CN1329494C - Combined extraction method for rosemary essential oil and rosemary antioxidant - Google Patents

Abstract

The present invention relates to a method for comprehensively extracting rosemary essential oil and rosemary antioxidants, which has the steps: directly and circularly extracting rosemary leaf materials for 0.08 to 6 hours by polar organic solvents which have the weight by 3 to 20 times of that of the rosemary leaf materials to obtain rosemary essential oil and rosemary antioxidants which are dissolved in the polar organic solvents; directly and circularly extracting the rosemary essential oil and the rosemary antioxidants for 0.08 to 6 hours at the temperature of 20 to 100DEGC by non-polar or low-polar organic solvents which have the weight by 3 to 200 times of that of the mixture of the rosemary essential oil and the rosemary antioxidants, and cooling the rosemary essential oil and the rosemary antioxidants to the temperature of 5 to 30 DEG C to obtain the rosemary essential oil and deposited rosemary antioxidants which are dissolved in the non-polar or low-polarorganic solvents; filtering the rosemary essential oil and the deposited rosemary antioxidants to obtain the deposit-rosemary antioxidants; steaming the extract at the temperature of 20 to 100 DEGC to remove the solvents so as to obtain rosemary essential oil products. The present invention has the advantages of short extraction period, high efficiency and low cost.

Description

Comprehensive extraction method of rosemary essential oil and rosemary antioxidant

technical field

The present invention relates to a kind of extracting method of rosemary essential oil and rosemary anti-oxidant, particularly relate to a kind of extracting by polar organic solvent, non-polar or weak polar organic solvent or its mixed solvent circulation extraction of rosemary dry leaf, If necessary, it is assisted by ultrasonic strengthening treatment, and the comprehensive extraction method of rosemary essential oil and rosemary antioxidant can be obtained simultaneously or successively.

Background technique

The extraction method of rosemary essential oil mainly uses the traditional steam distillation method, and recently also uses the _CO2 supercritical extraction method. The extraction methods of rosemary antioxidants include: "edible oil extraction method", "organic solvent extraction method", " _CO2 supercritical extraction method", "alkaline water extraction method" and "superheated water extraction method" and so on. "Edible oil extraction method" is to crush rosemary leaves and extract them directly with edible oil at room temperature or under heating, but the speed of filtering and removing residue is slow, and the oil will have a strong odor of rosemary essential oil, which is difficult "Organic solvent extraction" is a kind of extraction method that was used earlier and is economical and applicable. According to the different types of solvents used, the extraction methods and steps are also different; the extraction effect of " _CO2 supercritical extraction" Good, high product quality, but small scale, expensive equipment, high-pressure operation, and high operating costs. This method is beneficial to the extraction of volatile essential oils, and a small amount of organic solvents need to be added as entrainers for the extraction of non-volatile rosemary antioxidants or co-solvent, to improve the extraction yield or selectivity, in fact also lost the advantage of not using organic solvents; The use rate is low, and the pH range of the extract needs to be strictly controlled; the "superheated water extraction method" is only a preliminary research report, and the method has not yet been formed. The extraction device is special and the scale is very small, and it does not have application development value.

In the existing "organic solvent extraction method" close to the present invention, it includes extracting rosemary raw materials with ethanol or steamed residual leaves, removing the solvent to obtain a paste, and then boiling water to remove water-soluble substances. Obtain powdered rosemary antioxidants; extract with 2-95% ethanol-hexane mixed solvent, and dilute with water to obtain rosemary antioxidants; extract with acetone at room temperature, can remove pro-oxidant substances such as chlorophyll, and obtain complete oil Soluble rosemary antioxidant; at room temperature and nitrogen, presoaked with hexane, then ethanol extraction residue and decolorization, can get powdered rosemary antioxidant; use tetrafluoroethane and acetone mixed solvent to extract rosemary Fragrance, oily liquid rosemary antioxidant can be obtained, but the extraction rate is low, tetrafluoroethane has a high price and is difficult to obtain, and it is gaseous at room temperature, so the equipment requirements are more stringent (high pressure), and the solvent recovery requirements are high. Generally speaking, the above-mentioned extraction method is an extraction method independently established for a single product of rosemary antioxidant, and the extraction is mainly performed by a single batch extraction method, without more economical and reasonable comprehensive consideration of rosemary essential oil and rosemary antioxidant Simultaneous or sequential extraction, and there is no patented method that uses ultrasonic waves to strengthen the extraction process of rosemary essential oil and rosemary antioxidants.

Contents of the invention

The invention provides a comprehensive extraction method of rosemary essential oil and rosemary antioxidant with low cost, fast extraction speed, high extraction efficiency, less solvent residue, less pollution and convenient recovery.

The present invention provides following technical scheme:

A comprehensive extraction method of rosemary essential oil and rosemary antioxidant, which is characterized in that the rosemary is directly circulated and extracted at 20-100°C with a polar organic solvent equivalent to 3 to 20 times the weight of rosemary leaf material Germ leaf material 0.08～6h, obtain the solution of the rosemary essential oil and rosemary antioxidant that are dissolved in the polar organic solvent, use the mixture that is equivalent to rosemary essential oil and rosemary antioxidant 3～200 times weight Polar or weakly polar organic solvents are directly circulated to extract rosemary essential oil and rosemary antioxidants at 20-100°C for 0.08-6h and cooled to 5-30°C to obtain solutions dissolved in non-polar or weakly polar organic solvents The rosemary essential oil and the precipitated rosemary antioxidant are filtered to obtain the precipitate rosemary antioxidant, and the extract is evaporated at 20-100 DEG C to remove the solvent to obtain the rosemary essential oil product.

Wherein directly obtain the solution of rosemary essential oil and rosemary anti-oxidant being dissolved in polar organic solvent with polar organic solvent extraction, and separate, and method is as follows:

A comprehensive extraction method of rosemary essential oil and rosemary antioxidant, comprising the following two steps:

The first step: at 20-100°C, use a polar organic solvent equivalent to 3-20 times the weight of rosemary leaf material to directly circulate and extract rosemary leaf material for 0.08-6h, and distill the extract at 20-100°C. Desolvation to obtain a mixture of rosemary essential oil and rosemary antioxidant;

The second step: at 20-100 DEG C, use a non-polar or weakly polar organic solvent equivalent to 3 to 20 times the weight of the mixture of the above-mentioned rosemary essential oil and rosemary antioxidant to directly circulate and extract the above-mentioned rosemary essential oil and the mixture of rosemary antioxidant for 0.5-6h, cooled to 5-30°C, and filtered to obtain a solid rosemary antioxidant product, and the filtrate was evaporated at 20-100°C to remove the solvent to obtain rosemary essential oil product.

In addition, direct extraction with a mixture of nonpolar or weakly polar organic solvents and polar organic solvents to obtain rosemary essential oil dissolved in nonpolar or weakly polar organic solvents and precipitated rosemary antioxidants, and separated ,Methods as below:

A comprehensive extraction method of rosemary essential oil and rosemary antioxidants. First, at 20-100°C, use a mixed organic solvent of polar organic solvents and non-polar or weakly polar organic solvents to directly extract rosemary Geranium leaf material 0.08～6h, wherein the total weight of the mixed organic solvent of non-polar or weak polar organic solvent and polar organic solvent is 3～20 times of the weight of rosemary leaf material, and the weight of polar organic solvent accounts for non-polar organic solvent The percentage of the total weight of the polar or weakly polar organic solvent and the polar organic solvent is 0.1 to 20%, and after circulating extraction, it is cooled to 5 to 30°C to obtain an extract containing light-colored insoluble solid rosemary antioxidants, filtered , the obtained solid is a rosemary antioxidant product, and the filtrate is evaporated to remove the solvent at 20-100 DEG C to obtain a rosemary essential oil product.

The present invention can also synchronously adopt ultrasonic waves to enhance the extraction effect during the circular extraction process of the rosemary leaf material, the ultrasonic frequency is 20-40KHz, the ultrasonic power is 100-2000W, and the circular extraction time is 5-60min.

Principle of the present invention:

The circulation extraction device that the present invention relates to can be a Soxhlet extractor type circulation extraction device, and can also be a simple power transmission circulation extraction device. Reflux (i.e. Soxhlet extractor type), or power transmission (i.e. power transmission cycle type), heating and cooling unit, to realize the forced circulation of organic solvent between the extractor and the receiver, to achieve multiple times for rosemary leaves The purpose of recycling extraction and improving extraction yield.

The working process and flow of the Soxhlet extractor type circulation extraction device:

(1) Put a little cotton at the connection between the extractor of the Soxhlet extractor type circulation extraction device and the bottom of the overflow siphon, and put the rosemary leaves into the extractor. The height of the leaves should not exceed the top of the overflow siphon , the lower part of the extractor is connected with a receiver, the upper part of the extractor is connected with a condenser, the receiver has a heating unit and an evaporation conduit communicates with the condenser at the upper part of the extractor;

(2) Slowly add the organic solvent for extraction into the extractor filled with rosemary leaves from the upper part of the extractor, so that the leaves are completely soaked, and the excess solvent slowly flows into the bottom receiver along with the overflow siphon;

(3) Open the heating reflux unit, the solvent in the bottom receiver is continuously heated and evaporated, enters the condenser on the top of the extractor through the evaporation conduit, and is quickly condensed, and flows into the extractor filled with rosemary leaves. The leaves are extracted, and the liquid level of the organic solvent that has extracted rosemary essential oil and rosemary antioxidants in the extractor is gradually raised. The organic solvent of rosemary antioxidants flows quickly through the siphon into the bottom receiver;

(4) The organic solvent containing rosemary essential oil and rosemary antioxidant in the bottom receiver is continuously heated and evaporated to form an organic solvent vapor that basically does not contain rosemary essential oil and completely does not contain rosemary antioxidant. The condenser condenses, and then enters the extractor for extraction, and it goes round and round to realize the "evaporation-condensation-extraction" cycle extraction process, while the rosemary antioxidant does not participate in this "evaporation-condensation-extraction" solvent cycle process, and gradually accumulates in the receiver In the process, some low boiling point components of rosemary essential oil may participate in this cycle process, but the main components are also accumulated in the receiver;

(5) The leaf residue that has been fully extracted with rosemary essential oil and rosemary antioxidant remains in the extractor, and after draining the adsorbed organic solvent, the residue is poured out and discarded.

The working process and flow of the power transmission cycle type extraction device:

(1) A filter screen is installed at the bottom of the extractor of the power transmission circulation type extraction device, and is connected to the receiver at the lower part of the extractor. The top of the extractor is equipped with an organic solvent spray head, and there is a cooling unit and a power unit outside the receiver. The pump circulation unit, the circulation pipeline is communicated with the spray head on the top of the extractor through the receiver through the power pump and the pipeline with the heating unit. Evenly load the rosemary leaves onto the filter screen of the extractor;

(2) Slowly add the organic solvent for extraction into the extractor filled with rosemary leaves from the spray head on the upper part of the extractor, so that the leaves are half-soaked or completely soaked, and at the same time, the excess solvent flows slowly through the screen in the bottom receiver;

(3) Turn on the power pump and the heating and cooling unit, and the solvent in the bottom receiver is continuously entered into the extractor by the power pump through the receiver, heating pipe and spray head, and the leaves of rosemary are leached. The organic solvent with rosemary essential oil and rosemary antioxidant is filtered through the bottom screen, and then enters the bottom receiver with cooling unit;

(4) The organic solvent containing rosemary essential oil and rosemary antioxidant in the bottom receiver is continuously transmitted, sprayed and leached by the power pump, and the concentration of rosemary essential oil and rosemary antioxidant in the organic solvent gradually increases. Improvement, the content of essential oils and antioxidants in rosemary leaves of the extractor gradually decreased with the increase of the dissolution amount, thereby realizing a circular extraction process. In this cyclic extraction process, rosemary essential oil always participates in this cyclic process, and rosemary antioxidants are different according to different types of extraction solvents. In the state of polar solvents, rosemary antioxidants always participate in this cyclic process , in the state of a non-polar solvent containing some polar solvents, rosemary antioxidants are gradually saturated and precipitated in the receiver due to the temperature difference between the extractor and the receiver, and gradually accumulate in the receiver;

(5) The leaf residue that has been fully extracted with rosemary essential oil and rosemary antioxidant remains in the extractor, and after draining the adsorbed organic solvent, the residue is poured out and discarded.

Direct extraction with polar organic solvents to obtain a solution of rosemary essential oil and rosemary antioxidants dissolved in polar organic solvents, and separation, in this technical scheme: the first step is to use rosemary essential oils and rosemary antioxidants They are all soluble in organic polar solvents to extract them, and the second step uses the principle that rosemary antioxidants are insoluble in non-polar solvents to separate rosemary antioxidants and rosemary essential oil from the extraction mixture. Rosemary essential oil is a mixture of small molecular hydrocarbons in non-polar or weakly polar organic solvents such as α-pinene, 1,8-cineole, camphene, β-pinene, etc. Organic polar solvents can be dissolved, and can be dissolved by non-polar or weakly polar organic polar solvents; rosemary antioxidants are composed of carnosic acid, carnosol, rosmarinic acid, rosmanol, and It is composed of other small molecule phenolic acids and flavonoids and other highly polar compounds. These components have good solubility in polar organic solvents and poor solubility in non-polar or weakly polar organic solvents. The rosemary leaf residue, which is mainly composed of polymer compounds such as cellulose, hemicellulose and lignin, has poor solubility in polar organic solvents, non-polar or weakly polar organic solvents. Therefore, rosemary essential oil and rosemary antioxidant can be extracted and separated separately through a two-step cyclic extraction process.

Rosemary essential oil and precipitated rosemary antioxidants dissolved in non-polar or weakly polar organic solvents are extracted with a mixture of non-polar or weakly polar organic solvents and polar organic solvents, and separated, this scheme Using the petroleum ether mixture containing some polar solvents to distinguish the solubility of rosemary essential oil and rosemary antioxidants at different temperatures and concentrations, to achieve both rosemary essential oil and rosemary antioxidants simultaneously with rosemary The rosemary leaf residue separates and separates itself in solid and solution states, respectively. First of all, the petroleum ether mixture containing some polar solvents is basically insoluble to the rosemary leaf residues whose main components are polymer compounds such as cellulose, hemicellulose and lignin, so the rosemary leaf residues will not enter the bottom receiver; secondly, the petroleum ether mixture containing some polar solvents has a good effect on the rosemary essential oil with weak polar small molecular hydrocarbons as the main component, no matter at higher or lower temperatures. The solubility of rosemary antioxidants remains in the solvent phase after being extracted; moreover, the petroleum ether mixture containing part of the polar solvent has certain solubility to rosemary antioxidants at a higher temperature (lower concentration), while The solubility is poor at lower temperature (higher concentration). In the process of repeated circulation, rosemary antioxidants are continuously dissolved from the extractor, and will continue to be separated from the mixed solvent after entering the bottom receiver. Separation of the solvent phase of essential oils.

The present invention obtains following technical effect:

(1) Based on solvent circulation extraction, the present invention can extract and dissolve rosemary essential oil and rosemary antioxidant with polar organic solvent, and then separate with non-polar or weak polar solvent; The mixed solution of the organic solvent and the nonpolar organic solvent directly and simultaneously extracts the rosemary essential oil and the rosemary antioxidant, and simultaneously separates the rosemary essential oil from the precipitated rosemary antioxidant. These two methods can realize the synchronous or sequential extraction of rosemary essential oil and rosemary antioxidant, with short extraction period, high efficiency and low cost;

(2) Use conventional and easy-to-get organic solvents, which are cheap, easy to recycle, have little residue, and little pollution;

(3) The present invention is supplemented with ultrasonic intensified extraction treatment in rosemary leaf material circulation extraction process, makes ultrasonic intensified extraction treatment and organic solvent circulation extraction combine, utilizes the cavitation effect of specific frequency ultrasonic wave, makes organic solvent more moderate Under certain conditions (low extraction temperature and short extraction time), it quickly penetrates into the cell wall of rosemary leaves, so that rosemary essential oil and rosemary antioxidants can be fully and quickly dissolved and dispersed in organic solvents to achieve efficient and rapid extraction process In the present invention, ordinary circulation extraction usually takes 2 to 6 hours, and after supplemented with ultrasonic enhanced extraction treatment, the extraction time is shortened to 5 to 60 minutes, which is more conducive to retaining the active ingredients of rosemary essential oil and rosemary antioxidant, ensuring The quality of rosemary essential oil and rosemary antioxidants is stable. Ultrasonic enhanced extraction is easy to operate, which is beneficial to industrial application, and the operating cost increases very little.

(4) The present invention has realized the separation of effective components and residues in rosemary leaves at a lower temperature and in a shorter time, and also realized the separation of rosemary essential oil and rosemary antioxidant in a lower temperature and in a shorter time. Separation, low energy consumption, no need to use special high-pressure equipment, less investment in equipment, and the product is less likely to change during processing (when the temperature is too high, the essential oil is easy to volatilize and lose, and the rosemary antioxidant will partially deteriorate).

(5) The crude product of rosemary antioxidant is decolorized by activated carbon in ethanol aqueous solution, and the light-colored rosemary antioxidant without chlorophyll can be obtained.

Detailed ways

Example 1

A comprehensive extraction method of rosemary essential oil and rosemary antioxidant, which is characterized in that the rosemary is directly circulated and extracted at 20-100°C with a polar organic solvent equivalent to 3 to 20 times the weight of rosemary leaf material Germ leaf material 0.08～6h, obtain the solution of the rosemary essential oil and rosemary antioxidant that are dissolved in the polar organic solvent, use the mixture that is equivalent to rosemary essential oil and rosemary antioxidant 3～200 times weight Polar or weakly polar organic solvents are directly circulated to extract rosemary essential oil and rosemary antioxidants at 20-100°C for 0.08-6h and cooled to 5-30°C to obtain solutions dissolved in non-polar or weakly polar organic solvents The rosemary essential oil and the precipitated rosemary antioxidant are filtered to obtain the precipitate rosemary antioxidant, and the extract is evaporated at 20-100 DEG C to remove the solvent to obtain the rosemary essential oil product.

In this embodiment, the solution of rosemary essential oil and rosemary antioxidant dissolved in a polar organic solvent can be obtained directly by extraction with a polar organic solvent, and then the two are separated. The specific process can refer to Example 2; it can also be used A mixture of non-polar or weakly polar organic solvents and polar organic solvents is directly extracted to obtain rosemary essential oil dissolved in non-polar or weakly polar organic solvents and precipitated rosemary antioxidants, and separated, the specific process Can refer to embodiment 3,

Among them, the dry leaves of rosemary as raw material can be mature dry leaves or fresh leaves dried naturally, and the water content is all ≤ 10%. Non-toxic organic solvents can be alcohols (such as methanol, ethanol, propanol, butanol and other solvents, or their aqueous mixtures), ketones (acetone, methyl ethyl ketone, cyclohexanone and other solvents), esters (methyl acetate, ethyl acetate Solvents such as esters, butyl acetate), etc., the circulation extraction equipment can adopt heating reflux circulation extraction (such as Soxhlet extractor). Also can adopt power transmission circulation type (as pump power circulation); Circulation extraction temperature can be 25 ℃, 30 ℃, 35 ℃, 60 ℃, 75 ℃, the weight of polar organic solvent can be equivalent to rosemary leaf material 4 times, 5.2 times, 6.5 times, 7.5 times, 8.3 times, 9.4 times, 10.5 times, 11.8 times, 12.5 times, 13.5 times, 14 times, 15.5 times, 16.5 times, 17.5 times, 19.2 times, cycle time can be 0.1 h, 0.2h, 0.3h, 0.42h, 0.5h, 0.8h, 1h, 2h, 3h, 3.1h, 3.3h, 3.1h, 3.5h, 3.8h, 3.9h, 4h, 4.5h, 5.3h, 5.9 h, the temperature for evaporating organic solvents can be 25°C, 30°C, 60°C, 75°C; non-polar or weakly polar organic solvents for extraction include alkanes (n-hexane, cyclohexane, petroleum ether with different boiling ranges, etc.) , substituted alkanes (1,1-dichloroethane, 1,2-dichloroethane, dichloromethane, chloroform, etc.), aromatics (benzene, toluene, etc.), ethers (ether, methyl ethyl ether, etc.); cycle The extraction temperature can be 25°C, 30°C, 35°C, 60°C, 75°C, and the weight of non-polar or weakly polar organic solvent can be 4 times, 5.2 times, 6.5 times, 7.5 times that of rosemary leaf material times, 8.3 times, 9.4 times, 10.5 times, 11.8 times, 12.5 times, 13.5 times, 14 times, 15.5 times, 16.5 times, 17.5 times, 19.2 times, 40 times, 70 times, 150 times, 185 times, cycle time can 0.1h, 0.2h, 0.3h, 0.42h, 0.5h, 0.8h, 1h, 2h, 3h, 3.1h, 3.3h, 3.1h, 3.5h, 3.8h, 3.9h, 4h, 4.5h, 5.3h , 5.9h, the temperature for evaporating the organic solvent can be 25°C, 30°C, 60°C, 75°C.

Example 2

A comprehensive extraction method of rosemary essential oil and rosemary antioxidant, comprising the following two steps:

The first step: mix the rosemary leaf material with a polar organic solvent equivalent to 3 to 20 times the weight of rosemary leaf material in a circulating extraction equipment, and directly circulate and extract at 20-100 ° C for 0.08-6 hours, and the rosemary Leaf residue is left in the extractor, and the extract in the bottom receiver is evaporated to remove the solvent at 20-100°C to obtain a mixture of rosemary essential oil and rosemary antioxidant; wherein, the raw rosemary dried leaves can be It is mature dry leaves, or fresh leaves that are dried naturally, and the moisture content is ≤10%. Methanol, ethanol, propanol, butanol and other solvents, or their aqueous mixture), ketones (acetone, methyl ethyl ketone, cyclohexanone and other solvents), esters (methyl acetate, ethyl acetate, butyl acetate and other solvents), etc. , Circulation extraction equipment can adopt heating reflux circulation extraction (such as Soxhlet extractor). Also can adopt power transmission circulation type (as pump power circulation); Circulation extraction temperature can be 25 ℃, 30 ℃, 35 ℃, 60 ℃, 75 ℃, the weight of polar organic solvent can be equivalent to rosemary leaf material 4 times, 5.2 times, 6.5 times, 7.5 times, 8.3 times, 9.4 times, 10.5 times, 11.8 times, 12.5 times, 13.5 times, 14 times, 15.5 times, 16.5 times, 17.5 times, 19.2 times, cycle time can be 0.1 h, 0.2h, 0.3h, 0.42h, 0.5h, 0.8h, 1h, 2h, 3h, 3.1h, 3.3h, 3.1h, 3.5h, 3.8h, 3.9h, 4h, 4.5h, 5.3h, 5.9 h, the temperature for evaporating the organic solvent can be 25°C, 30°C, 60°C, 75°C;

The second step: mix the above-mentioned mixture of rosemary essential oil and rosemary antioxidant with a non-polar or weakly polar organic solvent equivalent to 3 to 20 times the weight of the mixture in a circulating extraction device, and mix it at 20 to 100 ° C. Directly circulate and extract for 0.5-6 hours, cool and filter, and the obtained solid is a rosemary antioxidant product, and the extract is evaporated at 20-100° C. to remove the solvent to obtain a rosemary essential oil product.

Among them, non-polar or weakly polar organic solvents for extraction include alkanes (normal hexane, cyclohexane, petroleum ether with different boiling ranges, etc.), substituted alkanes (1,1, dichloroethane, 1,2-dichloro ethane, dichloromethane, chloroform, etc.), aromatics (benzene, toluene, etc.), ethers (ether, methyl ethyl ether, etc.); the circulation extraction temperature can be 25°C, 30°C, 35°C, 60°C, 75°C, The weight of nonpolar or weakly polar organic solvent can be 4 times, 5.2 times, 6.5 times, 7.5 times, 8.3 times, 9.4 times, 10.5 times, 11.8 times, 12.5 times, 13.5 times of the rosemary leaf material , 14 times, 15.5 times, 16.5 times, 17.5 times, 19.2 times, cycle time can be 0.1h, 0.2h, 0.3h, 0.42h, 0.5h, 0.8h, 1h, 2h, 3h, 3.1h, 3.3h, 3.1h, 3.5h, 3.8h, 3.9h, 4h, 4.5h, 5.3h, 5.9h, the temperature for evaporating the organic solvent can be 25°C, 30°C, 60°C, 75°C.

Example 3

A comprehensive extraction method of rosemary essential oil and rosemary antioxidants. First, at 20-100°C, use a mixed organic solvent of polar organic solvents and non-polar or weakly polar organic solvents to directly extract rosemary Geranium leaf material 0.08～6h, wherein the total weight of the mixed organic solvent of non-polar or weak polar organic solvent and polar organic solvent is 3～20 times of rosemary leaf material weight, the weight of polar organic solvent accounts for non-polar organic solvent The percentage of the total weight of the polar or weakly polar organic solvent and the polar organic solvent is 0.1 to 20%, and after circulating extraction, it is cooled to 5 to 30°C to obtain an extract containing light-colored insoluble solid rosemary antioxidants, Filtration, the obtained solid is a rosemary antioxidant product, and the filtrate is evaporated to remove the solvent at 20-100° C. to obtain a rosemary essential oil product,

Among them, the dry leaves of rosemary as the raw material can be mature dry leaves or fresh leaves dried naturally, and the water content is ≤10%. Extraction equipment can adopt heating reflux circulation extraction (such as Soxhlet extractor), or power transmission circulation (such as pump power circulation), mixture of polar solvents and non-polar or weakly polar organic solvents, including petroleum One of ether, petroleum ether-ethanol, petroleum ether-ethanol-water, petroleum ether-ethyl acetate, petroleum ether-ethanol-ethyl acetate, petroleum ether-ethyl acetate-water, petroleum ether-water and other mixed solutions , the cycle extraction temperature can be 25°C, 30°C, 35°C, 60°C, 75°C, the total weight of non-polar or weakly polar organic solvent and polar organic solvent can be 4 times that of rosemary leaf material , 5.2 times, 6.5 times, 7.5 times, 8.3 times, 9.4 times, 10.5 times, 11.8 times, 12.5 times, 13.5 times, 14 times, 15.5 times, 16.5 times, 17.5 times, 19.2 times, polar organic solvents accounted for non-polar The percentage of the total weight of the polar or weakly polar organic solvent and the polar organic solvent can be 0.3%, 0.8%, 1.0%, 2.3%, 3.2%, 5.8%, 8.5%, 9.9%, 12.6%, 13.5%, 15.7%, 18.9%, cycle time can be 0.1h, 0.2h, 0.3h, 0.42h, 0.5h, 0.8h, 1h, 2h, 3h, 3.1h, 3.3h, 3.1h, 3.5h, 3.8h, 3.9 h, 4h, 4.5h, 5.3h, 5.9h, the temperature for evaporating the organic solvent can be 25°C, 30°C, 60°C, 75°C.

Example 4

A comprehensive extraction method of rosemary essential oil and rosemary antioxidant, comprising the following two steps:

Step 1: Mix rosemary leaf material with 3 to 20 times the weight of polar organic solvent in the circulation extraction equipment, directly circulate and extract at 20 to 100°C for 5 to 60 minutes, and simultaneously load ultrasonic waves during the circulation extraction time To strengthen the extraction process, the ultrasonic frequency is 20-40KHz, and the ultrasonic power is 100-2000W. You can use a bath-type ultrasonic generating device or a probe-type ultrasonic generating device, and then cool the rosemary leaf residue in the extractor. The extract in the receiver is evaporated to remove the solvent at 20-100° C. to obtain a mixture of rosemary essential oil and rosemary antioxidant;

Among them, the dry leaves of rosemary as raw material can be mature dry leaves or fresh leaves dried naturally, and the water content is all ≤ 10%. Non-toxic organic solvents can be alcohols (such as methanol, ethanol, propanol, butanol and other solvents, or their aqueous mixtures), ketones (acetone, methyl ethyl ketone, cyclohexanone and other solvents), esters (methyl acetate, ethyl acetate Solvents such as esters, butyl acetate), etc., the circulation extraction equipment can adopt heating reflux circulation extraction (such as Soxhlet extractor). Also can adopt power transmission circulation type (as pump power circulation); Circulation extraction temperature can be 25 ℃, 30 ℃, 35 ℃, 60 ℃, 75 ℃, the weight of polar organic solvent can be equivalent to rosemary leaf material 4 times, 5.2 times, 6.5 times, 7.5 times, 8.3 times, 9.4 times, 10.5 times, 11.8 times, 12.5 times, 13.5 times, 14 times, 15.5 times, 16.5 times, 17.5 times, 19.2 times, the ultrasonic power can be 300W, 700W, 1000W, 1500W, the cycle time can be 0.1h, 0.2h, 0.25h, 0.3h, 0.32h, 0.42h, 0.5h, 0.66h, 0.8h, 0.9h, the temperature of evaporating organic solvent can be 25 ℃, 30℃, 60℃, 75℃;

The second step: the above-mentioned mixture of rosemary essential oil and rosemary antioxidant is mixed with 3 to 20 times (weight ratio) non-polar (or weak polar) solvent in a circulating extraction device, and the mixture is mixed at 20 to 100 ° C Directly circulate and extract for 0.5-6 hours, cool and filter, and the obtained solid part is rosemary antioxidant, and the extract is evaporated at 20-100° C. to remove the solvent to obtain rosemary essential oil.

Among them, non-polar or weakly polar organic solvents for extraction include alkanes (normal hexane, cyclohexane, petroleum ether with different boiling ranges, etc.), substituted alkanes (1,1-dichloroethane, 1,2-dichloro ethane, dichloromethane, chloroform, etc.), aromatics (benzene, toluene, etc.), ethers (ether, methyl ethyl ether, etc.); the circulation extraction temperature can be 25°C, 30°C, 35°C, 60°C, 75°C, The weight of nonpolar or weakly polar organic solvent can be 4 times, 5.2 times, 6.5 times, 7.5 times, 8.3 times, 9.4 times, 10.5 times, 11.8 times, 12.5 times, 13.5 times of the rosemary leaf material , 14 times, 15.5 times, 16.5 times, 17.5 times, 19.2 times, cycle time can be 0.1h, 0.2h, 0.3h, 0.42h, 0.5h, 0.8h, 1h, 2h, 3h, 3.1h, 3.3h, 3.1h, 3.5h, 3.8h, 3.9h, 4h, 4.5h, 5.3h, 5.9h, the temperature for evaporating the organic solvent can be 25°C, 30°C, 60°C, 75°C.

Example 5

A comprehensive extraction method of rosemary essential oil and rosemary antioxidant, first rosemary leaf material, polar solvent and non-polar solvent are mixed in a circulation extraction equipment, wherein the non-polar solvent or weakly polar organic The total weight of the solvent and the polar organic solvent is 3 to 20 times the weight of the rosemary leaf material, and the percentage of the polar organic solvent to the total weight of the nonpolar or weakly polar organic solvent and the polar organic solvent is 0.1 to 20 times. 20%, and then at 20-100°C, direct circulation extraction for 5-60 minutes, in the process of direct circulation extraction, ultrasonic enhanced extraction is used synchronously, ultrasonic frequency is 20-40KHz, ultrasonic power is 100-2000W, bath type ultrasonic generator can be used, Probe-type ultrasonic generating device can also be used, the rosemary leaf residue is left in the extractor, cooled, and the extract containing a large amount of light-colored insoluble solids is obtained from the bottom receiver, filtered, and the light-colored rosemary antioxidant can be directly obtained solid, and the filtrate was evaporated to remove the solvent at 20-100°C to obtain rosemary essential oil.

Among them, the dry leaves of rosemary as the raw material can be mature dry leaves or fresh leaves dried naturally, and the water content is ≤10%. The extraction equipment can adopt heating reflux circulation extraction (such as Soxhlet extractor), or power transmission circulation (such as pump power circulation), and the mixture of polar solvent and non-polar or weakly polar organic solvent can include Petroleum ether, petroleum ether-ethanol, petroleum ether-ethanol-water, petroleum ether-ethyl acetate, petroleum ether-ethanol-ethyl acetate, petroleum ether-ethyl acetate-water, petroleum ether-water, cycle extraction The temperature can be 25°C, 30°C, 35°C, 60°C, 75°C, and the total weight of non-polar or weakly polar organic solvent and polar organic solvent can be 4 times or 5.2 times that of rosemary leaf material , 6.5 times, 7.5 times, 8.3 times, 9.4 times, 10.5 times, 11.8 times, 12.5 times, 13.5 times, 14 times, 15.5 times, 16.5 times, 17.5 times, 19.2 times, polar organic solvents account for non-polar or weak The percentage of the total weight of polar organic solvent and polar organic solvent can be 0.3%, 0.8%, 1.0%, 2.3%, 3.2%, 5.8%, 8.5%, 9.9%, 12.6%, 13.5%, 15.7%, 18.9%, the cycle time can be 0.1h, 0.2h, 0.3h, 0.42h, 0.5h, 0.65h, 0.8h, 0.9h, the temperature of evaporating organic solvent can be 25℃, 30℃, 60℃, 75℃.

Example 6

Put 10.0g of crushed rosemary leaves (particles less than 2mm) into the circulating extractor, and put 50-150mL of polar solvent (such as acetone, methanol, ethanol, 95% ethanol, ethyl acetate or 1 : 1 ethanol-ethyl acetate mixed solvent), circulation extraction 3～4h, cooling; The extraction liquid of polar solvent is distilled under normal pressure or reduced pressure, obtains brown or dark green extract (being total extract); Then put it into the extractor, use 50mL non-polar or weak polar solvent for low-temperature extraction, the extract is distilled under reduced pressure to obtain a dark semi-liquid and semi-solid substance, and then distilled by water steam to obtain a colorless or light yellow mist Rosemary essential oil; the total extract was extracted with a non-polar or weakly polar solvent to obtain crude rosemary antioxidants (results are shown in Table 1).

Table 1 The comprehensive extraction results of rosemary essential oil and rosemary antioxidants under different polar solvent conditions

no Polar solvent Total extract (g) Essential oil (g) Crude rosemary antioxidant (g) 1 Acetone 1.65 0.26 0.96 2 Methanol 2.48 0.16 1.78 3 ethanol 1.83 0.11 1.09 4 95% ethanol 2.48 0.13 1.43 5 Ethyl acetate 1.80 0.28 0.95 6 Ethanol-ethyl acetate (1:1, v/v) 1.88 0.21 0.98

Example 7

Put 10.0g rosemary leaf pulverized material (particle is less than 2mm) in the circulation extractor, put 50～150mL polar solvent (such as 95% ethanol) in the bottom acceptor, extract 1～6h circulation, cooling; Normal pressure or reduced pressure distillation of the extract of neutral solvent to obtain brown or dark green extract (i.e. the total extract); put the extract into the extractor again, and use 50mL non-polar or weak polar solvent for low-temperature extraction , the extract is distilled under reduced pressure to obtain a dark semi-liquid and semi-solid substance, and then distilled by steam to obtain colorless or light yellow rosemary essential oil; the total extract is obtained after extraction with a non-polar or weak polar solvent Crude rosemary antioxidants (results are shown in Table 2).

Table 2 Comprehensive extraction results of rosemary essential oil and rosemary antioxidants under different cycle extraction time

no Extraction time (h) Total extract (g) Essential oil (g) Crude rosemary antioxidant (g) 7 1 1.81 0.11 1.26 8 2 1.97 0.13 1.39 9 3 2.09 0.14 1.40 10 4 2.25 0.11 1.69 11 5 2.98 0.10 1.90 12 6 2.90 0.08 2.17

Example 8

Put 10.0g rosemary leaf pulverized material (particle is less than 2mm) into the circulating extractor, put 50～150mL polar solvent (such as 95% ethanol) in the bottom acceptor, extract 3～4h circularly, cooling; normal pressure or reduced pressure distillation of the extract of neutral solvent to obtain brown or dark green extract (i.e. the total extract); the extract is repacked in the extractor, with 50mL non-polar or weakly polar solvent (such as 30 ～60℃ petroleum ether, 60～90℃ petroleum ether, n-hexane, chloroform, diethyl ether, dichloromethane, 1,2-dichloroethane) for low-temperature extraction, and the extract is distilled under reduced pressure to obtain dark half liquid and half solid matter, and then obtained colorless or light yellow rosemary essential oil through steam distillation; the rosemary antioxidant crude product obtained after the extract was extracted with a non-polar or weak polar solvent (results are shown in Table 3).

Table 3 Comprehensive extraction results of rosemary essential oil and rosemary antioxidants under different non (weak) polar solvent conditions

no Non (weak) polar solvents Total extract (g) Essential oil (g) Crude rosemary antioxidant (g) 13 30～60℃ petroleum ether 1.79 0.12 1.69 14 60～90℃ petroleum ether 1.79 0.13 1.57 15 n-Hexane-chloroform (1:1) 1.79 0.14 0.98 16 Chloroform 1.79 0.16 0.78 17 n-Hexane 1.79 0.10 1.50 18 Ether 1.79 0.08 1.18 19 dichloromethane 1.79 0.12 1.26 20 1,2-Dichloroethane 1.79 0.08 1.06

Example 9

Put 36.0～72.0g of rosemary leaves (with or without essential oil, not crushed) into the circulating extractor, add petroleum ether mixture containing some polar solvents (such as petroleum ether, petroleum ether-ethanol, petroleum ether - ethanol-water, petroleum ether-ethyl acetate, petroleum ether-ethanol-ethyl acetate, petroleum ether-ethyl acetate-water, petroleum ether-water, etc.) 150-400mL, heated and refluxed for 3-4 hours, cooled; Directly obtain light-colored solid and dark-colored extract from the extraction collector, filter and wash with a little petroleum ether to obtain light yellow or light yellow-green rosemary antioxidant (results are shown in Table 4), dark-colored extract normal pressure or reduced pressure Distillation can also recover some antioxidants. When using rosemary leaves that contain the essential oil, a small amount of rosemary essential oil can be obtained from the solvent-removed extract.

Table 4 The results of one-step extraction of rosemary antioxidants with petroleum ether mixture containing some polar solvents

no rosemary leaves (g)   Petroleum ether mixture Light Rosemary Antioxidant (g) twenty one 72.0 Petroleum ether 0.8 twenty two 30.0 Petroleum ether ~ water (90:10) 0.3 twenty three 36.0 Petroleum ether - ethanol (95:5) 3.0 twenty four 36.0 Petroleum ether-ethanol～water (90:7.5:2.5) 3.0 25 36.0 Petroleum ether - ethanol - water (80:15:5) 5.5 26 50.7 Petroleum ether-ethanol-water (94:5:1) 4.3 27 30.0 Petroleum ether ~ ethyl acetate (90:10) 0.8 28 30.0 Petroleum ether - ethanol - ethyl acetate (90:7:3) 3.6

Example 10

Put 50.0g of rosemary leaves (with or without essential oil, not crushed) into the circulating extractor, add 300-400mL of ethanol (or 95% ethanol, etc.), and load ultrasonic waves (trough ultrasonic generator or probe) type ultrasonic generator), strengthen the cyclic extraction process, extract at room temperature or at natural temperature for 10-30min, filter and concentrate, and extract with non-polar or weakly polar solvent to obtain colorless or light yellow powder respectively Crude rosemary essential oil and rosemary antioxidants (results are shown in Table 5).

Table 5 Comprehensive extraction results of rosemary antioxidants under different ultrasonic conditions

no Ultrasound Rosemary Antioxidant Product (g) Way Frequency(KHz) Power (W) Extraction time (min) 29 Trough 33 250 30 6.40 30 probe type 20～25 1000 10 6.70

Example 11

The other steps of cyclic extraction are the same as in Example 6. Add 30-120mL of 50-95% ethanol aqueous solution and 0.6-1.5g of activated carbon to 6.0g of rosemary antioxidant product, and stir in a water bath at 50-100°C for 15-30min. Filtration; the filtrate was concentrated at low temperature and reduced pressure, then diluted with 30-120 mL of distilled water, filtered and dried to obtain 4.6 g of light yellow or light flesh-colored rosemary antioxidant.

Claims (5)

1. the combined extraction method of rosemary ethereal oil and rosemary antioxidant, it is characterized in that comprising: the polar organic solvent with 3～20 times of weight that are equivalent to the rosemary leave material extracts rosemary leave material 0.08～6h 20～100 ℃ of direct down circulations, acquisition is dissolved in the rosemary ethereal oil of polar organic solvent and the solution of rosemary antioxidant, extracting solution is boiled off solvent under 20～100 ℃, obtain the mixture of rosemary ethereal oil and rosemary antioxidant, nonpolar or weakly polar organic solvent with 3～200 times of weight of mixture that are equivalent to rosemary ethereal oil and rosemary antioxidant extracts rosemary ethereal oil and rosemary antioxidant 0.08～6h 20～100 ℃ of direct down circulations again, and be cooled to 5～30 ℃, acquisition is dissolved in the rosemary ethereal oil of nonpolar or weakly polar organic solvent and the rosemary antioxidant of precipitation shape, filter, obtain the throw out rosemary antioxidant, extracting solution boils off solvent under 20～100 ℃, obtain the rosemary ethereal oil product.

2. the combined extraction method of rosemary ethereal oil and rosemary antioxidant, it is characterized in that: under 20～100 ℃, mixed organic solvents with polar organic solvent and nonpolar or weakly polar organic solvent, directly rosemary leave material 0.08～6h is extracted in circulation, the gross weight of the mixed organic solvents of wherein nonpolar or weakly polar organic solvent and polar organic solvent is 3～20 times of rosemary leave material weight, it is 0.1～20% that the weight of polar organic solvent accounts for per-cent nonpolar or weakly polar organic solvent and polar organic solvent gross weight, postcooling to 5～30 ℃ are extracted in circulation, obtain containing the extracting solution of light insoluble solids rosemary antioxidant, filter, the solid that obtains is the rosemary antioxidant product, and filtrate boils off solvent and obtains the rosemary ethereal oil product under 20～100 ℃.

3. the combined extraction method of rosemary ethereal oil according to claim 1 and 2 and rosemary antioxidant, it is characterized in that: rosemary leave material circulation leaching process adopts ultrasonic wave to strengthen the effect of extraction synchronously, ultrasonic frequency 20～40KHz, ultrasonic power 100～2000W, circulation extraction time 5～60min.

4. the combined extraction method of rosemary ethereal oil according to claim 1 and rosemary antioxidant is characterized in that polar organic solvent is 95% ethanol.

5. the combined extraction method of rosemary ethereal oil according to claim 1 and rosemary antioxidant is characterized in that nonpolar or weakly polar organic solvent is a sherwood oil, and it is 20～100 ℃ that temperature is extracted in circulation.