinc active ingredients will directly affect the catalytic effect of the prepared products. When preparing zinc-containing aqueous solutions, too low or 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] Effect Example 2

[0100] In order to verify the effect of the calcination temperature of the solid catalyst of the present invention on the use of the prepared product during the preparation process, the products obtained in Examples 5 to 9 and Comparative Example 1 were subjected to the same natural oil acylamino acid surfactant preparation as in Effect Example 1, and the yield and product APHA chromaticity were statistically analyzed. The test results are shown in Table 2.

[0101] Table 2

[0102]

[0103] It can be clearly seen from the test results that during the preparation process of the solid catalyst of the present invention, the calcination treatment has a great influence on its final catalytic effect. At a lower temperature, the soluble zinc cannot form active zinc with catalytic activity, so the product cannot be used as a catalyst. In this case, the natural oil acylamino acid surfactant cannot be synthesized. As the calcination temperature increases, the active zinc is gradually generated, and the degree of catalysis is also improved. However, during calcination, the temperature will also affect the loading effect and dispersion of the solid catalyst. When the calcination temperature is further increased, the yield of the product is reduced. From the results, when the calcination temperature is preferably between 250 and 350°C, the synthesized product has the best effect.

[0104] Effect Example 3

[0105] In order to verify the effect of the particle size of the carrier on the preparation of the solid catalyst of the present invention, the products obtained in Examples 10 to 12 were subjected to the same natural oil acylamino acid surfactant preparation as in Effect Example 1, and the yield and product APHA chromaticity were statistically analyzed. The test results are shown in Table 3.

[0106] Table 3

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

[0108] It can be seen from Table 3 that when preparing the solid catalyst, the γ-Al 2 O 3The powder has different specific surface areas based on the particle size, and the loading effect of active zinc and the uniform effect of the overall solid catalyst are also different. These differences directly affect the catalytic efficiency when it is used. Too large or too small a particle size will eventually lead to a decrease in the yield of the product catalyzed by the solid catalyst. Therefore, γ-Al with a particle size of 3 to 5 mm is used. 2 O 3 Powders work best.

[0109] Effect Example 4

[0110] In order to verify the catalytic effect of the natural oil acyl amino acid salt obtained by the solid catalyst of the present invention, the catalysts described in Examples 1 / 2 / 4 / 7 / 9 and Comparative Examples 2 / 3 were used to prepare natural oil acyl amino acid surfactants according to the method described in Effect Example 1, and then a facial cleanser was prepared according to the formula described in Table 4;

[0111] The specific preparation method is:

[0112] (1) mixing a natural oil acyl amino acid surfactant, sodium methyl cocoyl taurate, glycerin and a portion of water, and then stirring and dissolving them in a 93° C. water bath to obtain a mixture A;

[0113] (2) Add modified corn starch dispersed in water to mixed material A, keep warm and stir for 30 minutes, add acrylic acid (ester) copolymer dispersed in water, keep warm and stir for 10 minutes, then add cocamidopropyl betaine, stir for 5 minutes, stop heating, add capryloyl glycine and citric acid dissolved in water, and some water, and cool while stirring;

[0114] (3) When the mixed material is cooled to 45°C, add preservatives and flavors and adjust the speed to 100 rpm. Continue stirring until the material turns white and thickens. Continue stirring for 30 minutes and then discharge the material.

[0115] Table 4

[0116] Components Weight parts (total 100 parts) Natural oil acyl amino acid surfactant 30 Sodium Methyl Cocoyl Taurate 3 Sodium Lauroyl Aspartate 5 Cocamidopropyl Betaine 7.5 Acrylic acid (ester) copolymer 1.5 Modified corn starch 1 glycerin 15 Citric Acid 1.1 Capryloyl Glycine 0.5 preservative 1 essence 0.001 water Remaining quantity up to 100 copies

[0117] At the same time, a control group of traditional preparations and a control group of commercially available products were set up. The preparation method of the traditional preparations was as follows:

[0118] (1) 100 g of commercially available coconut oil, 50 g of glycerol, 50 g of sodium glycinate and 2 g of sodium hydroxide were mixed, and then the pressure was reduced to 0.03-0.1 MPa under a protective atmosphere and heated at 110° C. for 5 h. After the heating was completed, the mixture was cooled for 30 min to obtain a viscous mixture;

[0119] (2) diluting the viscous mixture with 300 g of pure water, and adding citric acid to adjust the pH to neutral, thereby obtaining the natural oil acylamino acid surfactant prepared by the traditional process.

[0120] During the preparation process, a relatively high concentration of pungent odor is still produced under ventilation conditions, and production personnel need to wear protective masks in addition.

[0121] Prepare a cleanser according to the same recipe;

[0122] Commercially available sodium cocoyl glycinate (CAS: 90387-74-9) was used to prepare a facial cleanser according to the same formula, and then the facial cleanser was tested as follows:

[0123] (1) Product stability test: Conduct multiple environmental tests: Take parallel samples and place them at (1.1) 48±2℃ for 30 days; (1.2) 0±2℃ for 60 days; (3) 30 days of regular fluorescent light exposure at room temperature; (4) Extreme condition test: 1 day at 48±2℃, 1 day at room temperature, and 1 day at -18±2℃ as one cycle, and repeat 7 cycles; if no situation occurs, record it as normal, otherwise record the specific situation;

[0124] (3) Product foaming effect test and product use test: 90 female volunteers aged 20 to 40 years old, with no history of facial skin diseases and low average moisture content of the skin on the cheeks and forehead after cleansing and before the test (the skin moisture content of permanent residents in South China in July is greater than 20% but less than 30%) were selected and randomly divided into 9 groups, with 10 people in each group (the average moisture content of the skin in the group must be maintained at 24.0-26.0%, otherwise re-screening), each group was given the embodiment group, comparative example group and control group products to clean the cheeks and forehead of the face, and after cleaning for 1 hour, the average moisture content was tested using a skin moisture test SK-III model instrument, and each group finally calculated the average value of the data of all volunteers in the group; at the same time, the use experience was scored, and the specific scores are as follows:

[0125] Total score is 5 points, 5 points: No irritation when used, skin is moisturized and comfortable after use;

[0126] 4 points: No irritation during use, skin feels more comfortable and moisturized after use;

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

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

[0129] 1 point: There is obvious irritation during or after use.

[0130] Each group will finally calculate the average of the scores of all volunteers in the group.

[0131] At the same time, the same operation needs to be adopted when using it, that is, moisten the area to be cleaned, then place the product the size of a thumb nail 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 with 1 to 5 points, where 5 points are rich foaming and 1 point is almost no foaming. Each group will finally calculate the average score of all volunteers in the group.

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

[0133] Table 5

[0134]

[0135]

[0136] From the test results, it can be seen that the natural oil acyl amino acid surfactant prepared by the solid catalyst of the present invention is different from the product prepared by the traditional process or the similar product on the market in the preparation of the facial cleanser. The stability, foaming effect and the benefit effect on the skin are different. This is mainly attributed to the difference in the active content of the natural oil acyl amino acid salt in the product and the retention content of the unsaponifiable active matter in the natural oil. It can be seen that the product obtained in Example 2 of the present invention has good stability after preparing the facial cleanser, can give full play to the role of the surfactant, has good foaming effect, and can also have a more obvious benefit effect on the skin. After use, the skin is highly moisturized, and the water content of the skin is improved after use, and the comprehensive use effect is excellent; at the same time, even if a similar solid catalyst is used for preparation, the use effect of the obtained product is different. Comparative Examples 2 and 3 respectively use magnesium oxide with the same catalytic activity as a catalyst alone, or as a carrier to construct a catalyst. It can be seen that the facial cleanser prepared by the product catalytically synthesizing the natural oil acyl amino acid surfactant is equivalent to the traditional process preparation group or the commercially available group in terms of stability and foaming effect, and the benefit effect and experience sensory experience for the skin are better, but still not as good as the product in Example 2.

[0137] In addition, it can be seen from the comparison of the products of each embodiment group that during the preparation process, the loading and crystallization process of the zinc active ingredient 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 based on the different components and proportions of the amino acid salt and the unsaponifiable matter. However, compared with the existing products, the embodiments can basically achieve the same stability level, and even the product of Example 2 can still maintain a non-stratified effect under extreme cycles, and its stability is better than that of the existing products.

[0138] Effect Example 5

[0139] In order to verify the recyclability of the solid catalyst of the present invention, the solid catalyst of Example 2 separated in Effect Example 1 was recovered, washed with deionized water, and dried, and the same steps of Effect Example 1 were repeated to prepare the natural oil acyl 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 Recycling 1 time Recycling 2 times Recycling 3 times Recycling 4 times Yield (%) 97.33 96.47 94.31 92.68 APHA Chroma 60 60 60 60

[0142] It can be seen that the solid catalyst of the present invention is recyclable, and the purity of the product will not be affected after multiple recycling and reuse. Moreover, after recycling 4 times, the yield (98.56%) decreased by less than 6% compared with the yield of the new product catalysis. However, further testing of the similar existing solid catalyst product described in Comparative Example 3 failed to achieve the same level.

[0143] Effect Example 6

[0144] In order to verify the catalytic synthesis universality of the solid catalyst of the present invention, 100g of coconut oil used in the preparation of the natural oil acyl amino acid surfactant of Example 2 in Effect Example 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 equivalent to that of the product of Example 2. At the same time, it was also used in the preparation of the facial cleanser of Effect Example 4, and the 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 an ideal use effect, indicating that the solid catalyst is suitable for a variety of natural oils and fats. In addition, the inventors also used the same method to verify the universality of corn oil, rapeseed oil and camellia oil, and the results were similar to those of the avocado oil group, and all achieved the expected effect.

[0148] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A solid catalyst, characterized in that The invention comprises a γ-Al2O3 carrier and a zinc active catalytic component loaded on the carrier.

2. The method for preparing a solid catalyst as claimed in claim 1, characterized in that: The preparation method of the solid catalyst comprises the following preparation steps: (1) preparing an aqueous solution of a soluble zinc source, then placing γ-Al2O3 powder in the mixture to mix and disperse the mixture evenly, ultrasonically treating the mixture, separating the solid from the liquid, and drying the mixture to obtain an intermediate solid; (2) The intermediate solid is calcined at 200-500° C. for 3-5 hours in an air atmosphere to obtain the solid catalyst.

3. The method for preparing a solid catalyst as claimed in claim 2, characterized in that: The temperature of the calcination treatment in the step (2) is 250-350°C.

4. The method for preparing a solid catalyst as claimed in claim 2, characterized in that: The average particle size of the γ-Al2O3 powder is 3 to 5 mm.

5. The method for preparing a solid catalyst as claimed in claim 2, characterized in that: In the step (1), the concentration of the soluble zinc source in the prepared aqueous solution is 5-20% w / v; the soluble zinc source includes at least one of zinc chloride, zinc nitrate and zinc sulfate.

6. Use of the solid catalyst as claimed in claim 1 in the preparation of natural oil acylamino acid salts.

7. A natural oil acylamino acid surfactant, characterized in that: The preparation method comprises the following raw materials in parts by weight: 100 parts of natural oil, 40-60 parts of glycerol, 40-60 parts of amino acid salt and 1-5 parts of the solid catalyst according to claim 1; the natural oil comprises at least one of coconut oil, avocado oil, corn oil, rapeseed oil and camellia oil.

8. The method for preparing the natural oil acylamino acid surfactant according to claim 7, characterized in that: The following steps are involved: (1) mixing natural oil, glycerol, amino acid salt and the solid catalyst according to claim 1, then heating under reduced pressure in a protective atmosphere, and cooling to obtain a viscous mixture; (2) diluting the viscous mixture with water and separating the solid catalyst to obtain the natural oil acylamino acid surfactant containing the natural oil acylamino acid salt.

9. A skin care cleaning product, characterized in that: The method comprises the natural oil acylamino acid surfactant as described in claim 8.

10. The skin care cleaning product according to claim 9, characterized in that: Based on 100 parts, the following components are included in parts by weight: 10 to 40 parts of the natural oil acyl amino acid surfactant as claimed in claim 8, 5 to 20 parts of an auxiliary surfactant, 0.1 to 5 parts of a thickener, 5 to 20 parts of a moisturizer, 0.1 to 5 parts of a pH adjuster, 0.1 to 3 parts of a preservative, 0.0005 to 0.01 parts of a flavor and the balance in weight of water.

Images