Preparation method of citrus chirocarpus compound essential oil composition based on step-by-step extraction-gradient coupling technology

Abstract

The invention discloses a preparation method of a citrus chirocarpus compound essential oil composition based on a step-by-step extraction-gradient coupling technology. The preparation method comprises the following steps: S1, pretreatment of raw materials: slicing fresh citrus chirocarpus fruits, performing vacuum freeze drying, and crushing the sliced citrus chirocarpus fruits to 60-100 meshes; drying the dried orange peel with hot air at 50-55 DEG C, and removing inner flesh; the essential oil yield is increased to 2.3-2.8% (3-5 times of that of a traditional process) through a step-by-step strategy of supercritical COextraction (non-polar components) and low-pressure steam distillation (polar components); a dynamic gradient coupling technology (magnetic stirring and ultrasonic assistance) induces oriented arrangement of molecules, and the retention rate of phenethyl alcohol is larger than or equal to 98% and is improved by 15% compared with a traditional mixing technology.

Description

Technical Field

[0001] The invention relates to the technical field of preparation of composite essential oil compositions, and in particular to a preparation method of a Sichuan Buddha's Hand composite essential oil composition based on a step-by-step extraction-gradient coupling technology. Background Art

[0002] 1. Existing technical bottlenecks

[0003] (1) Monoterpenes have poor thermal stability: Traditional steam distillation requires high temperature operation (>100°C), which leads to severe thermal decomposition of monoterpenes (such as limonene). Literature shows that the retention rate of aroma substances is less than 50%, and the yield of bergamot essential oil is only 0.5%-0.8%.

[0004] (2) Insufficient synergistic compatibility of compound essential oils: Existing compound essential oils mostly adopt simple physical mixing (such as directly blending single essential oils), lacking systematic optimization of medicinal material pretreatment, extraction process and ingredient ratio, resulting in mutual inhibition of characteristic components (such as the antagonistic effect of curculigo saponin and rose phenylethanol), and low efficacy synergy.

[0005] (3) Application stability defects: Commercially available essential oil products have a short shelf life (usually ≤12 months), are easily oxidized and deteriorate (peroxide value exceeds the standard), and are prone to cause skin irritation when added to skin care products (half of the samples showed mild erythema in the HRIPT test).

[0006] 2. Analysis of relevant existing technologies

[0007] Existing technology 1: Using a single supercritical CO2 extraction method to extract bergamot essential oil, although it avoids high temperature damage, it can only extract non-polar components (such as terpenes) and cannot take into account the efficient capture of polar components such as phenylethanol.

[0008] Existing technology 2: In the research on compound essential oils, the types of compatible medicinal materials are limited (such as only bergamot + tangerine peel), the synergistic enhancement mechanism of rose and curculigo is not involved, and there is a lack of molecular directional arrangement technology, resulting in uneven dispersion of active ingredients. Summary of the Invention

[0009] In order to overcome the deficiencies of the prior art, one of the objects of the present invention is to provide a method for preparing a Sichuan Buddha's Hand composite essential oil composition based on a step-by-step extraction-gradient coupling technology.

[0010] One of the objectives of the present invention is achieved by the following technical solution: a method for preparing a Sichuan Buddha's hand composite essential oil composition based on step-by-step extraction-gradient coupling technology, comprising the following steps:

[0011] S1: Raw material pretreatment:

[0012] a. Slice the fresh Sichuan Buddha's Hand fruit and freeze-dry it in a vacuum oven and crush it into 60-100 mesh;

[0013] b. Dry the dried tangerine peel with hot air at 50-55℃ and remove the inner pulp;

[0014] c. Quickly freeze the rose petals in liquid nitrogen within 2 hours after picking;

[0015] d. Curculigo is soaked in yellow wine and then dried to a moisture content of 12-15%. After the enzyme is inactivated, the irritant components are removed by adsorption on activated carbon.

[0016] S2: Step-by-step extraction:

[0017] a. Supercritical CO2 extraction: Extract non-polar terpenes at a pressure of 20-30 MPa and a temperature of 40-50°C, using a CO2 flow rate of 10-15 L / h and ethanol as an entrainer (3-7% v / v);

[0018] b. Low-pressure steam distillation: distillation time 25-35 minutes, condensation temperature 2-6°C, extracting heat-sensitive components such as phenylethanol;

[0019] c. Dynamic gradient coupling: The extracts from steps a and b were mixed and subjected to molecular alignment at a cooling rate of 0.3-0.8°C / min under magnetic stirring (200-400 rpm) and ultrasonic assistance (35-45 kHz);

[0020] S3: Optimization of the four-element ratio: prepare the compound essential oil according to the mass ratio of Sichuan Buddha's Hand: Tangerine Peel: Rose: Curculigo = 5-7:1-3:1-2:0.3-0.7, and the optimal ratio is 6:2:1.5:0.5.

[0021] Furthermore, in the supercritical CO2 extraction step, the entrainer is 5% ethanol, the pressure is 25 MPa, and the temperature is 45°C.

[0022] Furthermore, in the dynamic gradient coupling step, the coupling container is made of 316L stainless steel, and the cooling rate is 0.5°C / min.

[0023] Furthermore, in the Curculigo pretreatment step, the mass ratio of rice wine to Curculigo is 1:5, the enzyme inactivation condition is 105° C. hot air treatment for 3 minutes, and the amount of activated carbon added is 5%.

[0024] Furthermore, the shelf life of the composite essential oil is 24 months at 25° C., and its skin irritation is certified as non-irritating by HRIPT.

[0025] Furthermore, its components include limonene, phenylethyl alcohol, sterol glycoside hydrolyzate and rose characteristic aroma components, and the essential oil yield is 2.3-2.8%.

[0026] Application of Sichuan Buddha's Hand compound essential oil composition in the preparation of anxiety relief products, with a concentration of 0.5-2 μL / m in an aromatherapy diffuser3 , daily exposure time 30-90 minutes.

[0027] The Sichuan Buddha's Hand composite essential oil composition is used in the preparation of skin care products, with the addition amount in the emulsion matrix being 1-3% and the pH value being adjusted to 5.5-6.5.

[0028] Furthermore, the skin care product is a facial mask, and in a 40°C / 75% RH accelerated test, the oxidation rate of the composite essential oil is reduced by 59% compared with the single essential oil, and the particle size growth is inhibited by 30%.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] 1. Process innovation advantages

[0031] (1) Step-by-step extraction-gradient coupling technology:

[0032] A step-by-step strategy of supercritical CO2 extraction (non-polar components) + low-pressure steam distillation (polar components) increases the essential oil yield to 2.3-2.8% (3-5 times that of traditional processes);

[0033] Dynamic gradient coupling technology (magnetic stirring + ultrasonic assistance) induces molecular directional alignment, and the phenylethanol retention rate is ≥98%, which is 15% higher than the traditional mixing process.

[0034] 2. Breakthrough in compatibility synergy

[0035] (1) Four-component ratio optimization system: The optimal ratio of bergamot: dried tangerine peel: rose: curculigo = 6:2:1.5:0.5 was determined by orthogonal experiment, and the objective function Y value reached 0.92 (significant synergistic effect);

[0036] (2) Active ingredient synergism: Sterol glycoside hydrolysis products (Curculigo orchioides) form a hydrogen bond network with rose phenylethanol, synergistically enhancing the anxiety relief effect (onset time is shortened to 15-20 minutes, 50% faster than commercially available products).

[0037] 3. Improved application performance

[0038] (1) Enhanced stability:

[0039] The shelf life is extended to 24 months (25°C), and the peroxide value is controlled below 3.2mmol / kg (commercially available products are ≥7.8mmol / kg);

[0040] Adding 1.5% of compound essential oil to the mask matrix reduces the oxidation rate by 59% and inhibits the growth of emulsion particle size by 30%.

[0041] (2) Safety assurance: Activated carbon adsorption is used to remove irritating ingredients such as curculigo saponins, and HRIPT certification shows that it has no skin irritation (the mild irritation rate of commercially available products is 50%).

[0042] 4. Energy saving and environmental protection benefits

[0043] The energy consumption of pilot production is 41% lower than that of traditional processes, and the ethanol entrainer (3-7% v / v) can be recycled, meeting the requirements of green chemistry.

[0044] The above description is only an overview of the technical solution of the present invention. In order to more clearly understand the technical means of the present invention, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of the present invention more obvious and easy to understand, the following preferred embodiments are specifically cited and described in detail with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 This is a flow chart of this embodiment; DETAILED DESCRIPTION

[0046] The present invention will be further described below in conjunction with the accompanying drawings and specific implementation methods. It should be noted that, under the premise of no conflict, the various embodiments or technical features described below can be arbitrarily combined to form new embodiments.

[0047] It should be noted that when a component is referred to as being "fixed to" another component, it may be directly on the other component or there may also be a central component. When a component is considered to be "connected to" another component, it may be directly connected to the other component or there may also be a central component. When a component is considered to be "set on" another component, it may be directly set on the other component or there may also be a central component. The terms "vertical", "horizontal", "left", "right" and similar expressions used herein are for illustrative purposes only.

[0048] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention pertains. The terms used in this specification of the present invention are for the purpose of describing specific embodiments only and are not intended to limit the present invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0049] Example 1:

[0050] See also Figure 1 A method for preparing a Sichuan Buddha's hand composite essential oil composition based on step-by-step extraction-gradient coupling technology comprises the following steps:

[0051] S1: Raw material pretreatment:

[0052] a. Slice the fresh Sichuan Buddha's Hand fruit and freeze-dry it in a vacuum oven and crush it into 60-100 mesh;

[0053] b. Dry the dried tangerine peel with hot air at 50-55℃ and remove the inner pulp;

[0054] c. Quickly freeze the rose petals in liquid nitrogen within 2 hours after picking;

[0055] d. Curculigo is soaked in yellow wine and then dried to a moisture content of 12-15%. After the enzyme is inactivated, the irritant components are removed by adsorption on activated carbon.

[0056] S2: Step-by-step extraction:

[0057] a. Supercritical CO2 extraction: Extract non-polar terpenes at a pressure of 20-30 MPa and a temperature of 40-50°C, using a CO2 flow rate of 10-15 L / h and ethanol as an entrainer (3-7% v / v);

[0058] b. Low-pressure steam distillation: distillation time 25-35 minutes, condensation temperature 2-6°C, extracting heat-sensitive components such as phenylethanol;

[0059] c. Dynamic gradient coupling: The extracts from steps a and b were mixed and subjected to molecular alignment at a cooling rate of 0.3-0.8°C / min under magnetic stirring (200-400 rpm) and ultrasonic assistance (35-45 kHz);

[0060] S3: Optimization of the four-element ratio: prepare the compound essential oil according to the mass ratio of Sichuan Buddha's Hand: Tangerine Peel: Rose: Curculigo = 5-7:1-3:1-2:0.3-0.7, and the optimal ratio is 6:2:1.5:0.5.

[0061] In the supercritical CO2 extraction step, the entrainer was 5% ethanol, the pressure was 25 MPa, and the temperature was 45°C.

[0062] The coupling container is made of 316L stainless steel, and the cooling rate is 0.5°C / min.

[0063] In the Curculigo pretreatment step, the mass ratio of rice wine to Curculigo is 1:5, the enzyme inactivation condition is hot air treatment at 105° C. for 3 minutes, and the amount of activated carbon added is 5%.

[0064] The shelf life of the compound essential oil is 24 months at 25°C, and its skin irritation is certified as non-irritating by HRIPT.

[0065] The components include limonene, phenylethyl alcohol, sterol glycoside hydrolyzate and rose characteristic aroma components, and the essential oil yield is 2.3-2.8%.

[0066] The concentration used in aromatherapy diffusers is 0.5-2μL / m 3 , daily exposure time 30-90 minutes.

[0067] The Sichuan Buddha's Hand composite essential oil composition is used in the preparation of skin care products. The addition amount to the emulsion matrix is 1-3%, the pH value is adjusted to 5.5-6.5, and the skin care product is a facial mask. In an accelerated test at 40°C / 75% RH, the oxidation rate of the composite essential oil is reduced by 59% compared with the single essential oil, and the particle size growth is inhibited by 30%.

[0068] Example 2: Material pretreatment process optimization

[0069] Experimental purpose: To verify the effect of pretreatment process of dried tangerine peel and curculigo on the release efficiency of essential oil.

[0070] Experimental procedures

[0071] 1. Tangerine peel processing:

[0072] Take three-year-old Sichuan Dahongpao dried tangerine peel and dry it with hot air at 50℃ until the moisture content is ≤8%.

[0073] Mechanically remove the white inner flesh and crush to 60 mesh;

[0074] The changes in fiber structure were observed by scanning electron microscopy (SEM).

[0075] 2. Treatment of Curculigo:

[0076] Curculigo and yellow rice wine (alcohol content 12%) were soaked in a mass ratio of 1:5 for 6 hours;

[0077] Bake at 60°C until the moisture content reaches 12-15%, then maintain at 50°C for 2 hours to activate β-glucosidase.

[0078] Inactivate the enzyme with hot air at 105°C for 3 minutes, add 5% activated carbon and adsorb with shaking for 30 minutes;

[0079] The dissolution of the epidermal wax layer was observed by SEM.

[0080] Experimental results

[0081]

[0082]

[0083] Example 3: Comparison of extraction processes in different stages

[0084] Experimental purpose: To verify the stability and energy consumption advantages of the step-by-step extraction process in laboratory and pilot production.

[0085] Experimental procedures

[0086] 1. Laboratory scale (50g raw material):

[0087] Supercritical CO2 extraction: pressure 25 MPa, temperature 45°C, CO2 flow rate 12 L / h, entrainer 5% ethanol;

[0088] Low-pressure steam distillation: distillation time 30 minutes, condensation temperature 4°C;

[0089] Dynamic gradient coupling: magnetic stirring 300 rpm, ultrasonic 40 kHz, cooling rate 0.5 °C / min.

[0090] 2. Pilot production (50kg raw materials):

[0091] The process parameters are consistent with those in the laboratory, and the production scale is enlarged;

[0092] Record yield stability and energy consumption data.

[0093] Experimental results

[0094]

[0095] Example 4: Quaternary ratio optimization experiment

[0096] Experimental purpose: To determine the optimal ratio of compound essential oils through orthogonal experiment.

[0097] Experimental design

[0098] Orthogonal table: L9(3 4 ), investigating the four factors of bergamot (5-7), dried tangerine peel (1-3), rose (1-2), and curculigo (0.3-0.7);

[0099] Objective function: Y = 0.35X1 + 0.28X2 + 0.22X3 + 0.15X4 (the higher the Y value, the better the synergistic effect).

[0100]

[0101] Optimal ratio: Y max =0.92, bergamot: tangerine peel: rose: curculigo=6:2:1.5:0.5.

[0102] Example 5: Stability test of compound essential oil in facial mask matrix

[0103] Experimental purpose: To verify the oxidative stability and physical stability of compound essential oils in skin care product matrix.

[0104] Experimental design

[0105] Test sample: optimal ratio of compound essential oil (6:2:1.5:0.5);

[0106] Control group: commercially available bergamot essential oil;

[0107] Mask matrix: water phase (glycerin 5% + hyaluronic acid 0.5%) + oil phase (squalane 3% + lecithin 1.2%);

[0108] Addition concentration: 1.5%;

[0109] Test conditions: 40°C / 75% RH accelerated test (equivalent to 6 months at room temperature).

[0110] Experimental results

[0111]

[0112] in conclusion

[0113] The oxidation rate of the compound essential oil was 59% lower than that of the single essential oil (P<0.01);

[0114] The growth of emulsion particle size was inhibited by 30% (P<0.05), and the stability was significantly improved.

[0115] The above embodiments are only preferred embodiments of the present invention and cannot be used to limit the scope of protection of the present invention. Any non-substantial changes and replacements made by technicians in this field on the basis of the present invention fall within the scope of protection required by the present invention.

Claims

1. A method for preparing a Sichuan bergamot compound essential oil composition based on step-by-step extraction-gradient coupling technology, characterized in that: The following steps are involved: S1: Raw material pretreatment: a Sichuan Buddha's hand fresh fruit slices after vacuum freeze-drying, crushed to 60-100 mesh; b. Dry the dried tangerine peel with hot air at 50-55℃ and remove the inner pulp; c. Quickly freeze the rose petals in liquid nitrogen within 2 hours after picking; d. Curculigo is soaked in rice wine and then dried to a moisture content of 12-15%. After the enzyme is inactivated, the irritant components are removed by activated carbon adsorption. S2: Step-by-step extraction: a. Supercritical CO2 extraction: Extract non-polar terpenes at a pressure of 20-30 MPa and a temperature of 40-50°C, using a CO2 flow rate of 10-15 L / h and ethanol as an entrainer (3-7% v / v). b. Low-pressure steam distillation: distillation time 25-35 minutes, condensation temperature 2-6°C, extracting heat-sensitive components such as phenylethanol; c. Dynamic gradient coupling: The extracts from steps a and b were mixed and subjected to molecular alignment at a cooling rate of 0.3-0.8°C / min under magnetic stirring (200-400 rpm) and ultrasonic assistance (35-45 kHz); S3: Optimization of the four-element ratio: prepare the compound essential oil according to the mass ratio of Sichuan Buddha's Hand: Tangerine Peel: Rose: Curculigo = 5-7:1-3:1-2:0.3-0.7, and the optimal ratio is 6:2:1.5:0.

5.

2. The preparation method according to claim 1, wherein In the supercritical CO2 extraction step, the entrainer is 5% ethanol, the pressure is 25 MPa, and the temperature is 45°C.

3. The preparation method according to claim 1, characterized in that In the dynamic gradient coupling step, the coupling container is made of 316L stainless steel, and the cooling rate is 0.5°C / min.

4. The preparation method according to claim 1, characterized in that In the Curculigo pretreatment step, the mass ratio of rice wine to Curculigo is 1:5, the enzyme inactivation condition is 105° C. hot air treatment for 3 minutes, and the amount of activated carbon added is 5%.

5. The preparation method according to claim 1, characterized in that The composite essential oil has a shelf life of 24 months at 25° C., and its skin irritation is certified as non-irritating by HRIPT.

6. A Sichuan Buddha's Hand composite essential oil composition prepared according to any one of claims 1 to 5, characterized in that: Its components include limonene, phenylethyl alcohol, sterol glycoside hydrolysis products and rose characteristic aroma components, and the essential oil yield is 2.3-2.8%.

7. The use of the Sichuan Buddha's Hand composite essential oil composition according to claim 6 in preparing an anxiety relief product, characterized in that, The concentration used in aromatherapy diffusers is 0.5-2 μL / m³, and the daily exposure time is 30-90 minutes.

8. The application of the Sichuan Buddha's Hand composite essential oil composition according to claim 6 in preparing skin care products, characterized in that, The addition amount to the emulsion matrix is 1-3%, and the pH value is adjusted to 5.5-6.

5.

9. The use according to claim 8, characterized in that The skin care product is a facial mask. In an accelerated test at 40°C / 75%RH, the oxidation rate of the composite essential oil is reduced by 59% compared with that of the single essential oil, and the particle size growth is inhibited by 30%.

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