JP2024007436A - Liquid dispersion device and liquid dispersion apparatus using the same - Google Patents

Abstract

To provide a liquid dispersion device and a liquid dispersion apparatus using the liquid dispersion device capable of reducing energy required for various operations such as distillation, mixing, and agitation of processing liquid.SOLUTION: A liquid dispersion device of the present invention includes at least one liquid flow member that can be mounted to a rotation shaft. The liquid flow member includes: at least one cylindrical liquid absorption portion extending along the rotation shaft and including a liquid absorption port in a lower end thereof; at least one discharge portion having one end communicating with an upper end of the liquid absorption portion, including a discharge port in the other end, extending while being inclined with respect to the liquid absorption portion; and an agitation blade extending along a rotation radial direction of the rotation shaft and capable of rotating along with rotation of the rotation shaft.SELECTED DRAWING: Figure 1

Description

The present invention relates to a liquid dispersion device and a liquid dispersion apparatus using the same.

In recent years, oils and fats have attracted attention as raw materials for conversion into fuels and chemicals. In particular, active attempts are being made to synthesize long-chain fatty acid esters from animal oils and/or vegetable oils through chemical reactions and to utilize this as biodiesel fuel that can replace light oil.

On the other hand, techniques for synthesizing various compounds through reactions such as asymmetric synthesis reactions in reaction systems of two or more liquid phases using phase transfer catalysts or slurry catalysts are attracting attention. Many of these reactions are promoted by vigorously stirring the reaction system.

Two-liquid phase reactions may be employed, for example, in the production of biodiesel fuel. For example, a transesterification reaction may be carried out by an enzyme-catalyzed method using an enzyme such as lipase as a catalyst. In such a transesterification reaction using an enzyme contact method, an enzyme (immobilized enzyme) immobilized on a carrier such as a liquid enzyme or an ion exchange resin is used as the enzyme. Liquid enzymes are less expensive than immobilized enzymes because they are made from concentrated and purified culture fluids. Furthermore, since the enzyme remains in the glycerin water, which is a by-product produced by the transesterification reaction, this can be used in the next batch of reactions. This makes it possible to repeatedly use the liquid enzyme and reduce the cost required for producing biodiesel fuel (Non-Patent Document 1).

In the transesterification reaction using a liquid enzyme, a two-phase system of an oil layer and an aqueous layer is used, and an emulsion is formed by, for example, stirring the reactants at high speed. Here, high-speed stirring of the reactants requires a considerable energy load to the stirrer. On the other hand, in order to increase productivity as an industrial product, it is desired to reduce the energy required for operations such as stirring of reactants. However, this results in a contradiction in that the ability to form an emulsion using the above-mentioned reactants is reduced and the transesterification reaction cannot be carried out effectively.

Alternatively, there is also a method of using an alkaline catalyst instead of the above enzyme. In this case as well, a two-liquid phase reaction system is employed, and the reaction requires vigorous stirring.

M. Nordblad et al., Biotechnology and Bioengineering, 2014, Vol.11, No.12, pp.2446-2453

The present invention aims to solve the above problems, and its purpose is to provide a liquid dispersion device and a liquid dispersion device that can reduce the energy required for various operations such as distillation, mixing, and stirring of processing liquids. An object of the present invention is to provide a liquid dispersion device using the same.

The present invention is a liquid dispersion device comprising at least one liquid flow member attachable to a rotating shaft,
The liquid flow member is
at least one cylindrical liquid suction portion extending along the rotation axis and having a liquid suction port at the lower end;
at least one discharge portion, one end communicating with the upper end of the liquid suction portion, the other end having a discharge port, and extending obliquely with respect to the liquid suction portion;
The liquid dispersion device includes a stirring blade that extends along the rotation radius direction of the rotating shaft and is rotatable as the rotating shaft rotates.

In one embodiment, the liquid suction portion of the liquid flow member is a linear tube extending substantially parallel to the axial direction of the rotating shaft.

In one embodiment, the liquid dispersion device of the present invention includes a plurality of the liquid-absorbing portions, and all of the lower ends of the liquid-absorbing portions are provided at the same position with respect to the rotation axis.

In one embodiment, the liquid suction part is constituted by one tube and comprises at least two of the said discharge parts at the upper end of the liquid suction part.

In one embodiment, the stirring blade is fixed to an outer wall of the liquid suction portion.

The present invention also provides a liquid dispersion apparatus comprising a processing tank for accommodating a processing liquid, the above-mentioned liquid dispersion device provided in the processing tank, and a rotating shaft to which the liquid dispersion device is attached. .

In one embodiment, the treatment liquid is comprised of an oil phase and an aqueous phase.

According to the liquid dispersion device of the present invention, the scooped-up treatment liquid can be moved above the liquid level and dispersed. Thereby, the vertical movement and circulation of the processing liquid placed around the liquid dispersion device can be promoted. The liquid dispersion device of the present invention can be incorporated as a part of a liquid dispersion apparatus, thereby reducing the energy required for physical operations such as distillation, mixing, stirring, etc. of the treatment liquid. For example, when the liquid dispersion apparatus of the present invention accommodates a reaction liquid consisting of two phases, an oil phase and an aqueous phase, as a treatment liquid, the efficiency from the start of the reaction to the end of the reaction can be improved without using extra power. Emulsification of the reaction solution and/or extraction of by-products (eg, glycerin) with water can be promoted.

1 is a schematic diagram showing an example of a liquid dispersion device of the present invention. FIG. 2 is a perspective view schematically illustrating an example of a liquid flowing member that constitutes the liquid dispersion device shown in FIG. 1. FIG. (a) is a cross-sectional view of the liquid dispersion device shown in FIG. 1 in the AA direction, (b) is a cross-sectional view of the liquid dispersion device shown in FIG. 1 in the BB direction, and (c) is a cross-sectional view of the liquid dispersion device shown in FIG. FIG. 2 is a cross-sectional view of the liquid dispersion device shown in FIG. It is a schematic diagram showing other examples of the liquid dispersion device of the present invention provided with various forms of stirring blades. It is a schematic diagram showing another example of the liquid dispersion device of the present invention. FIG. 2 is a schematic diagram showing an example of a dispersion apparatus (reaction apparatus) in which the dispersion device shown in FIG. 1 is incorporated. FIG. 6 is a schematic diagram showing an example of a dispersion apparatus (reaction apparatus) in which the dispersion device shown in FIG. 5 is incorporated. FIG. 2 is a schematic diagram of a test device (C1) produced in Comparative Example 1. It is a perspective view of the baffle plate arrange|positioned in the test apparatus (C1) shown in FIG. FIG. 2 is a schematic diagram of a test device (C2) produced in Comparative Example 2. FIG. 2 is a schematic diagram of the test device (E1) produced in Example 1. (a) Transesterification reactions (Example 2 and Comparative Examples 3 and 4) were performed using the test apparatuses (C1), (C2), and (E1) prepared in Comparative Examples 1 and 2 and Example 1, respectively. 2 is a graph showing the amount of methyl ester produced versus the reaction time shown in (a), and (b) is the logarithm value (ln(BG ₀ /BG)).

The invention will now be described with reference to the accompanying drawings. It should be noted that structures that are given the same reference numerals in all the drawings below are the same as those shown in other drawings.

(dispersion device)
FIG. 1 is a schematic diagram showing an example of a liquid dispersion device of the present invention.

A liquid dispersion device 100 of the present invention shown in FIG. 1 includes two cylindrical liquid flow members 120 and 120' that can be attached to a rotating shaft 121. Furthermore, in FIG. 1, one rotating shaft 121 is arranged along the vertical direction. Although two liquid flow members are shown in FIG. 1, the present invention is not limited to this, and it is sufficient to include at least one cylindrical liquid flow member.

The liquid flowing member 120, 120' has a cylindrical liquid suction part 122, 122', one end communicates with the upper end of the liquid suction part 122, 122', and the other end has a discharge port 125, 125'. It is composed of parts 123 and 123'.

The liquid flow members 120, 120' also include stirring blades 128, 128' that extend along the rotational radius direction of the rotating shaft 121 and are rotatable as the rotating shaft 121 rotates.

FIG. 2 is a perspective view schematically showing the liquid flow member 120 shown in FIG. 1. FIG. On the other hand, the liquid dispersing member 120' shown in FIG. 1 is the same as the liquid flowing member 120, and therefore will be omitted.

The liquid suction portion 122 constituting the liquid dispersion member 120 is provided with a liquid suction port 124 whose lower end is open. In FIG. 2, the liquid suction portion 122 is constituted by a tube whose outer diameter and inner diameter extend substantially in a straight line from the upper end toward the liquid suction port 124 at the lower end.

The cross-sectional shape of the liquid absorbing portion 122 is not particularly limited as long as it is cylindrical. Examples of cross-sectional shapes that may constitute the liquid-absorbing portion 122 include circular, oval, triangular, rectangular, and other polygonal shapes. The liquid dispersion device of the present invention may be composed of a plurality of liquid absorption parts having mutually different cross-sectional shapes. In the present invention, it is preferable that the liquid absorbing portion 122 has a circular or elliptical cross-sectional shape in order to reduce resistance during movement within a processing liquid, which will be described later. Alternatively, instead of what is shown in FIG. 2, the liquid suction portion may be composed of a tube twisted around the rotating shaft 121.

Although the size of the liquid absorbing portion 122 is not particularly limited, for example, when the liquid absorbing portion 122 has a circular cross-sectional shape, its outer diameter is, for example, 5 mm to 100 mm.

The shape of the liquid suction port 124 is also not particularly limited. The cross-sectional shape of the liquid absorbing portion 122 may be the same or different. Examples of the shape of the liquid suction port 124 include a circle, an ellipse, a triangle, a rectangle, and other polygons. Note that the liquid suction port 124 may be cut obliquely to the axis of the liquid suction portion 122 to expand the opening area so that more processing liquid can be introduced into the liquid suction portion 122. good.

The straight line structure (length) of the liquid absorbing portion 122 is approximately parallel to the rotation axis 121 shown in FIG. It is designed accordingly. From the lower end (liquid suction port 124) of the liquid suction part 122 constituting this linear structure, to the lowermost part of the joint between the liquid suction part 122 and the discharge part 123 (the bending point P of the liquid dispersion member 120). ) is _not particularly limited. For example, the distance _t1 can be adjusted as appropriate by those skilled in the art depending on the capacity of the processing tank 110 used.

The discharge portion 123 has one end communicating with the upper end of the liquid suction portion 122 and is provided at an angle with respect to the liquid suction portion 122 . Further, the other end of the discharge portion 123 is provided with a discharge port 125 for discharging the processing liquid that has passed through the cylinder of the discharge portion 123 to the outside. Further, the discharge portion 123 shown in FIG. 2 has a cylindrical shape.

In the present invention, the inclination angle θ of the discharge portion 123 with respect to the axial direction of the liquid suction portion 122 can be set to any angle by those skilled in the art, but is, for example, 10° to 89°, preferably 15° to 45°. When the inclination angle θ is less than 10°, it is necessary to rotate the liquid dispersing member 120 at a higher speed in order for the processing liquid sucked up from the liquid suction portion 122 to pass through the discharge portion 123 and be discharged from the discharge port 125. However, the resulting dispersion device may require a lot of energy to operate. If the inclination angle θ exceeds 89°, the discharge portion 123 may exceed the level of the processing liquid and immerse into the interior, and the function of the liquid dispersion may not be properly performed. Note that the inclination angle θ of the discharge portion 123 and the corresponding inclination angle of the discharge portion 123' shown in FIG. 1 may be the same or different.

The shape of the discharge port 125 of the discharge portion 123 is also not particularly limited. The cross-sectional shape of the liquid absorbing portion 122 may be the same or different. Examples of the shape of the discharge port 125 include a circle, an ellipse, a triangle, a rectangle, and other polygons. In the present invention, the inner diameter of the discharge portion 123 may be constant from the side communicating with the liquid suction portion 122 to the discharge port 125, or may be reduced in diameter gradually or in stages.

The length of the discharge portion 123 (for example, the shortest distance from the bending point P of the liquid dispersion member 120 to the discharge port 125) is not particularly limited, and can be set to any length by those skilled in the art.

The stirring blades 128 shown in FIG. 2 are fixed to the outer wall of the liquid suction portion 122. The stirring blade 128 shown in FIG. 2 is composed of a rectangular plate piece having a predetermined thickness, but its shape is not particularly limited. For example, it may be a structure in which a predetermined thin piece is twisted, or a paddle or screw shape having a predetermined shape. Note that when the stirring blades 128 are composed of rectangular plate pieces as shown in FIG. preferable. This is because the rotation of the liquid dispersion member 120 can prompt the stirring blades 128 to move the processing liquid located around the liquid suction port 124 upward, for example. From this point of view, the angle θ ₂ between the stirring blade 128 and the horizontal direction is preferably set to 0° to 90°, more preferably 0° to 60°.

In FIG. 2, the stirring blade 128 is provided between the bottom of the liquid suction portion 123 (liquid suction port 124) and the bending point P, and is arranged, for example, at a predetermined distance _t2 from the bottom. . The distance _t2 is not particularly limited, and an appropriate length can be determined depending on the overall size of the liquid dispersion member 120, the shape and size of the stirring blade 128, the height _t3 and width s of the stirring blade 128, etc. can be selected by a person skilled in the art.

Referring again to FIG. 1, the ends of the liquid suction ports 124, 124' of the liquid suction portions 122, 122' are aligned in a substantially straight line in the horizontal direction. In such a case, the liquid dispersion members 120 and 120' constituting the liquid dispersion device 100 both supply the stored treatment liquid from a portion at approximately the same depth through the liquid suction ports 124 and 124'. can absorb liquid.

In the liquid dispersion device 100 of the present invention, the liquid dispersion members 120, 120' are fixed to, for example, the rotating shaft 121 (for example, around the axis of the rotating shaft 121). Note that it is preferable that the liquid dispersing members 120, 120' be arranged in a dense manner so as to be located as close to the rotating shaft 121 as possible. Since the liquid dispersing members 120, 120' are all densely packed together, the horizontal cross section of the liquid dispersing members 120, 120' with respect to the rotating shaft 121 becomes smaller. As a result, the resistance in the processing liquid when the liquid dispersion members 120, 120' rotate via the rotating shaft 121 can be reduced as much as possible.

(a), (b), and (c) of FIG. 3 are cross-sectional views of the liquid dispersion device of the present invention shown in FIG.

As shown in FIGS. 3A and 3B, in the present invention, the stirring blades 128, 128' extend in a direction substantially perpendicular to the rotational direction of the liquid dispersion members 120, 120'. As a result, in the vicinity of the cross section in the BB direction in FIG. (b)). On the other hand, since the stirring blades 128, 128' are not present in the vicinity of the cross section in the CC direction in FIG. This can be avoided.

In addition, in the present invention, the stirring blades may be attached to various liquid flowing members, for example, as described below.

For example, as shown in FIG. 4(a), the stirring blades 128a ₁ , 128'a ₁ , 128a ₂ , 128'a ₂ are provided separately in the middle and lower stages of the liquid flow members 120 and 120'. Good too. In particular, in (a) of FIG. 4, compared to the stirring blades 128a ₁ , 128'a ₁ provided in the middle stage of the fluid flow members 120, 120', the lower stage (near the bottom) of the flow fluid members 120, 120' The provided stirring blades 128a ₂ and 128'a ₂ are designed to be long. In this case, more effective stirring can be performed in the lower stage of the liquid flow members 120, 120' than in the middle stage by the stirring blades 128a ₂ , 128'a ₂ .

Alternatively, as shown in FIG. 4(b), the stirring blades 128, 128' have discharge ports 125a, 125'a arranged in the horizontal direction, or from 90° downward to 20° upward with respect to the horizontal direction (0°). The liquid flow member 120a, 120'a may be provided in the direction of the angle (ie, −90° to 20°).

Alternatively, as shown in FIG. 4(c), the stirring blade is a thin plate (for example, a disk-shaped plate piece) extending perpendicularly to the axial direction of the rotating shaft 121 in the middle or lower stage of the flowing liquid member 120, 120'. It may have a shape having a plurality of claws 129 provided on the claws 130d and 130d'. The stirring blades 128d, 128'd as shown in FIG. 4(c) enable the surrounding processing liquid to be stirred under shear by the thin plates 130d, 130'd and the plurality of claws 129.

FIG. 5 is a schematic diagram showing another example of the liquid dispersion device of the present invention.

The liquid dispersing device 100e shown in FIG. 5 is composed of one liquid dispersing member 120e.

The liquid dispersion member 120e shown in FIG. 5 includes a liquid absorption portion 122e extending in a straight line along the axial direction of one rotating shaft 121, and two discharge portions 123e and 123'e are inclined at the upper end thereof. It is provided. The inclination angles of the discharge portions 123e and 123'e with respect to the axial direction of the rotating shaft 121 may be the same or different.

One liquid suction port 124e is provided at the lower end of the liquid suction portion, and the shape of the liquid suction port 124e is not particularly limited. Examples of the shape of the liquid suction port 124e include a circle, an ellipse, a triangle, a rectangle, and other polygons. In addition, in the present invention, the inner diameter of the liquid absorbing portion 122 may be constant from the lower end to the upper end, may be reduced in diameter gradually or in stages, or may be expanded in diameter gradually or in stages. It may be something. Further, although the inner diameter of the liquid suction portion 122 is shown to be larger than the inner diameter of the discharge portions 123e and 123'e in FIG. 5, it is not particularly limited to this size. The inner diameter of the liquid suction portion 122 may be smaller than the inner diameter of the discharge portions 123e, 123'e, or the inner diameters of the liquid suction portion 122 and the discharge portions 123e, 123'e may be substantially the same. .

On the other hand, in FIG. 5, the stirring blades 128, 128' are provided at predetermined positions of the liquid suction portion 122 of the liquid flowing member 120e, for example, in the same manner as described above.

In the embodiment shown in FIG. 5, one liquid suction part 122 rotates due to the rotation of the rotating shaft 121, and thus stirring is performed around the rotating liquid suction part 122, compared to, for example, the case shown in FIG. Turbulent flow of the processing liquid caused by blades other than the blades 128, 128' can be reduced. As a result, the processing liquid is sucked through the liquid suction portion 124e while being stirred relatively quietly, and is discharged from the discharge ports 125, 125'e of the discharge portions 123e, 123'e. This makes it possible to mix and/or stir the absorbed processing liquid in a quiet state.

The liquid dispersion member and fixture that constitute the liquid dispersion device of the present invention are both made of a material that has sufficient strength and has appropriate durability against the processing liquid. Materials that can be used to construct the liquid dispersion member and fixture include, but are not necessarily limited to, metals such as iron, stainless steel, Hastelloy, and titanium; polylactic acid, polypropylene, polystyrene, polycarbonate, acrylate resin, and ABS (acrylonitrile-butadiene). -Styrene) resin, epoxy resin, urea resin, Teflon (registered trademark), and other synthetic resins; and combinations thereof; These may be provided with a coating known in the art, such as Teflon (registered trademark), glass lining, or rubber lining, to increase chemical resistance.

(Sprinkling device)
FIG. 6 is a schematic diagram showing an example of a liquid dispersion apparatus in which the liquid dispersion device shown in FIG. 1 is incorporated. In FIG. 6, a case will be described in which the liquid dispersion apparatus 200 is used as a reaction apparatus in which a two-phase reaction liquid composed of an oil phase 116a and an aqueous phase 116b is used as the treatment liquid 116.

The liquid dispersion apparatus 200 of the present invention includes a processing tank 110 for making use of a processing liquid, a liquid dispersion device 100 shown in FIG. Equipped with.

The processing tank 110 is a sealable tank capable of containing and stirring the processing liquid 116, and has, for example, a flat bottom, a round bottom, a conical bottom, or a bottom portion 109 that slopes downward.

The size (capacity) of the treatment tank 110 is appropriately set depending on the purpose of the liquid dispersion device 200 (for example, the type of operation such as reaction or distillation performed using it), the amount of treatment liquid to be processed, etc. For example, but not necessarily limited to, from 0.1 liter to 1,000,000 liter.

In one embodiment, the processing tank 110 also includes a processing liquid inlet 112 and a product outlet 114. The processing liquid supply port 112 is an inlet for newly supplying the processing liquid 116 into the processing tank 110. The processing liquid supply port 112 is provided, for example, above the processing tank 110 (for example, on the top lid). Alternatively, the processing liquid supply port 112 may be provided on the side surface of the processing tank 110. The number of processing liquid supply ports 112 provided in the processing tank 110 is not limited to one. For example, a plurality of processing liquid supply ports may be provided in the processing tank 110.

The product etc. outlet 114 is an outlet for taking out products and concentrates (herein collectively referred to as "products etc.") obtained in the processing tank 110 from the processing tank 110. The product outlet 114 can discharge reaction residues, waste liquid, etc. in addition to the products, and the discharge can be regulated, for example, by opening and closing a valve 115 provided downstream of the product outlet 114. The product outlet 114 is also provided, for example, in communication with the center of the bottom 109 in the processing tank 110.

The upper part of the processing tank 110 may have a structure that can be opened and closed, such as a lid or a maintenance hole. Furthermore, a pressure adjustment port (not shown) may be provided at the top of the processing tank 110 to adjust the pressure inside the processing tank 110. Furthermore, the pressure adjustment port may be connected to, for example, a decompression pump (not shown).

The processing liquid 116 contained in the processing tank 110 is, for example, a liquid such as an aqueous solution or a slurry. When the liquid dispersion device 200 is used, for example, to produce a fatty acid ester by a transesterification reaction described below, the treatment liquid 116 is composed of a two-phase system including, for example, an oil phase 116a and an aqueous phase 116b. and aqueous phase 116b each contain a reactant such as a starting material and a medium such as a solvent.

The processing tank 110 is made of, for example, the same material as the above-mentioned liquid dispersion member. If necessary, the same surface treatment as that for the liquid spray member may be performed.

The rotating shaft 121 is a shaft having a predetermined rigidity, and has, for example, a cylindrical or cylindrical shape. The rotating shaft 121 is normally arranged in the vertical direction within the processing tank 110. The thickness of the rotating shaft 121 is, for example, 8 mm to 200 mm, although it is not necessarily limited. The length of the rotating shaft 121 varies depending on the size of the processing tank 110 used, and an appropriate length can be selected by a person skilled in the art.

One end of the rotating shaft 121 is connected to rotating means such as a motor 140 at the upper part of the processing tank 110. For example, the other end of the rotating shaft 121 is not connected to the bottom 109 of the processing tank 110 and is arranged at a constant distance from the bottom 109 of the processing tank 110. Thereby, the area in which the rotating shaft 121 contacts the reaction liquid 116 can be reduced. Alternatively, the other end of the rotating shaft may be accommodated in a predetermined bearing provided at the bottom 109 of the processing tank.

The rotating shaft 121 is made of, for example, the same material as the liquid dispersion member. If necessary, the same surface treatment as that for the liquid spray member may be performed.

In the embodiment shown in FIG. 6, the liquid dispersion device 100 is fixed directly around the axis of rotation 121. In the embodiment shown in FIG.

According to the liquid dispersion device 200 shown in FIG. 6, by rotating the rotating shaft 121 with the motor 140, the liquid flow members 120, 120' in the liquid dispersion device 100 supply the processing liquid 116 from the liquid suction ports 124, 124'. imbibe (i.e., taken up). The sucked processing liquid moves to the discharge ports 125, 125' through the flow paths in the liquid suction parts 122, 122' and the discharge parts 123, 123' due to the centrifugal force accompanying the rotation of the rotating shaft 121. The liquid is discharged from the discharge ports 125 and 125' into the processing tank 110, specifically above the liquid level 132 of the processing liquid 116 in the processing tank 110. This allows the processing liquid 116 to collide with the inner wall 111 and the liquid surface 132 of the processing tank 110 and to move upward from the bottom 109 of the processing tank 110, so that the processing liquid 116 in the height direction of the processing tank 110 Mixing back (for example, stirring or circulation in the vertical direction) and flowing down after colliding with the inner wall 111 can be promoted. On the other hand, the stirring blades 128, 128' fixed to the outer walls of the liquid suction parts 122, 122' of the liquid flow members 120, 120' can directly stir the inside of the processing liquid 116 by the rotation of the rotating shaft 121. As a result, for example, when a predetermined reaction liquid is used as the treatment liquid, the production of the reaction product performed within the liquid dispersion apparatus 200 can proceed more effectively.

In the liquid dispersion apparatus 200 of the present invention, a predetermined amount of the treatment liquid 116 is stored in the treatment tank 110 in order to efficiently discharge the treatment liquid 116 from the liquid dispersion device 100 by rotating the rotation shaft 121. It is preferable. Specifically, whether the rotating shaft 121 rotates or not, the liquid level 132 of the processing liquid 116 is the same as that between the liquid suction portions 122, 122' and the discharge portions 123, 123' that constitute the liquid dispersion device 100. The joint part, more specifically, from the lower end of the liquid suction part 122 (liquid suction port 124) to the lowest part of the joint part between the liquid suction part 122 and the discharge part 123 (i.e., the part of the liquid dispersion member 120). It is preferable that the processing liquid 116 is contained in the processing tank 110 so as to be located above the bending point P). When the liquid dispersion device 100 and the liquid level 132 of the processing liquid 116 satisfy such a relationship, the processing liquid 116 exists up to a part of the lower end direction of the discharge parts 123, 123' together with the liquid absorption parts 122, 122'. become. In this relationship, when the liquid dispersion device 100 is rotated via the rotation shaft 121, the processing liquid 116 forms a vortex (eddy current) as the liquid dispersion device 100 rotates, and the internal slope of the discharge portions 123, 123' The flow path can be raised to the discharge ports 125, 125' by centrifugal force based on the rotation. Then, the processing liquid 116 that has finally risen can be effectively discharged from the discharge ports 125, 125' to the outside of the liquid dispersion members 120, 120'.

In order for the processing liquid 116 to be effectively discharged from the discharge ports 125, 125' to the outside of the liquid dispersion members 120, 120' in the above, the above-mentioned vortex must be formed as the liquid dispersion device 100 rotates. It is preferable that the liquid level (vortex surface) of the processing liquid 116 is located above the bending point P of the liquid dispersion member 120 even when the liquid dispersion member 120 is in the liquid dispersion member 120 .

In addition, in the liquid dispersion device 100 constituting the liquid dispersion apparatus 200 shown in FIG. 6, an example has been described in which the two liquid dispersion members 120, 120' are arranged symmetrically with respect to the rotation axis 121, but the present invention The number and arrangement of such liquid dispersion members are not particularly limited. The liquid dispersion device may be composed of only one liquid dispersion member, or may be composed of a plurality of (for example, two, three, four, five, six, seven, eight) liquid dispersion members. You can leave it there. When using a plurality of liquid dispersion members, it is preferable that the interval (for example, angle) between each liquid dispersion member is kept substantially constant so that the rotating shaft can rotate smoothly.

In the embodiment shown in FIG. 6, a case has been described in which the aqueous phase 116b is arranged below the oil phase 116a, but the liquid dispersion device of the present invention It is not limited only to placement. For example, in a system in which methanol is added to the water phase, the arrangement of the oil phase and the water phase may be reversed, and the oil phase may be located below the water phase. The liquid dispersion device of the present invention can also be used for a two-phase reaction liquid including an oil phase and a water tank arranged in this manner.

FIG. 7 is a schematic diagram illustrating an example of a dispersion apparatus (reaction apparatus) in which the dispersion device shown in FIG. 5 is incorporated.

In the liquid dispersing device 200e shown in FIG. 7, the liquid suction port 124e of the liquid dispersing member 120e constituting the liquid dispersing device 100e is oriented toward the bottom 109 of the stirring tank 110. In FIG. 7, the liquid suction port 124e of the liquid dispersion member 120e is arranged near the interface between the oil phase 116a and the water phase 116b of the processing liquid 116, but the arrangement is not particularly limited to this. When the treatment liquid 116 is in a stationary state, the liquid suction port 124e of the liquid dispersion member 120e may be placed on either the oil phase 116a side or the aqueous phase 116b side.

In such a configuration, when the rotating shaft 121 is rotated through the motor 140, the oil phase 116a and the water phase 116b are mixed and absorbed from the liquid suction port 124e of the liquid dispersion member 120e due to the rotation of the liquid dispersion device 100e. . The processing liquid 116 sucked from the liquid suction port 124e can be discharged from the discharge ports 125e, 125'e of the liquid dispersion member 120e toward the liquid surface 132 or the inner wall 111 of the processing tank 110, respectively, for example. . On the other hand, the stirring blades 128, 128' fixed to the outer walls of the liquid suction parts 122, 122' of the liquid flow members 120, 120' can directly stir the inside of the processing liquid 116 by the rotation of the rotating shaft 121.

For example, when the liquid dispersion device of the present invention is used as a reaction device, the device is useful in the production of various reaction products in which stirring of the reaction solution (reactant) is desired. In particular, when using a conventional stirrer in a two-phase system (heterogeneous reaction system) such as an oil phase and an aqueous phase, or a reaction system consisting of multi-phase (e.g. two-phase) chemical substances. The reaction product can be obtained more effectively than the conventional method. For example, two-phase systems include transesterification reactions to produce fatty acid esters.

In the present invention, the liquid-absorbing portion of the liquid-sprinkling member constituting the liquid-sprinkling device extends in the vertical direction, and the liquid-absorbing portion can be rotated with a relatively small rotation radius by the attached rotating shaft. On the other hand, since the discharge portion is inclined at a predetermined angle, the processing liquid can pass through the internal flow path and be easily discharged to the outside by utilizing the centrifugal force accompanying the rotation. Furthermore, since the stirring blade is rotatable with the rotation of the rotating shaft, it is possible to directly stir the processing liquid present around the liquid dispersion member. As a result, the liquid dispersion device of the present invention can rotate within the processing liquid with less energy, and can efficiently discharge the processing liquid, that is, perform various operations such as mixing, stirring, reaction, evaporation, and distillation of the processing liquid. can.

(Method for producing reaction product)
Next, a method for producing a predetermined reaction product using a dispersion apparatus incorporating the dispersion device of the present invention will be described.

In the manufacturing method of the present invention, stirring is performed by circulating the treatment liquid within a dispersion apparatus incorporating the above-mentioned dispersion device. Here, in this specification, the term "agitation by circulation" refers to agitation by applying rotation in the horizontal direction to a target liquid (for example, a reaction liquid), and agitation by applying rotation in the horizontal direction to a target liquid (for example, a reaction liquid), as well as agitation when using the above-mentioned liquid dispersion device. This includes both vertical movement of the liquid and mixing of the entire liquid through circulation.

The processing liquid used in the present invention contains an inorganic or organic liquid medium, and generally allows a chemical reaction to proceed and be controlled through stirring with a stirrer or the like. For example, the processing liquid is a heterogeneous reaction liquid. For example, a reaction solution composed of an oil phase and an aqueous phase is useful in that emulsification of the reaction solution can be improved and promoted through stirring by the above-mentioned circulation.

When the treatment liquid is a heterogeneous reaction liquid, the treatment liquid contains, for example, raw material fats and oils, a liquid enzyme, an alcohol having 1 to 8 carbon atoms, and water.

The raw material fat is a fat that can be used, for example, in the production of fatty acid ester for biodiesel fuel. The raw material fat may be either a previously refined fat or oil or an unrefined fat containing impurities. Examples of feedstock fats and oils include edible fats and their waste edible fats, crude oil, and other waste-based fats and oils, and combinations thereof. Examples of edible fats and fats and their waste edible fats include vegetable oils, animal fats, fish oils, microbially produced fats and oils, these waste oils, and mixtures thereof (mixed fats and oils). Examples of vegetable oils include, but are not limited to, soybean oil, rapeseed oil, palm oil, and olive oil. Examples of animal fats and oils include, but are not necessarily limited to, beef tallow, pork fat, chicken fat, whale oil, and mutton fat. Fish oils include, but are not necessarily limited to, sardine oil, tuna oil, and squid oil. Examples of microorganism-produced fats and oils include, but are not necessarily limited to, fats and oils produced by microorganisms such as Mortierella or Schizochytrium.

Crude oil is an unrefined or unprocessed fat obtained, for example, from a conventional edible oil extraction process, free of gummy impurities such as phospholipids and/or proteins, free fatty acids, pigments, trace metals and other chars. It may contain hydrogen-based oil-soluble impurities, as well as combinations thereof. The content of the impurity contained in crude oil is not particularly limited.

Examples of waste oils and fats include soapstock, heat-treated oil, press oil, and rolling oil obtained by refining crude oil produced in the process of producing food oils and fats in the presence of an alkali, and combinations thereof. .

The raw material oil or fat may contain any amount of water within a range that does not impede the inherent properties of the oil or fat. Furthermore, as the raw material oil or fat, unreacted oil or fat remaining in a solution used in a separate fatty acid ester production reaction may be used.

Examples of liquid enzymes include those that have liquid properties at room temperature among any enzyme catalysts that can be used in the fatty acid ester production reaction. Examples of liquid enzymes include lipase, cutinase, and combinations thereof. Here, the term "lipase" as used herein refers to a linear enzyme that has the ability to act on glycerides (also referred to as acylglycerols) and decompose the glycerides into glycerin or partial glycerides and fatty acids, and An enzyme that has the ability to generate fatty acid esters by transesterification in the presence of lower alcohols.

Lipases can be 1,3-specific or non-specific. The lipase is preferably non-specific in that it can produce linear lower alcohol esters of fatty acids. Examples of lipases include lipases derived from filamentous fungi belonging to the genus Rhizomucor (Rhizomucor miehei), Mucor, Aspergillus, Rhizopus, Penicillium, etc.; lipase derived from yeast belonging to the genus Pseudomonas, Candida rugosa, Candida cylindracea, Pichia, etc.; lipase derived from bacteria belonging to the genus Pseudomonas, Serratia, etc.; and porcine pancreas Examples include lipases derived from animals such as. Liquid lipase can be obtained, for example, by concentrating and purifying a culture solution of these microorganisms containing lipase produced by these microorganisms, or by dissolving powdered lipase in water. Commercially available liquid lipases may also be used.

The amount of the liquid enzyme used is not necessarily limited, as it varies depending on the type and/or amount of the raw material fat, for example, but is preferably 0.1 parts by mass to 50 parts by mass, preferably 0.1 parts by mass to 100 parts by mass of raw material fats and oils used. is 0.2 parts by mass to 30 parts by mass. If the amount of the liquid enzyme used is less than 0.1 part by mass, it may not be possible to catalyze the transesterification reaction effectively, which may reduce the yield and/or yield of the desired fatty acid ester. When the amount of liquid enzyme used exceeds 50 parts by mass, no change is observed in the yield and/or yield of the desired fatty acid ester obtained through the transesterification reaction, and there is a possibility that the production efficiency may be reduced.

The alcohol is a linear or branched lower alcohol (for example, an alcohol having 1 to 8 carbon atoms, preferably an alcohol having 1 to 4 carbon atoms). Straight chain lower alcohols are preferred. Examples of straight chain lower alcohols include, but are not necessarily limited to, methanol, ethanol, n-propanol, and n-butanol, and combinations thereof.

The amount of the alcohol used is not necessarily limited as it varies depending on the type and/or amount of the raw material fat or oil, for example, but is preferably 5 parts by mass to 100 parts by mass, preferably 10 parts by mass based on 100 parts by mass of the raw material fat or oil. parts to 30 parts by mass. If the amount of alcohol used is less than 5 parts by mass, an effective transesterification reaction cannot be carried out, and there is a possibility that the yield and/or yield of the desired fatty acid ester may be reduced. When the amount of alcohol used exceeds 100 parts by mass, there is no longer any change in the yield and/or yield of the desired fatty acid ester obtained through the transesterification reaction, and there is a possibility that the production efficiency may be reduced.

The water used in the present invention may be distilled water, ion exchange water, tap water, or pure water. The amount of water to be used is not necessarily limited as it varies depending on the type and/or amount of the raw material fat and oil, for example, but is preferably 0.1 parts by mass to 50 parts by mass, preferably 0.1 parts by mass to 100 parts by mass of raw material fats and oils. The amount is 2 parts by mass to 30 parts by mass. If the amount of water used is less than 0.1 part by mass, the amount of water layer formed in the reaction system will be insufficient, making it impossible to carry out an effective transesterification reaction using the raw material oil, liquid enzyme, and alcohol. , the yield and/or yield of the desired fatty acid ester may be reduced. When the amount of water used exceeds 50 parts by mass, there is no longer any change in the yield and/or yield of the desired fatty acid ester obtained through the transesterification reaction, and there is a possibility that the production efficiency may be reduced.

In the method of the present invention, a predetermined electrolyte may be added to the treatment liquid. Anions constituting the electrolyte include, but are not necessarily limited to, bicarbonate ions, carbonate ions, chloride ions, hydroxide ions, citrate ions, hydrogen phosphate ions, dihydrogen phosphate ions, and phosphate ions. and combinations thereof. Examples of cations constituting the electrolyte include alkali metal ions, alkaline earth metal ions, and combinations thereof; more specific examples include sodium ions, potassium ions, calcium ions, and combinations thereof. can be mentioned. Examples of electrolytes include sodium bicarbonate (baking soda), sodium carbonate, calcium chloride, calcium hydroxide, trisodium citrate, sodium hydrogen phosphate, sodium dihydrogen phosphate, sodium chloride, and trisodium phosphate; A combination of these is preferred. Sodium hydrogen carbonate (baking soda) is more preferred because it is highly versatile and easily available.

The raw material oil, catalyst, alcohol, and water are added simultaneously or in any order to the treatment tank 110 of the liquid dispersion apparatus 200 shown in FIG. A processing liquid 116 is formed. Thereafter, by rotating the liquid flow members 120, 120' of the liquid dispersion device 100 within the processing tank 110 through the rotation of the rotating shaft 121, the processing liquid 116 is absorbed from the liquid flow members 120, 120' as described above. The sucked processing liquid moves upward through the channels in the liquid suction parts 122, 122' and the discharge parts 123, 123', and is discharged from the discharge ports 125, 125' of the liquid flow members 120, 120'. Ru. On the other hand, the stirring blades 128, 128' fixed to the outer walls of the liquid suction parts 122, 122' of the liquid flow members 120, 120' can directly stir the inside of the processing liquid 116 by the rotation of the rotating shaft 121.

By such movement and direct stirring of the processing liquid 116, more complicated stirring is promoted in the processing liquid 116, and a fatty acid ester, which is a reaction product, is produced. The temperature applied in the processing tank 110 is not necessarily limited, but is, for example, 5°C to 80°C, preferably 15°C to 80°C, more preferably 25°C to 50°C.

Note that the rotation shaft in the liquid dispersion device 200 does not necessarily have to be rotated at high speed (for example, 600 rpm or more). For example, the speed may be set to a low speed (for example, 80 rpm or more and less than 300 rpm) or a medium speed (for example, 300 rpm or more and less than 600 rpm). Furthermore, since the reaction time varies depending on the amounts of the raw material oil, catalyst, alcohol, and water used, it is not necessarily limited and can be set as any time by those skilled in the art.

After completion of the reaction, the products and reaction residues are taken out from the treatment tank 110 of the liquid dispersion device 200 and separated into a layer containing the fatty acid ester and a layer containing the by-product glycerin, for example, using means well known to those skilled in the art. separated. Thereafter, the layer containing the fatty acid ester can be further isolated and purified, if necessary, using methods well known to those skilled in the art.

The fatty acid ester obtained as described above can be used, for example, as a biodiesel fuel or a component thereof.

Hereinafter, the present invention will be explained in detail with reference to Examples. However, the present invention is not limited to these.

(Comparative Example 1: Production of test device (C1))
A test device (C1) 300 shown in FIG. 8 was manufactured as follows. Specifically, a baffle plate 320 was placed in a round-bottom processing tank 310 with an inner diameter of 130 mm, and a rotating shaft 340 with one paddle blade 330 attached to one end was inserted onto the baffle plate 320 (note that As shown in FIG. 9, the baffle plate 320 has a shape in which two U-shaped members are combined in a cross shape). The other end of the rotating shaft 340 was connected to a motor (not shown). This paddle blade 330 was inclined at 45° from the horizontal direction toward the rotation direction of the rotation shaft 340, and was provided with four blade portions 334 evenly arranged in the rotation direction. Regarding the test device (C1) 300, the positions of the liquid level 332 (representing the liquid level in a stationary state immediately before the rotating shaft 340 rotates) and each component when a reaction liquid to be described later is stored in the processing tank 310. The relationships and lengths were as shown in FIG.

(Comparative Example 2: Production of test device (C2))
A test device (C2) 400 shown in FIG. 10 was produced as follows. Specifically, a test apparatus (C2 ) 400 were produced. Regarding the test device (C2) 400, the positions of the liquid level 432 (representing the liquid level in a stationary state immediately before the rotating shaft 340 rotates) and each component when a reaction liquid to be described later is stored in the processing tank 310. The relationships and lengths were as shown in Figure 10.

(Example 1: Production of test device (E1))
A test device (E1) 500 shown in FIG. 11, which corresponds to the liquid dispersion device of the present invention, was manufactured as follows. Specifically, a baffle plate 320 similar to that in Comparative Example 1 was placed in a round-bottom processing tank 310 with an inner diameter of 130 mm, and a liquid dispersion device 560 was attached to the baffle plate 320 via a fixture 512. The rotating shaft 540 was inserted. The other end of the rotating shaft 340 was connected to a motor (not shown).

This liquid dispersion device 560 is composed of tube bodies 562 and 562' made of polylactic acid cylindrical tubes having an inner diameter of 10 mm and connected so as to be inclined at 30 degrees with respect to the axial direction of the rotating shaft 540 and bent at a point P. It was to be done. Further, a paddle blade 530 was attached near the lower end of the liquid dispersion device 560. This paddle blade 530 was inclined at 45° from the horizontal direction toward the rotational direction of the rotating shaft 540, and was provided with two blade portions 534 equally arranged in the rotational direction. Regarding the test device (E1) 500, the positions of the liquid level 532 (representing the liquid level in a stationary state immediately before the rotating shaft 540 rotates) and each component when a reaction liquid to be described later is stored in the processing tank 310. The relationships and lengths were as shown in FIG.

(Example 2: Production of methyl ester using test device (E1))
1100 g of palm oil having an acid value of 0.423 mg-KOH/g, liquid enzyme (liquid lipase; Callera Trans L, Novozyme) were placed in the processing tank 310 of the test device (E1) 500 obtained in Example 1 shown in FIG. 11 g of distilled water, 165 g of distilled water, and 5 M equivalent of methanol were respectively added, and while the inside of the treatment tank 810 was maintained at 40° C., the rotation speed of the rotary shaft 850 was set to 300 rpm, and a transesterification reaction was carried out. During the reaction, the reaction solution in the treatment tank 810 was periodically sampled, and the methyl ester (ME) content contained in the reaction solution was measured by gas chromatography (GC-2030, manufactured by Shimadzu Corporation). The obtained results are shown in FIG. 12(a).

In addition, from this sampled reaction solution, the logarithm value (ln (BG ₀ /BG)) of the index of residual glyceride in the oil phase was calculated by using gas chromatography and inputting the measured values of various glycerides. . Here, BG is calculated using the concentrations of monoglyceride (MAG), diglyceride (DAG), and triglyceride (TAG) contained in the oil phase of the sampled reaction solution.BG=0.2591MAG+0.1488DAG+0.1044TAG
BG ₀ refers to BG at zero reaction time (oil phase before enzyme reaction starts). The obtained results are shown in FIG. 12(b).

(Comparative Example 3: Production of methyl ester using test device (C1))
Methyl ester was produced in the same manner as in Example 1, except that the test device (C1) produced in Comparative Example 1 was used instead of the test device (E1). The measurement results of _the methyl ester (ME) content contained in the reaction solution are shown in FIG. The results are shown in FIG. 12(b).

(Comparative Example 4: Production of methyl ester using test device (C2))
Methyl ester was produced in the same manner as in Example 1, except that the test device (C2) produced in Comparative Example 2 was used instead of the test device (E1). The measurement results of _the methyl ester (ME) content contained in the reaction solution are shown in FIG. The results are shown in FIG. 12(b).

As shown in FIG. 12(a), the results of methyl ester (Example 2) obtained using the test apparatus (E1) of Example 1 are different from those obtained using the test apparatus (C1) of Comparative Examples 1 and 2 and ( Compared to the methyl ester results obtained using C2) (Comparative Examples 3 and 4), more methyl ester was produced at the initial stage of the reaction (for example, within 5 hours after the start of the reaction). Further, even in the late stage of the reaction (for example, 22 to 24 hours), more methyl ester was produced when the test apparatus (E1) of Example 1 was used (Example 2).

On the other hand, when these reaction systems are evaluated from the viewpoint of the logarithm value (ln(BG ₀ /BG)) of the index of residual glycerides in the oil phase, as shown in FIG. The result of the logarithmic value obtained using (E1) (Example 2) is the result of the logarithmic value obtained using the test apparatuses (C1) and (C2) of Comparative Examples 1 and 2 (Comparative Example Compared to 3 and 4), the longer the reaction was continued, the higher the value was, indicating that the reaction rate became faster in the latter stage of the reaction and that high-quality methyl ester could be produced.

In addition, in general, when a relationship (graph) that can be approximately linearly approximated by logarithmic notation is obtained, its "slope" indicates the reaction rate (rate constant). Here, when each graph in (b) of FIG. 12 is approximated by a straight line, the slope of the graph of Example 2 (using the test device (E1) of Example 1) is 0.1826, and The slope of the graph for Comparative Example 3 (using the test apparatus (C2) of Comparative Example 1) was 0.1606, and the slope of the graph for Comparative Example 3 (using the test apparatus (C1) of Comparative Example 1) was 0.1409. From this, the rate constant when using the test device (E1) of Example 1 is the largest, and the test device (E1) of Example 1 is the same as the test devices (C1) and (C2) of Comparative Examples 1 and 2. It can be seen that the reaction system was superior to that of the above reaction system.

In addition, in (b) of FIG. 12, since the value of ln(BG0/BG) is approximately 4 when the triglyceride concentration is less than 0.2% by mass (the upper limit standard value for biodiesel fuel), ln When (BG ₀ /BG) is at least 4, it is an indicator that high-quality methyl ester could be produced. Here, only the reaction system of Example 2 using the test apparatus (E1) of Example 1 had a value of ln (BG ₀ /BG) exceeding 4 at a reaction time of 24 hours, and was superior among the above reaction systems. It turns out that it was something.

100, 100e, 560 Liquid dispersion device 109 Bottom 110, 310 Processing tank 111 Inner wall 112 Processing liquid supply port 114 Product outlet 115 Valve 116 Processing liquid 116a Oil phase 116b Water phase 120, 120', 120e Liquid flowing member 121, 340 , 540 Rotating shaft 122, 122' Liquid suction part 123, 123' 123e, 123'e Discharge part 124, 124' 124e Liquid suction port 125, 125', 125a, 125'a, 125e, 125'e Discharge port 128, 128', 128a ₁ , 128'a ₁ , 128a ₂ , 128'a ₂ , 128d, 128'd Stirring blade 129 Claw 130d, 130'd Thin plate 132 Liquid level 140 Motor 200, 200e Liquid dispersion device 300, 400, 500 Test device 320 Baffle plate 330, 330', 530 Paddle blade 332, 432, 532 Liquid level 334, 534 Wing portion 512 Attachment

Claims (7)

A liquid dispersion device comprising at least one liquid flow member attachable to a rotating shaft,
The liquid flow member is
at least one cylindrical liquid suction portion extending along the rotation axis and having a liquid suction port at the lower end;
at least one discharge portion, one end communicating with the upper end of the liquid suction portion, the other end having a discharge port, and extending obliquely with respect to the liquid suction portion;
A liquid dispersion device comprising: a stirring blade that extends along the rotation radius of the rotating shaft and is rotatable as the rotating shaft rotates. The liquid dispersion device according to claim 1, wherein the liquid absorbing portion of the liquid flowing member is a linear tube extending substantially parallel to the axial direction of the rotating shaft. The liquid dispersion device according to claim 1, comprising a plurality of the liquid absorption parts, and wherein all of the lower ends of the liquid absorption parts are provided at the same position with respect to the rotation axis. 2. The liquid dispersion device according to claim 1, wherein the liquid suction part is constituted by one tube, and the liquid suction part is provided with at least two of the discharge parts at the upper end thereof. The liquid dispersion device according to claim 1, wherein the stirring blade is fixed to an outer wall of the liquid absorption portion. comprising a processing tank for accommodating a processing liquid, a liquid dispersion device according to any one of claims 1 to 6 provided in the processing tank, and a rotating shaft to which the liquid dispersion device is attached. Sprinkling equipment. The liquid dispersion device according to claim 6, wherein the treatment liquid is composed of an oil phase and an aqueous phase.

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