JP3156186B2 - Mixing method and mixing device - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a mixing method and a mixing apparatus for mixing gas, liquid and solid in various combinations. The mixture of the present invention includes a case involving a chemical reaction in addition to a case involving no chemical reaction. The mixing method and the mixing device of the present invention include a device for dissolving or dispersing a gas, a liquid or a solid (powder) in a liquid, an emulsifying device, a microcapsule manufacturing device, a chemical reaction device in which dissolution or dispersion is rate-determining, or a liquid. Used for liquid chemical reaction equipment.

[0002] There are various fields in which a gas, liquid or solid (powder) is dissolved or dispersed in a liquid to cause a chemical reaction. First, gas (a substance having a high vapor pressure) is brought into contact with a liquid to dissolve the gas in a liquid phase, which can be used in the field of a chemical reaction. There are gas reaction absorption (water treatment of exhaust gas), polymerization reaction (monomer is gas), and reaction between metal salt and gas (precipitation generation reaction). Further, it can be used for a reaction between liquids. This can be widely used from incompatible to compatible, but is particularly suitable for an incompatible liquid-liquid reaction in which an interfacial reaction or diffusion from an interface governs the reaction rate.
In a liquid-liquid reaction having no compatibility, there is a reaction using a phase transfer catalyst or interfacial polymerization (polyamide). It can also be used in the case where a reaction is performed in a liquid such as a solid catalyst or a chemical treatment of a powder surface. There is a chemical reaction using a heterogeneous catalyst.

[0003]

2. Description of the Related Art A conventional mixing method uses a stirring blade or uses ultrasonic waves.

[0004]

In the case of mixing using a stirring blade, the shearing force (velocity gradient X viscosity) does not increase due to the large amount of laminar components, so that the mixing efficiency is high for the input energy. There is no problem. Further, there is a problem that the stirring effect varies in the tank because the stirring effect is in accordance with the distance from the stirring blade. Therefore, it is necessary to lengthen the stirring time or to use a large amount of a dispersant (emulsifier or the like) which becomes an impurity. In recent years, ultrasonic mixing has been
It is used in fields requiring micro-mixing, and an ultrasonic stirrer is used for this mixing. An ultrasonic stirrer utilizes pressure fluctuations in a liquid based on vibration of an ultrasonic vibration element (such as a piezoelectric element) in an ultrasonic region and cavitation accompanying the fluctuation, for dispersion. However, this method and apparatus have a problem that the magnitude of the vibration energy varies depending on the distance and the direction from the ultrasonic vibration element, so that the stirring effect varies in the machine. Further, it is necessary to cool the vibrating element in order to prevent the vibrating element from being overheated and damaged by vibrating heat, so that there is a problem that continuous operation cannot be performed for a long time. In addition, there is a problem that it is not suitable for use under pressure because of the normal pressure specification. Further, since the frequency of the general-purpose machine is fixed at about 20 to 40 kHz and there is no degree of freedom, there is a problem that there is no effect depending on the reaction system.

[0005]

SUMMARY OF THE INVENTION In view of the above, the present invention has been devised to solve the above-mentioned problems in the prior art. A method of mixing a substance to be mixed by putting a substance to be mixed into a mixing chamber formed by a bellows, and expanding and contracting the bellows , wherein an operating pressure of the bellows,
Pressure of the substance, spring constant of the bellows and bellows
The frequency above the resonance frequency determined by the mass of Rose
And vibrating the bellows . Also forming a mixing chamber by the bellows and the bellows case, have a drive source for expansion and contraction of the bellows
Operating pressure of the bellows, sealing pressure of the substance to be mixed,
According to the spring constant of the bellows and the mass of the bellows
The bellows at a frequency equal to or higher than the resonance frequency determined
Provided is a mixing device characterized by vibrating .

[0006]

[Action] mixing method and mixing apparatus of the present invention is mechanically stretch the bellows (hereinafter, the vibrating both referred) is allowed by the target substance mixture in the mixing chamber and mixed, in particular hydraulic pressure of the bellows, the mixed
Pressure of compound, bellows spring constant and bellows
Above the resonance frequency, determined by the mass of the
Mixing chamber by vibrating bellows with number
Be one that mixing of the mixing materials, interest the stirring action by the pressure fluctuations and flow in a room based on the vibration of the bellows
To mix the substances to be mixed in the mixing chamber. As described above, mixing includes both cases involving no chemical reaction and cases involving a chemical reaction. The following examples can be given as examples of combinations of substances to be mixed. a. Liquid (medium) + gas (dispersion) b. Liquid (medium) + gas + liquid (dispersion) c. Liquid (medium) + gas + powder (dispersion) d. Liquid (medium) + gas + liquid (dispersion) + powder (dispersion)

FIG. 1 and FIG. 2 schematically show components of the present invention. The components include a bellows 1, a mixing chamber 3 is formed by the bellows 1 and the bellows case 2, and a drive source (not shown) for expanding and contracting the bellows 1 is provided. The shape of the bellows 1 includes a peak and a trough with a radius, a diaphragm and the like. The dimensions of the bellows 1, the pitch, the height and the depth of the valleys and the thickness of the bellows 1 are designed according to the stirring conditions. The spring constant of the bellows 1 is adjusted according to the elastic modulus, shape and thickness of the material used. The thickness, pitch, diameter and the like may be distributed within one bellows 1. The bellows 1 is arranged at the center of the case 2 or at a position shifted from the center.
The material of the bellows 1 is at least one of metal, ceramics and polymer material. Generally, these elastic recovery limit strains are ceramics <metal <polymer, and the elastic modulus tends to be opposite to this. Therefore, the properties of the substances to be mixed (eg, chemically corrosive, hard powder) or mixing conditions (eg, frequency,
The bellows 1 is designed according to the amplitude, pressure, and temperature. The method of forming the bellows 1 differs depending on the material. Therefore, there are restrictions on the shape and vibration amplitude of the bellows 1 from the viewpoint of preventing damage to the bellows 1 and fatigue life. In addition, when the bellows 1 comes into contact with the reaction solution, it has excellent chemical corrosiveness, and there is no contamination due to the adhesion of the reaction solution.
It is required to be chemically inert. In some cases, it is conceivable to impart chemical activity. Bellows 1
As shown in FIGS. 3 and 4,
The bellows 1 has the same diameter in the length direction (made cylindrical),
Alternatively, it is conceivable that the diameters are different (tapered or distributed) (conical), and the stirring and mixing state can be changed by giving a distribution to the wall thickness or a frequency to the bellows 1. It is possible. As a method of forming the bellows 1, drawing, cutting, vapor deposition, coating, and the like, which are generally performed, are selected according to the material, shape, and cost. It is necessary to provide an interval between the bellows 1 and the bellows case 2 that is at least as long as they do not come into contact with each other when the bellows 1 vibrates, and at least as long as it does not hinder the circulation of the substance to be mixed. The material of the bellows case 2 is selected according to stirring or mixing conditions (pressure, temperature, dissolution, chemical corrosion, physical wear, etc.). A drive source for vibrating the bellows 1 is a hydraulic pump (in the case of FIG. 1), a vibrator (in the case of FIG. 2),
The crank, cam, air cylinder and the like are selected according to the spring constant of the bellows 1, the pressure fluctuation width, the vibration amplitude, and the vibration frequency. If the frequency of the drive source is made variable, the state of agitation in the room can be set arbitrarily, and appropriate conditions can always be set by monitoring the progress of mixing.

In the mixing of the present invention, a compressible substance is sealed in the mixing chamber 3 in order to easily vibrate the bellows 1 at a low pressure, to adjust the amplitude, and to adjust the spring constant. The compressible substance is selected from the viewpoints of compression elastic modulus, encapsulation amount, cost, etc. according to the use conditions, but generally, a gas having low solubility in a liquid serving as a matrix, a chemically inert gas, a sponge, or the like. A balloon made of rubber, plastics or the like is used. When a gas is dispersed and mixed in a liquid, the gas to be dispersed is used as a compressible substance. The pressure fluctuation width of the reaction solution can be changed by the amount of the compressible substance and the spring constant to be put into the apparatus with respect to the vibration of the bellows 1. Therefore, in a gas reaction in which a gas is dissolved and diffused in a liquid to react, the reaction can be performed at a lower pressure without using a high-pressure autoclave. At the same pressure, the reaction can be performed at a higher speed.

FIGS. 5 to 8 schematically show a typical structure of a bellows type mixing apparatus including the bellows 1, the bellows case 2, the mixing chamber 3 and the driving source described above. The operation of the bellows type mixing device will be described with reference to FIG.
Figure 5 is a single bellows-type mixing apparatus of the simplest batch, the mixing chamber 3 placed liquid 4 which is a predetermined amount of matrix, showing a state where press-fitting the predetermined gas 5 as gas spring ( Example of dispersion and mixing of gas into liquid) . When a drive source such as a pump is operated, the bellows 1 starts vibrating according to the operating pressure, the vibration frequency and the spring constant of the bellows 1.
When the frequency of the drive source is gradually increased, the frequency of the bellows 1 is gradually increased accordingly. At this time, the contents of the bellows 1 repeat the compression and expansion of the gas, which is a compressible substance. It is known that the dissolution of a gas into a liquid is generally proportional to pressure. Therefore, the gas in the bellows 1 is rapidly dispersed in the liquid by stirring and dissolving as the bellows 1 vibrates. Therefore, the time required for mixing as well as the frequency decreases. This method creates a gas in a liquid
Particularly effective means for efficient and high-concentration dispersion mixing
It is effective. That is, the pressure of the gas is
Vibration occurs and gas dissolution is promoted, while stirring also occurs.
Wear. That is, the gas can be dispersed and mixed under pressure. one
On the other hand, conventional stirring blades are liquid phase stirring and are inefficient.
However, ultrasonic waves are usually used at normal pressure,
Orientation. If the operating pressure is gradually increased instead of increasing the frequency, the time required for mixing is shortened due to the intense compression and expansion of the gas. However, it is not always infinitely short. The reason is that the bellows type mixing device is a vibration system. That is, resonance occurs due to the spring constant and the mass of the system. The resonance frequency F is determined by the operating pressure, the gas filling pressure, the spring constant of the bellows 1 and the mass of the bellows 1. The pressure fluctuation in the bellows 1 is complicated in the pressure frequency range of the driving source of F or more. Complex vibrations in which N times the frequency, that is, higher-order vibrations, are seen. In this region accompanied by higher-order vibrations, when the inside of the bellows case 2 was observed using a transparent bellows case 2 to observe the state of stirring and mixing, the stirring and mixing inside the bellows 1 were macro (liquid circulation in the tank) and micro ( (Sub-micron dispersion of gas). In this state, the gas is milky white because the gas is finely dispersed in the liquid. As it gets more intense, it becomes transparent. This cannot be quantitatively described as the particle diameter and its distribution, but indicates that the dispersed particle diameter of the gas has become smaller than the wavelength of visible light. In this state, not only gas but also liquid or powder are extremely vigorously stirred,
Mixed. In particular, it is observed that the aggregate of the fine powder is easily disintegrated into the primary particles and dispersed. This dispersion effect is presumed to be caused not only by compression and expansion of the gas dispersed below the submicron, but also by cavitation. This is supported by the fact that the gas starts to boil out of the transparent liquid portion immediately after the vibration stops. The preferred operating state of the bellows mixer is therefore in this region. However, the stirring and mixing are carried out even in a state other than this state, so that the present invention is not limited to this. When the frequency of the driving source is F or less,
The stirring effect in the mixing chamber 3 improves with the frequency.

FIG. 6 shows a mixing device in which ports 6 and 7 are provided in the bellows case 2 to circulate the solution in the bellows 1 and gradually replenish the new solution while discharging the mixed solution. . The positions or numbers of the entrances 6 and 7 are not limited. 7 and 8 show a multi-stage bellows-type mixing apparatus in which a plurality of bellows 1 are connected. The following method is generally used as the method of connection, but is not particularly limited. a. A plurality of bellows type mixers of the same specification are connected in series or in parallel. b. A plurality of bellows 1 are provided in one bellows case 2. c. A plurality of bellows 1 of different specifications are connected in series. d. A plurality of bellows-type mixing devices or bellows 1 are connected to operate under different vibration, temperature, and pressure conditions. e. A plurality of bellows type mixing devices or bellows 1 are connected to sequentially mix different substances. In a multi-stage system, it is meaningful not only to arrange a plurality of units but also to change operating conditions. For example, in the case of a gas-liquid reaction, the pressure of the gas gradually decreases as the reaction proceeds. Therefore, the reaction rate or the composition of the reaction product gradually changes. Generally, in such a case, a gas amount corresponding to the reacted gas is added. However, in such a case, the amount of the unreacted gas at the time of stopping the reaction remains the same as that in the initial state. If you adopt a method that changes the operating state in contrast to this method,
Even when the amount of gas decreases, the reaction rate can be increased or the composition of the reaction product can be kept constant. By doing so, it is possible to end the reaction in high yield without leaving much unreacted gas. Specifically, the excitation force of the drive source is increased, or the vibration frequency is increased. As shown in the embodiment, the cycle and amplitude of the pressure oscillation in the mixing device are more complicated than those of the hydraulic system.
Although this pressure is the average pressure in the fluid, it indicates that higher-order vibration is occurring. From a microscopic point of view, it can be easily estimated that higher-order vibrations are occurring. The bellows type mixing device produces a mixing effect by such vibration.

[0011]

Next, embodiments of the present invention will be described. The following examples show examples in which the substances to be mixed are mixed using the mixing apparatus of FIG. 9, respectively. The mixing apparatus of FIG. 9 has the following specifications. That is, the bellows case 2 is made of a transparent acrylic resin pipe as a body, and both ends thereof are made of SUS30.
And 4. The inner diameter of the bellows case 2 is 30 mm. The material of the bellows 1 is SUS304, and the spring constant is 0.
6 kg / mm, the distance between the peaks and valleys of the bellows 1 is 5 mm, the distance between the peaks is 2.5 mm, and the number of peaks is 24. The internal volume under no load is 37 cc. One end of the bellows case 2 is connected to a hydraulic pump (not shown), and a pressure gauge (pressure sensor) 8 is fitted to measure the pressure on the hydraulic side. The other end is closed, and a pressure gauge (pressure sensor) 9 is fitted to measure the pressure on the mixture side. A ring 10 made of PTFE is provided at the tip of the bellows 1 to prevent the bellows 1 from contacting the bellows case 2.
May be fitted. Reference numeral 11 denotes a supply port for the substance to be mixed. In each of the following embodiments, the conditions (circulatory vessel, temperature, device operation conditions, time, etc.) are not necessarily the optimum conditions, but are examples in which effects are recognized.

Example 1 Dispersion and mixing of nitrogen gas in paraffin oil 15 cc of paraffin oil (viscosity of 35 centipoise) and 3.5 cc of nitrogen gas (12.5 kg / c) were added to the mixing device shown in FIG.
m ² , 20 ° C.), and the rotation speed of the plunger type hydraulic pump was gradually increased. At this time, 50k
g / cm ² was applied. At 500 rpm (hydraulic frequency 58 Hz), it was visually observed that a part of the nitrogen gas was dispersed in the paraffin oil. At 1000 rpm (oil pressure frequency: 117 Hz), paraffin oil flowed violently in the mixing chamber 3, and about half of the gas was sprayed and dispersed, and the paraffin oil became clouded. Furthermore, about 2000 rpm (hydraulic frequency 233 Hz,
10), the paraffin oil in the mixing chamber 3 flowed violently like a jet, and most of the nitrogen gas was finely dispersed in the paraffin oil, and the turbidity increased. Further, when the pump rotation speed was further increased, the dispersion diameter of the gas became smaller, and it became milky white. That is, the gas was in a micro-mixed state (FIG. 11, hydraulic pressure frequency: 875 Hz). After stopping the hydraulic pump, nitrogen gas dissolved or dispersed in the paraffin oil springs out and returns to its original state through a collection of visible-sized bubbles.
It was confirmed that the nitrogen gas was dispersed in the paraffin oil on a micro order.

Example 2 Dispersion and mixing of nitrogen gas in water 15 cc of water and 4 cc of nitrogen gas (5 kg
/ Cm ² ) and a pressure of 10 kg / cm ² was applied to a hydraulic pump. When the rotation speed of the hydraulic pump was gradually increased, the situation was the same as in the first embodiment. FIG. 12 shows the hydraulic pump pressure and the mixed liquid pressure fluctuation at this time. When the hydraulic frequency was higher than 240 Hz, it was confirmed that the nitrogen gas was micro-dispersed in the water from the cloudiness of the water and the gas flowing out when the hydraulic pump was stopped.

Example 3 Dispersion and Mixing of Non-Phase Solution Paraffin oil and water, which are a combination of immiscible liquids, were selected, and the two components were dispersed and mixed using the mixing apparatus shown in FIG. . 10 cc of water, 5 cc of paraffin oil, and 4 cc of nitrogen gas (pressure 5 kg / cm ² ) were sealed, and a pressure of 10 kg / cm ² was applied to a hydraulic pump. When the number of revolutions of the hydraulic pump was gradually increased, the mixing state in the apparatus was the same as in Example 1. The rotation speed of the hydraulic pump is about 500
When the rpm became 58 (oil pressure frequency: 58 Hz), the two liquids became cloudy, and some of them became milky white. When the rotation speed of the hydraulic pump was further increased, the entire liquid became cloudy at about 1250 rpm (hydraulic frequency 146 Hz), and the proportion of the milky white portion increased. At this time, the liquid was flowing violently in the container. It became a jet at about 2200 rpm (oil pressure frequency: 257 Hz), and the whole liquid became milky white. The rotation speed was further increased to 6000 rpm to mix. Observation of the dispersed particle size at the time of mixing with an optical microscope at a magnification of 200 revealed that the particles could not be accurately measured due to violent flow.
Dispersed particles of 50 to 50 microns could be observed. Compared to gas-liquid mixing, after mixing was stopped, there was a margin for time until phase separation, so that the dispersed particle diameter after stopping was observed under a microscope at 400 times. Table 1 shows the results. However, since the dispersion stabilizer was not added and the phase separation was gradually occurring, the dispersion particle size at the time of mixing was not accurately measured, but is only a guideline.

[Table 1]

Example 4 Dispersion and Mixing of Non-Phase Solution Added with Dispersion Stabilizer To Example 3, 0.05 g of sodium stearate was added as a dispersion stabilizer, and the mixture was similarly mixed. The differences in the situation at the time of mixing are that the dispersion liquid (emulsified state) is slightly transparent compared to Example 3, and that the emulsified liquid has a slightly blue color when mixed at a hydraulic frequency of 890 Hz. It is presumed from the above that the dispersed particle diameter is small. Table 2 shows the number average particle size under various mixing conditions.
Shown in

[Table 2]

Example 5: Dispersion and mixing of powder in liquid As an example of dispersion and mixing of powder in liquid, carbon black was dispersed in water. In the mixing device of FIG.
cc, 3 g of carbon black (Asahi Thermal manufactured by Asahi Carbon Co., Ltd.), 5 cc (5 kg / cm ² ) of nitrogen gas, and 0.1 g of sodium stearate.
A pressure of kg / cm ² was applied. The mixture was dispersed and mixed at a hydraulic frequency of 700 Hz for 10 minutes. After the treatment, the presence or absence of agglomerates was examined, and almost no residue remained on the 0.5-micron men's len filter.

Example 6 Dispersion and Mixing of Non-Phase Solution by PTFE Bellows The spring constant of the bellows 1 is 0.3 kg / mm, the distance between the peaks and valleys of the bellows 1 is 4 mm, the distance between the peaks is 3 mm, and the number of peaks is 20.
9 cc of water, 4.5 cc of paraffin oil, 4.5 cc of nitrogen gas (2.5 kg / cm)
² , 20 ° C.) and a pressure of 5 kg / cm ² was applied to the hydraulic pump. The rotation speed of the hydraulic pump was gradually increased. The mixing condition in the device is approximately 1400 rpm of the hydraulic pump.
Some white turbidity occurs at rpm (hydraulic frequency 163 Hz)
At about 2550 rpm (hydraulic frequency 298 Hz), a liquid circulating flow occurred and the liquid became cloudy. Further, the rotation speed is 4700 rpm
m (hydraulic frequency 548 Hz), the liquid violently flowed in the container and turned milky.

Example 7 Radical Polymerization (Olefin) Radical emulsion copolymerization of olefins having different boiling points of monomers is taken as an example. The monomers used were vinylidene fluoride and 6
With propylene fluoride, the physical properties of the polymer obtained by the polymerization are determined by the copolymer composition, and when the amount of vinylidene fluoride is large, the resin becomes a crystalline resin.
It becomes rubber at 0 to 30 mole percent. Therefore, it is important to control the copolymer composition. This copolymerization reaction has the following characteristics. The boiling points of the monomers are different from −85.7 ° C. for vinylidene fluoride and −29.4 ° C. for propylene hexafluoride. The critical temperatures are 30.1 each
C. and 85.degree. C., the polymerization temperature being 50 to 80.degree. C. , one of which is above the critical temperature and the other is below. The critical pressures are 45.21 Kg / cm ² and 32 Kg / cm ² . Therefore, during the polymerization reaction, the former is mostly in the gas phase, and the latter is mostly in the liquid phase. That is, the former exhibits dissolution diffusion from the gas phase to the aqueous phase of the reaction phase, and the latter exhibits a solution diffusion controlled reaction from the liquid phase (emulsification). The solubility of the monomer in water is approximately 10 ^-2 cc / g, atm. Vinylidene fluoride has homopolymerizability, whereas propylene hexafluoride does not. Therefore, the latter has poor polymerization reactivity and is copolymerized in a manner that it enters during the former sequence. Since the boiling points of both monomers are below the polymerization temperature, high-pressure polymerization (autoclave,
For stirring, an external magnetic stirring blade is often used.) The higher the temperature in the aqueous phase of vinylidene fluoride having high polymerization reactivity, the higher the polymerization rate becomes, and a polymer having a high vinylidene fluoride copolymer composition can be obtained. When both monomers are charged at the same time, a copolymer having a high former concentration and a large molecular weight is obtained in the early stage of the reaction from the difference in polymerization reactivity and the monomer concentration in the aqueous phase, and the former concentration is increased as the polymerization reaction proceeds. A low and low molecular weight copolymer is obtained. That is, as the polymerization reaction proceeds, polymers having different molecular weights and copolymer compositions are generated.
Since the concentration of vinylidene fluoride in the aqueous phase depends on dissolution and diffusion, a stirring step is extremely important in the reaction process.
The polymerization reaction is slow only by dissolution and diffusion from the gas surface, and the molecular weight is low, so that it is not practical. Therefore, it is important how to efficiently supply gas to the aqueous phase. Polymerization reactivity and a polymerization reaction having different monomer concentrations in the reaction phase are not limited to this embodiment, and are often seen in many copolymerization reactions and copolymerization of crosslinkable monomers in rubber molecules. In the polymerization reaction having such characteristics, various measures are taken in batch polymerization. For example, there are regulation of monomer pressure, regulation of polymerization temperature or regulation of monomer temperature. However, in order to obtain a polymer having a constant composition and molecular weight, it is difficult to partially sacrifice the polymerization rate, suppress the reaction yield low, or satisfy all of them. In the present invention, the polymerization reaction can be remarkably improved by efficiently dispersing and mixing a gas in a liquid phase by the following effects. Before showing this example, the results of the prior art (batch type autoclave polymerization) will be shown. FIG. 15 shows the stirring effect in the copolymerization reaction of vinylidene fluoride and propylene hexafluoride. The conditions are as follows. The polymerization reaction conditions (3l autoclave, 70 ° C.) deionized water 1540ml emulsifier (manufactured by KK Neos FS1110) 2 g vinylidenefluoride pressure 40 kg / cm ² constant hexafluoropropylene 360g polymerization initiator persulfate ammonium (special grade) of the test The results show that the consumption rate of vinylidene fluoride increases as the stirring speed increases. Table 3 below shows the polymer solution viscosity η _ap / C and the average composition of the polymer as indices of the molecular weight of the obtained polymer. As the stirring speed increases, η _ap / C increases, which indicates that the molecular weight of the produced polymer is high and the copolymerization ratio of vinylidene fluoride is high.

From the above results, it can be seen how important the step of supplying the reactive monomer in the gas phase into the liquid phase is. Since the gas of the present invention can be mixed into the liquid phase at a high speed, the reaction speed can be increased, and the gas pressure can be reduced. This example shows the results using a bellows-type reactor, Comparative Example 1 shows the results without stirring, and Comparative Example 2 shows the results of autoclave polymerization with a conventional electromagnetic stirrer. 28.5 cc of ion-exchanged water and 0.04 of FS1110 in a bellows-type apparatus having an internal volume of 37 cc when no load is applied as described above.
g, 0.07 g of ammonium persulfate, 6.5 g of propylene hexafluoride as a monomer, and 40 kg / cm ² of vinylidene fluoride (70 ° C.). Temperature 70 ° C
With the plunger type hydraulic pump at 7000 rpm
(Frequency 817 Hz), and operated at a load oil pressure of 50 kg / cm ² . FIG. 16 shows a pressure change over time. Comparative Example 1 The same conditions were used as in this example except that the hydraulic pump was not operating. FIG. 16 shows a pressure change over time. Comparative Example 2 In a 100 cc autoclave equipped with an electromagnetic stirrer, 51 cc of ion-exchanged water, 0.05 g of FS1110, 0.11 g of ammonium persulfate, 12 g of propylene hexafluoride as a monomer, and 40 kg / cm ² of vinylidene fluoride
(70 ° C.). The polymerization was carried out at a constant temperature of 70 ° C. and a rotation speed of the stirrer of 500 rpm. FIG. 16 shows a pressure change over time. Comparative Example 1 without stirring
The pressure drop (indicating the consumption of vinylidene fluoride which accounts for most of the reactor pressure and also indicating the progress of the copolymerization reaction) is extremely slow, indicating that the copolymerization reaction hardly progresses. Is shown. In addition, the pressure drop rate of this embodiment is higher than that of the conventional stirring type reaction apparatus, and the effect is recognized. The pressure in the reaction tank of this Example and Comparative Example 2 was 40 kg.
/ Cm ² was added so as to be constant. FIG. 17 shows the amount of added vinylidene fluoride, that is, the amount of consumed vinylidene fluoride. Since the internal volumes of the reaction tanks are different, the values are shown in grams of vinylidene fluoride per gram of propylene hexafluoride as a standard. The reaction solution of this example was gradually poured into 500 cc of a 10% by weight aqueous solution of sodium at 90 ° C., and the produced polymer was recovered, and its weight was measured to determine the reaction yield. Table 4 shows the results.

As is clear from the above results, it has been confirmed that the apparatus of the present invention has a remarkable reaction promoting effect as compared with the conventional autoclave equipped with a stirrer.

Example 8 Precipitation reaction (magnetite) A method for producing magnetite by alkali hydrolysis of an aqueous iron salt solution is advantageous in terms of cost. However, since this reaction is a precipitation formation reaction due to the addition of alkali, the magnetite generation rate, particle size, chemical structure, etc. become non-uniform due to the effects of alkali addition speed, stirring speed, temperature, concentration, etc. There was a problem that the chemical properties within the batch and between batches and the chemical and physical stability of the properties were insufficient. In particular, when the base concentration is increased or the addition rate is increased in order to increase the reaction rate, unreacted iron salts are included in the resulting precipitate. At present, as a method of solving such a problem, a stirring process is generally used. That is, ideally, the alkali is dispersed and mixed faster than the reaction rate. However, the conventional method based on the rotation of the stirring blade has a limitation, and the particle diameter of the precipitated particles is increased or aggregates are easily formed. The device of the present invention is effective in such a problem. No load internal volume 3 of the above specifications
In a 7 cc bellows type device at 25 ° C, 35
16 cc of a weight percent aqueous solution and 17 cc of a 35 weight percent aqueous ferrous chloride solution are charged. Next, 8cc of nitrogen gas
(10 kg / cm ² , 20 ° C.). Hydraulic pump 7000 rpm (frequency 817 Hz), hydraulic load 15
It was operated at kg / cm ² . One minute after the rotation, 4 cc of a 30% aqueous sodium hydroxide solution was injected while rotating. After 3 minutes, the temperature was raised to 90 ° C. in 20 minutes. After a further 10 minutes, the contents were taken out and the particle size was measured with a scanning electron microscope. The result was 83 Å (number average particle size). As a comparative example with respect to this example, the results of a conventional stirring-type reactor are shown. 10
A stirrer with a turbine blade was attached to a 0 cc stainless steel container, and 40 cc of a 35 weight percent aqueous solution of ferric chloride and a 35 weight percent aqueous solution of ferrous chloride were added at 25 ° C.
Insert 5cc. Next, the stirring motor is rotated, and 200,
It was set to 500, 2000, and 3000 rpm, respectively. To these, 12 cc of a 30% aqueous sodium hydroxide solution was added over 1 minute. After 5 minutes, the temperature was raised to 90 ° C. in 20 minutes while rotating. After a further 10 minutes, the contents were taken out and the particle size was measured. In most cases, only large powders of micron to milliorder were obtained. In order to obtain particles of the same order as in this example, the temperature of sodium hydroxide had to be reduced to 1/5 or less and the dropping speed had to be increased to 10 times or more.

Example 9: Hydrogenation Reaction In order to observe the effect of accelerating the gas-liquid reaction, the amount of hydrogen reaction in the hydrogen reduction reaction of heptanal, which is a general hydrogenation reaction, was used as an index. Table 5 below shows the reaction conditions and results.
The reactor used was the same as in each of the above-mentioned embodiments.

[Table 5] The bellows type reactor has a remarkably higher reaction rate than the conventional autoclave reactor with a stirring blade, indicating that it is suitable for a short-time reaction.

[0021]

The mixing method and the mixing apparatus of the present invention are as follows.
Mechanically expand and contract the bellows as described above
Mix the substances to be mixed in the
Filling pressure of mixed substance, spring constant of bellows and bellows
At frequencies above the resonance frequency determined by the
The substance to be mixed in the mixing chamber by vibrating the rose
The present invention has a stirring effect by vibration of the bellows, a dissolution promotion by pressure fluctuation, and a micro-dispersion effect by cavitation. Therefore, the following effects are obtained. a. When dissolving a gas with low solubility in a liquid or dispersing a gas in a liquid, the steps can be shortened because of the stirring effect due to the vibration of the bellows and the dissolution promoting effect due to the pressure fluctuation caused by the vibration. b. Since the frequency or amplitude of the bellows can be arbitrarily controlled for an arbitrary time, the supply speed of the gas can be controlled, and the reaction speed can be controlled. c. Since a hydraulic pressure or a vibrator can be used as a vibration source of the bellows, the pressure amplitude and the cycle can be arbitrarily adjusted, and a favorable mixing effect can be expected. d. As the vibration period of the bellows is shortened, a cavitation phenomenon appears. In this region, a dispersion at a submicron level can be obtained. e. Since one peak and valley of the bellows can be regarded as one stirring unit, the dispersion of the stirring force in the mixing chamber is small. f. The area involved in mixing is large because the outer wall surface of the bellows vibrates. In other words, the residence time in the stirring area is long. g. The stirring time can be controlled by changing the length of the bellows. h. Pressure fluctuations can be given in the reaction liquid by the vibration of the bellows. Dissolution and vaporization of the gas are repeated in accordance with the frequency of the pressure oscillation, and at this time, a stirring effect is accompanied. That is, the mixing device of the present invention, when viewed as a reaction device in a narrow sense, is a multifunction type reaction device having a stirring function, a reaction solution concentration adjusting function, and a reaction rate adjusting function. Further, the reaction apparatus can be any of a batch type, a circulation type and a continuous type. i. The bellows has a stirring effect by macro flow and a stirring effect accompanied by micro cavitation depending on the frequency or amplitude. Therefore, uniform microdispersion and mixing are possible, so that a uniform reaction product can be obtained particularly in the molecular weight and copolymer composition in the polymer synthesis reaction. j. In regions where cavitation occurs due to the vibration of the bellows, an extremely large shearing force acts, so that substances having low solubility and forming aggregates (clusters), substances having poor dispersibility and easy to aggregate, and incompatible liquid-liquid reactions,
A remarkable reaction promoting effect is observed in a chemical reaction using a catalyst having a significantly different distribution number.

[Brief description of the drawings]

FIG. 1 is an explanatory view of a mixing device according to the present invention.

FIG. 2 is an explanatory view of a mixing device according to the present invention.

FIG. 3 is an explanatory view of a bellows.

FIG. 4 is an explanatory view of a bellows.

FIG. 5 is an explanatory view of a mixing device according to the present invention.

FIG. 6 is an explanatory view of a mixing device according to the present invention.

FIG. 7 is an explanatory view of a mixing device according to the present invention.

FIG. 8 is an explanatory view of a mixing device according to the present invention.

FIG. 9 is a sectional view of a mixing apparatus according to an embodiment of the present invention.

FIG. 10 is a graph showing a pressure fluctuation state in the mixing device.

FIG. 11 is a graph showing a pressure fluctuation state in the mixing device.

FIG. 12 is a graph showing a pressure fluctuation state in the mixing device.

FIG. 13 is an enlarged view of a substance to be mixed.

FIG. 14 is an enlarged view of a substance to be mixed;

FIG. 15 is a graph showing the consumption of vinylidene fluoride.

FIG. 16 is a graph showing the pressure in a reaction tank.

FIG. 17 is a graph showing consumption of vinylidene fluoride.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Bellows 2 Bellows case 3 Mixing chamber 4 Liquid 5 Gas 6,7 Outlet 8,9 Pressure gauge (pressure sensor) 10 Ring 11 Supply port

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) B01F 3/00-11/04

Claims (2)

(57) [Claims] 1. A substance (4) (5) to be mixed is put in a mixing chamber (3) formed by a part of a wall surface with a bellows (1).
The substance to be mixed (4) is expanded and contracted by the bellows (1).
A method of mixing (5) , wherein the bellows (1)
Working pressure, pressure for filling the mixed substances (4) and (5), before
The spring constant of the bellows (1) and the bellows (1)
Above the resonance frequency (F) determined by the mass of
And vibrating the bellows (1) . 2. A bellows (1) and a bellows case (2).
Form a mixing chamber (3), and the bellows (1)
The bellows (1) having a drive source for expanding and contracting
Pressure, sealing pressure of the substance to be mixed (4) (5), the bellows
The spring constant of the bellows (1) and the mass of the bellows (1)
At a frequency equal to or higher than the resonance frequency (F) determined by
A mixing device characterized by vibrating a rose (1) .