CN100581630C - Ultrasonic reinforced subcritical water extraction method of natural product effective ingredient and device - Google Patents

Abstract

The invention provides an extraction method and a device used for extracting ultrasonic reinforced sub-critical water of effective component of a natural outcome. The method is mainly characterized in that a pre-disposed raw material is arranged in an extraction kettle; the sub-critical water is taken as an extraction solvent to carry out the exaction under the conditions of 1 to 20MPa of extraction pressure, 50 to 500W of ultrasonic power and 20 to 80KHz of ultrasonic frequency. The method has high extraction efficiency and short extraction time. The device is mainly characterized in that the extraction kettle is provided with an ultrasonic reinforced part which comprises an ultrasonic generator and an energy changing head; the ultrasonic generator is arranged on the external surface of the extraction kettle and at the upper part of the extraction kettle; the energy changing head and the extraction kettle cover are processed into a whole; the piezoelectric ceramic wafer of the energy changing head is arranged at the upper end of the extraction kettle cover; the variable-spoke rod of the energy changing head is directly arranged in the extraction kettle by the extraction kettle cover. The device can carry out selectable exaction of the articles to be extracted by changing the extraction parameters (temperature, pressure, time, etc.), thus realizing static extraction or dynamic circulation extraction.

Description

Ultrasound-enhanced subcritical water extraction method and device for active ingredients of natural products

technical field

The invention relates to a device and a method for extracting active ingredients in natural products, in particular to a device and a method for extracting active ingredients in natural products by ultrasonic enhanced subcritical water extraction technology.

Background technique

Heat reflux extraction and organic solvent extraction are traditional extraction methods of active ingredients in natural products, which are simple in process and easy to operate, but there are problems such as long extraction time, low extraction efficiency, and high energy consumption. In order to solve these problems, people have applied supercritical _CO2 extraction technology to the extraction of active ingredients of natural products in recent years. Fluid CO ₂ is characterized by non-polarity and low relative molecular mass. This technology can only be used for the extraction of non-polar compounds. It lacks sufficient solubility for many substances with polarity and large relative molecular mass, so the extraction efficiency is not high, and it is difficult to To achieve the ideal extraction effect. Therefore, in actual operation, an organic entrainer must be added to the extraction system to increase the solubility and selectivity of the solute in the CO ₂ fluid, which not only increases the complexity of the operation, but also has the problem of residual organic solvents. In addition, since water is insoluble in CO ₂ , the supercritical CO ₂ extraction process usually needs to pre-dry the raw material, which increases the cost. Therefore, it has become a research hotspot in recent years to find a green and efficient extraction technology with high extraction efficiency, low energy consumption, non-toxic and harmless, and continuous extraction of non-polar, weakly polar, and strongly polar compounds.

Subcritical water, also known as superheated water, high-pressure hot water or hot liquid water, refers to heating water to a high temperature above 100°C and below the critical temperature of 374°C under a certain pressure, and the water remains in a liquid state. In the subcritical state, the hydrogen bond, ion hydration, ion association, cluster structure, etc. of the fluid microstructure have changed, so the properties of subcritical water and water at normal temperature and pressure are quite different. In the subcritical state, as the temperature rises, the polarity of water can change in a wide range, and the polarity of water can gradually change from strong polarity to non-polarity. Its properties are more similar to organic solvents, and solutes can be separated Extracted from high to low polarity. In this way, the continuous extraction of active ingredients in natural products from water-soluble components to fat-soluble components can be realized by controlling the temperature and pressure of subcritical water, and selective extraction can be realized. In addition, because subcritical water extraction uses cheap and non-polluting water as the extraction agent, subcritical water extraction technology is regarded as a transformative technology with green environmental protection and broad prospects.

Among the existing domestic subcritical related extraction devices, the utility model patent (95242232.8) published on October 23, 1996 provides a vortex type supercritical and subcritical gas extraction device, which is used in conjunction with the pharmaceutical industry and food industry It is designed for the new technology of supercritical and subcritical gas extraction at normal temperature. With supercritical and subcritical gas as extraction agent, multi-stage vortex forming plates are used in structure to form a vortex forming chamber, which is beneficial to carrier gas and The comprehensive and effective contact of materials speeds up the extraction speed, prevents the extraction dead zone, and improves the extraction efficiency. The invention patent (200510018433.0) published on September 7, 2005 provides a sample pretreatment method and device for the analysis of pesticide residues in fruits and vegetables. The device includes a microprocessor, a heater, a sample pool, a temperature sensor, a power supply, an input device and an output device, and the device has a simple structure, is convenient to use, and has a high degree of automation.

Among the existing subcritical related extraction methods in China, the invention patent (01113903.X) disclosed on November 21, 2001 provides a kind of use _{of CO} in a subcritical state as an extraction agent to extract flavonoids and The method of terpenes; the invention patent (200510061998.7) disclosed on August 23, 2006 provides a method for subcritical water extraction of fat-soluble components in the traditional Chinese medicine Salvia miltiorrhiza Clean, environment-friendly, fast extraction speed and so on.

The related devices and methods for subcritical extraction disclosed in China above have different purposes and different extraction agents, so the structures of the devices and the methods used are also different. In order to further improve the extraction rate of active ingredients in natural products, the present invention makes full use of the advantages of subcritical water extraction technology and ultrasonic extraction technology, introduces ultrasound into the subcritical water extraction process, and utilizes the unique characteristics of ultrasonic waves when propagating in liquid media. The cavitation effect, coupled with the multi-pole effects such as mechanical vibration, micro-jet, and micro-acoustic flow generated by ultrasonic propagation, makes it easier to extract effective substances. Therefore, according to their respective technical principles and advantages, a set of devices with simple structure, convenient use and high degree of automation is designed, and the method of using this device to extract active ingredients in natural products is described in detail.

Contents of the invention

The purpose of the present invention is to overcome the above-mentioned defects existing in the prior art, to provide a method for ultrasonically enhanced subcritical water extraction of active ingredients of natural products, another aspect of the present invention is to provide an ultrasonically enhanced subcritical water extraction of active ingredients of natural products device.

The method provided by the invention is realized through the following scheme:

A method for ultrasonically enhanced subcritical water extraction of natural product active ingredients, mainly comprising the following steps:

(1) The raw material is placed in the extraction kettle;

(2) Inject the preheated deoxidized deionized water into the extraction kettle at a flow rate less than or equal to 100ml/min;

(3) Under the conditions of extraction temperature of 70-150°C, extraction pressure of 1-20MPa, ultrasonic power of 50-500W, and ultrasonic frequency of 20-80KHz, the active ingredients of the raw materials are extracted, and the extraction time is 0.5-2h;

(4) After the extraction is finished, cool the extract to room temperature and collect it.

The following steps describe the extraction process in detail:

① The specific operation process of raw material processing is: the raw materials used for extraction need to remove gravel, sand and other foreign matter, and the fresh raw materials are directly broken into small pieces.

②The specific process of ultrasonically enhanced subcritical water extraction of active ingredients in natural products is: put the raw materials treated in ① into the extraction kettle according to the capacity of 50-400g/L extraction tank; use nitrogen to remove the water in the reservoir Oxygen; Then use the pre-heater to heat the water to the set temperature, and pump the water into the extraction kettle at a flow rate of less than or equal to 100ml/min through the pressure pump; use ultrasonically enhanced subcritical water extraction, the extraction temperature The temperature is 70-150°C, the extraction pressure is 1-20MPa, the extraction time is 0.5-2h, the ultrasonic power is 50-500W, and the ultrasonic frequency is 20-80KHz. Finally, the extract can be collected after rapid cooling.

The ultrasonic enhanced subcritical water extraction device provided by the present invention is realized by the following scheme:

The ultrasonic enhanced subcritical water extraction device includes a control system part, an operating system part and an ultrasonic strengthening part, the control system part and the operating system part are connected by means of electrical signals, and the operating system part includes an extraction kettle; the ultrasonic strengthening part includes An ultrasonic generator and a transducer head, the ultrasonic generator is placed outside the extraction kettle, and the transducer head is placed on the upper part of the extraction kettle; the transducer head and the extraction kettle cover are processed as a whole, and the piezoelectric ceramic wafer of the transducer head is located On the upper end of the extraction kettle cover, the spoke rod of the transducer head is directly placed in the extraction kettle through the extraction kettle cover.

The following three major parts of the device are further described below:

Control system part: including temperature adjustment control switch, pressure adjustment control switch, over-temperature and over-pressure alarm safety system, and the electrical switch of the whole machine. For the convenience of operation, this part is designed as a control panel, and the whole machine is controlled through the switches, buttons and knobs on the panel.

Operating system part: This part is mainly composed of nitrogen tank, reservoir, pressure pump, preheater, constant temperature device, extraction kettle, regulating valve, cooler and collector, etc. The nitrogen tank is connected to the reservoir through the pipeline and regulating valve connection; nitrogen is used to remove oxygen in the extraction solvent water in the reservoir; one end of the pressure pump is respectively connected to the reservoir and the cooler through a regulating valve, and the other end is connected to the pre-heater through a regulating valve; the pre-heater is connected to the extraction kettle Connection, the extraction kettle is connected to the cooler through the regulating valve to store nitrogen in the nitrogen tank, connected to the reservoir through the pipeline, the pre-heater is used to heat the water to the required temperature, and the water is pumped at a certain pressure and flow rate through the pressure pump Pumped into the extraction kettle; the constant temperature device is used to ensure that the extraction system is at a constant temperature; in order to avoid the loss of volatile components due to high temperature, the cooler is used to quickly cool the outflowing extract; a pressure regulating valve is installed between the cooler and the collector. Used to adjust the pressure in the extraction tank to maintain the water in the extraction tank in a liquid state. In addition, in order to keep track of the working temperature and pressure in the extraction kettle, the device is also equipped with a pressure measuring device and an electric contact temperature measuring device at the extraction kettle. Inside the kettle. The extraction kettle is a cylindrical device made of high temperature and high pressure stainless steel. There is a stainless steel filter at the bottom of the extraction kettle to prevent the raw material powder from clogging the outlet of the pipeline. An outlet at the lower end is connected to the cooler through a pipeline; the constant temperature device is a constant temperature ceramic sleeve. The device is wrapped on the outer wall of the extraction kettle; the cooler is a tube cooler, which is cooled by continuously feeding cooling water, the lower side of the cooler is provided with a cooling water inlet, and the upper side is provided with a cooling water outlet; the collector It is a cylindrical or rectangular container made of stainless steel or glass; the pressure pump is a digital water pressure metering pump or a special pump for high performance liquid chromatography, which can adjust and display the pressure, and the pressure range is 0-25MPa. The storage tank is a cylindrical or rectangular device made of stainless steel or plastic; the preheater is a tubular annular preheater made of stainless steel; the constant temperature device is a ceramic casing heat preservation device, and the temperature maintenance range is: normal temperature to 250 ° C .

Ultrasonic strengthening part: this part includes an ultrasonic generator and a transducer head, the ultrasonic generator is placed outside the extraction kettle, and the transducer head is placed on the upper part of the extraction kettle; the transducer head and the lid of the extraction kettle are processed as a whole, and the transducer The piezoelectric ceramic chip of the head is located on the upper end of the extraction kettle cover, and the spoke rod of the energy-transforming head is directly placed in the extraction kettle through the extraction kettle cover. The piezoelectric ceramic chip is located at the upper end of the extraction cover; the extraction kettle is provided with a thermostat, and the thermostat is located on the periphery of the extraction kettle, and the extraction kettle is also provided with a pressure measuring device and a temperature measuring device, both of which are One end is located inside the extraction kettle. This part is the key part of the device of the present invention, and mainly consists of an ultrasonic generator and a transducing head. In order to give full play to the intensifying effect of ultrasonic waves, the present invention places the ultrasonic generator outside the extraction kettle, the transducer head is placed on the upper part of the extraction kettle, and the transducer head and the lid of the extraction kettle are processed as a whole, fully considering the location of the subcritical water. In the high temperature state, the piezoelectric ceramic chip is placed on the upper end of the extraction kettle cover, and the spoke rod adopts the built-in method, and is directly placed in the extraction kettle through the extraction kettle cover. The ultrasonic strengthening part is the key equipment of the whole set of equipment. This part introduces ultrasound into the subcritical water extraction process. The multi-pole effects such as mechanical vibration and micro-jet generated by ultrasonic propagation make it easier to extract effective substances.

Advantages of the present invention:

1. Give full play to the advantages of subcritical water extraction technology and ultrasonic extraction technology, which can significantly increase the extraction rate and shorten the extraction time.

2. It can realize the selective extraction of active ingredients in natural products or continuous extraction from strong polar, medium polar to non-polar ingredients, and when the regulating valves 16, 20 are closed, the regulating valves 14, 15, 17, 18 are opened , 19 o'clock, the whole extraction process can realize static extraction; After opening the regulating valves 17 and 18 to inject the required water into the extraction kettle, then close the regulating valve 17, open the regulating valves 16, 18 and 19, and realize dynamic circulation extraction , That is, the extraction liquid coming out of the cooler can be cyclically extracted through regulating valves 16, 18 and 19.

3. The device of the present invention has a simple structure, does not require too high pressure, is low in cost, and is easy to popularize and apply.

4. The method provided by the present invention is simple to operate, and is a new method for extracting active ingredients in natural products with high efficiency, low consumption and environmental protection.

Description of drawings:

Fig. 1 is a device structure diagram of the present invention.

Fig. 2 is a structural diagram of an extraction kettle with an ultrasonic transducer head device.

Detailed ways:

As shown in Figure 1, for the convenience of operation, the control system part is designed as a control panel 21, including a temperature adjustment control switch 22, a pressure adjustment control switch 23, an over-temperature and over-pressure alarm safety system 24, and an electrical switch 25 of the entire machine, During operation, the whole machine can be easily controlled by adjusting these switches; the operating system part includes nitrogen tank 1, water storage tank 2, pressure pump 3, preheater 4, extraction kettle 5, extraction kettle cover 6, and constant temperature device 7 , cooler 8 and receiver 11, 7 regulating valves 14, 15, 16, 17, 18, collector 9 and other components, and also equipped with pressure display 10, temperature display 19, 20 and cooling water on both sides of the cooler Inlet 12 and cooling water outlet 13. The whole device has the advantages of simple structure, convenient use and high degree of automation. All devices can be designed according to actual needs, and can be large or small.

As shown in Figure 2, the ultrasonic strengthening device is a key part of the whole equipment, mainly composed of an ultrasonic generator 26 and a transducer head 29, the ultrasonic generator is placed outside the extraction kettle, and the transducer head is placed on the top of the extraction kettle; The energy head and the extraction tank cover are processed as a whole, fully considering the high temperature state of the subcritical water, so that the piezoelectric ceramic wafer 28 is located on the upper end of the extraction kettle cover, and the radial rod 27 adopts a built-in method, which is directly placed through the extraction kettle cover. in the extraction kettle.

Ultrasonic enhanced subcritical water extraction device extraction is carried out as follows: Weigh the pretreated raw materials, put them into the extraction kettle, add a certain amount of preheated deoxygenated deionized water, and extract under the set extraction parameters , and the resulting extract was collected after cooling. The present invention will be further described below in conjunction with examples of implementation.

When the regulating valves 16 and 20 are closed and the regulating valves 14, 15, 17, 18 and 19 are opened, the whole extraction process can realize static extraction; Regulating valve 17, opening regulating valves 16, 18 and 19 can realize dynamic circulation extraction, that is, the extraction liquid coming out from the cooler can realize circulating extraction through regulating valves 16, 18 and 19.

Example 1: Extraction of volatile oil from cloves

Slowly open the regulating valve of the nitrogen tank, pass the nitrogen gas into the deionized water of the reservoir, and process for about 30 minutes; weigh 0.5 kg of clove powder that has been crushed to 60 meshes, put it into a 2L extraction kettle, and set the Temperature, pressure, ultrasonic and other parameters, turn on the pre-heater and pressure pump, add about 1.5 kg of pre-heated water at a flow rate of 10ml/min, under the conditions of temperature 150°C, pressure 2MPa, ultrasonic power 100W, ultrasonic frequency 20KHz, the effect After 60min, the extract was discharged from the bottom of the extraction kettle, cooled and collected by a cooler; then 50g of sodium chloride was added to the collected extract to break the water-oil equilibrium state of the extract, and 400ml of hexane was separated hexane layer, and remove the hexane with a vacuum rotary evaporator to obtain the volatile oil of cloves; then the volatile oil of gained is detected and analyzed by GC-MS as can be seen, the proportion of three main components eugenol in cloves is 17.20%, cloves Phenyl acetate was 3.11%, and syringin was 0.37%. The experimental results show that the ultrasonic-enhanced subcritical water extraction technology can quickly and efficiently extract the active ingredients. This technology can greatly improve the extraction efficiency and shorten the production cycle.

Implementation Case 2: Extraction of Anthraquinones from Morinda Citrifolia Root

Slowly open the regulating valve of the nitrogen tank, pass nitrogen gas into the deionized water of the reservoir, and process for about 60 minutes; weigh 0.6 kg of Morinda officinalis powder that has been crushed to 100 meshes, put it into a 2L extraction kettle, and set up the control panel Turn on the pre-heater and pressure pump, add about 1.6 kg of pre-heated water at a flow rate of 30ml/min, under the conditions of temperature 120°C, pressure 5MPa, ultrasonic power 150W, and ultrasonic frequency 40KHz After 120 minutes of action, the extract was released from the bottom of the extraction kettle, cooled and collected by a cooler. At the same time, a comparative experiment between ultrasonically enhanced subcritical water extraction and traditional solvent method and ultrasonic-assisted extraction method was carried out. The experimental results showed that when the extraction rate of anthraquinones was 80%, the solvent method required 72 hours, and the ultrasonic-assisted extraction method required 72 hours. 2h, ultrasonic enhanced subcritical water extraction only needs 1h.

Example 3: Extraction of fennel oil from fennel leaves

Slowly open the regulating valve of the nitrogen tank, pass the nitrogen gas into the deionized water of the reservoir, and process for about 20 minutes; weigh 0.2 kg of fennel coarse powder crushed to 40 meshes, put it into a 2L extraction kettle, and set the Temperature, pressure, ultrasonic and other parameters, turn on the preheater and pressure pump, add about 1 kg of preheated water at a flow rate of 70ml/min, under the conditions of temperature 110°C, pressure 7MPa, ultrasonic power 200W, ultrasonic frequency 80KHz, the effect After 30 minutes, the extract was discharged from the bottom of the extraction kettle, cooled and collected by a cooler; then 30 g of sodium chloride and 100 ml of hexane were added to the collected extract, the hexane layer was separated, and the hexane was removed by a vacuum rotary evaporator. Alkanes can be used to obtain volatile oil; then the resulting volatile oil is analyzed and detected by GC-MS. At the same time, a comparative experiment with the steam distillation method was also done. The experimental results show that the amount of the target substance obtained by ultrasonically enhanced subcritical water extraction for 25 minutes is equivalent to that of steam distillation for 4 hours, and the energy consumption is far less than that of the steam distillation method.

Implementation Case 4: Extracting Syringin from Acanthopanax

Slowly open the regulating valve of the nitrogen tank, pass the nitrogen gas into the deionized water of the reservoir, and process for about 20 minutes; weigh 0.3 kg of Acanthopanax powder that has been crushed to 130 mesh, put it into a 2L extraction kettle, and set it on the control panel. Turn on the pre-heater and pressure pump, add about 1.2 kg of pre-heated water at a flow rate of 100ml/min, at a temperature of 150°C, a pressure of 10MPa, an ultrasonic power of 500W, and an ultrasonic frequency of 80KHz. After acting for 50 minutes, the extract was released from the bottom of the extraction kettle, cooled and collected by a cooler; the obtained extract was analyzed and detected by HPLC-UV, and a comparative experiment with Soxhlet extraction was also done. The experimental results showed that ultrasonic The amount of the target substance obtained by enhanced subcritical water extraction for 50 minutes is equivalent to that obtained by Soxhlet extraction for 24 hours.

Claims (9)

1, the ultrasound-enhanced Subcritical Water Extraction method of active ingredient of natural product is characterized in that this method in turn includes the following steps:

(1) raw material is placed extraction kettle;

(2) will be injected in the extraction kettle with the flow velocity that is less than or equal to 100ml/min through the deoxidation deionized water of preheating;

(3) under the condition of 100～150 ℃ of extraction temperature, extracting pressure 1～20MPa, ultrasonic power 50～500W, supersonic frequency 20～80KHz, raw material is carried out the extraction of active ingredient, the extraction time is 0.5～2h;

(4) after extraction finishes extract being cooled to room temperature can collect.

2, the method for claim 1 is characterized in that in the step (1), described raw material is a dried feed, needs to cross after powder essence 30～140 purposes sieve; The inventory of described raw material is the capacity of 50～400g/L extraction kettle.

3, realize the ultrasound-enhanced Subcritical Water Extraction device of the described method of claim 1, comprise control system part, operating system part and ultrasound-enhanced part, control system partly with between the operating system part adopts the mode of the signal of telecommunication to be connected, and operating system partly includes extraction kettle (5); It is characterized in that: described ultrasound-enhanced part comprises ultrasonic generator (26) and transducing head (29), and ultrasonic generator (26) places the outside of described extraction kettle (5), and transducing head (29) places the top of extraction kettle; Transducing head is in aggregates with extraction kettle cover (6) processing, and the piezoelectric ceramic wafer (28) of transducing head (29) is positioned at the upper end of extraction kettle cover (6), and the horn,amplitude transformer (27) of transducing head (29) directly places extraction kettle by extraction kettle cover (6).

4, ultrasound-enhanced Subcritical Water Extraction device according to claim 3 is characterized in that: described piezoelectric ceramic wafer (28) is positioned at the upper end of extraction lid (6); Described extraction kettle (5) is provided with a thermostat (7), thermostat (7) is positioned at extraction kettle (5) periphery, extraction kettle also is provided with a pressure tester (10) and a temperature measuring device (11), and pressure tester (10) and temperature measuring device (11) all have an end to be located at extraction kettle (5) inside.

5, ultrasound-enhanced Subcritical Water Extraction device according to claim 4 is characterized in that: described operating system part also comprises nitrogen pot (1), cistern (2), compression pump (3), pre-heater (4) and cooler (8); Nitrogen pot (1) is connected with cistern (2) with control valve (15) by pipeline; One end of compression pump (3) is connected with cooler (8) with cistern (2) respectively by control valve (17,16), and the other end is connected with pre-heater (4) by control valve (18); Pre-heater (4) is connected with extraction kettle (5), and extraction kettle (5) is connected with cooler (8) by control valve (19).

6, ultrasound-enhanced Subcritical Water Extraction device according to claim 5 is characterized in that: described operating system part also comprises gatherer (9), and the end that cooler (8) is connected with compression pump (3) also is connected with gatherer (9) by control valve (14).

7, ultrasound-enhanced Subcritical Water Extraction device according to claim 6, it is characterized in that: described extraction kettle (5) is the cylindric device of the stainless steel of high temperature resistant, high pressure, one stainless steel filtering net is arranged at extraction kettle (5) bottom, in case the outlet of material powder blocking pipe, the lower end has an outlet to link to each other with cooler by pipeline; Described thermostat (7) is the porcelain bushing thermostat, is wrapped in the outer wall of extraction kettle; Described cooler (8) is a chimney cooler, cools off by continuous feeding cooling water, and the cooler downside is provided with a cooling water inlet (12), and upside has a coolant outlet (13); Described gatherer (9) is the cylindric or rectangular-shaped container of stainless steel or glass material; Compression pump is digital water pressure metering pump or high performance liquid chromatography dedicated pump, can regulate and show the pressure size, and pressure limit is 0～25MPa.

8, ultrasound-enhanced Subcritical Water Extraction device according to claim 7, it is characterized in that: described control system partly is designed to control panel (21), and panel is provided with the electric switch (25) of adjustment gauge tap (22), pressure regulation control switch (23) and over-temp and over-pressure warning security system (24) and whole device.

9, device as claimed in claim 8 is characterized in that: described cistern (2) is the cylindrical or rectangular devices of stainless steel or plastic material; Pre-heater (4) is the tubular type annular preheater of stainless steel; Thermostat (7) is the porcelain bushing attemperator, and the temperature hold in range is: normal temperature～250 ℃.

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