CN1696145A - A kind of preparation technology of saponin and its application - Google Patents

Abstract

A process for preparing the gleditschiasaponin used for agricultural chemical, detergent and shampoo features that the absolute alcohol is used for its extraction and separation.

Description

A kind of preparation technology of saponin and its application

technical field

The invention belongs to the field of forest product chemical industry and applied chemistry, and relates to a preparation process of saponin and its application in pesticides, detergents and shampoos.

Background technique

Gleditisia sinensis Saponin, also known as Gleditisia sinensis Saponin, is a pentacyclic triterpenoid saponin composed of basic units such as ligands, sugar bodies and organic acids. The saponin molecule is composed of hydrophilic sugar body and hydrophobic coordination group, so it has various surface active properties such as emulsification, dispersion, wetting, decontamination, and foaming, and is a natural non-ionic Surfactant. In addition, saponin also has obvious anti-inflammatory, anti-penetration ability and anti-inflammatory, expectorant, analgesic, bactericidal, insecticidal and other effects. Therefore, saponin can be used to manufacture various types of emulsifiers, detergents, insecticides or fungicides, etc., and is a very promising natural surfactant in the current daily chemicals, cosmetics, skin care, medicine and pesticide industries. agent.

Honey locust tree has well-developed root system, is drought-resistant, water-saving, and strong. It is an ideal ecological tree species for building farmland shelter forests, soil and water conservation forests, and urban and rural landscape forests. There are wild acacia forests in Shaanxi, Henan, Hebei, and Sichuan. At present, artificial acacia forests have been developed in these areas, with a planting area of more than 300,000 mu. The seed content in the whole fruit of Acacia locust is 15-30%, and the seed is rich in high-quality polysaccharide gum. The preparation process has been applied for an invention patent (CN03132340.5); The yield is 3-5 times of seed yield. Therefore, the development and utilization of honey locust peel has decisive significance for the efficient utilization and comprehensive utilization of honey locust resources. Among the more than 30 patents related to saponins, the raw materials of saponins or their water extracts are mainly used to compound traditional Chinese medicines, pesticides and detergents (CN1424102A, CN1301533A, CN1060313C, etc.), and there are no patent reports on the preparation process of saponins.

The production of saponin mainly includes water extraction method and organic solvent method. Water extraction production, its production process and production equipment are simple, but there are disadvantages such as large water treatment capacity, difficult conventional separation, low product purity, and high energy consumption. The organic solvent method mainly uses 70-95% alcohol-water solvent to extract the raw materials. This process has the advantages of high extraction efficiency, good product quality, and suitable for industrial production. However, the process is complicated, the investment is large, and the product needs to be further purified. refined.

Contents of the invention

The object of the present invention is to propose a novel high-efficiency and concise process suitable for the preparation of saponin and its application in pesticides, detergents and shampoos.

The invention discloses a process for preparing saponins, which is characterized in that absolute ethanol is used for extraction and separation.

Technology of the present invention, it comprises the steps:

(1) the whole fruit of the Chinese acacia is cleaned up to remove impurities;

(2) Fragmentation is carried out to whole fruit, removes seed;

(3) crush the peel;

(4) adding extractant to extract and separate fat-soluble components in pericarp;

(5) defatted pericarp extracts and separates saponin with dehydrated alcohol;

(6) Concentrating the extract to crystallize the saponin;

(7) Saponin crystals are vacuum filtered, washed and dried.

Preferably, it includes the steps of:

(1) Select the whole fruit of Acacia locust with water content≤8%, clean and remove impurities, and the impurity content rate≤0.5%;

(2) crush the whole fruit, remove the seeds, and the seed removal rate is more than or equal to 95%;

(3) crushing the pericarp, the particle size of the crushed and sieved pericarp is 2-5mm;

(4) adding an extractant to extract and separate the fat-soluble components in the pericarp, the weight ratio of the extractant to the pericarp is 2-7:1, and the extraction time is 2-8 hours;

(5) The defatted peel is extracted with absolute ethanol to separate saponin, the weight ratio of absolute ethanol and defatted peel is 3-9:1, the extraction temperature is 40-80° C., and the extraction time is 3-9 hours;

(6) Concentrating the extract to crystallize the saponin, the weight ratio of saponin to ethanol is 1:0.3-1.5, and the crystallization temperature of saponin is 5-30°C;

(7) Vacuum filtration of the saponin crystals, washing the saponin crystals, the amount of detergent used is twice the weight of the saponin, and drying at a temperature of 50-100°C.

More preferably, it includes the steps of:

(1) Select the whole fruit of Acacia locust with water content ≤ 8%, clean and remove impurities, the impurity rate ≤ 0.5%, and do not contain iron impurities;

(2) crush the whole fruit, remove the seeds, and the seed removal rate is more than or equal to 95%;

(3) crushing the pericarp, the particle size of the crushed and sieved pericarp is 2-5mm;

(4) adding No. 6 extraction solvent oil (distillation range 60-90 ℃) or petroleum ether to extract and separate the fat-soluble components in the pericarp, the weight ratio of the extractant and the pericarp is 3.5:1, and the extraction time is 4 hours;

(5) Degreased pericarp is extracted with absolute ethanol to separate saponin, the weight ratio of absolute ethanol and defatted pericarp is 4.5:1, the extraction temperature is 60-70° C., and the extraction time is 5 hours;

(6) Concentrating the extract to crystallize the saponin, the weight ratio of saponin to ethanol is 1:0.8, and the crystallization temperature of saponin is 15° C.;

(7) The saponin crystals are vacuum filtered, and the saponin crystals are washed with acetone. The amount of detergent used is twice the weight of the saponin, washed three times, and dried at a temperature of 80°C.

The process is detailed as follows:

(1) Raw material requirements: the moisture content of the whole fruit of Acacia saponica ≤ 8%, after cleaning and removing impurities, the impurity rate ≤ 0.5%, and does not contain iron impurities;

(2) The whole fruit is mechanically crushed with a rod mill or a hammer mill, and the seeds are removed by sieving or gravity, and the seed removal rate is ≥95%.

(3) The peel is crushed by using a hammer mill or a rod mill, and the particle size of the crushed and sieved peel is 2-5 mm.

(4) No. 6 extraction solvent oil (Jinling Petrochemical Co., Ltd.) (distillation range 60-90°C) or petroleum ether extracts and separates the fat-soluble components in the peel, and the weight ratio of the extractant to the peel is 2-7:1 , the best ratio is 3.5:1; the extraction time is 2 to 8 hours, and the best extraction time is 4 hours.

(5) Degreased pericarp extracts and separates saponin with absolute ethanol, and the weight ratio of dehydrated alcohol and defatted pericarp is 3-9: 1, and the optimum proportion is 4.5: 1; Extraction temperature is 40-80 ℃, optimum The extraction temperature is 60-70°C; the extraction time is 3-9 hours, and the optimum extraction time is 5 hours.

(6) The extract is concentrated, the weight ratio of saponin and ethanol is 1:0.3-1.5, and the optimum weight ratio is 1:0.8; the saponin crystallization temperature is 5-30°C, and the optimum crystallization temperature is 15°C; the extract is concentrated The recovered ethanol solvent is reused as an extractant after anhydrous treatment.

(7) Saponin crystal filtration adopts vacuum filter, all reclaims ethanol solvent; Wash saponin crystal with acetone, detergent consumption is 2 times of saponin weight, wash in three times; Saponin drying adopts box dryer or air flow Dryer, the drying temperature is 50-100°C, the best drying temperature is 80°C.

The invention provides the application of saponins prepared by the process in pesticides.

With 24.3% (percentage by weight, the same below) acacia saponin and 0.7% kung fu chrysanthemum ester mixed and diluted 2500 times the effect of killing vegetable aphids and 2.5% kung fu chrysanthemum ester mixed dilution 2500 times of killing vegetable aphid effect is basically the same, use acacia soap It can save 72% of the consumption of Kungfu permethrin after vegetarian treatment;

After adding 1500-3500mg/L of saponin in the 2500-fold dilution of Torke, the medicine liquid was dropped on the front and back of the leaves of the apple tree, and its contact angle was reduced by 15.2-24.6% and 13.5-21.3% respectively. Add 2500mg The amount of deposition of Torke liquid on the apple leaf surface after the /L saponin can be increased by 27.4%, and the same control effect can be achieved. Significantly reduced the pollution of pesticides to the environment.

Adding acacia saponin to the pesticide improves the adhesion, wet spreading and effective deposition of the liquid on the plant surface and target organisms, thereby improving the use effect of the pesticide. Therefore, acacia saponin can be used as a biological pesticide, It is also an excellent pesticide synergist.

The invention provides the application of the saponins prepared by the process in detergents.

Silk, wool detergent formula (percentage by weight): saponin 2-5%, diethanolamide (6501) 5-7%, lauryl alcohol polyoxyethylene ether sulfate (AES) 8-11%, sulfur Sodium phosphate 4-6%, carboxymethylcellulose (CMC) 1-2%, essence 0.5%, deionized water is added to 100%.

The invention provides the application of saponin prepared by the process in shampoo.

Shampoo formula (percentage by weight): saponin 1-4%, fatty alcohol polyoxyethylene ether ammonium sulfate (AESA) 8-12%, diethanolamide (6501) 1-3%, propyl betaine (CAB -30) 3-7%, citric acid 0.1-1%, cationic guar gum 0.1-0.5%, pearlescent diester 1-3%, silicone oil emulsion 0.5-3%, antipruritic agent 0.5%, essence 0.5%, detox Add ionized water to 100%.

The whole fruit of acacia is composed of two parts, the seed and the peel. To prepare saponin from the whole fruit of Acacia locust, because saponin exists in the pericarp, the pericarp and seeds are first separated by mechanical separation, which avoids the influence of various components in the seeds on the process of preparing saponin, and the separated seeds can be used as The raw material for preparing polysaccharide gum can kill two birds with one stone. In order to remove the influence of fat-soluble components in the peel on the preparation of saponin, the present invention uses No. 6 extraction solvent oil to extract the peel. The present invention adopts absolute ethanol to extract the saponin in the pericarp. Tests show that the water content in the organic solvent directly affects the purity of the product. The greater the water content within a certain range, the higher the one-time extraction rate of the product. However, the separation of the product and the extraction residue is more difficult, and the purity of the saponin is also reduced, resulting in the complexity of the purification process of the product. Considering the dissolution characteristics of the main components in the peel in ethanol, that is, saponin is slightly soluble in cold ethanol and easily soluble in hot ethanol, and the solubility of the rest of the ingredients in ethanol is so small that it can be ignored, using hot absolute ethanol as a solvent, The saponin is extracted by reflux and filtered while it is hot to quickly separate the saponin product from the raw material, and the saponin extraction and purification are carried out simultaneously, and the product yield and purity are significantly improved, and the preparation process is efficient and simple. The saponin crystals can be washed with acetone and dried to obtain the saponin finished product. The highest yield of saponin in the peel can reach 33%, the extraction rate is greater than 92%, and the product purity is greater than 96%.

Description of drawings

Fig. 1 preparation process flow chart of acacia saponin of the present invention

Detailed ways

Example 1:

Select the whole fruit of acacia with a water content of ≤8%. After cleaning and removing impurities, the impurity rate is ≤0.5%, and does not contain iron impurities; the whole fruit is mechanically crushed with a rod mill, and the seeds are separated, and the seed separation and extraction rate is ≥95% The acacia pericarp after the seeds are separated is pulverized and sieved by a hammer mill to obtain pericarp particles with a particle size of 2 to 3 mm. Use No. 6 extraction solvent oil (Jinling Petrochemical Co., Ltd.) to extract and separate the fat-soluble components in the pericarp. The weight ratio of the extractant to the pericarp is 3.5:1, and the extraction time is 5 hours. The defatted pericarp is extracted with absolute ethanol to separate saponin, the weight ratio of absolute ethanol and defatted pericarp is 4:1, the extraction temperature is 60° C., and the extraction time is 5 hours. The extract was concentrated until the weight ratio of saponin to ethanol was 1:0.8, and crystallized at 15°C. The saponin crystals are filtered through a vacuum filter, washed twice with acetone and dried in a box dryer to obtain the saponin product. The calculated product yield, saponin purity and saponin extraction rate were measured respectively, and the results are shown in Table 1.

Example 2:

The acacia pericarp after the seeds are separated is pulverized and sieved by a hammer mill to obtain pericarp particles with a particle size of 0.5-2 mm. Use No. 6 extraction solvent oil (Jinling Petrochemical Co., Ltd.) to extract and separate the fat-soluble components in the pericarp. The weight ratio of the extractant to the pericarp is 7:1, and the extraction time is 6 hours. The defatted pericarp is extracted with absolute ethanol to separate saponin, the weight ratio of absolute ethanol and defatted pericarp is 8:1, the extraction temperature is 60° C., and the extraction time is 8 hours. The extract was concentrated until the weight ratio of saponin to ethanol was 1:1, and then crystallized at 15°C. The saponin crystals are filtered through a vacuum filter, washed twice with acetone and dried in a box dryer to obtain the saponin product. The calculated product yield, saponin purity and saponin extraction rate were measured respectively, and the results are shown in Table 1.

Example 3:

The acacia pericarp after the seeds are separated is pulverized and sieved by a hammer mill to obtain pericarp particles with a particle size of 5-6mm. The fat-soluble components in the pericarp were extracted and separated with petroleum ether, the weight ratio of the extractant to the pericarp was 4:1, and the extraction time was 3 hours. The defatted pericarp is extracted with absolute ethanol to separate saponin, the weight ratio of absolute ethanol and defatted pericarp is 5:1, the extraction temperature is 60° C., and the extraction time is 4 hours. The extract was concentrated until the weight ratio of saponin to ethanol was 1:1, and then crystallized at 15°C. The saponin crystals are filtered through a vacuum filter, washed twice with acetone and dried in a box dryer to obtain the saponin product. The calculated product yield, saponin purity and saponin extraction rate were measured respectively, and the results are shown in Table 1.

Comparative example 1:

The acacia pericarp after the seeds are separated is pulverized and sieved by a hammer mill to obtain pericarp particles with a particle size of 2-3 mm. Use No. 6 extraction solvent oil to extract and separate the fat-soluble components in the pericarp, the weight ratio of the extractant to the pericarp is 3.5:1, and the extraction time is 5 hours. The defatted pericarp is extracted with 80% ethanol-water to separate the saponin, the weight ratio of the ethanol aqueous solution to the defatted pericarp is 5:1, the extraction temperature is 60° C., and the extraction time is 5 hours. The extract was concentrated until the weight ratio of saponin to ethanol was 1:1, and then crystallized at 15°C. The saponin crystals are filtered through a vacuum filter, washed twice with acetone and dried in a box dryer to obtain the saponin product. The calculated product yield, saponin purity and saponin extraction rate were measured respectively, and the results are shown in Table 1.

Product yield, saponin purity and saponin extraction rate of different embodiment conditions of table 1 Product yield (%) Saponin purity (%) Saponin extraction rate (%) Example 1 33.2 98.6 93.2 Example 2 33.5 96.5 92.8 Example 3 31.7 97.4 88.2 Comparative example 1 34.0 87.2 84.7

Application Example 1:

Experimental drug:

Medicament 1: Mix and dilute 24.3% saponin and 0.7% kungfuthrin (Wuhan Botian Chemical Co., Ltd.) 2500 times.

Medicament 2: 2.5% Kung fu permethrin (Wuhan Botian Chemical Co., Ltd.) was mixed and diluted 2500 times.

Table 2 kills vegetable aphid effect potion 1 potion 2 Vegetable aphid kill rate 98.7% 99.2%

Application Example 2:

Experimental drug:

Medicament 1: Add 1500mg/L saponin to the 2500-fold dilution of Torque

Medicament 2: Add 2500mg/L saponin to the 2500-fold dilution of Torque

Medicament 3: Add 3500mg/L saponin to the 2500-fold dilution of Torque

Drop the medicines 1, 2, and 3 on the front and back of the leaves of the apple tree respectively, and the reduction rates of the contact angles are shown in Table 3.

After adding saponin saponin in table 3 Thorke diluent, the reduction rate of the contact angle of the medicinal solution potion 1 potion 2 potion 3 apple tree leaves 15.2% 18.1% 24.6% back side of apple tree leaf 13.5% 17.9% 21.3%

Agent 2 can increase the deposition amount of Torque liquid on the surface of apple leaves by 27.4%, achieve the same control effect, and reduce the dosage of Torque original drug by 90.5%.

The results show that adding acacia saponin to the pesticide improves the adhesion ability, wet spreading ability and effective deposition amount of the liquid on the plant surface and the target organism, thereby improving the use effect of the pesticide, greatly reducing the cost of pesticide use, and greatly reducing the cost of pesticide use. Reduce the pollution of pesticides to the environment. , so saponin can be used not only as a biological pesticide, but also as an excellent pesticide synergist.

Application Example 3:

Add 1% (weight percent) of carboxymethylcellulose (CMC) into deionized water and stir until completely dispersed. Add lauryl alcohol polyoxyethylene ether sulfate (AES) 10% (Zhongwei Chemical Co., Ltd.), sodium sulfonate 4.5% in sequence, heat to 70 ° C, stir and dissolve; add diethanolamide (6501) 5% ( Haikou Xuhua Industry and Trade Co., Ltd.), heat preservation for 50min; cooling to 50°C, adding 4% saponin, 0.5% essence, etc., and stirring evenly to obtain silk and wool detergent products.

Application Example 4:

Add 0.3% (weight percentage) of the cationic guar gum conditioner into the deionized water and stir until completely dispersed. Add 0.2% citric acid, propyl betaine (CAB-30) 5% (Shanghai Jingwei Chemical Co., Ltd.), fatty alcohol polyoxyethylene ether ammonium sulfate (AESA) 10% (Ezhou Huifeng Auxiliary Co., Ltd.), and heat Stir to dissolve at 75°C; add 3% pearlescent diester, 2% diethanolamide (6501) (Haikou Xuhua Industry and Trade Co., Ltd.), keep warm for 30min; cool to 50°C, add saponin 3%, silicone oil emulsion 2 %, 0.5% antipruritic agent, 0.5% essence, etc., after stirring evenly, the shampoo product is obtained. The main technical indicators measured are as follows: milky white appearance, pH 6.0-7.0, viscosity (mPa.s) ≥ 500, foam (mm) ≥ 100, heat resistance (no layered precipitation and discoloration after 24 hours at 48°C), cold resistance Sexual (-20 ℃ 24h after returning to room temperature no change).

Claims (7)

1. A process for preparing saponin, characterized in that it adopts absolute ethanol extraction and separation. 2. The process according to claim 1, comprising the steps of: (1) the whole fruit of Acacia locust is cleaned to remove impurities; (2) Fragmentation is carried out to whole fruit, removes seed; (3) crush the peel; (4) adding extractant to extract and separate fat-soluble components in pericarp; (5) defatted pericarp extracts and separates saponin with dehydrated alcohol; (6) Concentrating the extract to crystallize the saponin; (7) Saponin crystals are vacuum filtered, washed and dried. 3. The process according to claim 2, comprising the steps of: (1) Select the whole fruit of Acacia locust with water content≤8%, clean and remove impurities, and the impurity content rate≤0.5%; (2) crush the whole fruit, remove the seeds, and the seed removal rate is more than or equal to 95%; (3) crushing the pericarp, the particle size of the crushed and sieved pericarp is 2-5mm; (4) adding an extractant to extract and separate the fat-soluble components in the pericarp, the weight ratio of the extractant to the pericarp is 2-7:1, and the extraction time is 2-8 hours; (5) The defatted peel is extracted with absolute ethanol to separate saponin, the weight ratio of absolute ethanol and defatted peel is 3-9:1, the extraction temperature is 40-80° C., and the extraction time is 3-9 hours; (6) Concentrating the extract to crystallize the saponin, the weight ratio of saponin to ethanol is 1:0.3-1.5, and the crystallization temperature of saponin is 5-30°C; (7) Vacuum filtration of the saponin crystals, washing the saponin crystals, the amount of detergent used is twice the weight of the saponin, and drying at a temperature of 50-100°C. 4. The process according to claim 3, comprising the steps of: (1) Select the whole fruit of Acacia locust with water content ≤ 8%, clean and remove impurities, the impurity rate ≤ 0.5%, and do not contain iron impurities; (2) crush the whole fruit, remove the seeds, and the seed removal rate is more than or equal to 95%; (3) crushing the pericarp, the particle size of the crushed and sieved pericarp is 2-5mm; (4) adding No. 6 extraction solvent oil or sherwood oil to extract and separate the fat-soluble components in the pericarp, the weight ratio of the extractant and the pericarp is 3.5:1, and the extraction time is 4 hours; (5) The defatted peel is extracted with absolute ethanol to separate saponin, the weight ratio of absolute ethanol and defatted peel is 4.5:1, the extraction temperature is 60-70° C., and the extraction time is 5 hours; (6) Concentrating the extract to crystallize the saponin, the weight ratio of saponin to ethanol is 1:0.8, and the crystallization temperature of saponin is 15° C.; (7) The saponin crystals are vacuum filtered, and the saponin crystals are washed with acetone. The amount of detergent used is twice the weight of the saponin, washed three times, and dried at a temperature of 80°C. 5. The application of saponins prepared by any one of the processes of claims 1-4 in pesticides. 6. The application of saponins prepared by any one of the processes of claims 1-4 in detergents. 7. The application of saponin prepared by any one of the processes of claims 1-4 in shampoo.