WO2024082329A1 - Freeze-drying method for rosmarinus officinalis - Google Patents

Freeze-drying method for rosmarinus officinalis Download PDF

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WO2024082329A1
WO2024082329A1 PCT/CN2022/127867 CN2022127867W WO2024082329A1 WO 2024082329 A1 WO2024082329 A1 WO 2024082329A1 CN 2022127867 W CN2022127867 W CN 2022127867W WO 2024082329 A1 WO2024082329 A1 WO 2024082329A1
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rosemary
freeze
drying
fresh
powder
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PCT/CN2022/127867
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French (fr)
Chinese (zh)
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蒋奇
蒋胜祥
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湖南祥民制药有限公司
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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/10—Natural spices, flavouring agents or condiments; Extracts thereof
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • A23L3/3463—Organic compounds; Microorganisms; Enzymes
    • A23L3/3481—Organic compounds containing oxygen
    • A23L3/3508—Organic compounds containing oxygen containing carboxyl groups
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • A23L3/3463—Organic compounds; Microorganisms; Enzymes
    • A23L3/3526—Organic compounds containing nitrogen
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/40—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by drying or kilning; Subsequent reconstitution
    • A23L3/44—Freeze-drying
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
    • A23L5/20—Removal of unwanted matter, e.g. deodorisation or detoxification
    • A23L5/27—Removal of unwanted matter, e.g. deodorisation or detoxification by chemical treatment, by adsorption or by absorption
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
    • A23L5/57—Chemical peeling or cleaning of harvested fruits, vegetables or other foodstuffs
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
    • A61K36/18—Magnoliophyta (angiosperms)
    • A61K36/185—Magnoliopsida (dicotyledons)
    • A61K36/53—Lamiaceae or Labiatae (Mint family), e.g. thyme, rosemary or lavender
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/02—Recovery or refining of essential oils from raw materials
    • C11B9/025—Recovery by solvent extraction
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B5/00—Drying solid materials or objects by processes not involving the application of heat
    • F26B5/04—Drying solid materials or objects by processes not involving the application of heat by evaporation or sublimation of moisture under reduced pressure, e.g. in a vacuum
    • F26B5/06—Drying solid materials or objects by processes not involving the application of heat by evaporation or sublimation of moisture under reduced pressure, e.g. in a vacuum the process involving freezing
    • F26B5/065—Drying solid materials or objects by processes not involving the application of heat by evaporation or sublimation of moisture under reduced pressure, e.g. in a vacuum the process involving freezing the product to be freeze-dried being sprayed, dispersed or pulverised
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B7/00—Drying solid materials or objects by processes using a combination of processes not covered by a single one of groups F26B3/00 and F26B5/00
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2236/00—Isolation or extraction methods of medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicine
    • A61K2236/10—Preparation or pretreatment of starting material
    • A61K2236/13—Preparation or pretreatment of starting material involving cleaning, e.g. washing or peeling
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2236/00—Isolation or extraction methods of medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicine
    • A61K2236/10—Preparation or pretreatment of starting material
    • A61K2236/17—Preparation or pretreatment of starting material involving drying, e.g. sun-drying or wilting
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Definitions

  • the invention belongs to the field of deep processing of natural plant ingredients and discloses a freeze-drying method for rosemary.
  • Rosemary Latin name (Rosmarinus officinalis), is a dicotyledonous plant, Lamiaceae, genus Rosmarinus shrub. It likes warm climates and is native to Europe and the Mediterranean coast of northern Africa. It was introduced to China as early as the Cao Wei period. It is occasionally used in gardens. Antioxidants and rosemary essential oil with excellent antioxidant properties can be extracted from rosemary flowers and leaves. Rosemary antioxidant. It is widely used in medicine, fried foods, oil-rich foods and various types of oils to preserve freshness and quality; while rosemary essence is used in spices, air fresheners, ant repellents, and daily chemical industries such as sterilization and insecticide.
  • Rosemary has a calming, refreshing and brain-awakening effect, and has a certain effect on indigestion and stomachache. It is often crushed, soaked in boiling water and drunk 2 to 3 times a day, which can have a calming and diuretic effect. It can also be used to treat insomnia, palpitations, headaches, indigestion and other diseases. External use can treat trauma and arthritis. It also has the effects of strengthening the heart, promoting metabolism, and promoting blood circulation in peripheral blood vessels. Rosemary is a frequently used spice in Western cuisine, especially in steak, potatoes and other dishes and baked products. It has a sweet smell and flavor with a pine aroma, a strong fragrance, and a bitter taste in the sweetness.
  • the harvested rosemary needs to be dried and the effective ingredients need to be extracted.
  • the drying methods of rosemary mainly include natural drying, heating and drying, and freeze drying. Freeze drying is becoming more and more popular because it can retain the rosemary antioxidants and essential oils in rosemary to the greatest extent and is convenient for long-term storage and transportation.
  • CN201410204635.3 discloses a method for preparing a rosemary composite extract, and the freeze drying method mentioned The method is as follows: (1) taking fresh rosemary stems, unfolding the stems, freezing them in an environment of -6 to -9°C, and freezing for 6 to 10 hours; (2) taking the stems out of the freezer, vacuum freeze drying the stems, the pressure of vacuum freeze drying is 11Pa to 17Pa, and the freeze drying time is 5 to 7 hours; (3) taking the stems out of the freeze dryer, crushing the stems to 200 to 300 meshes of stem powder, and placing them in a dry environment. (4) taking the rosemary stem powder, and stirring and extracting the rosemary stem powder with ethanol.
  • the maximum ethanol extraction rate of rosemary is only 20%, resulting in a huge waste of raw materials, and a large amount of organic solvents need to be consumed, the ethanol residue is high, and it is not green and environmentally friendly. Therefore, it is necessary to find a green, environmentally friendly and efficient rosemary freeze drying and extraction process.
  • the invention discloses a freeze-drying method for rosemary.
  • a freeze-drying method for rosemary characterized in that it comprises the following steps:
  • Prefreezing Spread the rosemary powder with a moisture content of less than 15% to a thickness of 5-10 cm, and perform rapid prefreezing at normal pressure for 30-60 minutes at a prefreezing temperature of -20 to -40°C;
  • Freeze drying Under the condition of maintaining the pre-freezing temperature, add 5-10% by mass of freeze-drying protective agent, mix it with rosemary powder, and put it into freeze drying machine for freeze drying.
  • the freeze drying procedure is as follows:
  • A -45 ⁇ -55°C, pressure 300-800Pa, freeze drying 30-60min;
  • the scheme fresh rosemary leaves are soaked and cleaned with a fresh-keeping cleaning liquid to wash away dust and soil on the rosemary leaves, and the leaves are kept fresh to prevent the loss of effective components.
  • the rosemary leaves are sterilized to remove pesticide residues.
  • the rosemary is first naturally dried and oven-dried to make the water content less than 15%, rather than being freeze-dried immediately, in order to reduce the moisture content, thereby reducing the freeze-drying time and energy consumption.
  • a freeze-drying protective agent is added during freeze-drying to further reduce the destruction of the effective components of the rosemary during freeze-drying, and programmed freeze-drying is used to ensure the freeze-drying quality while reducing the total freeze-drying time.
  • the fresh young leaves are fresh young leaves within 20 cm from the top of the rosemary stem.
  • the fresh young leaves within the above range are generally above the dividing line between phloem and xylem, have the best quality, and contain the most rosemary active ingredients.
  • the fresh-keeping cleaning solution in step 2) contains the following components in parts by weight:
  • the fresh-keeping cleaning liquid can be used to wash away dust and dirt on the young leaves of rosemary, and the young leaves can be kept fresh to prevent the loss of effective components, and the young leaves of rosemary can be sterilized to remove pesticide residues.
  • Chlorhexidine gluconate is a biguanide chlorobenzene with a wide range of antimicrobial activity, sodium lauryl sulfate has a strong decontamination ability and can directly wash away pesticide residues, while L-cysteine has a good detoxification and biological neutralization ability, can neutralize with pesticide residues that cannot be washed away, and can be used in conjunction with sodium lauryl sulfate to completely remove the impact of pesticide residues; L-ascorbic acid has a strong antioxidant effect and can prevent the loss of effective components of rosemary due to oxidation and deterioration.
  • the soaking time in step 2) is 2-6 hours, and the temperature is 15-30° C. If the soaking time is too short, dust and pesticide residues cannot be washed away, and if the soaking time is too long, it is easy to spoil. Experiments have found that 2-6 hours is easier to achieve the above balance.
  • the freeze-drying protectant in step 7) is selected from one of glycerol, gum arabic or trehalose.
  • the trehalose is modified by the following steps:
  • a process for extracting effective components of rosemary comprises the above freeze-drying method.
  • the extraction process of the rosemary active ingredient is characterized by comprising the following steps:
  • Prefreezing Spread the rosemary powder with a moisture content of less than 15% to a thickness of 5-10 cm, and perform rapid prefreezing at normal pressure for 30-60 minutes at a prefreezing temperature of -20 to -40°C;
  • Freeze drying Under the condition of maintaining the pre-freezing temperature, add 5-10% by mass of freeze-drying protective agent, mix it with rosemary powder, and put it into freeze drying machine for freeze drying.
  • the freeze drying procedure is as follows:
  • A -45 ⁇ -55°C, pressure 300-800Pa, freeze drying 30-60min;
  • the extract containing the rosemary freeze-dried powder is distilled to obtain rosemary essential oil.
  • low-toxic and environmentally friendly propylene glycol is used as the main component of the extract
  • L-ascorbic acid is used to extract the rosemary freeze-dried powder, which is green and environmentally friendly and can retain the effective active ingredients to the greatest extent.
  • rosemary essential oil is prepared by the above-mentioned extraction process of rosemary effective ingredients.
  • the present invention has the following beneficial effects:
  • the invention discloses a freeze-drying method for rosemary.
  • the method focuses on retaining the effective components of rosemary to the greatest extent from the beginning of picking, and selects fresh young leaves within 20 cm from the top of rosemary to the stem.
  • the fresh young leaves within the above range are generally above the boundary between phloem and xylem, have the best quality, and have the highest content of rosemary effective components.
  • a fresh-keeping cleaning liquid is used to soak and clean the fresh young leaves of rosemary, wash away dust and soil on the young leaves of rosemary, and keep the young leaves fresh to prevent the loss of effective components.
  • the young leaves of rosemary are sterilized to remove pesticide residues;
  • the rosemary is first naturally dried and dried to make the water content less than 15%, instead of being freeze-dried immediately, in order to reduce moisture, thereby reducing the time and energy consumption of freeze-drying, and then a freeze-drying protective agent is added during freeze-drying to further reduce the destruction of the effective components of rosemary during freeze-drying, and a freeze-drying program is used to ensure the freeze-drying quality while reducing the total time of freeze-drying, which can save half or two-thirds of the time compared to the ordinary freeze-drying program.
  • the present invention also prepares a fresh-keeping cleaning liquid, which can wash away dust and soil on the young leaves of rosemary, keep the young leaves fresh, prevent the loss of effective components, and sterilize the young leaves of rosemary to remove pesticide residues.
  • Chlorhexidine gluconate is a biguanide chlorobenzene with a wide range of antimicrobial activity.
  • Sodium lauryl sulfate has a strong decontamination ability and can directly wash away pesticide residues.
  • L-cysteine has a good detoxification and biological neutralization ability, can neutralize pesticide residues that cannot be washed away, and can be used in combination with sodium lauryl sulfate to completely remove the impact of pesticide residues;
  • L-ascorbic acid has a strong antioxidant effect and can prevent the loss of effective components of rosemary due to oxidation and deterioration.
  • the present invention uses modified trehalose, so that the specific surface area of trehalose is increased, the encapsulation ability is enhanced, and the effective components of rosemary can be prevented from sublimating and escaping with water vapor during freeze-drying, and the effective components are formed, so the freeze-drying protection of rosemary is the strongest.
  • the present invention uses low-toxic and environmentally friendly glycerol as the main component of the extract, and cooperates with L-ascorbic acid to leach the rosemary freeze-dried powder, which is green and environmentally friendly, and can retain the effective active ingredients to the greatest extent.
  • the method described in the present invention greatly reduces the amount of organic solvent used, and there is almost no ethanol residue in the final product.
  • the freeze-drying process is short, energy saving and emission reduction are significant, and the cost reduction effect is significant.
  • FIG1 is a schematic flow diagram of a freeze-drying method of the present invention.
  • Fig. 2 is a comparison of the essential oil qualities of the embodiment and the comparative example
  • Fig. 3 is the ⁇ -pinene content (mg) in 1g of essential oil in Examples and Comparative Examples;
  • FIG. 4 is the linalyl acetate content (mg) in 1 g of essential oil in the Examples and Comparative Examples.
  • a freeze-drying method for rosemary comprises the following steps:
  • Prefreezing Spread the rosemary powder with a moisture content of less than 15% to a thickness of 5-10 cm, and perform rapid prefreezing at normal pressure for 30-60 minutes at a prefreezing temperature of -20 to -40°C;
  • Freeze drying Under the condition of maintaining the pre-freezing temperature, add 5-10% by mass of freeze-drying protective agent, mix it with rosemary powder, and put it into freeze drying machine for freeze drying.
  • the freeze drying procedure is as follows:
  • A -45 ⁇ -55°C, pressure 300-800Pa, freeze drying 30-60min;
  • the extract containing the rosemary freeze-dried powder is distilled to obtain rosemary essential oil
  • the fresh young leaves are fresh young leaves within 20 cm from the top of the rosemary stem downward.
  • the fresh-keeping cleaning solution in step 2) contains the following components, calculated by weight:
  • the soaking time in step 2) is 2-6 hours and the temperature is 15-30° C.;
  • the freeze-drying protective agent in step 7) is selected from one of glycerol, gum arabic or trehalose;
  • the trehalose is modified by the following steps:
  • the reagents or instruments used in the examples of the present invention without indicating the manufacturer are all conventional reagent products that can be obtained through commercial purchase.
  • a freeze-drying method for rosemary comprises the following steps:
  • Prefreezing Spread the rosemary powder with a moisture content of less than 15% to a thickness of 5-10 cm, and perform rapid prefreezing at normal pressure for 30-60 minutes at a prefreezing temperature of -20 to -40°C;
  • Freeze drying Under the condition of maintaining the pre-freezing temperature, add 5-10% by mass of freeze-drying protective agent, mix it with rosemary powder, and put it into freeze drying machine for freeze drying.
  • the freeze drying procedure is as follows:
  • the extract containing the rosemary freeze-dried powder is distilled to obtain rosemary essential oil
  • the fresh young leaves are fresh young leaves within 20 cm from the top of the rosemary stem downward.
  • the fresh-keeping cleaning solution in step 2) contains the following components, calculated by weight:
  • the soaking time in step 2) is 2-6 hours and the temperature is 15-30° C.;
  • the lyoprotectant in step 7) is selected from glycerol.
  • a freeze-drying method for rosemary comprises the following steps:
  • Prefreezing Spread the rosemary powder with a moisture content of less than 15% to a thickness of 5-10 cm, and perform rapid prefreezing at normal pressure for 30-60 minutes at a prefreezing temperature of -20 to -40°C;
  • Freeze drying Under the condition of maintaining the pre-freezing temperature, add 5-10% by mass of freeze-drying protective agent, mix it with rosemary powder, and put it into freeze drying machine for freeze drying.
  • the freeze drying procedure is as follows:
  • the extract containing the rosemary freeze-dried powder is distilled to obtain rosemary essential oil
  • the fresh young leaves are fresh young leaves within 20 cm from the top of the rosemary stem downward.
  • the fresh-keeping cleaning solution in step 2) contains the following components by weight:
  • the soaking time in step 2) is 2-6 hours and the temperature is 15-30° C.;
  • the lyophilization protective agent in step 7) is selected from trehalose;
  • the trehalose is modified by the following steps:
  • a freeze-drying method for rosemary comprises the following steps:
  • Preliminary natural drying dry the soaked young leaves naturally for 6-12 hours in a ventilated and cool place at a temperature of 20-30°C;
  • Prefreezing Spread the rosemary powder with a moisture content of less than 15% to a thickness of 5-10 cm, and perform rapid prefreezing at normal pressure for 30-60 minutes at a prefreezing temperature of -20 to -40°C;
  • Freeze drying Under the condition of maintaining the pre-freezing temperature, add 5-10% by mass of freeze-drying protective agent, mix it with rosemary powder, and put it into freeze drying machine for freeze drying.
  • the freeze drying procedure is as follows:
  • the extract containing the rosemary freeze-dried powder is distilled to obtain rosemary essential oil
  • the fresh young leaves are fresh young leaves within 20 cm from the top of the rosemary stem;
  • the fresh-keeping cleaning solution in step 2) contains the following components by weight:
  • the soaking time in step 2) is 2-6 hours and the temperature is 15-30° C.;
  • the freeze-drying protective agent in step 7) is selected from gum arabic.
  • a freeze-drying method for rosemary wherein deionized water is used instead of a fresh-keeping cleaning liquid to clean the rosemary, and the other steps are the same as those in Example 2.
  • Example 2 A method for freeze-drying rosemary, using ordinary trehalose instead of the modified trehalose in Example 2, and the other steps are the same as Example 2.
  • a freeze-drying method for rosemary wherein the rosemary is not washed with a fresh-keeping washing liquid but with deionized water, and ordinary trehalose is used instead of the modified trehalose in Example 2, and the other steps are the same as in Example 2.
  • the freeze-dried powder of rosemary obtained by the freeze-drying method of Examples 1-3 and Comparative Examples 1-3, and the prepared essential oils were compared, and the mass of the freeze-dried powder obtained (g) and the mass of the essential oil obtained (g) were compared to represent the yield of freeze drying and essential oil extraction; the ⁇ -pinene content (mg) in 1g of essential oil and the linalyl acetate content (mg) in 1g of essential oil were used to represent the mass of the essential oil, that is, the retention capacity of the active substance during the freeze drying extraction process.
  • Table 1 and Figures 2-4 The results are shown in Table 1 and Figures 2-4.
  • the mass of the essential oils in Comparative Examples 2 and 3 is reduced more than that in the other embodiments, proving that the modified trehalose of the present invention can retain more essential oil components in rosemary during the freeze-drying process.
  • the ⁇ -pinene content (mg) and linalyl acetate content (mg) in the essential oils in Comparative Examples 1-3 are greatly reduced compared to Examples 1-3, proving that the modified trehalose of the present invention and the fresh-keeping cleaning solution have a combined effect to retain the active ingredients in rosemary.

Abstract

A freeze-drying method for Rosmarinus officinalis, comprising the following steps: 1) harvesting of Rosmarinus officinalis, 2) fresh-keeping cleaning of Rosmarinus officinalis, 3) preliminary natural drying, 4) crushing of Rosmarinus officinalis, 5) oven drying, 6) pre-freezing, and 7) freeze drying. In the freeze-drying method, the preparation process is adjusted, and compared with the prior art, a fresh-keeping cleaning solution and a freeze-drying protective agent which are self-developed are added, so that natural effective compositions of Rosmarinus officinalis can be reserved to the maximum extent; and furthermore, the composition of an extracting solution for extracting the Rosmarinus officinalis essential oil from Rosmarinus officinalis is improved. Compared with the prior art, the use amount of an organic solvent is greatly reduced, almost no ethanol residue exists in the final product; and meanwhile, the freeze-drying process is short, energy conservation and emission reduction are achieved, and the cost reduction effect is remarkable.

Description

一种迷迭香的冷冻干燥方法A kind of freeze-drying method of rosemary 技术领域Technical Field
本发明属于天然植物成分深加工领域，公开了一种迷迭香的冷冻干燥方法。The invention belongs to the field of deep processing of natural plant ingredients and discloses a freeze-drying method for rosemary.
背景技术Background technique
迷迭香，拉丁学名(Rosmarinus officinalis)，是双子叶植物纲、唇形科、迷迭香属植物灌木。性喜温暖气候，原产欧洲地区和非洲北部地中海沿岸。远在曹魏时期就曾引种中国。园林中偶有应用。从迷迭香的花和叶子中能提取具有优良抗氧化性的抗氧化剂和迷迭香精油。迷迭香抗氧化剂。广泛用于医药、油炸食品、富油食品及各类油脂的保鲜保质；而迷迭香香精则用于香料、空气清新剂、驱蚁剂以及杀菌、杀虫等日用化工业。Rosemary, Latin name (Rosmarinus officinalis), is a dicotyledonous plant, Lamiaceae, genus Rosmarinus shrub. It likes warm climates and is native to Europe and the Mediterranean coast of northern Africa. It was introduced to China as early as the Cao Wei period. It is occasionally used in gardens. Antioxidants and rosemary essential oil with excellent antioxidant properties can be extracted from rosemary flowers and leaves. Rosemary antioxidant. It is widely used in medicine, fried foods, oil-rich foods and various types of oils to preserve freshness and quality; while rosemary essence is used in spices, air fresheners, ant repellents, and daily chemical industries such as sterilization and insecticide.
迷迭香具有镇静提神、醒脑作用，对消化不良和胃痛均有一定疗效。多将其捣碎后，用开水浸泡后饮用，1天2～3次,可起到镇静、利尿作用。也可用于治疗失眠、心悸、头痛、消化不良等多种疾病。外用可治疗外伤和关节炎。还具有强壮心脏、促进代谢、促进末梢血管的血液循环等作用。在西餐中迷迭香是经常使用的香料，在牛排、土豆等料理以及烤制品中特别经常使用。清甜带松木香的气味和风味，香味浓郁，甜中带有苦味。Rosemary has a calming, refreshing and brain-awakening effect, and has a certain effect on indigestion and stomachache. It is often crushed, soaked in boiling water and drunk 2 to 3 times a day, which can have a calming and diuretic effect. It can also be used to treat insomnia, palpitations, headaches, indigestion and other diseases. External use can treat trauma and arthritis. It also has the effects of strengthening the heart, promoting metabolism, and promoting blood circulation in peripheral blood vessels. Rosemary is a frequently used spice in Western cuisine, especially in steak, potatoes and other dishes and baked products. It has a sweet smell and flavor with a pine aroma, a strong fragrance, and a bitter taste in the sweetness.
为了方便迷迭香运输和进一步的加工，需要对采收的迷迭香进行干燥并进行有效成分的提取，目前工业化中，对迷迭香的干燥主要有自然晾干，加热烘干以及冷冻干燥；冷冻干燥法由于能够最大程度的保留迷迭香之中的迷迭香抗氧化剂和精油，并且方便长期保存和运输，因此越来越普及，例如CN201410204635.3公开了一种迷迭香复配提取物的制备方法，提到的冷冻干燥方法如下：(1)取新鲜的迷迭香叶茎，将迷迭香叶茎展开，在温度为-6～-9℃的环境下进行冷冻，冷冻时间为6h～10h；(2)从冷冻室中取出迷迭香叶茎，将迷迭香叶茎真空冷冻干燥，真空冷冻干燥的压强为11Pa～17Pa，冷冻干燥时间为5h～7h；(3)将迷迭香叶茎从冷冻干燥机中取出，粉碎迷迭香叶茎，粉碎至叶茎粉为200～300目，放置在干燥环境中。(4)取迷迭香叶茎粉末，将迷迭香叶茎粉末用乙醇进行搅拌提取。上述发明的工艺过程中，迷迭香乙醇提取率最高仅为20％，造成对原料的巨大浪费，同时需要消耗大量的有机溶剂，乙醇残留量高，不够绿色环保。因此需要寻 找一种绿色环保高效的迷迭香冷冻干燥以及提取的工艺。In order to facilitate the transportation and further processing of rosemary, the harvested rosemary needs to be dried and the effective ingredients need to be extracted. At present, in industrialization, the drying methods of rosemary mainly include natural drying, heating and drying, and freeze drying. Freeze drying is becoming more and more popular because it can retain the rosemary antioxidants and essential oils in rosemary to the greatest extent and is convenient for long-term storage and transportation. For example, CN201410204635.3 discloses a method for preparing a rosemary composite extract, and the freeze drying method mentioned The method is as follows: (1) taking fresh rosemary stems, unfolding the stems, freezing them in an environment of -6 to -9°C, and freezing for 6 to 10 hours; (2) taking the stems out of the freezer, vacuum freeze drying the stems, the pressure of vacuum freeze drying is 11Pa to 17Pa, and the freeze drying time is 5 to 7 hours; (3) taking the stems out of the freeze dryer, crushing the stems to 200 to 300 meshes of stem powder, and placing them in a dry environment. (4) taking the rosemary stem powder, and stirring and extracting the rosemary stem powder with ethanol. In the process of the above invention, the maximum ethanol extraction rate of rosemary is only 20%, resulting in a huge waste of raw materials, and a large amount of organic solvents need to be consumed, the ethanol residue is high, and it is not green and environmentally friendly. Therefore, it is necessary to find a green, environmentally friendly and efficient rosemary freeze drying and extraction process.
发明内容Summary of the invention
为了解决上述问题，本发明公开了一种迷迭香的冷冻干燥方法。In order to solve the above problems, the invention discloses a freeze-drying method for rosemary.
本发明的技术方案如下：The technical solution of the present invention is as follows:
一种迷迭香的冷冻干燥方法，其特征在于，包括以下步骤：A freeze-drying method for rosemary, characterized in that it comprises the following steps:
1)迷迭香的采收：在3-11月上旬采收迷迭香的新鲜嫩叶；1) Harvesting rosemary: Harvest fresh young leaves of rosemary from March to early November;
2)迷迭香的保鲜清洗：使用保鲜清洗液对迷迭香新鲜嫩叶进行浸泡和清洗；2) Rosemary preservation and cleaning: Use a fresh-keeping cleaning solution to soak and clean the fresh young leaves of rosemary;
3)初步自然干燥：在通风阴凉处，温度为20-30℃条件下，对浸泡过的嫩叶进行自然干燥6-12h；3) Preliminary natural drying: In a ventilated and cool place at a temperature of 20-30°C, the soaked young leaves are naturally dried for 6-12 hours;
4)迷迭香粉碎：对干燥后的迷迭香进行机械粉碎，粉碎后的原料过100-200目筛，得到迷迭香粉；4) Rosemary crushing: The dried rosemary is mechanically crushed, and the crushed raw material is passed through a 100-200 mesh sieve to obtain rosemary powder;
5)烘干干燥：将迷迭香粉在30-50℃常压下进行进一步的烘干，使得含水量低于15％；5) Drying: Dry the rosemary powder at 30-50° C. under normal pressure to reduce the moisture content to less than 15%.
6)预冻：将上述含水量低于15％迷迭香粉摊铺开，摊铺厚度在5-10cm，在常压下进行快速预冻，预冻时间30-60min，预冻温度-20～-40℃；6) Prefreezing: Spread the rosemary powder with a moisture content of less than 15% to a thickness of 5-10 cm, and perform rapid prefreezing at normal pressure for 30-60 minutes at a prefreezing temperature of -20 to -40°C;
7)冷冻干燥：保持预冻温度的条件下，加入质量分数5-10％的冻干保护剂，与迷迭香粉充分混合后，放入冻干机进行冻干，冻干程序如下：7) Freeze drying: Under the condition of maintaining the pre-freezing temperature, add 5-10% by mass of freeze-drying protective agent, mix it with rosemary powder, and put it into freeze drying machine for freeze drying. The freeze drying procedure is as follows:
A:-45～-55℃，压强300-800Pa，冻干30-60min；A: -45～-55℃, pressure 300-800Pa, freeze drying 30-60min;
B：-60～-55℃，压强150-250Pa,冻干100-200min；B: -60～-55℃, pressure 150-250Pa, freeze drying 100-200min;
C：-75～-85℃，压强70-150Pa,冻干30-45min；C: -75～-85℃, pressure 70-150Pa, freeze drying 30-45min;
D：恢复到常温常压，获得迷迭香冻干粉，含水量低于5％，并真空包装。D: Return to normal temperature and pressure to obtain rosemary freeze-dried powder with a water content of less than 5%, and vacuum pack it.
本方案中，采用保鲜清洗液对迷迭香新鲜嫩叶进行浸泡和清洗，洗去迷迭香嫩叶上的灰尘，泥土，并对嫩叶进行保鲜，防止有效成分散失，同时对迷迭香嫩叶进行杀菌，去除农药残留；同时先对迷迭香进行自然干燥和烘干干燥，使得含水量低于15％，而不是马上进行冻干，是为了降低水分，从而降低冻干的时间和能耗，随后在冻干时加入冻干保护剂，进一步的降低迷迭香在冻干时有效成分的破坏，并使用程序的冻干，保证冻干质量的同时降低冻干的总时间。In the scheme, fresh rosemary leaves are soaked and cleaned with a fresh-keeping cleaning liquid to wash away dust and soil on the rosemary leaves, and the leaves are kept fresh to prevent the loss of effective components. At the same time, the rosemary leaves are sterilized to remove pesticide residues. At the same time, the rosemary is first naturally dried and oven-dried to make the water content less than 15%, rather than being freeze-dried immediately, in order to reduce the moisture content, thereby reducing the freeze-drying time and energy consumption. Subsequently, a freeze-drying protective agent is added during freeze-drying to further reduce the destruction of the effective components of the rosemary during freeze-drying, and programmed freeze-drying is used to ensure the freeze-drying quality while reducing the total freeze-drying time.
进一步的，上述一种迷迭香的冷冻干燥方法，所述新鲜嫩叶为从迷迭香顶端向下茎杆20cm以内的新鲜嫩叶。上述范围内的新鲜嫩叶一般来说处于韧皮部和木质部的分界线之上，质量最好，迷迭香有效成分含量最多。Further, in the freeze-drying method of rosemary, the fresh young leaves are fresh young leaves within 20 cm from the top of the rosemary stem. The fresh young leaves within the above range are generally above the dividing line between phloem and xylem, have the best quality, and contain the most rosemary active ingredients.
进一步的，上述一种迷迭香的冷冻干燥方法，所述步骤2)中的保鲜清洗液含有以下成分，按重量份数计包括：Furthermore, in the above-mentioned freeze-drying method for rosemary, the fresh-keeping cleaning solution in step 2) contains the following components in parts by weight:
Figure PCTCN2022127867-appb-000001
Figure PCTCN2022127867-appb-000001
采用上述保鲜清洗液，可以洗去迷迭香嫩叶上的灰尘，泥土，并对嫩叶进行保鲜，防止有效成分散失，同时对迷迭香嫩叶进行杀菌，去除农药残留。葡萄糖酸氯己定是一种双胍氯苯，有相当广的抗微生物活性，十二烷基硫酸钠具有强力的去污能力，并能够直接洗去农药残留，同时L-半胱氨酸具有很好的解毒中和生物中和能力，能够与无法洗去的农药残留中和，与十二烷基硫酸钠配合使用能够彻底去除农药残留影响；L-抗坏血酸具有强大的抗氧化作用，能够防止迷迭香的氧化变质有效成分丧失。The fresh-keeping cleaning liquid can be used to wash away dust and dirt on the young leaves of rosemary, and the young leaves can be kept fresh to prevent the loss of effective components, and the young leaves of rosemary can be sterilized to remove pesticide residues. Chlorhexidine gluconate is a biguanide chlorobenzene with a wide range of antimicrobial activity, sodium lauryl sulfate has a strong decontamination ability and can directly wash away pesticide residues, while L-cysteine has a good detoxification and biological neutralization ability, can neutralize with pesticide residues that cannot be washed away, and can be used in conjunction with sodium lauryl sulfate to completely remove the impact of pesticide residues; L-ascorbic acid has a strong antioxidant effect and can prevent the loss of effective components of rosemary due to oxidation and deterioration.
进一步的，上述一种迷迭香的冷冻干燥方法，所述步骤2)中的浸泡时间为2-6h，温度为15-30℃。浸泡时间过短无法实现灰尘和农药残留的洗涤，时间太长容易腐败，经过实验发现2-6小时比较容易实现上述的平衡。Furthermore, in the above freeze-drying method of rosemary, the soaking time in step 2) is 2-6 hours, and the temperature is 15-30° C. If the soaking time is too short, dust and pesticide residues cannot be washed away, and if the soaking time is too long, it is easy to spoil. Experiments have found that 2-6 hours is easier to achieve the above balance.
进一步的，上述一种迷迭香的冷冻干燥方法，所述步骤7)中的冻干保护剂选自甘油，阿拉伯胶或海藻糖中的一种。Furthermore, in the above-mentioned freeze-drying method for rosemary, the freeze-drying protectant in step 7) is selected from one of glycerol, gum arabic or trehalose.
进一步的，上述一种迷迭香的冷冻干燥方法，所述海藻糖经过如下步骤的改性：Furthermore, in the above-mentioned freeze-drying method of rosemary, the trehalose is modified by the following steps:
a.称取海藻糖原料投入含有质量分数为1-3％氢氧化钠溶液中超声波清洗10-20min，随后放入质量分数0.5-1％的冰醋酸溶液中，对海藻糖溶液进行抽滤，然后用95％以上乙醇沉淀洗涤，干燥获得预处理海藻糖；a. Weigh the trehalose raw material and put it into a sodium hydroxide solution containing a mass fraction of 1-3%, ultrasonic cleaning for 10-20 minutes, then put it into a glacial acetic acid solution with a mass fraction of 0.5-1%, filter the trehalose solution, then precipitate and wash with 95% or more ethanol, and dry to obtain pretreated trehalose;
b.将预处理海藻糖与质量分数5-10％醋酸溶液加入反应容器，所述海藻糖原料与所述醋酸溶液的质量体积比为1g：5-10mL；冰水浴控制反应温度在0～5℃； 在搅拌的状态下加入羟化卵磷脂；滴加完毕后撤去冰水浴，在室温下持续搅拌反应2～4h；经静置、沉淀、抽滤、干燥、重结晶得到改性海藻糖；其中所述预处理壳聚糖与羟化卵磷脂的质量比为1：(0.3～0.5)。b. Add pretreated trehalose and 5-10% acetic acid solution into a reaction vessel, wherein the mass volume ratio of the trehalose raw material to the acetic acid solution is 1 g: 5-10 mL; control the reaction temperature at 0-5°C in an ice-water bath; add hydroxylated lecithin under stirring; remove the ice-water bath after the addition is complete, and continue stirring the reaction at room temperature for 2-4 hours; obtain modified trehalose by standing, precipitating, filtering, drying, and recrystallizing; wherein the mass ratio of the pretreated chitosan to the hydroxylated lecithin is 1: (0.3-0.5).
经过申请人实验发现，使用上述改性的海藻糖，对于迷迭香的冻干保护力最强。The applicant has found through experiments that the use of the modified trehalose has the strongest freeze-drying protection for rosemary.
进一步的，上述一种迷迭香的冷冻干燥方法制备获得的迷迭香。Furthermore, the rosemary prepared by the above-mentioned freeze-drying method of rosemary.
进一步的，一种迷迭香有效成分的提取工艺，包含上述冷冻干燥方法。Furthermore, a process for extracting effective components of rosemary comprises the above freeze-drying method.
进一步的，上述迷迭香有效成分的提取工艺，其特征在于，包括以下步骤：Furthermore, the extraction process of the rosemary active ingredient is characterized by comprising the following steps:
1)迷迭香的采收：在3-11月上旬采收迷迭香的新鲜嫩叶；1) Harvesting rosemary: Harvest fresh young leaves of rosemary from March to early November;
2)迷迭香的保鲜清洗：使用保鲜清洗液对迷迭香新鲜嫩叶进行浸泡和清洗；2) Rosemary preservation and cleaning: Use a fresh-keeping cleaning solution to soak and clean the fresh young leaves of rosemary;
3)初步自然干燥：在通风阴凉处，温度为20-30℃条件下，对浸泡过的嫩叶进行自然干燥6-12h；3) Preliminary natural drying: In a ventilated and cool place at a temperature of 20-30°C, the soaked young leaves are naturally dried for 6-12 hours;
4)迷迭香粉碎：对干燥后的迷迭香进行机械粉碎，粉碎后的原料过100-200目筛，得到迷迭香粉；4) Rosemary crushing: The dried rosemary is mechanically crushed, and the crushed raw material is passed through a 100-200 mesh sieve to obtain rosemary powder;
5)烘干干燥：将迷迭香粉在30-50℃常压下进行进一步的烘干，使得含水量低于15％；5) Drying: Dry the rosemary powder at 30-50° C. under normal pressure to reduce the moisture content to less than 15%.
6)预冻：将上述含水量低于15％迷迭香粉摊铺开，摊铺厚度在5-10cm，在常压下进行快速预冻，预冻时间30-60min，预冻温度-20～-40℃；6) Prefreezing: Spread the rosemary powder with a moisture content of less than 15% to a thickness of 5-10 cm, and perform rapid prefreezing at normal pressure for 30-60 minutes at a prefreezing temperature of -20 to -40°C;
7)冷冻干燥：保持预冻温度的条件下，加入质量分数5-10％的冻干保护剂，与迷迭香粉充分混合后，放入冻干机进行冻干，冻干程序如下：7) Freeze drying: Under the condition of maintaining the pre-freezing temperature, add 5-10% by mass of freeze-drying protective agent, mix it with rosemary powder, and put it into freeze drying machine for freeze drying. The freeze drying procedure is as follows:
A:-45～-55℃，压强300-800Pa，冻干30-60min；A: -45～-55℃, pressure 300-800Pa, freeze drying 30-60min;
B：-60～-55℃，压强150-250Pa,冻干100-200min；B: -60～-55℃, pressure 150-250Pa, freeze drying 100-200min;
C：-75～-85℃，压强70-150Pa,冻干30-45min；C: -75～-85℃, pressure 70-150Pa, freeze drying 30-45min;
D：恢复到常温常压，获得迷迭香冻干粉，含水量低于5％，并真空包装；D: returning to normal temperature and pressure to obtain rosemary freeze-dried powder with a water content of less than 5%, and vacuum packaging;
8)迷迭香精油提取：将步骤7)获得的迷迭香冻干粉按质量比1:5-10的比例投入提取液中4-10℃浸泡12-24h，所述提取液由以下质量份数成分组成：8) Extraction of rosemary essential oil: The rosemary freeze-dried powder obtained in step 7) is put into an extracting solution at a mass ratio of 1:5-10 and soaked at 4-10° C. for 12-24 hours. The extracting solution consists of the following components in mass fractions:
去离子水         100份Deionized water 100 parts
丙三醇           10-20份Glycerol 10-20 parts
L-抗坏血酸       0.5-1份；L-ascorbic acid 0.5-1 part;
随后将含有迷迭香冻干粉提取液进行蒸馏提取获得迷迭香精油。Subsequently, the extract containing the rosemary freeze-dried powder is distilled to obtain rosemary essential oil.
本方案中，使用低毒对环境无害的丙三醇作为提取液主要成分，配合L-抗坏血酸对迷迭香冻干粉进行浸出，绿色环保，同时能够最大程度保留有效活性成分。In this scheme, low-toxic and environmentally friendly propylene glycol is used as the main component of the extract, and L-ascorbic acid is used to extract the rosemary freeze-dried powder, which is green and environmentally friendly and can retain the effective active ingredients to the greatest extent.
进一步的，经过上述迷迭香有效成分的提取工艺制备得到的迷迭香精油。Furthermore, rosemary essential oil is prepared by the above-mentioned extraction process of rosemary effective ingredients.
相比现有技术，本发明具有如下有益效果:Compared with the prior art, the present invention has the following beneficial effects:
1)本发明公开了一种迷迭香的冷冻干燥方法，从采摘开始就注重最大程度保留迷迭香的有效成分，选择从迷迭香顶端向下茎杆20cm以内的新鲜嫩叶。上述范围内的新鲜嫩叶一般来说处于韧皮部和木质部的分界线之上，质量最好，迷迭香有效成分含量最多。整个工艺中，采用保鲜清洗液对迷迭香新鲜嫩叶进行浸泡和清洗，洗去迷迭香嫩叶上的灰尘，泥土，并对嫩叶进行保鲜，防止有效成分散失，同时对迷迭香嫩叶进行杀菌，去除农药残留；同时先对迷迭香进行自然干燥和烘干干燥，使得含水量低于15％，而不是马上进行冻干，是为了降低水分，从而降低冻干的时间和能耗，随后在冻干时加入冻干保护剂，进一步的降低迷迭香在冻干时有效成分的破坏，并使用程序的冻干，保证冻干质量的同时降低冻干的总时间，相比普通的冻干程序，能够节省一半或者三分之二的时间。1) The invention discloses a freeze-drying method for rosemary. The method focuses on retaining the effective components of rosemary to the greatest extent from the beginning of picking, and selects fresh young leaves within 20 cm from the top of rosemary to the stem. The fresh young leaves within the above range are generally above the boundary between phloem and xylem, have the best quality, and have the highest content of rosemary effective components. In the whole process, a fresh-keeping cleaning liquid is used to soak and clean the fresh young leaves of rosemary, wash away dust and soil on the young leaves of rosemary, and keep the young leaves fresh to prevent the loss of effective components. At the same time, the young leaves of rosemary are sterilized to remove pesticide residues; at the same time, the rosemary is first naturally dried and dried to make the water content less than 15%, instead of being freeze-dried immediately, in order to reduce moisture, thereby reducing the time and energy consumption of freeze-drying, and then a freeze-drying protective agent is added during freeze-drying to further reduce the destruction of the effective components of rosemary during freeze-drying, and a freeze-drying program is used to ensure the freeze-drying quality while reducing the total time of freeze-drying, which can save half or two-thirds of the time compared to the ordinary freeze-drying program.
2)本发明还配制了一种保鲜清洗液，采用上述保鲜清洗液，可以洗去迷迭香嫩叶上的灰尘，泥土，并对嫩叶进行保鲜，防止有效成分散失，同时对迷迭香嫩叶进行杀菌，去除农药残留。葡萄糖酸氯己定是一种双胍氯苯，有相当广的抗微生物活性，十二烷基硫酸钠具有强力的去污能力，并能够直接洗去农药残留，同时L-半胱氨酸具有很好的解毒中和生物中和能力，能够与无法洗去的农药残留中和，与十二烷基硫酸钠配合使用能够彻底去除农药残留影响；L-抗坏血酸具有强大的抗氧化作用，能够防止迷迭香的氧化变质有效成分丧失。2) The present invention also prepares a fresh-keeping cleaning liquid, which can wash away dust and soil on the young leaves of rosemary, keep the young leaves fresh, prevent the loss of effective components, and sterilize the young leaves of rosemary to remove pesticide residues. Chlorhexidine gluconate is a biguanide chlorobenzene with a wide range of antimicrobial activity. Sodium lauryl sulfate has a strong decontamination ability and can directly wash away pesticide residues. At the same time, L-cysteine has a good detoxification and biological neutralization ability, can neutralize pesticide residues that cannot be washed away, and can be used in combination with sodium lauryl sulfate to completely remove the impact of pesticide residues; L-ascorbic acid has a strong antioxidant effect and can prevent the loss of effective components of rosemary due to oxidation and deterioration.
3)本发明使用改性的海藻糖，使得海藻糖的比表面积增大，包裹能力增强，在冻干时能防止迷迭香的有效组分随水蒸汽一起升华逸散，并使有效组分成形，对于迷迭香的冻干保护力最强，并且，在提取中，本发明使用低毒对环境无害的丙三醇作为提取液主要成分，配合L-抗坏血酸对迷迭香冻干粉进行浸出，绿色环保，同时能够最大程度保留有效活性成分。3) The present invention uses modified trehalose, so that the specific surface area of trehalose is increased, the encapsulation ability is enhanced, and the effective components of rosemary can be prevented from sublimating and escaping with water vapor during freeze-drying, and the effective components are formed, so the freeze-drying protection of rosemary is the strongest. In addition, during extraction, the present invention uses low-toxic and environmentally friendly glycerol as the main component of the extract, and cooperates with L-ascorbic acid to leach the rosemary freeze-dried powder, which is green and environmentally friendly, and can retain the effective active ingredients to the greatest extent.
综上的，本发明所述的方法相比现有技术，有机溶剂的使用量大大减少，最终产品中几乎没有乙醇残留，同时冻干流程短，节能减排，降低成本效果显著。In summary, compared with the prior art, the method described in the present invention greatly reduces the amount of organic solvent used, and there is almost no ethanol residue in the final product. At the same time, the freeze-drying process is short, energy saving and emission reduction are significant, and the cost reduction effect is significant.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为本发明冷冻干燥方法的流程示意图；FIG1 is a schematic flow diagram of a freeze-drying method of the present invention;
图2为实施例和对比例精油质量的比较；Fig. 2 is a comparison of the essential oil qualities of the embodiment and the comparative example;
图3为实施例和对比例中1g精油中β-蒎烯含量(mg)；Fig. 3 is the β-pinene content (mg) in 1g of essential oil in Examples and Comparative Examples;
图4为实施例和对比例中1g精油中中乙酸芳樟酯含量(mg)。FIG. 4 is the linalyl acetate content (mg) in 1 g of essential oil in the Examples and Comparative Examples.
具体实施方式Detailed ways
如图1所示一种迷迭香的冷冻干燥方法，包括以下步骤：As shown in Figure 1, a freeze-drying method for rosemary comprises the following steps:
1)迷迭香的采收：在3-11月上旬采收迷迭香的新鲜嫩叶；1) Harvesting rosemary: Harvest fresh young leaves of rosemary from March to early November;
2)迷迭香的保鲜清洗：使用保鲜清洗液对迷迭香新鲜嫩叶进行浸泡和清洗；2) Rosemary preservation and cleaning: Use a fresh-keeping cleaning solution to soak and clean the fresh young leaves of rosemary;
3)初步自然干燥：在通风阴凉处，温度为20-30℃条件下，对浸泡过的嫩叶进行自然干燥6-12h；3) Preliminary natural drying: In a ventilated and cool place at a temperature of 20-30°C, the soaked young leaves are naturally dried for 6-12 hours;
4)迷迭香粉碎：对干燥后的迷迭香进行机械粉碎，粉碎后的原料过100-200目筛，得到迷迭香粉；4) Rosemary crushing: The dried rosemary is mechanically crushed, and the crushed raw material is passed through a 100-200 mesh sieve to obtain rosemary powder;
5)烘干干燥：将迷迭香粉在30-50℃常压下进行进一步的烘干，使得含水量低于15％；5) Drying: Dry the rosemary powder at 30-50° C. under normal pressure to reduce the moisture content to less than 15%.
6)预冻：将上述含水量低于15％迷迭香粉摊铺开，摊铺厚度在5-10cm，在常压下进行快速预冻，预冻时间30-60min，预冻温度-20～-40℃；6) Prefreezing: Spread the rosemary powder with a moisture content of less than 15% to a thickness of 5-10 cm, and perform rapid prefreezing at normal pressure for 30-60 minutes at a prefreezing temperature of -20 to -40°C;
7)冷冻干燥：保持预冻温度的条件下，加入质量分数5-10％的冻干保护剂，与迷迭香粉充分混合后，放入冻干机进行冻干，冻干程序如下：7) Freeze drying: Under the condition of maintaining the pre-freezing temperature, add 5-10% by mass of freeze-drying protective agent, mix it with rosemary powder, and put it into freeze drying machine for freeze drying. The freeze drying procedure is as follows:
A:-45～-55℃，压强300-800Pa，冻干30-60min；A: -45～-55℃, pressure 300-800Pa, freeze drying 30-60min;
B：-60～-55℃，压强150-250Pa,冻干100-200min；B: -60～-55℃, pressure 150-250Pa, freeze drying 100-200min;
C：-75～-85℃，压强70-150Pa,冻干30-45min；C: -75～-85℃, pressure 70-150Pa, freeze drying 30-45min;
D：恢复到常温常压，获得迷迭香冻干粉，含水量低于5％，并真空包装；D: returning to normal temperature and pressure to obtain rosemary freeze-dried powder with a water content of less than 5%, and vacuum packaging;
8)迷迭香精油提取：将步骤7)获得的迷迭香冻干粉按质量比1:5-10的比例投入提取液中4-10℃浸泡12-24h，所述提取液由以下质量份数成分组成：8) Extraction of rosemary essential oil: The rosemary freeze-dried powder obtained in step 7) is put into an extracting solution at a mass ratio of 1:5-10 and soaked at 4-10° C. for 12-24 hours. The extracting solution consists of the following components in mass fractions:
去离子水         100份Deionized water 100 parts
丙三醇           10-20份Glycerol 10-20 parts
L-抗坏血酸       0.5-1份；L-ascorbic acid 0.5-1 part;
随后将含有迷迭香冻干粉提取液进行蒸馏提取获得迷迭香精油；Then, the extract containing the rosemary freeze-dried powder is distilled to obtain rosemary essential oil;
所述新鲜嫩叶为从迷迭香顶端向下茎杆20cm以内的新鲜嫩叶。The fresh young leaves are fresh young leaves within 20 cm from the top of the rosemary stem downward.
所述步骤2)中的保鲜清洗液含有以下成分，按重量份数计包括：The fresh-keeping cleaning solution in step 2) contains the following components, calculated by weight:
Figure PCTCN2022127867-appb-000002
Figure PCTCN2022127867-appb-000002
所述步骤2)中的浸泡时间为2-6h，温度为15-30℃；The soaking time in step 2) is 2-6 hours and the temperature is 15-30° C.;
所述步骤7)中的冻干保护剂选自甘油，阿拉伯胶或海藻糖中的一种；The freeze-drying protective agent in step 7) is selected from one of glycerol, gum arabic or trehalose;
所述海藻糖经过如下步骤的改性：The trehalose is modified by the following steps:
a.称取海藻糖原料投入含有质量分数为1-3％氢氧化钠溶液中超声波清洗10-20min，随后放入质量分数0.5-1％的冰醋酸溶液中，对海藻糖溶液进行抽滤，然后用95％以上乙醇沉淀洗涤，干燥获得预处理海藻糖；a. Weigh the trehalose raw material and put it into a sodium hydroxide solution containing a mass fraction of 1-3%, ultrasonic cleaning for 10-20 minutes, then put it into a glacial acetic acid solution with a mass fraction of 0.5-1%, filter the trehalose solution, then precipitate and wash with 95% or more ethanol, and dry to obtain pretreated trehalose;
b.将预处理海藻糖与质量分数5-10％醋酸溶液加入反应容器，所述海藻糖原料与所述醋酸溶液的质量体积比为1g：5-10mL；冰水浴控制反应温度在0～5℃；在搅拌的状态下加入羟化卵磷脂；滴加完毕后撤去冰水浴，在室温下持续搅拌反应2～4h；经静置、沉淀、抽滤、干燥、重结晶得到改性海藻糖；其中所述预处理壳聚糖与羟化卵磷脂的质量比为1：(0.3～0.5)。b. Add pretreated trehalose and 5-10% acetic acid solution into a reaction vessel, wherein the mass volume ratio of the trehalose raw material to the acetic acid solution is 1 g: 5-10 mL; control the reaction temperature at 0-5°C in an ice-water bath; add hydroxylated lecithin while stirring; remove the ice-water bath after the addition is complete, and continue stirring the reaction at room temperature for 2-4 hours; obtain modified trehalose by standing, precipitating, filtering, drying, and recrystallizing; wherein the mass ratio of the pretreated chitosan to the hydroxylated lecithin is 1: (0.3-0.5).
下面对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
本发明实施例中使用的试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规试剂产品。The reagents or instruments used in the examples of the present invention without indicating the manufacturer are all conventional reagent products that can be obtained through commercial purchase.
实施例1Example 1
一种迷迭香的冷冻干燥方法，包括以下步骤：A freeze-drying method for rosemary comprises the following steps:
1)迷迭香的采收：在3-11月上旬采收迷迭香的新鲜嫩叶,质量为1000g；1) Rosemary harvesting: fresh young leaves of rosemary were harvested from March to early November, with a mass of 1000 g;
2)迷迭香的保鲜清洗：使用保鲜清洗液对迷迭香新鲜嫩叶进行浸泡和清洗；2) Rosemary preservation and cleaning: Use a fresh-keeping cleaning solution to soak and clean the fresh young leaves of rosemary;
3)初步自然干燥：在通风阴凉处，温度为20-30℃条件下，对浸泡过的嫩叶进行自然干燥6-12h；3) Preliminary natural drying: In a ventilated and cool place at a temperature of 20-30°C, the soaked young leaves are naturally dried for 6-12 hours;
4)迷迭香粉碎：对干燥后的迷迭香进行机械粉碎，粉碎后的原料过100-200目筛，得到迷迭香粉；4) Rosemary crushing: The dried rosemary is mechanically crushed, and the crushed raw material is passed through a 100-200 mesh sieve to obtain rosemary powder;
5)烘干干燥：将迷迭香粉在30-50℃常压下进行进一步的烘干，使得含水量低于15％；5) Drying: Dry the rosemary powder at 30-50° C. under normal pressure to reduce the moisture content to less than 15%.
6)预冻：将上述含水量低于15％迷迭香粉摊铺开，摊铺厚度在5-10cm，在常压下进行快速预冻，预冻时间30-60min，预冻温度-20～-40℃；6) Prefreezing: Spread the rosemary powder with a moisture content of less than 15% to a thickness of 5-10 cm, and perform rapid prefreezing at normal pressure for 30-60 minutes at a prefreezing temperature of -20 to -40°C;
7)冷冻干燥：保持预冻温度的条件下，加入质量分数5-10％的冻干保护剂，与迷迭香粉充分混合后，放入冻干机进行冻干，冻干程序如下：7) Freeze drying: Under the condition of maintaining the pre-freezing temperature, add 5-10% by mass of freeze-drying protective agent, mix it with rosemary powder, and put it into freeze drying machine for freeze drying. The freeze drying procedure is as follows:
A:-45℃，压强300Pa，冻干30min；A: -45℃, pressure 300Pa, freeze-drying for 30min;
B：-55℃，压强150Pa,冻干100min；B: -55℃, pressure 150Pa, freeze-drying 100min;
C：-75℃，压强70Pa,冻干30min；C: -75℃, pressure 70Pa, freeze-drying for 30min;
D：恢复到常温常压，获得迷迭香冻干粉，含水量低于5％，并真空包装；D: returning to normal temperature and pressure to obtain rosemary freeze-dried powder with a water content of less than 5%, and vacuum packaging;
8)迷迭香精油提取：将步骤7)获得的迷迭香冻干粉按质量比1:5的比例投入提取液中4℃浸泡12h，所述提取液由以下质量份数成分组成：8) Extraction of rosemary essential oil: The rosemary freeze-dried powder obtained in step 7) is put into an extracting solution at a mass ratio of 1:5 and soaked at 4° C. for 12 hours. The extracting solution consists of the following components in mass parts:
去离子水         100份Deionized water 100 parts
丙三醇           10份 Glycerol 10 parts
L-抗坏血酸       0.5份；L-ascorbic acid 0.5 parts;
随后将含有迷迭香冻干粉提取液进行蒸馏提取获得迷迭香精油；Then, the extract containing the rosemary freeze-dried powder is distilled to obtain rosemary essential oil;
所述新鲜嫩叶为从迷迭香顶端向下茎杆20cm以内的新鲜嫩叶。The fresh young leaves are fresh young leaves within 20 cm from the top of the rosemary stem downward.
所述步骤2)中的保鲜清洗液含有以下成分，按重量份数计包括：The fresh-keeping cleaning solution in step 2) contains the following components, calculated by weight:
Figure PCTCN2022127867-appb-000003
Figure PCTCN2022127867-appb-000003
所述步骤2)中的浸泡时间为2-6h，温度为15-30℃；The soaking time in step 2) is 2-6 hours and the temperature is 15-30° C.;
所述步骤7)中的冻干保护剂选自甘油。The lyoprotectant in step 7) is selected from glycerol.
实施例2Example 2
一种迷迭香的冷冻干燥方法，包括以下步骤：A freeze-drying method for rosemary comprises the following steps:
1)迷迭香的采收：在3-11月上旬采收迷迭香的新鲜嫩叶,质量为1000g；1) Rosemary harvesting: fresh young leaves of rosemary were harvested from March to early November, with a mass of 1000 g;
2)迷迭香的保鲜清洗：使用保鲜清洗液对迷迭香新鲜嫩叶进行浸泡和清洗；2) Rosemary preservation and cleaning: Use a fresh-keeping cleaning solution to soak and clean the fresh young leaves of rosemary;
3)初步自然干燥：在通风阴凉处，温度为20-30℃条件下，对浸泡过的嫩叶进行自然干燥6-12h；3) Preliminary natural drying: In a ventilated and cool place at a temperature of 20-30°C, the soaked young leaves are naturally dried for 6-12 hours;
4)迷迭香粉碎：对干燥后的迷迭香进行机械粉碎，粉碎后的原料过100-200目筛，得到迷迭香粉；4) Rosemary crushing: The dried rosemary is mechanically crushed, and the crushed raw material is passed through a 100-200 mesh sieve to obtain rosemary powder;
5)烘干干燥：将迷迭香粉在30-50℃常压下进行进一步的烘干，使得含水量低于15％；5) Drying: Drying the rosemary powder at 30-50° C. under normal pressure until the water content is less than 15%;
6)预冻：将上述含水量低于15％迷迭香粉摊铺开，摊铺厚度在5-10cm，在常压下进行快速预冻，预冻时间30-60min，预冻温度-20～-40℃；6) Prefreezing: Spread the rosemary powder with a moisture content of less than 15% to a thickness of 5-10 cm, and perform rapid prefreezing at normal pressure for 30-60 minutes at a prefreezing temperature of -20 to -40°C;
7)冷冻干燥：保持预冻温度的条件下，加入质量分数5-10％的冻干保护剂，与迷迭香粉充分混合后，放入冻干机进行冻干，冻干程序如下：7) Freeze drying: Under the condition of maintaining the pre-freezing temperature, add 5-10% by mass of freeze-drying protective agent, mix it with rosemary powder, and put it into freeze drying machine for freeze drying. The freeze drying procedure is as follows:
A:50℃，压强500Pa，冻干45min；A: 50℃, pressure 500Pa, freeze drying 45min;
B：-58℃，压强200Pa,冻干150min；B: -58℃, pressure 200Pa, freeze drying 150min;
C：-80℃，压强133Pa,冻干40min；C: -80℃, pressure 133Pa, freeze-drying 40min;
D：恢复到常温常压，获得迷迭香冻干粉，含水量低于5％，并真空包装。D: Return to normal temperature and pressure to obtain rosemary freeze-dried powder with a water content of less than 5%, and vacuum pack it.
8)迷迭香精油提取：将步骤7)获得的迷迭香冻干粉按质量比1:8的比例投入提取液中8℃浸泡18h，所述提取液由以下质量份数成分组成：8) Extraction of rosemary essential oil: The rosemary freeze-dried powder obtained in step 7) is put into an extracting solution at a mass ratio of 1:8 and soaked at 8° C. for 18 hours. The extracting solution consists of the following components in mass parts:
去离子水         100份Deionized water 100 parts
丙三醇           15份 Glycerol 15 parts
L-抗坏血酸       0.75份；L-ascorbic acid 0.75 parts;
随后将含有迷迭香冻干粉提取液进行蒸馏提取获得迷迭香精油；Then, the extract containing the rosemary freeze-dried powder is distilled to obtain rosemary essential oil;
所述新鲜嫩叶为从迷迭香顶端向下茎杆20cm以内的新鲜嫩叶。The fresh young leaves are fresh young leaves within 20 cm from the top of the rosemary stem downward.
所述步骤2)中的保鲜清洗液含有以下成分，按重量份数计包括：The fresh-keeping cleaning solution in step 2) contains the following components by weight:
Figure PCTCN2022127867-appb-000004
Figure PCTCN2022127867-appb-000004
Figure PCTCN2022127867-appb-000005
Figure PCTCN2022127867-appb-000005
所述步骤2)中的浸泡时间为2-6h，温度为15-30℃；The soaking time in step 2) is 2-6 hours and the temperature is 15-30° C.;
所述步骤7)中的冻干保护剂选自海藻糖；The lyophilization protective agent in step 7) is selected from trehalose;
所述海藻糖经过如下步骤的改性：The trehalose is modified by the following steps:
a.称取海藻糖原料投入含有质量分数为2％氢氧化钠溶液中超声波清洗15min，随后放入质量分数0.75％的冰醋酸溶液中，对海藻糖溶液进行抽滤，然后用95％以上乙醇沉淀洗涤，干燥获得预处理海藻糖；a. Weigh the trehalose raw material and put it into a 2% sodium hydroxide solution containing ultrasonic cleaning for 15 minutes, then put it into a 0.75% glacial acetic acid solution, filter the trehalose solution, then precipitate and wash with 95% or more ethanol, and dry to obtain pretreated trehalose;
b.将预处理海藻糖与质量分数7.5％醋酸溶液加入反应容器，所述海藻糖原料与所述醋酸溶液的质量体积比为1g：7.5mL；冰水浴控制反应温度在0～5℃；在搅拌的状态下加入羟化卵磷脂；滴加完毕后撤去冰水浴，在室温下持续搅拌反应2～4h；经静置、沉淀、抽滤、干燥、重结晶得到改性海藻糖；其中所述预处理壳聚糖与羟化卵磷脂的质量比为1：0.4。b. Add pretreated trehalose and 7.5% acetic acid solution into a reaction vessel, wherein the mass volume ratio of the trehalose raw material to the acetic acid solution is 1 g:7.5 mL; control the reaction temperature at 0-5°C in an ice-water bath; add hydroxylated lecithin under stirring; remove the ice-water bath after the addition is complete, and continue stirring the reaction at room temperature for 2-4 hours; obtain modified trehalose by standing, precipitation, suction filtration, drying, and recrystallization; wherein the mass ratio of the pretreated chitosan to the hydroxylated lecithin is 1:0.4.
实施例3Example 3
一种迷迭香的冷冻干燥方法，包括以下步骤：A freeze-drying method for rosemary comprises the following steps:
1)迷迭香的采收：在3-11月上旬采收迷迭香的新鲜嫩叶,质量为1000g；1) Rosemary harvesting: fresh young leaves of rosemary were harvested from March to early November, with a mass of 1000 g;
2)迷迭香的保鲜清洗：使用保鲜清洗液对迷迭香新鲜嫩叶进行浸泡和清洗；2) Rosemary preservation and cleaning: Use a fresh-keeping cleaning solution to soak and clean the fresh young leaves of rosemary;
3)初步自然干燥：在通风阴凉处，温度为20-30℃条件下，对浸泡过的嫩叶进行自然干燥6-12h；3) Preliminary natural drying: dry the soaked young leaves naturally for 6-12 hours in a ventilated and cool place at a temperature of 20-30°C;
4)迷迭香粉碎：对干燥后的迷迭香进行机械粉碎，粉碎后的原料过100-200目筛，得到迷迭香粉；4) Rosemary crushing: The dried rosemary is mechanically crushed, and the crushed raw material is passed through a 100-200 mesh sieve to obtain rosemary powder;
5)烘干干燥：将迷迭香粉在30-50℃常压下进行进一步的烘干，使得含水量低于15％；5) Drying: Dry the rosemary powder at 30-50° C. under normal pressure to reduce the moisture content to less than 15%.
6)预冻：将上述含水量低于15％迷迭香粉摊铺开，摊铺厚度在5-10cm，在常压下进行快速预冻，预冻时间30-60min，预冻温度-20～-40℃；6) Prefreezing: Spread the rosemary powder with a moisture content of less than 15% to a thickness of 5-10 cm, and perform rapid prefreezing at normal pressure for 30-60 minutes at a prefreezing temperature of -20 to -40°C;
7)冷冻干燥：保持预冻温度的条件下，加入质量分数5-10％的冻干保护剂，与迷迭香粉充分混合后，放入冻干机进行冻干，冻干程序如下：7) Freeze drying: Under the condition of maintaining the pre-freezing temperature, add 5-10% by mass of freeze-drying protective agent, mix it with rosemary powder, and put it into freeze drying machine for freeze drying. The freeze drying procedure is as follows:
A:-55℃，压强800Pa，冻干60min；A: -55℃, pressure 800Pa, freeze drying 60min;
B：-60℃，压强250Pa,冻干200min；B: -60℃, pressure 250Pa, freeze-drying 200min;
C：-85℃，压强150Pa,冻干45min；C: -85℃, pressure 150Pa, freeze-drying 45min;
D：恢复到常温常压，获得迷迭香冻干粉，含水量低于5％，并真空包装；D: returning to normal temperature and pressure to obtain rosemary freeze-dried powder with a water content of less than 5%, and vacuum packaging;
8)迷迭香精油提取：将步骤7)获得的迷迭香冻干粉按质量比1:10的比例投入提取液中10℃浸泡24h，所述提取液由以下质量份数成分组成：8) Extraction of rosemary essential oil: The rosemary freeze-dried powder obtained in step 7) is put into an extracting solution at a mass ratio of 1:10 and soaked at 10° C. for 24 hours. The extracting solution consists of the following components in mass parts:
去离子水         100份Deionized water 100 parts
丙三醇           20份 Glycerol 20 parts
L-抗坏血酸       1份；L-ascorbic acid       1 part;
随后将含有迷迭香冻干粉提取液进行蒸馏提取获得迷迭香精油；Then, the extract containing the rosemary freeze-dried powder is distilled to obtain rosemary essential oil;
所述新鲜嫩叶为从迷迭香顶端向下茎杆20cm以内的新鲜嫩叶；The fresh young leaves are fresh young leaves within 20 cm from the top of the rosemary stem;
所述步骤2)中的保鲜清洗液含有以下成分，按重量份数计包括：The fresh-keeping cleaning solution in step 2) contains the following components by weight:
Figure PCTCN2022127867-appb-000006
Figure PCTCN2022127867-appb-000006
所述步骤2)中的浸泡时间为2-6h，温度为15-30℃；The soaking time in step 2) is 2-6 hours and the temperature is 15-30° C.;
所述步骤7)中的冻干保护剂选自阿拉伯胶。The freeze-drying protective agent in step 7) is selected from gum arabic.
对比例1Comparative Example 1
一种迷迭香的冷冻干燥方法，未使用保鲜清洗液对迷迭香清洗，而是使用去离子水，其他同实施例2。A freeze-drying method for rosemary, wherein deionized water is used instead of a fresh-keeping cleaning liquid to clean the rosemary, and the other steps are the same as those in Example 2.
对比例2Comparative Example 2
一种迷迭香的冷冻干燥方法，使用普通海藻糖，而不是使用实施例2中的改性海藻糖，其他同实施例2。A method for freeze-drying rosemary, using ordinary trehalose instead of the modified trehalose in Example 2, and the other steps are the same as Example 2.
对比例3Comparative Example 3
一种迷迭香的冷冻干燥方法，未使用保鲜清洗液对迷迭香清洗，而是使用去离子水，使用普通海藻糖，而不是使用实施例2中的改性海藻糖，其他同实施例2。A freeze-drying method for rosemary, wherein the rosemary is not washed with a fresh-keeping washing liquid but with deionized water, and ordinary trehalose is used instead of the modified trehalose in Example 2, and the other steps are the same as in Example 2.
测试例1Test Example 1
对实施例1-3以及对比例1-3的冷冻干燥方法提取获得迷迭香冻干粉，以及制备的精油进行比较，比较获得的冻干粉质量(g)，获得的精油质量(g)，用以代表冷冻干燥和精油提取的得率；1g精油中β-蒎烯含量(mg)，1g精油中乙酸芳樟酯含量(mg)，用以代表精油的质量，即冷冻干燥提取过程中对活性物质的保留能力，结果见表1和图2-4。The freeze-dried powder of rosemary obtained by the freeze-drying method of Examples 1-3 and Comparative Examples 1-3, and the prepared essential oils were compared, and the mass of the freeze-dried powder obtained (g) and the mass of the essential oil obtained (g) were compared to represent the yield of freeze drying and essential oil extraction; the β-pinene content (mg) in 1g of essential oil and the linalyl acetate content (mg) in 1g of essential oil were used to represent the mass of the essential oil, that is, the retention capacity of the active substance during the freeze drying extraction process. The results are shown in Table 1 and Figures 2-4.
表1不同催化过程的反应结果Table 1 Reaction results of different catalytic processes
Figure PCTCN2022127867-appb-000007
Figure PCTCN2022127867-appb-000007
由表1的数据可知，对比例2和3的精油的质量较其余实施例减少较多，证明，经过本发明改性的海藻糖可以在冻干过程中较多的保留迷迭香中的精油成分。从表1中还可知，对比例1-3中精油中的β-蒎烯含量(mg)和乙酸芳樟酯含量(mg)相比实施例1-3由巨大的降低，证明本发明改性的海藻糖和保鲜清洗液综合作用，可以保留迷迭香中的活性成分。As can be seen from the data in Table 1, the mass of the essential oils in Comparative Examples 2 and 3 is reduced more than that in the other embodiments, proving that the modified trehalose of the present invention can retain more essential oil components in rosemary during the freeze-drying process. It can also be seen from Table 1 that the β-pinene content (mg) and linalyl acetate content (mg) in the essential oils in Comparative Examples 1-3 are greatly reduced compared to Examples 1-3, proving that the modified trehalose of the present invention and the fresh-keeping cleaning solution have a combined effect to retain the active ingredients in rosemary.
上述实施例只是本发明的有限几种优选实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。The above embodiments are only limited preferred implementations of the present invention, and their descriptions are relatively specific and detailed, but they cannot be understood as limiting the scope of the present invention. It should be pointed out that for ordinary technicians in this field, several modifications and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention.

Claims (10)

  1. 一种迷迭香的冷冻干燥方法，其特征在于，包括以下步骤：A freeze-drying method for rosemary, characterized in that it comprises the following steps:
    1)迷迭香的采收：在3-11月上旬采收迷迭香的新鲜嫩叶；1) Harvesting rosemary: Harvest fresh young leaves of rosemary from March to early November;
    2)迷迭香的保鲜清洗：使用保鲜清洗液对迷迭香新鲜嫩叶进行浸泡和清洗；2) Rosemary preservation and cleaning: Use a fresh-keeping cleaning solution to soak and clean the fresh young leaves of rosemary;
    3)初步自然干燥：在通风阴凉处，温度为20-30℃条件下，对浸泡过的嫩叶进行自然干燥6-12h；3) Preliminary natural drying: In a ventilated and cool place at a temperature of 20-30°C, the soaked young leaves are naturally dried for 6-12 hours;
    4)迷迭香粉碎：对干燥后的迷迭香进行机械粉碎，粉碎后的原料过100-200目筛，得到迷迭香粉；4) Rosemary crushing: The dried rosemary is mechanically crushed, and the crushed raw material is passed through a 100-200 mesh sieve to obtain rosemary powder;
    5)烘干干燥：将迷迭香粉在30-50℃常压下进行进一步的烘干，使得含水量低于15％；5) Drying: Dry the rosemary powder at 30-50° C. under normal pressure to reduce the moisture content to less than 15%.
    6)预冻：将上述含水量低于15％迷迭香粉摊铺开，摊铺厚度在5-10cm，在常压下进行快速预冻，预冻时间30-60min，预冻温度-20～-40℃；6) Prefreezing: Spread the rosemary powder with a moisture content of less than 15% to a thickness of 5-10 cm, and perform rapid prefreezing at normal pressure for 30-60 minutes at a prefreezing temperature of -20 to -40°C;
    7)冷冻干燥：保持预冻温度的条件下，加入质量分数5-10％的冻干保护剂，与迷迭香粉充分混合后，放入冻干机进行冻干，冻干程序如下：7) Freeze drying: Under the condition of maintaining the pre-freezing temperature, add 5-10% by mass of freeze-drying protective agent, mix it with rosemary powder, and put it into freeze drying machine for freeze drying. The freeze drying procedure is as follows:
    A:-45～-55℃，压强300-800Pa，冻干30-60min；A: -45～-55℃, pressure 300-800Pa, freeze drying 30-60min;
    B：-60～-55℃，压强150-250Pa,冻干100-200min；B: -60～-55℃, pressure 150-250Pa, freeze drying 100-200min;
    C：-75～-85℃，压强70-150Pa,冻干30-45min；C: -75～-85℃, pressure 70-150Pa, freeze drying 30-45min;
    D：恢复到常温常压，获得迷迭香冻干粉，含水量低于5％，并真空包装。D: Return to normal temperature and pressure to obtain rosemary freeze-dried powder with a water content of less than 5%, and vacuum pack it.
  2. 根据权利要求1所述的一种迷迭香的冷冻干燥方法，其特征在于，所述新鲜嫩叶为从迷迭香顶端向下茎杆20cm以内的新鲜嫩叶。The freeze-drying method of rosemary according to claim 1, characterized in that the fresh young leaves are fresh young leaves within 20 cm from the top of the rosemary stem.
  3. 根据权利要求1所述的一种迷迭香的冷冻干燥方法，其特征在于，所述步骤2)中的保鲜清洗液含有以下成分，按重量份数计包括：The freeze-drying method of rosemary according to claim 1, characterized in that the fresh-keeping cleaning solution in step 2) contains the following components in parts by weight:
    Figure PCTCN2022127867-appb-100001
    Figure PCTCN2022127867-appb-100001
  4. 根据权利要求1所述的一种迷迭香的冷冻干燥方法，其特征在于，所述步骤2)中的浸泡时间为2-6h，温度为15-30℃。The freeze-drying method of rosemary according to claim 1, characterized in that the soaking time in step 2) is 2-6 hours and the temperature is 15-30°C.
  5. 根据权利要求1所述的一种迷迭香的冷冻干燥方法，其特征在于，所述步骤7)中的冻干保护剂选自甘油，阿拉伯胶或海藻糖中的一种。The freeze-drying method of rosemary according to claim 1, characterized in that the lyoprotectant in step 7) is selected from one of glycerol, gum arabic or trehalose.
  6. 根据权利要求1所述的一种迷迭香的冷冻干燥方法，其特征在于，所述海藻糖经过如下步骤的改性：The freeze-drying method of rosemary according to claim 1, characterized in that the trehalose is modified by the following steps:
    a.称取海藻糖原料投入含有质量分数为1-3％氢氧化钠溶液中超声波清洗10-20min，随后放入质量分数0.5-1％的冰醋酸溶液中，对海藻糖溶液进行抽滤，然后用95％以上乙醇沉淀洗涤，干燥获得预处理海藻糖；a. Weigh the trehalose raw material and put it into a sodium hydroxide solution containing a mass fraction of 1-3%, ultrasonic cleaning for 10-20 minutes, then put it into a glacial acetic acid solution with a mass fraction of 0.5-1%, filter the trehalose solution, then precipitate and wash with 95% or more ethanol, and dry to obtain pretreated trehalose;
    b.将预处理海藻糖与质量分数5-10％醋酸溶液加入反应容器，所述海藻糖原料与所述醋酸溶液的质量体积比为1g：5-10mL；冰水浴控制反应温度在0～5℃；在搅拌的状态下加入羟化卵磷脂；滴加完毕后撤去冰水浴，在室温下持续搅拌反应2～4h；经静置、沉淀、抽滤、干燥、重结晶得到改性海藻糖；其中所述预处理壳聚糖与羟化卵磷脂的质量比为1：(0.3～0.5)。b. Add pretreated trehalose and 5-10% acetic acid solution into a reaction vessel, wherein the mass volume ratio of the trehalose raw material to the acetic acid solution is 1 g: 5-10 mL; control the reaction temperature at 0-5°C in an ice-water bath; add hydroxylated lecithin while stirring; remove the ice-water bath after the addition is complete, and continue stirring the reaction at room temperature for 2-4 hours; obtain modified trehalose by standing, precipitating, filtering, drying, and recrystallizing; wherein the mass ratio of the pretreated chitosan to the hydroxylated lecithin is 1: (0.3-0.5).
  7. 如权利要求1-6任一项所述的冷冻干燥方法制备获得的迷迭香。Rosemary prepared by the freeze-drying method according to any one of claims 1 to 6.
  8. 一种迷迭香有效成分的提取工艺，其特征在于，包含如权利要求1-6任一项所述的冷冻干燥方法。A process for extracting effective ingredients of rosemary, characterized by comprising the freeze-drying method according to any one of claims 1 to 6.
  9. 根据权利要求8所述的一种迷迭香有效成分的提取工艺，其特征在于，包括以下步骤：The process for extracting the active ingredients of rosemary according to claim 8, characterized in that it comprises the following steps:
    1)迷迭香的采收：在3-11月上旬采收迷迭香的新鲜嫩叶；1) Harvesting rosemary: Harvest fresh young leaves of rosemary from March to early November;
    2)迷迭香的保鲜清洗：使用保鲜清洗液对迷迭香新鲜嫩叶进行浸泡和清洗；2) Rosemary preservation and cleaning: Use a fresh-keeping cleaning solution to soak and clean the fresh young leaves of rosemary;
    3)初步自然干燥：在通风阴凉处，温度为20-30℃条件下，对浸泡过的嫩叶进行自然干燥6-12h；3) Preliminary natural drying: In a ventilated and cool place at a temperature of 20-30°C, the soaked young leaves are naturally dried for 6-12 hours;
    4)迷迭香粉碎：对干燥后的迷迭香进行机械粉碎，粉碎后的原料过100-200目筛，得到迷迭香粉；4) Rosemary crushing: The dried rosemary is mechanically crushed, and the crushed raw material is passed through a 100-200 mesh sieve to obtain rosemary powder;
    5)烘干干燥：将迷迭香粉在30-50℃常压下进行进一步的烘干，使得含水量低于15％；5) Drying: Dry the rosemary powder at 30-50° C. under normal pressure to reduce the moisture content to less than 15%.
    6)预冻：将上述含水量低于15％迷迭香粉摊铺开，摊铺厚度在5-10cm，在常压下进行快速预冻，预冻时间30-60min，预冻温度-20～-40℃；6) Prefreezing: Spread the rosemary powder with a moisture content of less than 15% to a thickness of 5-10 cm, and perform rapid prefreezing at normal pressure for 30-60 minutes at a prefreezing temperature of -20 to -40°C;
    7)冷冻干燥：保持预冻温度的条件下，加入质量分数5-10％的冻干保护剂，与迷迭香粉充分混合后，放入冻干机进行冻干，冻干程序如下：7) Freeze drying: Under the condition of maintaining the pre-freezing temperature, add 5-10% by mass of freeze-drying protective agent, mix it with rosemary powder, and put it into freeze drying machine for freeze drying. The freeze drying procedure is as follows:
    A:-45～-55℃，压强300-800Pa，冻干30-60min；A: -45～-55℃, pressure 300-800Pa, freeze drying 30-60min;
    B：-60～-55℃，压强150-250Pa,冻干100-200min；B: -60～-55℃, pressure 150-250Pa, freeze drying 100-200min;
    C：-75～-85℃，压强70-150Pa,冻干30-45min；C: -75～-85℃, pressure 70-150Pa, freeze drying 30-45min;
    D：恢复到常温常压，获得迷迭香冻干粉，含水量低于5％，并真空包装；D: returning to normal temperature and pressure to obtain rosemary freeze-dried powder with a water content of less than 5%, and vacuum packaging;
    8)迷迭香精油提取：将步骤7)获得的迷迭香冻干粉按质量比1:5-10的比例投入提取液中4-10℃浸泡12-24h，所述提取液由以下质量份数成分组成：8) Extraction of rosemary essential oil: The rosemary freeze-dried powder obtained in step 7) is put into an extracting solution at a mass ratio of 1:5-10 and soaked at 4-10° C. for 12-24 hours. The extracting solution consists of the following components in mass fractions:
    去离子水    100份Deionized water 100 parts
    丙三醇      10-20份Glycerol 10-20 parts
    L-抗坏血酸  0.5-1份；L-ascorbic acid 0.5-1 part;
    随后将含有迷迭香冻干粉提取液进行蒸馏提取获得迷迭香精油。Subsequently, the extract containing the rosemary freeze-dried powder is distilled to obtain rosemary essential oil.
  10. 如权利要求9所述的一种迷迭香有效成分的提取工艺制备获得的迷迭香精油。Rosemary essential oil obtained by the extraction process of rosemary active ingredients as claimed in claim 9.
PCT/CN2022/127867 2022-10-20 2022-10-27 Freeze-drying method for rosmarinus officinalis WO2024082329A1 (en)

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