JP4252993B2 - Mixer and reactor - Google Patents

Description

  The present invention relates to a mixer and a reaction apparatus suitable for continuous chemical reaction, particularly organic chemical synthesis.

  Conventionally, as a method of performing a chemical reaction by mixing a plurality of raw materials, as shown in FIG. 30, a raw material such as a reagent is put in a container 200 and mixed by a stirring member such as a stirring blade 202 for a predetermined time. There is a batch process that makes it possible to obtain the product only in a predetermined volume, and to use a relatively large container to obtain the desired product in a single batch process. Therefore, it is difficult to set sufficient mixing and detailed temperature conditions.

  31 and 32, so-called forced stirring mixers 210 and 212 using stirring members such as a stirring bar 206 and a stirring blade 208 are provided in a liquid chromatograph in a container 204 that continuously circulates fluid. It is often used in a graph gradient device (eluent mixing device). However, in these apparatuses, as shown in FIG. 33, each reagent is always present in an excessive amount in the introduction portion of the container 204, there is a concentration unevenness, and it is difficult to perform mixing at a uniform concentration ratio. Yes, high efficiency mixing cannot be achieved.

  On the other hand, in recent years, a microchannel chip that causes various chemical reactions while flowing a solution or a gas using a channel (microchannel) having a minute channel cross-sectional area has been attracting attention. A microchannel chip is provided with a region for mixing, heating, reaction, and the like on one chip and a flow path for communicating them, and a specific reaction is performed if a material (raw material) is supplied to this. It is comprised so that. The mixed region is usually formed by joining a plurality of flow paths. In the microchannel chip, a continuous process is basically possible, and detailed temperature control is also possible.

ここでＡは頻度因子、Ｅａは活性化エネルギであり、これらは反応に固有な定数である。またＲは気体定数、Ｔは絶対温度である。さらにｋは速度定数と呼ばれ、大きくなるほど反応速度は速くなる。 Here, in general chemical reactions, suitable temperature conditions exist for each reaction. This is because when the temperature is increased in the chemical reaction, the thermal kinetic energy of the particles in the solution increases. In order for a chemical reaction to occur, particles such as atoms, molecules, and ions must collide, and atomic recombination must occur between the particles. The atomic recombination that occurs between particles does not occur in all of the colliding particles. As shown in FIG. 34, an active complex in an unstable state with high energy is once created between particles having a certain energy or more called activation energy, and only particles that have formed an active complex are formed. It turns into a product. In FIG. 34, the vertical axis represents energy, and the horizontal axis represents the direction of reaction progress. Here, the case where the energy of the product is lower than that of the reactant is an exothermic reaction, and the opposite case is the endothermic reaction, and FIG. 34 shows the case of the exothermic reaction. Therefore, in a chemical reaction, the reaction rate tends to increase with increasing temperature. This tendency is also clearly shown by the Arrhenius equation shown in Equation 1 below.

Here, A is a frequency factor, Ea is activation energy, and these are constants inherent to the reaction. R is a gas constant and T is an absolute temperature. Further, k is referred to as a rate constant, and the reaction rate increases as the value increases.

  However, an extremely high temperature reaction causes undesirable phenomena such as chemical decomposition of the reagent before the reaction. Therefore, suitable temperature conditions exist for each chemical reaction, and temperature control in the reaction region is very important. If the temperature control is insufficient, the chemical reaction is not performed as scheduled, and a system with poor productivity such as a decrease in the yield of the target main product is forced. However, in conventional chemical reactions using flasks, beakers, and large reaction tanks, it is very easy to adjust the temperature of the entire reaction area quickly and uniformly because chemical reactions are performed using a certain amount of reagent solution. It was difficult. On the other hand, in the chemical reaction in the microchannel chip, since the mass of the reagent solution in the reaction region is extremely small, the temperature can be set quickly and uniformly. Therefore, it is possible to obtain a temperature condition suitable for the chemical reaction. This can be mentioned as one of the great advantages in the chemical reaction using the microchannel chip.

  However, there are various concerns when operating a microchannel chip. One of the biggest concerns at the time of microchannel chip operation is that mixing does not proceed sufficiently when different types of reagents are mixed in the microchannel chip. In general, in a microchannel chip, mixing by stirring or the like is not promoted as compared with a reaction vessel (mixer) such as a test tube, a beaker, or a flask. Molecular diffusion and turbulent diffusion act to mix the fluid. Compared with molecular diffusion, turbulent diffusion has a great effect on mixing. For example, when you drop milk into coffee, you can intuitively understand that it is faster and more reliable to mix by turbulent diffusion by stirring with a spoon etc. than waiting for the milk to mix by molecular diffusion while looking still .

ここでＶは流速、およびνは動粘性係数である。Ｄは代表寸法と呼ばれ、流体が流れる流路の断面寸法（幅や高さ）などを用いる。Re数が小さい流れを層流、Reが大きい流れを乱流と呼ぶ。層流および乱流の流動様相の一例として、流れ場中に障害物（円柱）を置いた場合の流れの可視化写真を図３５（ａ）、および図３５（ｂ）に示す。例えばRe?32である図３５（ａ）においては、障害物の下流側で流れはきれいな層状に流れ、乱れなどが生じていないことが分かる。このようなきれいな層状の流れを層流と呼ぶ。ところがRe?161の図３５（ｂ）においては、障害物の下流側ではカルマン渦列と呼ばれる千鳥状の渦列が生じ、渦の効果によって混合が促進されているのがうかがえる。また図示してはいないが、Re数が10³〜10⁵の領域では、障害物の左右から放出される渦は、下流に行くに従って拡散し、流れ全体が不規則に乱れた流れになる。このような流れ場を乱流と呼ぶ。 Theoretically, the Reynolds number Re, which is the term of fluid engineering, is used as an indicator of the above matters. The definition formula of Reynolds number Re is shown in Formula 2.

Here, V is a flow velocity, and ν is a kinematic viscosity coefficient. D is referred to as a representative dimension, and uses a cross-sectional dimension (width and height) of the flow path through which the fluid flows. A flow with a small Re number is called laminar flow, and a flow with a large Re is called turbulent flow. As an example of laminar and turbulent flow patterns, flow visualization photographs when an obstacle (cylinder) is placed in the flow field are shown in FIGS. 35 (a) and 35 (b). For example, in FIG. 35A which is Re? 32, it can be seen that the flow flows in a clean layer on the downstream side of the obstacle, and there is no turbulence. Such a clean laminar flow is called a laminar flow. However, in FIG. 35B of Re? 161, it can be seen that a staggered vortex street called Karman vortex street is formed on the downstream side of the obstacle, and mixing is promoted by the effect of the vortex. Although not shown, in the region where the Re number is 10 ³ to 10 ⁵ , vortices discharged from the left and right sides of the obstacle diffuse toward the downstream and the entire flow becomes irregularly turbulent. Such a flow field is called turbulent flow.

となりRe数が小さい層流領域であるため、混合流路ではきれいな層状の流れとなり、混合が促進されづらいことが予測される。 It is known that the flow in the tube, such as the flow in the microchannel chip, transitions from laminar flow to turbulent flow with a Re number of about 1000. To obtain the turbulent diffusion effect, It can be said that it is better that the channel width is larger and the flow velocity is larger. A typical microchip mixing channel in the prior art has a width of about 100 μm and a flow rate of about 0.01 m / s. The Re number under the conditions is calculated assuming that the representative dimension D is 100 μm of the channel width, the flow velocity is 0.001 m / s in the mixing channel, and the flowing fluid is water.

Since this is a laminar flow region with a small Re number, it is predicted that the mixing channel will have a clean laminar flow and mixing will be difficult to promote.

  Furthermore, the microchannel chip is suitable for continuous synthesis of hardly reactive substances because the flow path itself is very small, but the amount produced by the reaction itself is small. Moreover, since the shape of the mixing channel cannot be changed flexibly and easily in the microchannel chip, it is necessary to manufacture again if the intended chemical reaction cannot be achieved after manufacturing. As a result, the chip becomes expensive and the manufacturing time is long, so that the work efficiency of the process optimization is low and the cost is high. In addition, the microchannel chip has the disadvantages that the cleanability in the mixer flow path is low, and foreign substances and products are cheaply clogged.

  This invention was made in view of the above circumstances, promotes diffusion in the mixer when the reagent is charged, and performs a chemical reaction quickly and continuously, can obtain a sufficient production rate, and An object of the present invention is to provide a mixer and a reaction apparatus that can realize high reaction efficiency by detailed temperature control or the like.

In order to achieve the above object, the mixer according to claim 1 is a mixer used in a reaction system that performs continuous processing, and a mixing space that is rotationally symmetric about a vertical axis, And a stirring bar having a plurality of radial portions extending from the axis toward the peripheral edge, a drive mechanism for driving the stirring bar, and an outer peripheral surface of the mixing space. It has at least two or more introduction flow paths opening at different positions, each having an introduction flow path for allowing different fluids to flow into the mixing space, and a discharge flow path opening at the upper surface of the mixing space. And
In the first aspect of the invention, by driving the stirrer, the fluid is forcibly stirred in the mixing space and is quickly and reliably mixed. In addition, the intermolecular distance between both supply fluids that mix, diffuse and react is reduced, improving the efficiency of mixing and reaction, and promoting the discharge of gas generated in the mixing space.

The mixer according to claim 2 is characterized in that, in the invention according to claim 1, the outlet flow path is formed by a plurality of flow paths that open to a radially intermediate portion on the upper surface. . Thereby, discharge | emission of the gas produced | generated in mixing space is accelerated | stimulated more.

The mixer according to claim 3 is characterized in that, in the invention according to claim 1 or 2, the outlet channel has a channel cross-sectional area that is narrow in the downstream portion. This promotes rapid mixing by molecular diffusion.

According to a fourth aspect of the present invention, there is provided the mixer according to any one of the first to third aspects, wherein at least two or more introduction flow channels for allowing the different fluids to flow into the mixing space are opened at positions close to each other. It is characterized by that. Thereby, immediately after flowing into the mixing space, the mixing proceeds rapidly, and the state where the concentration becomes non-uniform is suppressed.

The mixer according to claim 5 is characterized in that a plurality of sets of at least two or more introduction flow paths opened at positions close to each other are arranged at equal intervals on the outer peripheral surface.

A reactor according to claim 6 is a mixer according to any one of claims 1 to 5, a supply source for supplying a raw material fluid thereto, and a recovery container for recovering a reaction product in the mixer. It is characterized by having.
According to a seventh aspect of the present invention, there is provided the reaction apparatus according to the sixth aspect, further comprising a control device that controls a stirring speed of the stirrer in the mixer.

A reaction apparatus according to an eighth aspect is characterized in that, in the invention according to the sixth or seventh aspect, a control apparatus for controlling a temperature in the mixer is provided.
A reaction apparatus according to a ninth aspect is characterized in that, in the invention according to any one of the sixth to eighth aspects, an analysis apparatus for analyzing the reaction product is provided.

According to the mixer of the first to fifth aspects, reliable mixing can be performed at a practical processing speed by the stirring force of the stirring bar arranged in the mixing space.

According to the reaction apparatus according to any one of claims 6 to 9, reliable mixing can be performed at a practical processing speed by the stirring force of the stirring bar arranged in the mixing space, and the reaction has a good quality. The product can be obtained with good productivity.

  Embodiments of the present invention will be described below with reference to the drawings. In the following embodiment, since the reaction is caused by mixing to obtain a product, the mixer is a reactor at the same time, and the mixing system is a reaction system.

  FIG. 1 shows a mixer according to a first embodiment of the present invention, in which a mixing space 14 is formed by a base part (container body) 10 and a cover part (lid part) 12 covering the base part (container body) 10. 16 is configured, and a stirring bar 18 is provided in the mixing space 14. The mixing space 14 is formed rotationally symmetrical around the vertical axis, and is a slightly flat cylindrical space in this embodiment. The base portion 10 is provided with two introduction flow passages 20 that are opened at positions facing each other with the axis line on the outer peripheral surface side, and the cover portion 12 is provided with a lead-out flow passage 22 that opens substantially on the central axis line. Each outer end portion is provided with a joint 24 so that a tube 26 for supplying or discharging a fluid can be attached. The cover portion 12 and the base portion 10 are provided with a seal structure necessary for processing, and maintenance and the like can be easily performed by a simple opening / closing mechanism. Since this mixer can be easily connected to the fluid supply source and other mixers and the like by the joint 24 and the tube 26, the assembly, maintenance, or design change of the processing system can be easily performed.

  If the size of the mixing space 14 is reduced, the ratio of the surface area to the volume of the fluid in the mixing space increases, so that an effect of promoting temperature control and fluid mixing of the fluid in the container can be obtained. The representative dimension (inner diameter) D of the mixing space 14 is desirably 200 mm or less, more preferably 100 mm or less, and still more preferably 10 mm or less.

  In this embodiment, the stirrer 18 is a member extending in a direction perpendicular to the axis of the mixing space 14, and is forcibly rotated around the axis of the mixing space 14 by a drive mechanism 28 installed on the lower side of the mixing container 16. Driven. This drive mechanism 28 rotates the stirrer 18 remotely by rotating a disk 34 on which a permanent magnet 32 is mounted by a motor 30, and is provided with a power supply device 36 and a controller 38. The controller 38 adjusts the rotation speed of the motor 30 so as to be optimal for obtaining a product with a high yield with respect to a target chemical reaction. In this embodiment, the stirrer 18 has a columnar shape in which the central portion swells, and is a so-called football shape. However, the stirrer 18 does not have to be a complete rotating body around the axis, and has a flat shape with different height h and width w. There may be. In addition, mixing of the fluid in a container can also be accelerated | stimulated by fluctuating a rotation speed temporally or carrying out forward / reverse rotation.

  The stirrer 18 is made of a magnetic material or metal coated with a material having characteristics of an organic fluid-resistant material such as a tetrafluoroethylene polymer, ceramic, or glass. Of course, the stirrer 18 itself may be formed of a material having the characteristics of an organic fluid-resistant fluid. The shape and size of the stirring bar 18 are set in accordance with the shape and size of the mixing space 14. That is, the gap formed between the stirring bar 18 and the mixing space 14 is a flow path through which the introduced mixed fluid passes, and stirring and mixing is performed by the swirl flow formed by the rotation of the stirring bar 18. It is a space made. It is set so that the fluid does not stay in the flow path from the introduction flow path 20 to the discharge flow path 22 and is not derived without having the opportunity to mix with other fluids. The shape and size of such a space are determined in consideration of the rotational speed of the stirrer 18, the physical properties such as the viscosity of the fluid to be mixed, and the physical properties of the substance produced by the reaction resulting from the mixing. Need to be done.

  The joint 24 may have any shape and standard as long as a general piping screw or the like is formed. With regard to the joint 24, the main point is that the reagent can be introduced into the mixer or reactor according to the present invention, or the pipe for extracting the product after mixing, or the tube 26 and the mixer can be joined (connected) without leakage. Any may be used.

  Hereinafter, an operation when two fluids are mixed using the mixer configured as described above will be described with reference to FIG. The two fluids are directed toward the center of the mixing space 14 from the introduction flow path 20 provided in the circumferential position facing each other in the vicinity of the lower portion of the mixing container 16 as shown in FIG. It is pumped and led out from the upper outlet channel 22. In this process, in the mixing space 14, the stirrer 18 rotates so as to shear the fluid in the space as shown in FIG. 5B, so that the fluid flows in the circumferential direction and randomly flows in the vertical direction. To do. Accordingly, each fluid has a velocity component in the central direction and the circumferential direction, and as shown in FIG. 5B, first, a layered vortex flow is formed, and the fluid flows up and down each time it collides with the stirrer 18 and is stirred. As a whole, it gradually flows upward.

  In this process, a shearing force acts on each supply fluid introduced into the mixing space 14 by the rotation of the stirrer 18, the fluid layer of each supply fluid is refined, and each supply fluid forms a thin layer. While mixing. This reduces the intermolecular distance between the two supply fluids that mix and diffuse and react to improve mixing and reaction efficiency.

  As shown in FIG. 3, if the introduction flow path 20 a to the mixing container 16 is inclined in the circumferential direction from the direction toward the center of the mixing space 14, the relative velocity of the inflowing fluid with respect to the stirrer 18 is increased, and a stronger shearing force is obtained. And the mixing efficiency is further improved. The role of the stirrer 18 is to give a strong shearing force to the fluid flowing into the container. If the mixing vessel 16 has a mechanism that applies such shearing force to the inflowing fluid, not only the stirrer 18, the fluid layer of each supply fluid is instantly miniaturized. The supply fluid is not limited to a liquid. For example, when one of the fluids is a gas, the bubbles that are torn off with a strong shearing force are converted into microbubbles (fine bubbles) and are mixed in the mixing container 16. Evenly distributed. In the microbubble, since the bubble surface area with respect to the gas volume is dramatically increased, the reaction efficiency is improved.

  In this mixer, as the ratio (ds / D) of the diameter D of the mixing space 14 to the length ds of the stirrer 18 is closer to 1, scraping of each mixed supply fluid is more effective by the rotation of the stirrer 18 ( A thin layer of the supply fluid in the mixing space 14 is effectively formed. As a result, the intermolecular distance between the supply fluids is also reduced, so that mixing by molecular diffusion is promoted. On the other hand, if this ratio is too small, the rotational speed of the stirrer 18 becomes small, or the flow of the fluid becomes unsmooth and has an adverse effect.

The rotational speed of the stirrer 18 will be described. In this mixer, the introduction flow velocity V of the supply fluid is
V = (4 · Q) / (π · di ² ) Equation 4
(Q is the supply amount QA or QB of the supply fluid, di is the inner diameter of the introduction flow path 20), and the peripheral speed Vc of the stirring bar 18 is
Vc = π · ds · ω Equation 5
(Ds is the length of the stirring bar 18). Here, if the relative (circumferential) speed, which is the difference between the flow velocity and the peripheral speed of the stirrer 18, increases, that is, if the ratio of the introduction flow rate / stirrer peripheral speed decreases, the mixture is introduced into the mixing space 14. In addition, the fluid layer of each supply fluid is miniaturized, the fluid layer between the supply fluids becomes thin, and the number of supply fluids stacked in the mixing space 14 increases. Thereby, the intermolecular distance between the supply fluids is also reduced, so that mixing by molecular diffusion is promoted. It is desirable that the ratio of the feed fluid introduction speed / stirrer peripheral speed is 1/3 or less, more preferably 1/5 or less, and even more preferably 1/8 or less.

  In the example shown in the figure, by forming the stirrer 18 with a smooth curved surface, smooth rotation and flow can be ensured even if the dimensional difference is reduced. In order to obtain the same effect, the volume ratio between the volume of the mixing space 14 and the volume of the stirrer 18 (volume of the stirrer / volume of the mixing space 14) may be reduced. . In order to reduce the dimensional difference and the volume ratio, the flatness ratio (= h / w) of the stirrer 18 may be made larger than 1, but the remotely driven stirring as in this embodiment is performed. A child 18 and a simple rod shape is difficult because the posture becomes unstable. It can be employed in the case of a radial stirrer 18 extending in three or more directions as described later or a system directly driven by a drive shaft.

  Moreover, it is necessary to select the optimal volume ratio of the volume of the mixing space 14 and the volume of the stirring bar 18 for the target reaction. For example, if the volume ratio (rotor volume / mixing chamber volume) is decreased in the precipitation-type reaction, it is possible to suppress the stop of the stirrer 18 due to the retention of the precipitate in the mixing space 14. The volume ratio is preferably 5% to 80%, more preferably 15% to 60%, and even more preferably 20% to 40%, but it is needless to say that the optimum value is selected according to the target chemical reaction in a timely manner. No.

  Another factor that is important in controlling the mixing state is the overall transit time of the fluid in the mixing vessel 16. This can be adjusted by the supply pressure of the fluid, the degree of constriction in the introduction flow path 20 and the discharge flow path 22, and the like. Accordingly, the inner diameters di and de of the introduction flow path 20 and the discharge flow path 22 must be set so that sufficient mixing or a reaction time associated therewith can be obtained.

  When this passage time is T, the number of layers of the supply fluid in the mixing space 14 is related to the product (ω · T) of the rotational speed ω per unit time of the stirrer 18 and time T. Here, the thickness of one layer is a function of a value obtained by dividing the mixed space 14 diameter D by the number of layers. Thereby, in the mixer according to the present invention, the smaller the mixing space 14 diameter D and the larger the rotation speed ω of the stirrer 18, the finer the fluid layer of the supply fluid in the mixing space 14, and the smaller D becomes, The residence time of the supply fluid in the mixing space 14 is reduced, so that an effective mixing can be achieved in a short time. The inner diameters of the supply fluid introduction flow path and the mixed (reaction) product discharge flow path 22 formed in the cover section 12 and the base section 10 are φ8.0 mm or less, more preferably φ1.0 mm or less. Is desirable.

  As mentioned above, the mixing action in the mixer according to the invention is governed by a combination of complex factors. Among these are the supply of fluid, the discharge speed, the viscosity of the fluid, the mixing ratio of the supply fluid, the type of reaction and product that occur as a result of mixing. In particular, the remotely driven stirrer 18 as in this embodiment has an advantage of preventing fluid contamination by the drive mechanism 28, but it is also difficult to completely control the rotation speed of the stirrer 18. Therefore, it is desirable to try the shape, size, and other conditions of each part of the apparatus for each mode of mixing or reaction treatment and adopt the optimum one. In the following, various variations of this device will be described.

  FIG. 4 is a modification of the shape of the stirrer 18, (a) is a capsule type in which both ends are hemispherical and cylindrical in the center, (b) is cylindrical, and (c) is prismatic. Further, (d) is a football type, (e) is a columnar shape, and (f) is a prismatic shape made into a cross shape. Each of them has a radial portion 40 having an axis extending in a direction orthogonal to the rotation axis (the axis of the mixing space 14). The cross-sectional shape of the radial portion 40 is not limited to the above example, and any curved or linear shape can be adopted. For example, the curved shape includes a circle, an ellipse, or an appropriate quadratic or cubic closed curve, and the linear shape includes an arbitrary polygon including a triangle. Of course, a mixed shape of a curved shape and a linear shape may be used. For example, as described above, a vertically flat ellipse is difficult to employ because it falls down in the types (a) and (b), but may be employed in the types (d) and (e).

  Moreover, the number of the radial parts 40 is not restricted to the case of 2, 4 shown above, A suitable number can be employ | adopted. It is not necessary to make the shape, length and other dimensions of the radial portions 40 the same. For example, one direction that intersects in (e) may be shortened. This is because actions such as ensuring the stability of the posture can be obtained. Moreover, although the radial part 40 of (a), (d) is not an equal cross section along the axis line, others are isotropic along an axis line, and it is clear that either may be sufficient. It is desirable that the corners are appropriately chamfered (rounded).

  FIG. 5A shows the shape of the ceiling portion of the mixing space 14 matched with the shape of the upper surface of the stirring bar 18, thereby reducing the stagnation of the fluid flow. As a result, when the fluid passes through a narrow flow path formed by two members that move relative to each other, it is considered that a large shearing force acts on the fluid and exerts a strong stirring action. FIG. 5 (b) is a diagram using FIG. 4 (b), (c), etc., which also reduces the stagnation of the flow of the fluid. Smooth rotation is promoted.

  In each of the above examples, the volume of the mixing space 14 and the volume of the stirring bar 18 or the diameter of the mixing space 14 and the length of the stirring bar 18 or the height of the mixing space 14 and the diameter of the stirring bar 18 (outer diameter). As described above, the dimensional relationship of each or each dimension itself is a factor that affects the mixing result, and it is necessary to try variously to find a suitable one for each processing condition. The diameter ratio between the diameter of the mixing space 14 and the rotating diameter of the stirring bar 18 (stirring bar rotating diameter / mixing space 14 diameter) is preferably 50% or more. This is an effective range in which the effect of promoting mixing by the rotating flow (swirl flow) generated by driving the stirrer 18 acts when the supply fluid in the mixing space 14 is mixed by driving the stirrer 18.

Further, as shown in FIG. 5C, there is an optimum positional relationship between the height direction position hi of the introduction flow path in the mixer and the height direction center position hs of the stirrer 18, To apply a strong shear force at the moment when the fluid is introduced,
hs−h / 2 <hi <hs + h / 2 ・ ・ ・ ・ Formula 6
It is desirable to satisfy this relationship.

In the above example, the introduction channel 20 is provided on the lower side and the outlet channel 22 is provided on the upper side. However, the present invention is not limited to this. Moreover, although the outlet channel 22 is provided on the axis, the present invention is not limited to this. Hereinafter, another embodiment relating to the method of forming the inlet channel 20 and the outlet channel 22 will be described with reference to FIGS.

  FIG. 6 shows an introduction flow path 20 or a discharge flow path 22 (hereinafter referred to as a liquid introduction flow path) on the base portion 10 side. (A) and (b) are provided with three liquid introduction flow paths. In addition, although it is suitable for mixing three fluids, it is also suitable for mixing two fluids having different flow rates, for example. Although (a) is Y-shaped with equiangular arrangement, (b) is T-shaped and may be other angular arrangements. (C) is an example of a 4 liquid flow path, (d) is an example of a 6 liquid flow path, and these are also suitable for dispersing and supplying 2 fluids. This is because the flow rate and the relative (circumferential) speed of the stirring bar 18 are increased. About the number of liquid introduction flow paths, it can set suitably. In addition, it can be selected each time depending on the target chemical reaction, which supply fluid is introduced into each liquid introduction channel, and which one is used as the outlet channel 22. For example, in the case of the six liquid guiding channels in (d), if two different fluids are alternately introduced from each channel, the fluid layer shown in FIG. , Mixing can be further promoted.

  FIG. 7 shows an example of forming the liquid introduction flow path on the cover part 12 side. (A) is the same as that of FIG. (B) is one in which a plurality of liquid introduction channels 22 b that open to the periphery of the mixing space 14 are merged into one channel 22, and (c) opens to the intermediate portion in the radial direction of the mixing space 14. A plurality of liquid introduction channels 22 c are merged into one channel 22. In the example of (c), the concave portion 42 is formed in the opening of the liquid introduction flow path on the lower surface of the cover portion 12 to promote the discharge of the gas generated in the mixed space 14. FIG. 6D shows a case in which a protrusion 44 protruding into the mixing space 14 is formed on the lower surface of the cover 12, and a plurality of liquid introduction channels 22 d are formed on the outer periphery of the protrusion 44. This example also has an effect of promoting the discharge of the gas generated in the mixing space 14.

  FIG. 8 shows another embodiment of the cover portion 12 and has a structure in which the flow passage cross-sectional area is narrowed in the downstream portion of the outlet flow passage 22a. When the fluid mixed in the mixing container 16 is guided to the narrow channel cross-sectional area, the distance between the refined fluid masses is further narrowed, and the effect of promoting rapid mixing by molecular diffusion is obtained. In the conventional batch process, stirring can only be expected by the effect of stirring and mixing, and in the mixer using the microchannel chip, only the effect of diffusion mixing can be expected. Therefore, a high mixing effect can be obtained. In addition, although the form which narrowed down a part of pipe line was shown in FIG. 8, if it is a structure which can reduce a flow-path cross-sectional area, the effect of a diffusive mixing can be increased irrespective of the form.

  FIG. 9 shows another example of the liquid introduction flow path provided in the base portion 10. (A) shows that the flow path opens in the outer periphery of the mixing space 14 described above, but (b) shows that the liquid introduction flow path 20b is bent not in the outer periphery of the mixing space 14, but in the middle in the radial direction. Furthermore, in (c), the liquid introduction flow path 20c is opened substantially in the center. Further, (d) is to perform preliminary mixing by fluid mixing of the supply fluid before guiding the flow paths from the two introduction flow paths 20 to the mixing space 14 and then to the mixing space 14. Needless to say, the base portion 10 and the cover portion 12 described above can be used in appropriate combinations. These liquid introduction channels can be used as both the introduction channel 20 and the outlet channel 22 as described above.

  FIG. 10 shows another embodiment of the drive mechanism 28 of the stirring bar 18. (A) integrates the mixing container 16 and the drive mechanism 28 by an appropriate technique such as screwing or bonding. (B) shows a case in which the stirring bar 18 in the mixing space 14 is mechanically integrated by a motor 30 and a shaft 46 which are drive mechanisms 28. The remote drive type stirring bar 18 is suitable for preventing contamination, but the rotation speed of the stirring bar 18 and the rotation speed of the motor 30 of the drive mechanism 28 do not always coincide with each other, and there is a delay in control. Such inconsistencies and delays are due to friction between the stirrer 18 and the wall of the mixing space 14 and viscous resistance of the fluid. Depending on the intended chemical reaction, strict speed control is required. Delay can be a problem. This embodiment is for dealing with problems.

  In this embodiment, since the stirrer 18 is directly connected to the output shaft of the motor 30 by the shaft 46, the bearing 48 that receives thrust and radial load, the entry of contaminants from the drive mechanism 28 to the mixing space 14, and A shaft seal 50 for avoiding the supply fluid in the mixing space 14 from entering the drive mechanism 28 is provided. The shaft seal 50 is made of an organic chemical-resistant material such as a tetrafluoroethylene polymer.

  FIG. 11 shows another embodiment of the drive mechanism 28 of the stirring bar 18. In this embodiment, a magnetic drive mechanism 70 using a plurality of coils is provided on both the lower surface side and the upper surface side of the mixing container 16. A plurality of coils 72 are installed on the upper and lower surfaces of the mixing container 16 at equal positions on the same circumference, and the current to each coil 72 is output from the coil excitation controller 74. Here, the stirrer 18 is a magnetic body or a magnetic body coated with a resin or the like.

  In this drive mode, excitation current is sequentially input from the controller 74 to the coils 72 arranged on the same circumference on the upper and lower surfaces, and the coils 72 are sequentially magnetized with polarity (N, S). The stirrer 18A is rotated by this, and the principle of a so-called stepping motor is used. In addition, if the upper and lower coils 72 are always excited so as to have the same polarity as the stirrer 18A, it is expected that the stirrer 18A is automatically levitated.

In this embodiment, by controlling the exciting current, it is possible to rotate the stirrer 18A intentionally biased to either the upper surface or the lower surface. For example, the magnetic field on the upper surface is turned on and the magnetic field on the lower surface is turned off to bring the stirrer 18A close to the upper surface where the outlet channel 22 exists, and a narrow microspace is formed between the stirrer 18A and the upper surface. It is. At this time, as one means for securing a minute distance from the wall surface, a minute protrusion (notch) 76 is provided on the upper surface of the stirring bar 18A as in the shape example of the stirring bar 18A in the drawing. While passing through the microspace toward the outlet channel 22, each fluid mixed in the container is rapidly subjected to molecular diffusion mixing due to the characteristics of the microspace, and high mixing efficiency can be realized.
In the present embodiment, it is possible to realize an optimum reaction by performing ON / OFF control of the magnetic field according to the reaction state.

  FIG. 12 shows a mixer according to another embodiment of the present invention. (A) installs the heater (heater) 52 and the temperature sensor 53 which detects the temperature of a mixing chamber in the base part 10, and adjusts the temperature of the mixed fluid. Thereby, it becomes possible to perform mixing and reaction under optimum temperature conditions in various chemical reactions, and an effect of obtaining a product in a high yield can be obtained.

  The heater 52 according to the present invention is preferably installed in the mixed space 14 or as a wall that forms the mixed space 14. However, if the heater 52 is in a positional relationship capable of controlling the temperature in the mixed space 14, the heater 52 is a partition wall. Also, it may be in any position such as an upper part, a lower part, or an outer periphery, or may have a plate shape or a bar shape. The heater 52 and the temperature sensor 53 may be installed in the supply fluid introduction flow path 20 formed in the base portion 10 or the cover portion 12. The heater 52 is preferably driven by a direct current or alternating current power source and variably temperature-controllable by the controller 38, but may be a constant temperature output.

  FIG. 12B is a combination of the direct drive stirrer 18 described in FIG. 10B and the heater 52. In this embodiment, the heater 52 is installed between the shaft seal 50 and the mixing space 14, and the temperature sensor 53 is installed at a position for detecting the temperature in the mixing chamber. You may install in the supply flow path 20 of a supply fluid, or both. In this embodiment, the optimum temperature condition for obtaining a product in the target chemical reaction by controlling the temperature of the mixing space 14 by the heater 52 and the temperature sensor 53 and controlling the optimum number of revolutions of the stirrer 18 by the controller 38. Mixing or reaction is performed under the rotational speed condition of the stirrer 18, and the effect of obtaining the product in a high yield is obtained. The controller 38 may be provided separately for each of the heater 52 and the drive mechanism 28, or may be controlled simultaneously using a computer or a sequencer.

  FIG. 13 shows still another embodiment of the present invention. This is because, as a temperature control means, instead of the heater 52, a heat medium passage 54 for flowing a heating or cooling medium M is formed in the base portion 10, and the temperature sensor 53 is installed at a position for detecting the temperature of the mixing chamber. Is. Although not shown, a flow rate adjusting valve for adjusting the flow rate of the heating or cooling medium M is provided, and the temperature of the mixing space 14 can be adjusted. The flow rate adjusting valve may be electrically controlled and automatically controlled by the controller 38, but may be manually operated. A heat transfer plate in which such a heat medium flow path 54 is formed may be installed on the lower side of the base portion 10. Accordingly, it is possible to achieve optimum temperature control for a target chemical reaction by heating or cooling, and to perform the chemical reaction with high efficiency. The heat medium channel 54 may be installed in the mixing space 14, the supply fluid introduction channel 20, or both, or may be installed in the cover portion 12. Such a heat medium channel 54 may be used in the mixer of the stirrer direct drive type shown in FIG.

  In the present invention, the internal pressure of the entire container can be increased in addition to the temperature by increasing the line pressure in the pump that pumps the supply fluid. By placing pressure sensors at appropriate positions in each flow path or in the mixing chamber where pressure can be detected, pressure control based on the signals is performed, so that optimum pressure conditions according to the target reaction process can be obtained. Can be set.

  FIG. 14 shows another embodiment of the present invention, in which an analyzer 56 is installed in the mixer of FIG. 10 (b). The analyzer 56 is installed in the outlet pipe 58 connected to the outlet channel 22 of the mixer via the joint 24. Note that the analyzer 56 may be installed in the outlet channel 22 in the mixer. The analysis device 56 is a device that analyzes the components of the mixed (reaction) product, and is a device that analyzes the components of the mixed (reaction) product, such as a chromatography device.

  In this embodiment, the product components after mixing (reaction) by the mixer are sequentially analyzed, and the analysis results (such as yield) are output to the controller 38 in real time. Based on the analysis result, the controller 38 makes a determination based on a predetermined determination criterion, outputs a control signal for the motor speed and the temperature of the heater 52 to the motor and the heater 52, and the component (yield) of the target product is maximized. These are controlled so as to become a value or a target value. By this method, it is possible to efficiently obtain the desired product of the required components (yield).

  In the mixer in the above-described embodiment, when the mixing space 14 is maintained, only the cover portion 12 is disassembled and removed, and maintenance such as cleaning of the mixing space 14 can be easily performed. Similarly, assembly after maintenance is very simple, and only the cover 12 is installed. Therefore, the mixer is easier to maintain and manage than the existing microreactor.

Example 1
FIG. 15A shows a configuration in which a chemical reaction is performed by the mixer of the embodiment of FIG. There are two supply fluid introduction flow paths 20 facing each other across the center, and a discharge flow path 22 is provided upward along the central axis. The dimensions of the mixing space 14 of the mixer used for the reaction are 9 mm in diameter and 3.5 mm in height, and the shape of the stirrer 18 is a capsule having a diameter of 3 mm and a length of 8 mm. The rotating speed of the stirring bar 18 was 1000 rpm. The chemical reaction carried out was the reaction (acetylation) of diisopropylphenol shown in FIG.
1M 2,6 Diisopropylphenol 1M 1,3 Dimethoxybenzene / Pyridine and B: neat Acetic
Anhydride supply fluid was supplied by a syringe 60, and a recovery container 62 was connected to the outlet channel 22.

となる。
このRe数の状態では、流れが乱流に遷移している可能性も高く、拡散混合のみでなく乱流混合の効果も期待される。言及するまでもないが前記（コーヒーにミルクの例）のごとく混合においては、拡散混合と比較して乱流混合の効果は絶大である。よって本混合器を用いれば、マイクロチャネルチップでは著しく困難であった試薬の混合が容易に達成できると予測される。 Under the above conditions, a vortex having a diameter of 9 mm and a rotation speed of 1000 rpm is expected to be present in the mixer due to the rotation of the stirring bar 18. Therefore, when the representative dimension is 9 mm and the tangential speed is 0.5 m / s, the Re number is obtained from Equation 2.

It becomes.
In this Re number state, there is a high possibility that the flow has transitioned to turbulent flow, and not only diffusion mixing but also turbulent mixing effects are expected. Needless to say, in mixing as described above (in the case of coffee and milk), the effect of turbulent mixing is greater than that of diffusion mixing. Therefore, using this mixer, it is expected that reagent mixing, which was extremely difficult with a microchannel chip, can be easily achieved.

である。本混合器に流量0.47mL/minで連続的に2種類の試薬を投入・混合する場合を考えると、試薬が混合器内に滞在する時間は

である。
ここで、本混合器部分において、化学反応を促進するために試薬の温度を20℃上昇させる必要があると仮定する。試薬の比熱を4.2［kJ/kg・K］、試薬の比重を1000[kg/m³]として試算すると、必要な熱量は

となるため極めて小さい熱量で温度調整が可能であり、必要とする加熱・冷却の装置も安価で簡略なもので十分である。 Further, the mixer having a small volume as in the present invention has an advantage that temperature control is easy. For example, the volume inside the mixer excluding the volume of the stirrer 18 (φ3 mm, length 8 mm) from the mixing space 14 (φ9 mm, height 3.5 mm) is:

It is. Considering the case where two types of reagent are continuously charged and mixed in this mixer at a flow rate of 0.47 mL / min, the time for the reagent to stay in the mixer is

It is.
Here, it is assumed that the temperature of the reagent needs to be increased by 20 ° C. in order to promote the chemical reaction in the mixer section. When the specific heat of the reagent is 4.2 [kJ / kg · K] and the specific gravity of the reagent is 1000 [kg / m ³ ], the required heat is

Therefore, the temperature can be adjusted with an extremely small amount of heat, and the necessary heating and cooling apparatus is sufficient if it is inexpensive and simple.

を要する。さらに混合槽周辺への熱放射などを鑑みると現実的な加熱・冷却を行うためには、もっと大掛かりなシステムが不可欠であると予測される。よって本混合器では、化学反応に大きな影響を及ぼす温度調節を、極めて簡単な装置によって達成することが可能である。 In the case of using a conventional mixing tank or the like, for example, a case where a small-sized mixing tank having a volume of 100 mL is tried to adjust the temperature with the calorific value previously calculated. Similarly, the time required for the reagent temperature to rise by 20 ° C is

Cost. Furthermore, in view of the heat radiation around the mixing tank, it is predicted that a larger system is indispensable for realistic heating and cooling. Therefore, in this mixer, it is possible to achieve temperature control that has a great influence on the chemical reaction with a very simple device.

  As can be predicted from the above simple calculation results, this mixer has the same temperature control function as that of the microchannel chip, and further has the function of promptly promoting the mixing that was difficult with the microchannel chip. It can be said that it is an ideal form as a chemical reaction apparatus. This trial calculation was based on various assumptions. When actually operating this mixer, the operating conditions such as the reagents used, the physical properties of the mixer itself, the ambient environment used, and the flow rate were determined. It should be operated with strict consideration and consideration.

FIG. 16A is a time-yield diagram showing an example of the result of the reaction. From this, it can be seen that the product is obtained in the mixer at a high yield in the same mixing time as compared with the example of the conventional method shown in FIG.
FIG. 16B is a product flow rate-yield diagram, which is a result of comparing a general conventional microreactor with a mixer for the same example. Here, a general conventional microreactor used as a comparative example is for Y-type two-liquid mixing. From this result, it can be seen that the mixer of the present invention can obtain many products in high yield as compared with an example of a general microreactor. In addition, although these chemical reaction results using a mixer are an example to the last, it is thought that the same effect is acquired also in other embodiment of a mixer.

  FIG. 17 shows an example of the result of the chemical reaction in the embodiment of FIG. 15, and shows the relationship between the flow rate of the introduced fluid and the ratio of the peripheral speed of the stirrer 18 and the yield. From this, the feed fluid introduction speed / speed ratio of the peripheral speed of the stirrer 18 is 1/3, the yield is 20%, the speed ratio is 1/10, the yield is 40%, and the speed ratio is 1/50, the yield is 85% or more. It can be seen that

(Example 2)
FIG. 18 is an example showing the result of performing a chemical reaction by arranging the mixers according to the present invention in series. In FIG. 18 (a), the flow coming out from the outlet channel 22 of the first mixing vessel 16 is guided to a second mixing vessel (stirring vessel) 16A having one introduction channel, where further stirring is performed. And derived. In FIG. 18B, the flow from the second mixing container 16A is guided to a third mixing container (stirring container) 16A having one more introduction channel. As another form of the present arrangement example, the flow coming out from the outlet flow path of the first mixing container 16 is divided into two flow paths by a T-shaped branch pipe, and then the second mixing container There is also a method of leading to two introduction flow paths facing each other across the center of 16.

Here, the mixing space 14 has a diameter of 9 mm and a height of 3.5 mm, and the stirrer 18 has a capsule shape with a diameter of 3 mm and a length of 8 mm. The rotating speed of the stirring bar 18 was 1000 rpm. The implemented chemical reaction is the reaction (acetylation) of diisopropylphenol shown in FIG. 15 (b). In the first mixing vessel 16, A:
1M 2,6 Diisopropylphenol 1M 1,3 Dimethoxybenzene / Pyridine and B: neat Acetic
Anhydride feed fluid was supplied by syringe 60.

  FIG. 19 shows the experimental results. From this, it can be seen that the mixer in which the mixing container 16 and the stirring container 16A are arranged in series obtains a product with a higher yield in the same mixing time as compared with the case shown in FIG. In addition, although the example which connected the mixing container 16 and the stirring container 16A with the tube-shaped piping was shown in FIG. 18, this is only one form of the serial arrangement of the mixing containers 16 and 16A, for example, as shown in FIG. Good results can be obtained regardless of the embodiment, for example, the mixing containers 16 and 16A are arranged in series by a stacked structure in which they are stacked. Note that the stirrer 18 in the second mixing container 16A in FIG. 20 has a structure in which an independent drive mechanism is built in or a structure in which the stirrer 18 in the first mixing container 16 is directly connected. The number of rotations of the stirrer 18 in the first and second mixing vessels 16 and 16A is set to an optimum value for each reaction mixture and does not necessarily have to be the same.

  In the above, an example of improving the mixing / reaction efficiency by serial operation has been shown. However, it goes without saying that a large number of mixing containers 16 according to the present invention can be arranged in parallel to ensure a predetermined production amount. No. In that case, in order to ensure the quality of the product, the quality of the product is analyzed in a collection container in which the products from the individual mixing containers 16 are assembled, and the entire parallel system is operated and the individual reactions are performed. There are a sensoring in the container, a form in which the control is individually performed so as to ensure the quality of the final product, and an operation form in which these are combined.

  In the above examples, the superiority of the present invention in a chemical reaction has been shown, but it goes without saying that the present invention can be used for the purpose of fluid mixing without a chemical reaction. Since the fluid flowing in from the introduction flow path 20 is refined by the action of a strong shearing force by the stirrer 18 and mixed with the fluid in the container, it is also suitable for generating an emulsion.

(Example 3)
In this example, a phase transfer alkylation reaction (chemical formula: see FIG. 20A (a)) was performed using the mixer according to the present invention and the shape of a stirrer as a parameter. The configuration of the mixer is the same as that shown in FIG. 15 (a). The stirrer used in this reaction is of a capsule type (FIG. 4 (a)) and a cross shape (FIG. 4 (e)), and the actual volume of the mixing space of the stirring and mixing chamber using each stirrer is 0.18 ml (capsule type) and 0.08 ml (cross shape). In addition, in order to compare the performance of the mixer alone, the reaction product from the mixer was quenched with an ammonium chloride aqueous solution after the derivation.

  An implementation result is shown to FIG. 20A (b). From this result, it is clear that the mixer according to the invention has a performance superior to that of the conventional microreactor (Y type), and that the cross-shaped stirrer is more optimal than the capsule type in this reaction.

  FIGS. 21 to 26 show still another embodiment of the present invention. A rotor (stirrer) 118 is a rotating body having a shape substantially similar to the internal space of the mixing vessel 116, whereby both A micro gap (micro gap) portion G is formed between the opposing surfaces. In the embodiment described below, the microgap portion G is formed by conical surfaces facing each other, but is not limited to a conical surface having a straight ridgeline, and may be an appropriate rotating body such as a spherical surface (the ridgeline is a circle). In addition, it is possible to adopt a rotating body shape in which the ridge is an appropriate curve (for example, a parabola, an ellipse, etc.).

  FIGS. 21A and 21B show a mixer according to the first embodiment of the present invention, in which a mixing space 116 is formed inside by a base portion 110 and a cover portion 112 covering the base portion 110. The stirrer 118 is provided in the mixing space 114. The mixing space 114 is formed rotationally symmetrical around the vertical axis, and is a substantially conical space in this embodiment. As shown in FIG. 22, the base portion 110 is composed of three plate-like members, that is, a bottom plate 110a, an intermediate plate 110b, and an upper plate 110c. The bottom plate 110a is a flat plate, and the intermediate plate 110b and the upper plate 110c are mixed. It is a ring-shaped member that constitutes a part of the side wall of the container 116. A plurality (six in this example) of radial grooves 120b that open to the inner peripheral surface are formed at equal intervals on the middle plate 110b, and circumferential grooves 120a and 120c are formed on the upper plate 110c and the bottom plate 110a, respectively. ing. These constitute the introduction flow path 120 for the raw material fluid, and the radial grooves 120b are alternately opened upward or downward, so that they communicate alternately with the circumferential grooves 120a and 120c of the upper plate 110c or the bottom plate 110a. is doing. Each of the circumferential grooves 120a and 120c is provided with an opening 124 for the raw material fluid on the outer peripheral surface of the top plate 110c or the bottom plate 110a. Accordingly, the raw material fluids alternately flow into the mixing space 114 and mix as shown in FIG.

  The cover part 112 is integrated with the base part 110 so as to form a conical space inside, and a lead-out flow path 122 is formed at the upper part along the axis. As the material of the base part 110 and the cover part 112, resin, ceramic, stainless steel or the like having resistance to organic chemicals (reagents) is used. Each part constituting the base part 110 and this and the cover part 112 are fixed and integrated with a bolt or the like via bonding or packing. In this embodiment, micro dimensions can be adjusted by inserting a shim 126 between the upper plate 110c and the cover portion 112 and fixing them.

  The cover portion 112 is formed with a temperature control jacket 128 that holds and distributes the heat medium along the side wall of the conical surface, and is connected to the heat medium supply path. The temperature control jacket 128 is preferably formed of a material having corrosion resistance to organic chemicals and a high heat transfer coefficient. For example, there is a method of using glass lining on aluminum. The temperature control of the temperature control jacket 128 is performed by changing the temperature and flow rate of the heat medium passed through the temperature control jacket 128. Thus, the reaction temperature of the fluid (reaction reagent) passing through the microgap part G formed by the cover part 112, the base part 110, and the rotor 118 is controlled via the temperature control jacket 128. In this example, a fluid heat medium is used as the temperature control medium of the temperature control jacket 128. However, a temperature control device such as a Peltier element may be used as a medium and may be electrically performed.

  The rotor 118 (stirring bar) is composed of a conical rotor main body 130 similar to the internal space of the mixing container 116 and a cross-shaped stirring member 132 attached to the lower surface thereof. A convex portion 134 (pivot) is provided. As the material of the rotor main body 130, resin, ceramic, stainless steel, or the like having resistance to organic chemicals (reagents) is used. The stirring member and the rotor 118 are attached by various general joining methods such as screwing, or may be integrated with the stirring member. As the shape of the stirring member 132, various shapes such as a saddle shape and a streamline shape are appropriately selected according to a target chemical reaction. The stirring member 132 preferably has a radially extending portion. The stirrer 132 is made of a metal or magnetic material coated with a resin or ceramic that has corrosion resistance to organic chemicals (reagents). For rotating the rotor 118, means such as a magnetic drive type stirrer (magnet stirrer) shown in FIG. 10 is appropriately used.

  The convex portion 134 is inserted into a concave portion 136 (pivot receiving portion) provided at the center of the upper surface of the bottom plate 110a, and prevents the rotation shaft from swinging. Since the opposing surface of the convex part 134 and the concave part 136 becomes a bearing surface, as shown in FIG. 23, it is preferable to provide a groove 138 (groove) for reducing / relaxing the sliding friction therebetween. As shown in this figure, by adopting a spiral form (direction from the circumferential side toward the central axis) as the groove 138, a high pressure region is generated at the center of the bottom surface with the rotation of the rotor 118, The sliding friction can be further reduced. In this embodiment, in order to stabilize the rotation of the rotor 118, a magnet stabilizer 142 constituted by a permanent magnet 140 is provided at a corresponding portion between the top of the rotor 118 and the cover portion 112. This prevents the top from swinging and reduces the load between the convex portion 134 and the concave portion 136 by the attraction by the permanent magnet 140.

  The width of the micro gap G between the rotor body 130 and the side wall of the mixing vessel 116 is preferably set to a predetermined value for temperature control or the like for accurately performing mixing and subsequent reaction. This can be easily adjusted, for example, from 10 μm to 500 μm by changing the thickness of the shim 126 installed between the cover part 112 and the base part 110.

In addition, the gap between the bottom plate 110a and the bottom surface of the rotor 118 (the lower end of the stirring member 132) is preferably set to a predetermined value in order to sufficiently perform the stirring action. This can be adjusted by the height Hp at which the convex portion 134 protrudes from the bottom surface of the rotor 118 and the depth Hb of the concave portion 136 of the bottom plate 110a. Here, Hp-Hb <1 mm is desirable, more desirably Hp-Hb <0.5 mm, and even more desirably Hp-Hb <0.2 mm.
In addition, at the position of the stirring member 132, the difference between the outer diameter of the rotor 118 (the rotation diameter of the stirring member 132) with respect to the inner diameter of the mixing space 114, that is, the radial gap hr is different for each of the introduced fluids. In order to effectively apply a shearing force by rotation and promote mixing, it is desirable that hr <1.0 mm, more desirably hr <0.5 mm, and even more desirably hr <0.2 mm.

  In the mixer having the above-described configuration, when each raw material fluid is supplied from the introduction port 124, each raw material fluid passes through a flow passage formed in the intermediate plate 110b, and from a radial flow passage formed alternately in the circumferential direction. It is introduced into the mixing space 114. The raw material fluid is stirred and mixed by a strong shearing force generated by the stirring member 132 of the rotor 118 that is magnetically driven. Immediately thereafter, the stirred and mixed product is formed downstream and flows into the microgap part G, and is subjected to precise reaction temperature control using a large specific interface area by the temperature control jacket 128, and further, rapid by molecular diffusion. Mixing is performed, and reaction and mixing proceed. The mixed or reaction product is led out from a lead-out flow path 122 formed in the cover part 112. By the above operation, the target chemical reaction (mixing) is achieved quickly and with high yield.

The reaction temperature control performed here is the product of the target chemical reaction by monitoring the analysis results of the analyzer or the like installed in the downstream of the mixer or the reactor according to the present invention. In order to maximize the yield of the following, the following method is used.
(a) Manually adjust the electrical signal to the temperature control jacket 128. However, in this case, a “relationship diagram between the input electric signal and the temperature of the temperature-adjusting jacket contact surface” is experimentally obtained in advance.
(b) The monitoring result (electrical signal) of the analyzer is input to the temperature control jacket controller, and the controller uses the PID and other control laws to control the temperature so that the yield is maximized. A feedback system that calculates (electric signal) and outputs an input signal (electric signal) to the temperature control jacket is configured.

  FIG. 24 is a modification of the embodiment of FIG. 21, and the basic configuration is the same as described above. In this embodiment, the width of the downstream portion of the microgap part G is set so as to gradually increase toward the downstream side. Thereby, even if precipitates, such as a crystal | crystallization, generate | occur | produce with progress of reaction, obstruction | occlusion of the micro gap part G by a precipitate can be avoided. In other words, a device capable of avoiding the blockage can be configured by appropriately combining the micro space and the downstream macro space. In the case of this example, the micro gap portion G can be varied between 10 μm and 500 μm by adjusting the shim 126 at a pitch of 10 μm or more, desirably 5 μm or more, more preferably 1 μm or more, and the expanded gap has a tube diameter of 8 mm. The lead-out flow path 122 communicates.

In the mixer or reactor of this embodiment, for example, in the reaction that does not generate precipitates, the gap of the microgap part G is set to a minimum of 10 μm. This maximizes mixing by molecular diffusion in the micro space. On the other hand, in the reaction of the precipitation system that generates precipitates, the width of the microgap portion G is arbitrarily changed depending on the size of the precipitates.
In addition, pressure sensors are installed upstream and downstream of the mixer or reactor according to the present invention to monitor the upstream and downstream pressures, and the pressure loss ΔP (ΔP = | upstream pressure Pu in the mixer or reactor according to the present invention). -Changes in the downstream pressure Pd |) may be monitored. Here, when a pressure loss ΔP exceeding a specified value occurs during the chemical reaction, the interval of the micro gap is increased by the pitch until it falls within the specified value. Thereby, also in precipitation system reaction, the clearance of the micro gap part G can be made small to the limit of obstruction | occlusion, and it becomes possible to promote mixing by molecular diffusion as much as possible.

FIG. 25 is a further modification of the embodiment of FIG. In this embodiment, the diameter of the rotor 118 and the mixing container 116 is increased toward the downstream side, that is, toward the outlet flow path 122 side. The rotor 118 is not conical, but has a truncated cone shape with a small diameter surface facing down. Therefore, the microgap part G is formed not only between the side wall and the conical surface, but also between the upper surface of the truncated cone and the top plate 144 of the mixing container 116, thereby constructing a longer minute gap channel. Yes.
In this example, as shown in FIG. 26, a blade 146 for generating a pumping action is provided on the surface of the side surface of the rotor 118 in contact with the microgap part G. The blades 146 are configured by forming radial, spiral, or curved protrusions or grooves on the outer peripheral surface of the rotor 118.

  With this configuration, for example, the required discharge performance of an apparatus (for example, a pump) for pumping the raw material fluid can be reduced, or an external apparatus can be omitted by pumping by itself. In order to maintain the characteristics of the micro space, the height (depth) of the blade 146 or the groove is preferably 10 μm to 500 μm, but can be appropriately changed according to the required pressure rise and flow rate. .

  In the above description, the rotor 118 and the mixing container 116 have a conical shape or a truncated cone shape. However, the shape is not limited to these shapes. For example, it may be a simple cylindrical shape or a more complicated shape, for example, a shape in which the diameter of the rotor 118 changes so as to both expand and contract, or a ridgeline in the cross section is a curved line. Various shapes can be used according to the purpose.

  FIG. 27 shows a mixer according to still another embodiment of the present invention. In this embodiment, a recess that constitutes the mixing space 154 is formed on the base portion 152 side of the mixing container 150, and the introduction flow path 156 includes the vertical flow path 160 that descends from the joint 158 on the upper surface of the base section 152. , And a horizontal flow path 164 constituted by a groove formed in the joint surface between the base portion 152 and the cover portion 162. As shown in FIG. 5A, the outlet flow channel 166 is led out in the lateral direction from a pressing portion 162a installed on the cover portion 162. As shown in FIG. 5B, coils 168 are equally arranged on the same circumference on the upper surface of the base portion 152 and the lower surface of the cover portion 162, and an excitation current is input from the controller 169 to the coil 168. The magnets are sequentially magnetized with a polarity, whereby the rotor 170 is rotated. If the upper and lower coils 168 are always excited so as to have the same polarity with respect to the rotor 170, the rotor 170 can be automatically levitated in the mixing space 154.

  Further, temperature adjusting means 171 is provided on the lower surface of the base portion 152. Thus, for example, the temperature sensor 172 provided in the introduction flow path 156 and the controller 173 that feedback-controls the operation of the temperature adjusting means 171 according to a control law such as so-called PID control based on the output of the temperature sensor 172 via the base portion 152. Thus, the temperature of the fluid in the introduction channel 156 and the mixing space 154 can be controlled. As the temperature adjusting means 171, various types such as an electric plate type heater, a Peltier element, or a heat transfer block (plate) for adjusting the temperature of the temperature adjusted body by passing a heating or cooling medium are used. Note that the temperature adjusting means 171 may be installed in another part of the mixer or reactor. In addition, when using the heat transfer block, an electric valve or the like for adjusting the flow rate of the heating or cooling medium is installed at the front stage or the rear stage of the heat transfer block, and an electric signal (current) for adjusting the opening degree of the electric valve. (Or voltage) from the controller 173.

  As shown in FIG. 27 (c), the introduction flow path 156 (horizontal flow path 164) extends from the lower end of the vertical flow path 160 toward the center in the radial direction, and then branches into two so as to extend approximately in the circumferential direction. It extends about 80 degrees and further obliquely toward the center, and opens into the mixing space 154 at 90 degrees from the radial flow path. That is, the flow paths for supplying the reagent A and the reagent B open to the mixing space 154 at positions close to each other and at an angle at which the jet flow collides. Therefore, since the reagent A and the reagent B collide immediately after entering the mixing space 154 and are further stirred by the rotor 170, there is no density unevenness in the mixing space 154 as shown in FIG. Reaction under a mixing ratio becomes possible. Further, in this embodiment, since there is almost no halfway mixed state, the risk of explosion is extremely low even in a high-speed reaction such as a so-called explosive reaction.

The mixer of this embodiment is useful for a so-called diffusion-controlled reaction in which it is difficult to efficiently obtain a target product by a conventional batch method. A diffusion-controlled reaction is a reaction with a high molecular diffusion rate, for example,
A + B → C + D (A, B: Reagent C: Target product D: By-product)
For example, in the case of diffusion-controlled reaction, the target product C changes to the by-product D continuously and rapidly by molecular diffusion. At this time, in the conventional method (FIGS. 31 and 32), since the reaction volume in the reactor is large, the residence time becomes long, and it is difficult to stop the reaction at the stage of the target product C. However, by adopting the flow path configuration as shown in FIG. 27 (c), the reagents A and B are led to the mixing space 154 of the minute reaction volume without premixing, and are quickly forced in the minute reaction volume. By mixing, it was possible to suppress the generation of by-products and obtain the target product in high yield.

  FIG. 28 shows a mixer according to an embodiment obtained by further developing the embodiment shown in FIG. In this embodiment, as shown in FIG. 5A, the base portion 152a is composed of two base portions 174a and 174b. An annular flow path 176a of the first introduction flow path 156a is formed on the upper surface of the lower base portion 174a as shown in the same figure (b), and as shown in FIG. On the lower surface of the base plate 174b, an annular channel 176b of the second introduction channel 156b is formed at a position not overlapping the annular channel 176a of the first introduction channel 156a, and the first introduction flow Through holes 178 arranged in the circumferential direction and the like are formed at positions corresponding to the passages 156a and the annular passages 176a and 176b of the second introduction passage 156b. Then, on the lower surface of the cover portion 162, as shown in FIG. 4D, a mixing space is formed with a pair of adjacent through holes 178 from the first introduction channel 156a and the second introduction channel 156b. A V-shaped liquid introduction flow path 179 that opens at the same position of 154 is formed. The base plates 174a and 174b and the cover plate 162 and the base plates 174a and 174b are joined together by bonding or screwing via packing.

  With such a configuration, the introduction flow path 156 that is open only at two places in FIG. 27 can be opened at more places. Therefore, the effect of suppressing uniform explosion and reaction in the mixing space 154, which is the effect of the embodiment of FIG. 27, and the like can be obtained more remarkably.

  FIG. 29 shows a mixer according to still another embodiment of the present invention, in which the introduction channel 156a and the second introduction channel 156b are joined before entering the mixing space 154 and premixed. It is. The example of FIG. 29A is a modification of the shape of the horizontal flow path 164 of the cover portion 162 of FIG. 27C, and the branched introduction flow paths 156a and 156b respectively extend 90 degrees in the circumferential direction. The premixing flow path 180a that merges and then extends in the radial direction toward the mixing space 154 is formed. That is, mixing of the two reagents A and B is started in the pre-mixing flow path 180a in the previous stage that enters the mixing space 154. This ensures that the mixing reagent is uniformized at the time of introduction into the mixing space 154. This embodiment is preferably used for reactions that do not cause adverse effects due to premixing.

  In the example of FIG. 29 (b), the shape of the confluence is not a T-junction, but a Y-junction, whereby the premixing channel 180b is set short. By changing the angle of the oblique flow path, the length of the premix flow path 180b can be changed. The length may be set appropriately according to the reaction.

  In the example of FIG. 29 (c), the inclined flow path 182 reaching the premixing flow path 180c is branched to perform merging in multiple stages. Thereby, the reagent introduced into the mixing space 154 is multi-layered, and each fluid layer becomes thin. Therefore, the intermolecular distance between the reagents is also reduced, so that mixing is promoted by the effect of improving the mixing efficiency by molecular diffusion.

  Further, FIG. 29D is a view corresponding to the drawing of the cover portion 162 in FIG. 28D, and a Y-shaped premixing flow path 180d is provided at the tip of the liquid introduction flow path 179, so It is a mixed form. As a result, a large number of introduction flow paths 156a and 156b having a premixing flow path 180d are opened in the mixing space 154. The form of the introduction channel in each embodiment of FIG. 29 may be appropriately selected according to the type of reaction and the like.

In each embodiment of FIG. 29, the cross-sectional area of each introduction channel 156 is 1 mm ² or less, preferably 0.25 mm ² or less, more preferably 0.01 mm ² or less. In addition, the cross-sectional dimensions of the introduction channels 156, 156a, and 156b may be such that W ≦ H, where W is the width and H is the depth, as shown in FIGS. 29 (e) and 29 (f). desirable. Moreover, the cross-sectional shape of the introduction flow paths 156, 156a, and 156b is selected every time according to the target chemical reaction such as a rectangular shape or a semicircular shape. Although not shown in FIG. 29, it is particularly effective to use the temperature adjusting means 171, the temperature sensor 172, and the temperature controller 173 as shown in FIG. This is because the temperature can be controlled more precisely in the fine channel.

  By miniaturizing the introduction flow paths 156, 156a, and 156b in this manner, diffusion mixing using molecular diffusion can be performed in the process up to the mixing space 156, and the mixing efficiency can be improved. Therefore, high-efficiency mixing can be achieved by utilizing a synergistic effect in which both mixing promotion by molecular diffusion by miniaturization of the introduction flow paths 156, 156a, and 156b and mixing promotion by stirring in the micro reaction chamber are used in combination. Needless to say, by reducing the cross-sectional area of the flow path from the mixing space 154 to the beam outlet, molecular diffusion between the mixed reagents is promoted, and the mixing efficiency (yield) is improved.

  Thus, for example, the mixer of this embodiment is useful in reaction-limited chemical reactions. The reaction-controlled reaction usually does not proceed in the state where the reagent is mixed in the container, and conventionally, forced stirring for a long time has been required to obtain the target product in a high yield. On the other hand, in each embodiment of FIG. 29, a high yield target product can be obtained in a short time by mixing by molecular diffusion in the micro space of the premix flow channels 180a to 180d and forced mixing in the micro reaction chamber. It became possible to get.

BRIEF DESCRIPTION OF THE DRAWINGS It is the (a) external appearance perspective view and (b) sectional drawing which show the mixer of embodiment of this invention. It is the schematic which shows the effect | action of the mixer of FIG. 1, (a) Front sectional drawing, (b) Plane sectional drawing. It is a plane sectional view showing the modification of the mixer of Drawing 1. (A) thru | or (f) is a figure which shows the various modifications of a stirring element. (A) And (b) is a figure which shows the modification of the mixer of embodiment of FIG. (A) thru | or (d) is a figure which shows the various modifications of the base part 152a. (A) thru | or (d) is a figure which shows the various modifications of the cover part 162. FIG. It is a figure which shows the other modification of the cover part 162. FIG. (A) thru | or (d) is a figure which shows the various modifications of the base part 152a. (A) And (b) is a figure which shows the mixer of other embodiment. (A) thru | or (c) is a figure which shows the mixer of other embodiment. (A) And (b) is a figure which shows the mixer of other embodiment. It is a figure which shows the mixer of other embodiment. It is a figure which shows the mixer of other embodiment. (A) And (b) is a figure explaining the 1st Example by the mixer of embodiment of this invention. It is a graph which shows the result of the Example demonstrated in FIG. 15, (a) is a time-yield figure which shows an example of the result of reaction, (b) is a product flow rate-yield figure. In the Example demonstrated in FIG. 15, it is a graph which shows the relationship between the ratio of the flow rate of the introduction fluid, the peripheral speed of a stirrer, and the yield. (A) And (b) is a figure explaining other embodiment of the mixer of embodiment of this invention. It is a graph which shows the result of 2nd Example demonstrated in FIG. It is a figure explaining the mixer of other embodiment of this invention. It is a figure explaining the 3rd Example of this invention. (A) And (b) is a figure which shows the mixer of other embodiment of this invention. (A) thru | or (c) is a figure which shows the structure of the base part 152a. It is a figure which shows other embodiment of a stirrer. It is a figure which shows the mixer of other embodiment. It is a figure which shows the mixer of other embodiment. It is a figure which shows the structure of the stirrer of embodiment described in FIG. It is a figure which shows the mixer of other embodiment, (a) is an external view, (b) is sectional drawing, (c) is c arrow line view of (b). It is a figure which shows the mixer of other embodiment, (a) is sectional drawing, (b)-(d) is a dd arrow directional view of (a). It is a figure which shows the introduction flow path 156 of the mixer of other embodiment. It is a figure which shows the conventional batch type mixer. It is a figure which shows the conventional continuous mixer. It is a figure which shows the other example of the conventional continuous mixer. It is a figure which shows the effect | action of the conventional continuous mixer. It is a graph which shows the change of the energy in a chemical reaction. It is a figure which shows the state of the flow at the time of putting an obstruction in a flow field.

Explanation of symbols

10, 110, 152 Base part 12, 112, 162 Cover part 14, 114, 154 Mixing space 16, 116 Mixer 18, 118, 170 Stirrer 20, 120, 156 Introducing flow path 22, 122, 166 Deriving flow path 28 Drive mechanism 38, 169, 173 Controller 40 Radial part 52 Heater 53 Temperature sensor 54 Heat medium flow path 56 Analyzer 171 Temperature control means 180a-180d Premix flow path

Claims (9)

A mixer used in a reaction system that performs continuous processing,
A mixing space formed rotationally symmetric about a vertical axis ;
A stirrer having a plurality of radial portions disposed in the mixing space so as to be rotatable around the axis of the mixing space and extending from the axis toward the peripheral edge ;
A drive mechanism for driving the stirring bar;
At least two or more introduction channels that open at different positions on the outer peripheral surface of the mixing space, each of which introduces different fluids into the mixing space; and
A mixer having a lead-out channel that opens to an upper surface of the mixing space . 2. The mixer according to claim 1, wherein the outlet channel is formed by a plurality of channels that open to a radially intermediate portion of the upper surface . The mixer according to claim 1 or 2, wherein the outlet channel has a narrow channel cross-sectional area in a downstream portion . The mixer according to any one of claims 1 to 3, wherein at least two or more introduction flow paths for allowing the different fluids to flow into the mixing space are opened at positions close to each other . 5. The mixer according to claim 4 , wherein a plurality of sets of at least two or more introduction flow paths opened at positions close to each other are arranged at equal intervals on the outer peripheral surface .   6. A reaction apparatus comprising: the mixer according to claim 1; a supply source for supplying a raw material fluid to the mixer; and a recovery container for recovering a reaction product in the mixer. .   The reaction apparatus according to claim 6, further comprising a control device that controls a stirring speed of the stirring bar in the mixer.   The reaction apparatus according to claim 6, further comprising a control device that controls a temperature in the mixer. The reaction apparatus according to claim 6, further comprising an analysis apparatus for analyzing the reaction product.

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