JPS59169505A - Liquid-liquid extractive separation apparatus by ultrasonic emulsification - Google Patents

Abstract

PURPOSE:To remarkably improve the extraction efficiency and separation efficiency of the titled apparatus, by performing extraction in such a state that a material to be extracted is dispersed in an extractant in an emulsified state within an extracting tank by irradiating ultrasonic waves while performing the separation of the liquid extract and the extractant residual liquid in a separation tank by a modified filter material. CONSTITUTION:A material to be extracted is sent into an extracting tank 1 from the pipe 5a thereof to be irradiated with ultrasonic waves at the under surface of an ultrasonic vibrator 4 and the comminuted material is dispersed in the extractant sent from a pipe 5b while the liquid mixture brought to an emulsified state in an emulsifying part 6 is stayed in said apparatus while stirred by the straight forward stream at the time of irradiation to complete extraction. In the next step, a modified filter material 9 prepared by surface treating a glass fiber with a surfactant is provided in the separation tank 8 of a filtering separation apparatus 2 and the above mentioned liquid mixture is sent into said tank 8 from a pipe 5c while an extraction residual liquid is floated and separated above the filter material by the driving force of electrodes 10, 11 and a vacuum chamber 13 to pass a liquid extract and both components are respectively discharged from pipes 16, 15. By this method, the extraction efficiency and separation efficiency of the titled apparatus can be remarkably improved.

Description

Detailed Description of the Invention This invention is a liquid-liquid extraction separation device using ultrasonic emulsification, particularly a liquid-liquid extraction separation device that significantly improves the extraction efficiency of valuable ingredients such as vitamins, hormones, enzymes, organic pharmaceuticals, fragrances, and dyes. 0 Regarding equipment When extracting and separating extracts containing the above-mentioned valuable components (hereinafter simply referred to as extractable substances) with an extraction agent (a solvent for extracting extractable substances in the extract), conventional liquids are used. - Most liquid extraction devices have a base that allows the extraction material and extractant to flow countercurrently while mechanically stirring, and the contact area at the liquid-liquid interface is small, resulting in low extraction efficiency. There was a demand for the development of a more efficient extraction device.

The purpose of the present invention is to improve the drawbacks of the conventional devices described above and to provide an efficient liquid-liquid extraction and separation device. The contact interfacial area between the extraction liquid and the extracting agent according to the method is @
An extraction device that dramatically increases the mass transfer coefficient and improves extraction efficiency by several tens of times, and an emulsified supplementary liquid (extractant after extraction) produced by the above extraction and a raffinate liquid (extractant). More efficient liquid-liquid extraction separation can be achieved by combining this with a filtration and separation device that uses special offshore materials or special door materials to which a DC electric field is applied to separate the extract from the extracted material (after extracting the extract). The aim is to provide a device.

In order to achieve the above object, the present invention includes a liquid-liquid extraction and separation device consisting of an extraction device and a filtration separation device. By doing so, the oil-based extract containing the extracted substance is dispersed in an emulsified state in the extraction agent in the extraction tank, and the liquid-liquid interface is dramatically increased for extraction, and the replacement liquid and raffinate liquid are separated. The filtration separation device is equipped with a modified F material whose surface is treated with a surfactant to give it hydrophilicity and oleophobicity in the separation tank which forms the main part of the filtration separation device. A liquid obtained by ultrasonic emulsification is obtained by selectively filtering only the extracted oil liquid using the modified PU under pressure or in a vacuum to separate the replacement liquid and the raffinate liquid from the mixture of the replacement liquid and the raffinate liquid obtained in the extractor. A liquid extraction separation device is provided.

In addition, in order to achieve the same purpose, a liquid-liquid extraction and separation device consists of an extraction device and a filtration separation device. Particularly, in an extraction tank, the oil-based extract containing the extracted substance is dispersed in an emulsified state in the extractant, and the liquid-liquid interface is dramatically increased for extraction, and the replacement liquid and raffinate liquid are separated. The filtration separation device is constructed so as to form an emulsified mixture with A cathode is provided, the cathode is placed close to one wide surface of the modified F material, and the anode is arranged on the opposite side of the door material so as to be spaced apart from the surface, and the replacement fluid obtained by the above extraction device and An ultrasonic wave device configured to selectively filter only the replacement fluid from the raffinate mixture across the surface of the modified offshore wood on the anode side to the opposite side under pressure or vacuum to separate the replacement fluid and the raffinate. Liquid-liquid extraction separation device by emulsification'f:
provide.

As already mentioned, in conventional liquid-liquid extraction equipment, both the extractant and extraction agent are placed in an extraction tower equipped with an appropriate stirrer, mechanically stirred, and then transferred to a separation tank and left to stand still. Various methods have been put into practical use, including towers, Scheibel towers, and rotating disk towers. However, in each of these extraction devices, the droplet diameter due to mechanical stirring of the extraction material and extractant is 2 to 3 mm (8 degrees),
The liquid-liquid contact interface area is not very large, and therefore the extraction efficiency is not very high.

On the other hand, the unique feature of the liquid-liquid extraction and separation device according to the present invention is that the extraction material and extractant are fed into an extraction tank equipped with an ultrasonic vibrator at an appropriate ratio that is most easily emulsified. In addition: 1) By irradiating ultrasonic waves with a frequency of ia,
The point is that the extraction material can be dispersed in the extraction agent as fine particles of several micrometers. In this way, the contact interfacial area between the extractant and the extractant in an emulsified state is increased by several hundred times compared to the conventional mechanically stirred liquid droplets0.The extraction rate of the extracted substance is generally determined by the mass transfer coefficient. , is proportional to the multiplicative product of the interfacial area and the concentration difference between the extractant and the extracted substance in the extractant, so the extraction efficiency increases due to the dramatic increase in the contact interface area between the M material and the extractant due to ultrasonic emulsification. Significant improvement over conventional methods. The ultrasonic irradiation time required to almost complete the movement of the extracted substance in the extraction material toward the extraction material side is several seconds to several seconds.

Next, there is a device for separating oil liquid and raffinate liquid, but in conventional extraction equipment equipped with a mechanical stirring device, oil liquid and raffinate liquid are separated using gravity flotation separation method or centrifugal separation method. method is used. However, in the extraction apparatus of the present invention, the oil liquid and the raffinate liquid are in an emulsified state, so it is extremely difficult to separate the two liquids using the conventional separation method described above. As described in Japanese Patent Publication No. 51-28588, separation of the oil liquid in the emulsified state and the raffinate liquid is performed according to the positive or negative dynamic field position of the dispersed particles with respect to the dispersion medium. There is a device that accelerates the gravitational flotation or sedimentation of polydisperse particles by applying a DC voltage to upper and lower electrodes provided at the top and bottom of a separation tank. This can be carried out using a centrifugal separator that utilizes centrifugal force in place of gravity in the apparatus and accelerates separation with an electric field.

This invention separates the oil liquid in an emulsified state and the raffinate liquid by applying a DC electric field or using a novel filtration separation device using modified offshore wood whose surface has been modified with a surfactant as described above. Furthermore, a novel filtration and separation device using the modified door material described above is provided, whereby the separation can be carried out extremely efficiently.

This invention is a liquid-liquid extraction method that combines a highly efficient extraction device using ultrasonic flotation as described above and a device that effectively separates a mixed liquid of oil liquid in an emulsified state after extraction and raffinate liquid. This is a separation device, and such a device is completely unknown and new.

Of course, such devices can be efficiently operated in both batch and continuous operations.

Next, this invention will be described as methyl isobutyl ketone (hereinafter simply MI).
An example of extracting an oil-based extract containing butyric acid as an extractant (referred to as BK) using water as an extractant will be described with reference to the drawings. As shown in FIG. 1, the liquid-liquid extraction and separation device of the present invention includes an extraction device 11! : From the filtration separation device 2. The extraction device 1 consists of an extraction tank 8, an extractant feed pipe 5a, an extractant feed pipe 5b, and a discharge pipe 5C, and the Oki perseparator W2 includes a separation tank 8,
Vacuum device connection pulp 1Φ, oil liquid discharge pipe 15 and raffinate liquid m-fold pipe 16, extraction tank 8 and separation tank 8 are connected to discharge pipe 5
c and communicate with each other via valves.

A horn-shaped ultrasonic transducer 4 is attached to the upper part of the extraction tank 8, and the frequency of the transducer 4 may be selected to be optimal for emulsification, but usually a frequency of about 80 KHz is appropriate. An extractant feed pipe 5a is attached to the upper side of the extraction tank 3, and an extractant feed pipe 5b is attached to the lower side. The extract fed from the extract feed pipe 5a is irradiated with ultrasonic waves on the lower surface of the ultrasonic vibrator 4 and becomes atomized, dispersed in the extract fed through the extract feed pipe 5b, and emulsified. state. In this case, the operating conditions for obtaining the optimum emulsified liquid are: the ratio of the hole diameter d of the desk 7 to the diameter of the lower end of the vibrator 4 (1/D), the distance between the desk and the tip of the vibrator 11t, the diameter of the extracted material It is determined by the flow rate ratio with the extraction agent.The mixed liquid that has become emulsified at the emulsification part 6 near the bottom of the vibrator 4 is subjected to vigorous agitation by the straight flow, which is a characteristic of ultrasonic irradiation. Most of the extraction is completed after staying in the tank for a few seconds to a few seconds, and is transferred to the next separation tank 8 via the discharge pipe 5c at the bottom of the extraction tank. This separation tank 8 efficiently collects the emulsified mixed liquid. For good separation, it has the following sliding structure. Modified F material 9 with an average pore diameter of 0.5- or less, which is made by surface-treating glass fiber offshore wood with a surfactant so that it has hydrophilicity and oleophobicity. A net-like or porous plate-like upper electrode (anode) 10 and a lower electric field (negative &) 11 are attached to the separation tank 8 in which true-wall filtration is performed using a net-like or perforated plate-like upper electrode (anode) 11 so that a DC electric field can be applied for the purpose of accelerating the filtration speed.
Below the lower support porous plate 12 of the lower electrode is a vacuum chamber 18 connected to a vacuum device via a vacuum device communication pulp 14. This separation tank 8 has the following separation function. When the emulsified mixed liquid transferred from the extraction tank 8 to the separation tank 8 passes through the modified door material 9 by the driving force of both hydraulic pressure and vacuum, the hydrophilic and oleophobic properties of the P material are Therefore, the water containing butyric acid, which is the extraction liquid, passes through, but the MIBK fine particles in the oily extraction liquid cannot pass through, and they coalesce on the upper surface of the modified offshore wood 9 and are floated and separated into large droplets. .

By applying DC type S (normally 10 to 20 volts/brace) of appropriate strength with the upper electrode 1O as the anode and the lower electrode 11 as the cathode, the negatively charged MIBK particles are transferred to the anode and are electrically charged. Because of electrophoresis, separation efficiency is further promoted. Oil liquid (water containing butyric acid) accumulated below the vacuum chamber 13
The raffinate liquid (M
IBK) is discharged through the raffinate discharge pipe 16 and reused. The filtration in the separation tank may be under pressure instead of the vacuum method as described above. The extraction tank equipped with an ultrasonic vibrator is It does not necessarily have to be of the same type as the embodiment shown in FIG.
Any structure may be used as long as it provides an appropriate emulsified state. The same applies to the oil liquid and raffinate liquid separation tank, and the structure can be similar to that shown in the embodiment shown in FIG. That is, the mixed liquid in an emulsified state transferred from the extraction tank is led to a double concentric cylindrical separation tank 18 through a nokurubu 17. By the modified material 9', the oil liquid passes through the vacuum device communication pulp 14 toward the vacuum chamber 18 connected to the vacuum device, accumulates in the lower part of the vacuum chamber, and is discharged through the oil liquid discharge pipe 15. The MIBK particles in the raffinate coalesce on the inner surface of the door material, rise as large droplets, and are discharged through the raffinate discharge pipe 16. In addition to this operation, the central electrode (anode) 19 of the tank is If a DC electric field of appropriate strength is applied to the mesh electrode (cathode) 20 on the outer periphery of the door material, the separation effect (ratio of raffinate and oil liquid separated in the separation tank) will be further promoted.

The cylindrical modified F material 9' as shown in Figure 2, Chuo Toden & (
A filtration separation device that combines anode (anode) 19 and a mesh electrode (cathode) 20 on the outer periphery with a centrifugal separator can achieve even more effective separation. The experimental conditions and the actual measured value of the extraction capacity coefficient when an oily extract containing butyric acid as the extractant is extracted using water as the extracting agent are as follows: 0 Experimental conditions: MIBK-Butyric acid-Water system Ultrasonic output 110 Watts Ultrasonic irradiation time (residence time in extraction tank) 0.7 seconds MIBK volume in emulsion #degree approx. 2 volumes Measured value: Extraction capacity coefficient 2.lX10 1/sec Here, extraction capacity coefficient is the following formula (1) It is defined by Ka in the % formula % (1). In this formula, N:
Extraction rate CI/sec at which the extract moves from the extract to the extractant through the interface per unit time] V: Volume of the extraction tank a: Interfacial area of all extract particles in an emulsified state contained in the extraction tank: Mass transfer Coefficient CR: Concentration of extracted substance in extract CR*: Concentration of extracted substance at the interface between extracted substances. The extraction capacity coefficient Ka is a measure for comparing the extraction speed of the extraction device, that is, the extraction efficiency.

Now, the extraction capacity coefficient Ka can be calculated from equation (1) by actually measuring N, CR, and CR* by analyzing the extracted substance, and also actually measuring the volume V of the extraction tank.

The results of liquid-liquid extraction separation using the spray tower method and the multi-stage perforated plate spray tower method for the same extractant and extractant as above, that is, the MIBK-butyric acid-water system, are shown below.

Spray tower method: %formula%) The following experimental conditions and results are described.

Experimental conditions: MIBK-butyric acid-water system, single particle Spray tower method % formula % Multi-stage perforated plate spray tower method: Industrial and Engineering Kebastory, Process Design and Development Vol. 7, Page 166 ( (1968) The following is described below - Experimental conditions: MIBK-Butyric acid-Water system multi-stage perforated plate spray tower method Measured value Two extraction capacity coefficients (0.07 to 0.111) x
10-"1/sec. As is clear from comparing the extraction capacity coefficients (i.e., coefficients indicating extraction efficiency) in these experimental results, the extraction efficiency with the device of this invention is approximately 45 times that of the spray tower method. , which is about 20 to 80 times that of the multi-stage perforated plate spray tower system.

In the operation of separating emulsified oil and raffinate in the liquid-liquid extraction separation device shown in Figure 1, efficient separation was achieved even when no electric field was applied, but when a DC electric field of 20 volts/C7n was applied. As a result, separation efficiency approximately twice as high as that without applying an electric field was obtained.

As described above, separation of the emulsified aqueous oil liquid and oily raffinate using a liquid-liquid extraction device using ultrasonic emulsification is carried out using the above-mentioned specific denaturing furnace material, or by adding a DC electric field to the denaturing furnace material. A liquid-liquid separation device combined with a hyperseparation device can significantly improve extraction efficiency and separation efficiency, making it possible to improve productivity and downsize the device.

[Brief explanation of drawings]

FIG. 1 is a sectional view of a liquid-liquid separation device showing an embodiment of the present invention, and FIG. 2 is a sectional view of a filtration separation device showing another embodiment of the invention. 1... Extraction device 2... Filtration separation device 3.
...Extraction tank 4...Ultrasonic vibrator 5a...
・Drawing feed pipe 5b...Drawing feed pipe 5C...
・Exhaust pipe 6...Emulsification part 7...Desk
8...Separation tank 9.9'...Modified p material
10... Upper potential 11... Lower electrode
12...Support porous plate 18...Vacuum chamber 14...Vacuum device communication pulp 15...Oil liquid discharge pipe 16...Raffinate discharge pipe 17...Nokuru 18... Double concentric cylindrical separation tank

Claims (1)

[Claims] 1. The liquid-liquid extraction and separation device consists of an extraction device and a filtration separation device, and the extraction device irradiates ultrasonic waves with an ultrasonic vibrator installed in an extraction tank, which is the main part of the extraction device. The oil-based extract containing the extracted substance is dispersed in an emulsified state in the extraction tank in the extraction tank.
Extraction is performed by dramatically increasing the liquid-liquid interface to form an emulsified mixture of oil and raffinate. It is equipped with a modified door material whose surface is treated with an activator to give it hydrophilicity and oleophobicity, and the mixture of oil and raffinate obtained by the extraction device is extracted by the modified door material under pressure or vacuum. Liquid-liquid extraction and separation device by ultrasonic emulsification characterized by selectively filtering only liquid and separating oil liquid and raffinate liquid 02 The liquid-liquid extraction and separation device is a system consisting of an extraction device and a filtration separation device. The above-mentioned extraction device emulsifies the oil-based extract containing the substance to be extracted into the extraction agent in the extraction tank by irradiating ultrasonic waves with an ultrasonic vibrator installed in the extraction tank, which is the main part of the extraction device. separated into
The filtration separation device is configured to perform extraction by dramatically increasing the liquid-liquid interface to form an emulsified mixture of oil liquid and raffinate. It is equipped with a modified door material whose surface is treated with a surfactant to make it hydrophilic and oleophobic, an anode, and a cathode, the cathode being close to one wide side of the modified door material, and the anode being placed on the opposite side of the door material. The mixture of oil and raffinate obtained from the above extraction device is applied under pressure or to the opposite side of the modified door material on the positive and side sides. Liquid-liquid extraction and separation device Q using ultrasonic emulsification, characterized in that it is configured to selectively filter only oil liquid in vacuum and separate oil liquid and raffinate liquid.