JP2023000379A - Liquid dispersion device, and reactor with use thereof and reaction product manufacturing method - Google Patents

Abstract

To provide a liquid dispersion device which can reduce energy required for an operation such as mixing or stirring of a reactant, and a reactor with use of the same and a reaction product manufacturing method.SOLUTION: A liquid dispersion device comprises a rotary shaft located along a vertical direction, and at least one first flow liquid component and at least one second flow liquid component which are attached to the rotary shaft. Herein, both of the first flow liquid component and the second flow liquid component comprise a discharge part positioned at an upper end, a liquid absorption part located at a lower end, and a flow channel extending between the discharge part and the liquid absorption part. The liquid absorption part of the first flow liquid component is located above the liquid absorption part of the second flow liquid component.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to a liquid dispersion device, a reaction apparatus using the same, and a method for producing a reaction product.

In recent years, fats and oils have also attracted attention as raw materials for conversion into fuels and chemicals. In particular, attempts have been actively made to synthesize long-chain fatty acid esters from animal fats and/or vegetable fats by chemical reaction and to utilize them as biodiesel fuels that can replace light oil.

On the other hand, in a reaction system of two or more liquid phases using a phase transfer catalyst or a slurry catalyst, a technique for synthesizing various compounds through reactions such as asymmetric synthesis reactions has attracted attention. Many of these reactions are accelerated by vigorously stirring the reaction system.

Two-liquid phase reactions may be employed, for example, in the production of biodiesel fuel. Examples thereof include transesterification by an enzyme-catalyzed method using an enzyme such as lipase as a catalyst. In the transesterification reaction by such an enzyme-catalyzed method, for example, an enzyme immobilized on a carrier such as a liquid enzyme or an ion exchange resin (immobilized enzyme) is used. Liquid enzymes are less expensive than immobilized enzymes in that they are made from concentrated and purified culture media. In addition, since the enzyme remains in glycerin water, which is a by-product of the transesterification reaction, this can be used for the next batch reaction. As a result, the liquid enzyme can be used repeatedly, and the cost required for the production of biodiesel fuel can be reduced (Non-Patent Document 1).

In a 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, for example, by stirring the reactants at high speed. Here, high speed stirring of the reactants requires a substantial energy load on 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 leads to a contradiction in that the ability to form an emulsion using the reactants described above is lowered, 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

An object of the present invention is to solve the above problems, and the object thereof is to reduce the energy required for operations such as mixing and stirring of reactants in the production of reaction products. An object of the present invention is to provide a liquid dispersion device, a reaction apparatus using the same, and a method for producing a reaction product.

The present invention comprises a rotating shaft arranged along a vertical direction, and at least one first flowing member and at least one second flowing member mounted on the rotating shaft,
Both the first flowing liquid member and the second flowing liquid member define a discharge portion positioned at an upper end, a liquid absorption portion positioned at a lower end, and a flow path extending between the discharge portion and the liquid absorption portion. prepared,
The liquid dispersion device, wherein the liquid absorbing portion of the first liquid member is arranged above the liquid absorbing portion of the second liquid member.

In one embodiment, in each of the first liquid flow member and the second liquid flow member, the liquid absorption section is located closer to the axis of the rotating shaft than the discharge section. placed at an angle.

In one embodiment, both the first fluid member and the second fluid member have a cylindrical shape with both ends opened.

The present invention is also a reaction apparatus comprising a reaction tank for containing a reaction liquid, and the dispersion device provided in the reaction tank.

In one embodiment, the reaction liquid consists of an oil phase and an aqueous phase.

The present invention is also a method for producing a reaction product, which method includes the step of stirring by circulating the reaction solution in the reactor.

In one embodiment, the reaction liquid consists of an oil phase and an aqueous phase.

In one embodiment, the reaction product is a fatty acid ester, and the reaction liquid contains a raw material fat, a liquid enzyme, an alcohol having 1 to 8 carbon atoms, and water.

In a further embodiment, the raw material fat is at least one fat selected from the group consisting of vegetable fats, animal fats, fish oils, microbial fats and oils, and waste oils thereof.

According to the liquid dispersion device of the present invention, the reaction liquid can be efficiently mixed back by moving the scooped up reaction liquid upward from the liquid surface and dispersing the liquid. As a result, in addition to stirring based on rotation in the horizontal direction, movement and circulation in the vertical direction can be promoted for the liquid contained in the container. The dispersion device of the present invention can be incorporated into a reactor, thereby reducing the physical manipulation energy required to mix and agitate the reactants to produce a variety of reaction products. For example, when a reaction liquid composed of two phases, an oil phase and an aqueous phase, is accommodated in the reactor of the present invention, the reaction liquid is emulsified and/or by-products ( For example, glycerin) can be facilitated with water extraction.

1 is a schematic diagram showing an example of a reactor in which the dispersion device of the present invention is incorporated; FIG. 2 is a perspective view schematically showing an example of a second flowing member of the liquid dispersion device shown in FIG. 1. FIG. FIG. 4 is a schematic diagram showing another example of a reactor incorporating the liquid dispersion device of the present invention; FIG. 4 is a schematic diagram showing another example of a reactor incorporating the dispersion device of the present invention; 1 is a schematic diagram showing an example of a reactor incorporating another liquid dispersion device of the present invention; FIG. FIG. 6 is a perspective view schematically showing an example of a second flowing member of the liquid dispersion device shown in FIG. 5; 1 is a schematic diagram showing an example of a reactor incorporating another dispersion device of the present invention; FIG. 1 is a schematic diagram showing an example of a reactor incorporating another dispersion device of the present invention; FIG.

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

(dispersion device and reactor)
An example in which the liquid dispersion device of the present invention is incorporated in a reactor will be described below.

FIG. 1 is a schematic diagram showing an example of a reactor in which the dispersion device of the present invention is incorporated.

The liquid dispersion device 120 of the present invention shown in FIG. 1 includes a rotating shaft 121 arranged along a vertical direction and a first flow device mounted on the rotating shaft 121 via a fixture 122 preferably extending in a horizontal direction. It is composed of a liquid member 123a and a second liquid member 123b. The first liquid flowing member 123a includes a liquid absorption portion 124a, a discharge portion 125a, and a flow path 126a extending between the liquid absorption portion 124a and the discharge portion 125a. The second liquid flowing member 123b includes a liquid absorbing portion 124b, a discharging portion 125b, and a channel 126b extending between the liquid absorbing portion 124b and the discharging portion 125b.

As shown in FIG. 1, in the liquid dispersion device 120 of the present invention, the liquid absorbing portion 124a of the first liquid flowing member 123a and the liquid absorbing portion 124b of the second liquid flowing member 123b both absorb the liquid of the reaction liquid 116. Both the discharge portion 125a of the first liquid flow member 123a and the discharge portion 125b of the second liquid flow member 123b are disposed above the liquid surface 128 of the reaction liquid 116. . As a result, the liquid dispersion device 120 rotates the rotating shaft 121 and accompanies the centrifugal force acting on the first liquid flow member 123a and the second liquid flow member 123b. The reaction liquid 116 contained in 110 is drawn from the liquid absorbing portion 124a of the first liquid flowing member 123a and the liquid absorbing portion 124b of the second liquid flowing member 123b, and is drawn from below the reaction vessel 110 through the flow paths 126a and 126b. It can flow upwards. After that, the drawn reaction liquid is discharged above the liquid surface 128 from the discharging portion 125a of the first liquid flowing member 123a and the discharging portion 125b of the second flowing liquid member 123b.

In the present invention, the liquid absorption portions 124a and 124b and the discharge portions 125a and 125b are arranged with respect to the liquid surface 128 in the static stage (that is, without rotation of the rotating shaft 121, the liquid surface of the reaction liquid 116 spreads in a substantially horizontal direction). In addition to the stage of rotating the rotating shaft 121 at a desired rotation speed (that is, the state of stirring the reaction liquid 116 as described later through the rotation of the rotating shaft 121). ) is also retained. As a result, the reaction liquid 116 in the reaction vessel 110 can be easily scooped up from the liquid absorbing portions 124a and 124b of the liquid-flowing members by the rotation of the rotating shaft 121 and the liquid-flowing members 123a and 123b. It moves to discharge parts 125a and 125b through channels 126a and 126b in members 123a and 123b, and is discharged from discharge parts 125a and 125b toward inner wall 111 of reaction vessel 110 and liquid surface 128 of reaction liquid 116, for example. can be

Furthermore, in the liquid dispersion device 120 of the present invention, the liquid absorbing portion 124a of the first liquid flowing member 123a is arranged above the liquid absorbing portion 124b of the second liquid flowing member 123b. That is, the lowermost end portion 127a of the liquid absorbing portion 124a of the first liquid flowing member 123a and the lowermost end portion 127b of the liquid absorbing portion 124b of the second flowing liquid member 123b are separated by a distance Δd in the vertical direction. are placed. This distance Δd is determined by the size of the first liquid member 123a and the second liquid member 123b, the rotational speed imparted to the rotating shaft 121, the volume and depth of the reaction liquid 116 contained in the reaction vessel 110, and the Although it is not necessarily limited because it varies depending on the user, it is, for example, 0.5 cm to 1,000 cm, preferably 1 cm to 100 cm.

In one embodiment, when the reaction liquid 116 is composed of a two-phase system of an oil phase 116a and an aqueous phase 116b as shown in FIG. The lowermost end 127a of 124a is arranged in the oil phase 116a in the stationary state, and the lowest end 127b of the liquid absorbing portion 124b of the second liquid member 123b is arranged in the aqueous phase 116b in the stationary state. It is As a result, when the rotating shaft 121 rotates, the composition of the reaction liquid 116 drawn by each of the liquid absorbing portions 123a and 123b can be different rather than the same.

In the embodiment shown in FIG. 1, two liquid flow members (i.e., first flow member 123a and second flow member 123a and second Although the use of a dispersion device 120 with a liquid flow member 123b) of 123b) has been described, the present invention is not limited to such a configuration. For example, in the case where the reaction solution is separated into multiple phases (for example, three phases) by rotation of the rotating shaft, for the purpose of pumping up the reaction solution from each phase, multiple There may be (eg, three or more) flow members.

The rotating shaft 121 is a shaft having a predetermined rigidity, and has, for example, a cylindrical or columnar shape. The rotating shaft 121 is generally arranged vertically within the reaction vessel 110 . The thickness of the rotating shaft 121 is not necessarily limited, but is, for example, 8 mm to 200 mm. The length of the rotating shaft 121 varies depending on the size of the reaction vessel 110 to be used, etc., and an appropriate length can be selected by those skilled in the art.

One end of the rotating shaft 121 is connected to rotating means such as a motor 140 at the upper portion of the reaction vessel 110 . The other end of the rotating shaft 121 is not connected to the bottom 109 of the reaction vessel 110, and is arranged, for example, at a certain distance from the bottom 109 of the reaction vessel 110 (preferably away from the liquid surface 128 of the reaction liquid 116). It is As a result, the chances of the rotating shaft 121 coming into contact with the reaction liquid 116 can be reduced. Alternatively, the other end of the rotating shaft may be housed in a bearing provided on the bottom 109 of the reaction vessel.

In the liquid dispersion device 120 shown in FIG. 1, the liquid absorption portions 124a and 124b of the first liquid flow member 123a and the second liquid flow member 123b are arranged with respect to the axis J of the rotating shaft 121 relative to the discharge portions 125a and 125b. It is arranged at an angle so that it lies proximally. That is, in the liquid dispersion device 120, the shortest distance between the liquid absorbing portion 124a of the first liquid flowing member 123a and the axis J of the rotating shaft 121 is longer than the shortest distance between the discharging portion 125a and the axis J of the rotating shaft 121. and the shortest distance between the liquid absorbing portion 124b of the second liquid flowing member 123b and the axis J of the rotating shaft 121 is shorter than the shortest distance between the discharging portion 125b and the axis J of the rotating shaft 121. One flowing liquid member 123a and a second flowing liquid member 123b are arranged at an angle.

Alternatively, in the liquid dispersion device 120 shown in FIG. 1, the first fluid member 123a and the second fluid member 123b each have a predetermined angle (also referred to as a mounting inclination angle) θ with respect to the axial direction of the rotating shaft 121. It is installed at an angle of ₁ . The mounting inclination angle θ ₁ can be set to any angle by those skilled in the art, but is, for example, 10° to 45°, preferably 15° to 25°. The mounting inclination angle θ1 of the _first flowing liquid member 123a and the second flowing liquid member 123b may be the same or different.

In the liquid dispersion device 120 shown in FIG. 1, a first liquid flow member 123a and a second liquid flow member 123b are provided facing each other with the axis J of the rotating shaft 121 interposed therebetween. Here, the number of first flow members that can be provided in the liquid dispersion device of the present invention is not necessarily limited, but is, for example, at least one, preferably two to eight, and more preferably two. ~6. The number of second flow members that can be provided in the liquid dispersion device of the present invention is not necessarily limited, but is, for example, at least one, preferably two to eight, and more preferably two to six. is. When a plurality of first fluid members and a plurality of second fluid members are used, the first fluid members face each other through the axis of the rotating shaft, and the second fluid members face each other. Each may be provided. Moreover, it is preferable that the first fluid member and the second fluid member are mounted at substantially equal angles around the rotation shaft.

In the present invention, the first liquid-flowing member 123a and the second liquid-flowing member 123b are, for example, processed into a tubular shape (for example, a cylindrical shape, an elliptical shape, or a rectangular shape). Alternatively, the lower end and the upper end have a so-called gutter shape such as a semi-cylindrical shape, a half-square shape, a V-shape, and the intermediate portion between them is a cylindrical shape (for example, a cylindrical shape, an elliptical cylindrical shape , rectangular tube), only the lower end has such a gutter-like shape, and the other portion is cylindrical (for example, cylindrical, elliptical cylindrical, square tube) shape).

The sizes of the first flowing liquid member 123a and the second flowing liquid member 123b are not particularly limited. 2 is a perspective view schematically showing an example of a second flowing member of the liquid dispersion device shown in FIG. 1. FIG. For example, when a completely cylindrical member as shown in FIG. 2 is used as the second liquid dispersion member 123b, the inner diameter of the cylindrical portion is, for example, 2 mm to 200 mm. The length from the liquid absorption part 124b to the discharge part 125b (that is, the length of the passage 126b) is not necessarily limited. An appropriate length can be selected by _a person skilled in the art according to the size of the mounting inclination angle θ1 and the like. In FIG. 2, the inner diameter of the liquid absorbing portion 124b, the inner diameter of the passage 126b, and the inner diameter of the discharging portion 125b are described as if they are substantially the same size, but the present invention is limited to such a form. Not limited. For example, the inner diameter of the second liquid flowing member 123b may gradually or stepwise decrease from the liquid absorbing portion 124b to the discharging portion 125b. The diameter may gradually or gradually increase from the portion 124b to the discharge portion 125b.

The dispersion device 120 of the present invention is a mixing device or stirring device used when physical mixing or stirring of the contents is required, in addition to the reaction tank 110 of the reaction device 100 shown in FIG. It can also be used by incorporating it into a mixing tank or stirring tank.

Next, the reactor in which the liquid dispersion device of the present invention is incorporated will be described with reference to FIG. 1 again.

The reactor 100 of the present invention comprises a reaction vessel 110 and the dispersion device 120 described above.

The reaction vessel 110 is a sealable vessel in which the reaction liquid 116 can be contained and stirred, and has, for example, a flat bottom, a round bottom, a conical bottom, or a downwardly sloping bottom 109 .

The size (capacity) of the reaction tank 110 is not necessarily limited because it is appropriately set depending on the use of the reaction apparatus 100 (for example, the type of reaction performed using this) and the throughput of the reaction solution. , from 0.1 liters to 1,000,000 liters.

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

Product outlet 114 is an outlet for removing the product obtained in reactor 110 from reactor 110 . The product outlet 114 can discharge not only the product but also reaction residues, waste liquids, and the like, and the discharge can be adjusted by opening and closing a valve 115 provided downstream of the product outlet 114, for example. A product outlet 114 is also provided, for example, in communication with the center of the bottom 109 within the reaction vessel 110 .

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

The reaction liquid 116 contained in the reaction tank 110 is a liquid such as an aqueous solution or slurry. For example, when the reaction apparatus 100 is used for producing a fatty acid ester by transesterification to be described later, the reaction liquid 116 is composed of, for example, a two-phase system of an oil phase 116a and an aqueous phase 116b. Each of the aqueous phases 116b contains reactants such as starting materials and a medium such as a solvent.

According to the reaction apparatus 100 of FIG. 1, by rotating the rotating shaft 121, the first liquid flow member 123a and the second liquid flow member 123b in the liquid dispersion device 120 flow the reaction liquid from the liquid absorption ports 124a and 124b. Pick up 116. The drawn reaction liquid moves to the outlets 125a and 125b through the passages 126a and 126b by the centrifugal force accompanying the rotation of the rotary shaft 121, and enters the reaction vessel 110 from the outlets 125a and 125b. Specifically, it is discharged above the liquid surface 128 of the reaction liquid 116 in the reaction tank 110 . As a result, the reaction liquid 116 collides with the inner wall 111 and the liquid surface 128 of the reaction vessel 110, and can move upward from the bottom 109 of the reaction vessel 110. Agitation (eg, vertical agitation or circulation) can be encouraged. As a result, the production of reaction products in the reactor 100 can proceed more effectively.

In the present invention, the reaction vessel 110, the rotating shaft 121, the fixture 122, and the liquid flow member 123 are independently made of metals such as iron, stainless steel, Hastelloy, titanium, and combinations thereof. made up of materials. These may be provided with a coating known in the art, such as Teflon (registered trademark), glass lining, or rubber lining, in order to enhance chemical resistance.

FIG. 3 is a schematic diagram showing another example of the reactor of the present invention. In the reactor 200 of the present invention shown in FIG. 3, a plurality of baffle plates 210 extending from the bottom 109 of the reaction vessel 110 to a height above the liquid surface 128 of the reaction liquid 116 are provided on the inner wall 111 of the reaction vessel 110. there is In FIG. 3, the baffle plate 210 is positioned, for example, substantially in the center of the standing reaction liquid 116 (that is, the upper end of the baffle plate 210 is positioned inside the oil phase 116a, and the lower end of the baffle plate 210 is positioned inside the water phase). positioned inside the phase 116b, and the upper and lower ends thereof are positioned near the interface between the oil phase 116a and the water phase 116b)

The baffle plate 210 rotates the first liquid flow member 123a and the second liquid flow member 123b through the fixture 122 by the rotation of the rotating shaft 121, whereby the reaction liquid 116 in the reaction vessel 110 follows and joins. It plays a role in preventing rotational movement. In other words, the baffle plate 210 acts as a barrier when the reaction liquid 116 rotates horizontally within the reaction vessel 110, and can prevent the formation of a vortex. As a result, the reaction liquid 116 is given random motion within the reaction vessel 110, and as a result, the efficiency of mixing and stirring the reaction liquid 116 can be enhanced.

Although the number of baffle plates 210 provided in the reaction vessel 110 is not necessarily limited, for example, one to eight baffle plates 210 are provided at approximately equal intervals on the inner wall 111 of the reaction vessel 110 .

FIG. 4 is a schematic diagram showing another example of the reactor of the present invention. In the reactor 300 shown in FIG. 4, a jacket 310 for temperature control is provided around the outer circumference of the reaction vessel 110 . In FIG. 4, the jacket 310 is made of, for example, a hollow material, and a heat medium such as steam, water, or heat medium oil is introduced from the jacket inlet 320 through a tube (not shown) and discharged from the jacket outlet 330. can be done. The heat medium introduced into the jacket 310 heats the reaction liquid 116 from the outside of the reaction vessel 110 , thereby enabling temperature control of the reaction liquid 116 in the reaction vessel 110 .

In the embodiment shown in FIG. 4, the example of using the heating heat medium for heating the inside of the reaction tank 110 as the heat medium has been described, but the present invention is not limited to this. Instead of the heating heat medium, for example, a cooling heat medium such as liquefied nitrogen, water, brine, gas refrigerant (for example, carbon dioxide, Freon) may be introduced into the jacket 310 .

FIG. 5 is a schematic diagram showing an example of a reactor incorporating another dispersion device of the present invention. In the reaction device 400, the two liquid flow members (that is, the first liquid flow member 423a and the second liquid flow member 423b) that constitute the liquid dispersion section 420 have lower portions (eg, the liquid absorption section 424a, 424b has a tubular shape near the lowermost ends 427a and 427b thereof, and the upper portion thereof is provided with channels 426a and 426b having a gutter-like shape. In the liquid dispersion device 420, the liquid absorption portion 424a of the first liquid flow member 423a is also arranged above the liquid absorption portion 424b of the second liquid flow member 423b.

FIG. 6 is a perspective view schematically showing an example of the second liquid flow member 423b of the liquid dispersion device shown in FIG. For example, when the second liquid dispersion member 423b is a partly cylindrical member and the remaining gutter-shaped member as shown in FIG. 6, the inner diameter of the cylindrical portion is, for example, 2 mm to 200 mm. The length from the lowest end 427b of the liquid absorbing portion 424b to the uppermost end 428b of the liquid absorbing portion 424b (that is, the length of the cylindrical passage), and the length from the lowest end 427b of the liquid absorbing portion 424 to the discharge portion 425b _The length (that is, the length of the passage 426b) is not necessarily limited. An appropriate length can be selected by those skilled in the art depending on the length and the like. Although the second fluid member 423b has been described in FIG. 6, the first fluid member 423a shown in FIG. , are substantially the same.

Referring again to FIG. 5, the liquid dispersion device 420 also has the liquid absorbing portion 424a of the first liquid member 423a located below the liquid absorbing portion 424b of the second liquid member 423b. That is, the lowest end portion 427a of the liquid absorbing portion 424a of the first liquid flowing member 423a and the lowest end portion 427b of the liquid absorbing portion 423b of the second flowing liquid member 423b are separated by a predetermined distance in the vertical direction. are placed. In FIG. 5, the lowermost end 427a of the liquid absorbing portion 424a of the first liquid member 423a is provided at a position where the oil phase 116a of the reaction liquid 116 exists in the stationary state, and the second liquid member 423a is provided with the lowermost end 427a. A lowermost end portion 427b of the liquid absorbing portion 424b in 423b is provided at a position where the aqueous phase 116b of the reaction liquid 116 exists in a stationary state.

In such an arrangement, the first flowing liquid member 423a and the second flowing liquid member 423b can scoop up the reaction liquid 116 near the lowermost ends 427a and 427b as the rotating shaft 121 rotates. Next, the pumped reaction liquid 116 moves upward through the channel 426a of the first liquid member 423a and the channel 426b of the second liquid member 423b by the rotation of the rotating shaft 121, It is discharged toward the inner wall 111 of the reaction vessel 110 from the discharge portions 425a and 425b. The discharged reaction liquid flows down the inner wall 111 as it is and can be mixed with the reaction liquid 116 again.

FIG. 7 is a schematic diagram showing an example of a reactor incorporating another dispersion device of the present invention. In the reaction apparatus 500 shown in FIG. 7, the first liquid flow member 523a and the second liquid flow member 523b, which constitute the dispersion device 520, have a cylindrical shape such as a cylinder, and their upper ends are obliquely upward. , so that the ejection portions 525a and 525b are directed toward the inner wall 111 of the reaction vessel 110. As shown in FIG.

In the liquid dispersion device 520, the liquid absorbing portion 524a of the first liquid member 523a is also arranged above the liquid absorbing portion 524b of the second liquid member 523b. That is, the lowest end portion 427a of the liquid absorbing portion 424a of the first liquid flowing member 423a and the lowest end portion 427b of the liquid absorbing portion 423b of the second flowing liquid member 423b are separated by a predetermined distance in the vertical direction. are placed.

In this arrangement, the reaction liquid 116 sucked from the liquid absorbing portion 524a of the first liquid flowing member 523a and the liquid absorbing portion 524b of the second flowing liquid member 523b is rotated by the rotation of the rotating shaft 121. It passes through the flow path 526a of the liquid flow member 523a and the flow path 526b of the second liquid flow member 523b, moves upward, and is discharged toward the inner wall 111 of the reaction vessel 110 from the discharge portions 525a and 525b. As a result, the liquids of the oil phase 116a and the water phase 116b, which are present at different locations in the height direction of the reaction tank 110, are mixed on the inner wall 111. As shown in FIG. The discharged reaction liquid flows down the inner wall 111 as it is and can be mixed with the reaction liquid 116 again.

In the embodiment shown in FIG. 7, the first liquid flow member 523a and the second liquid flow member 523b are gently curved with a predetermined curvature, for example, but the present invention is not limited to this form. . For example, it may be bent by one or more bends above the liquid dispersion member, and the outlet may be directed toward the inner wall 111 of the reaction vessel 110 .

FIG. 8 is a schematic diagram showing an example of a reactor incorporating another dispersion device of the present invention. In the reaction apparatus 600 shown in FIG. 8, the first liquid flow member 623a and the second liquid flow member 623b, which constitute the liquid dispersion device 620, have a cylindrical shape such as a cylinder, and the upper part thereof is curved. Therefore, the ejection portions 625 a and 625 b are designed to face the liquid surface 128 of the reaction liquid 116 contained in the reaction vessel 110 .

In the liquid dispersion device 620, the liquid absorbing portion 624a of the first liquid member 623a is also arranged below the liquid absorbing portion 624b of the second liquid member 623b. That is, the lowest end portion 627a of the liquid absorbing portion 624a of the first liquid flowing member 623a and the lowest end portion 627b of the liquid absorbing portion 623b of the second flowing liquid member 623b are separated by a predetermined distance in the vertical direction. are placed.

In this arrangement, the reaction liquid 116 sucked from the liquid absorption portions 624a and 624b of the first liquid flow member 623a and the second liquid flow member 623b is moved by the rotation of the rotating shaft 121 to the first liquid flow member. 623a and the flow path 626b of the second liquid member 623b to move upward, and are discharged toward the liquid surface 128 of the reaction liquid 116 in the reaction tank 110 from the discharging portions 625a and 625b. .

In the embodiment shown in FIG. 8, the first flowing liquid member 623a and the second flowing liquid member 623b are gently curved with a predetermined curvature, for example, but the present invention is not limited to this form. . For example, it may be bent by one or more bends above the liquid dispersion member, and the outlet may be directed toward the liquid surface 128 of the reaction liquid 116 in the reaction vessel 110 .

A reactor incorporating the dispersion device of the present invention is useful in the production of various reaction products in which agitation of the reaction solution (reactant) is desired. In particular, in a two-phase system (heterogeneous reaction system) composed of an oil phase and an aqueous phase, a reaction product can be obtained more effectively than in the case of using a conventional stirrer. Examples of such biphasic systems include transesterification reactions to produce fatty acid esters.

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

In the production method of the present invention, agitation is performed by circulating the reaction solution in the reactor in which the dispersion device is incorporated. Here, in the present specification, the term "stirring by circulation" refers to stirring by applying horizontal rotation to the target liquid (e.g., reaction solution), and as in the case of using the reaction apparatus , both vertical movement of the liquid and remixing (or mixing) of the entire liquid through circulation.

The reaction 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 reaction liquid is a heterogeneous reaction liquid. For example, a reaction liquid composed of an oil phase and an aqueous phase is useful in that emulsification of the reaction liquid can be improved and accelerated through agitation due to circulation.

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

Raw material fats and oils are fats and oils that can be used, for example, in the production of fatty acid esters for biodiesel fuel. The raw material fat may be pre-refined fat or unrefined fat containing impurities. Examples of raw fats include edible fats and their waste edible fats, crude oil, and other waste-based fats, and combinations thereof. Examples of edible fats and oils and their waste edible fats include vegetable fats, animal fats, fish oils, microbial fats and oils, waste oils thereof, and mixtures thereof (mixed fats and oils). Examples of vegetable oils include, but are not necessarily limited to, soybean oil, rapeseed oil, palm oil, and olive oil. Examples of animal fats include, but are not necessarily limited to, beef tallow, lard, 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 microbially produced oils include, but are not necessarily limited to, oils produced by microorganisms such as Mortierella or Schizochytrium.

Crude oil is, for example, unrefined or unprocessed fats and oils obtained from conventional edible oil expression processes, which are free from, for example, gummy impurities such as phospholipids and/or proteins, free fatty acids, pigments, trace metals and other carbonized oils. It may contain hydrogen based oil soluble impurities, as well as combinations thereof. The content of the impurity contained in the crude oil is not particularly limited.

Waste oils and fats include, for example, slag obtained by refining crude oil produced in the production process of food fats and oils in the presence of alkali, heat-treated oil, press oil, rolling oil, and combinations thereof. .

The raw fats and oils may contain any amount of water as long as the original properties of the fats and oils are not impaired. Furthermore, as the raw material fat, an unreacted fat and oil remaining in the solution used in the reaction for producing the fatty acid ester may be used.

In the present invention, the liquid enzyme includes any enzymatic catalyst that can be used in the production reaction of fatty acid esters and that has liquid properties at room temperature. Examples of liquid enzymes include lipase, cutinase, and combinations thereof. Here, the term "lipase" as used herein has the ability to act on glycerides (also referred to as acylglycerols) to decompose the glycerides into glycerol or partial glycerides and fatty acids, and An enzyme that has the ability to produce fatty acid esters by transesterification in the presence of lower alcohols.

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

The amount of the liquid enzyme used in the present invention is not necessarily limited because it varies depending on the type and/or amount of the raw material fat, but is preferably 0.1 parts by mass to 50 parts by mass with respect to 100 parts by mass of the raw material fat used. parts, preferably 0.2 to 30 parts by mass. If the amount of the liquid enzyme used is less than 0.1 parts by mass, it may not be able to catalyze an effective transesterification reaction, resulting in a decrease in yield and/or yield of the desired fatty acid ester. If the amount of the liquid enzyme used exceeds 50 parts by mass, the yield and/or the yield of the desired fatty acid ester obtained through the transesterification reaction may no longer change, and rather the production efficiency may decrease.

Alcohols in the present invention are linear or branched lower alcohols (eg, alcohols having 1 to 8 carbon atoms, preferably alcohols 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 because it varies depending on the type and/or amount of the raw material fat used, 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. parts to 30 parts by mass. If the amount of alcohol used is less than 5 parts by mass, effective transesterification reaction cannot be carried out, and 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 change in the yield and/or yield of the desired fatty acid ester obtained through the transesterification reaction, and rather the production efficiency may be lowered.

The water used in the present invention may be distilled water, ion-exchanged water, tap water, or pure water. The amount of water used is not necessarily limited because it varies depending on the type and / or amount of the raw material fat used, but is preferably 0.1 to 50 parts by mass, preferably 0.1 to 50 parts by mass, preferably 2 parts by mass to 30 parts by mass. If the amount of water used is less than 0.1 parts by mass, the amount of the aqueous layer formed in the reaction system is insufficient, and the effective transesterification reaction cannot be carried out with the raw material fat, liquid enzyme, and alcohol. , may reduce yield and/or yield of the desired fatty acid ester. If the amount of water used exceeds 50 parts by mass, there is no change in the yield and/or yield of the desired fatty acid ester obtained through the transesterification reaction, and rather the production efficiency may be lowered.

In the production method of the present invention, a predetermined electrolyte may be added to the reaction solution. Anions constituting the electrolyte are not necessarily limited, but for example, hydrogen carbonate ion, carbonate ion, chloride ion, hydroxide ion, citrate ion, hydrogen phosphate ion, dihydrogen phosphate ion, and phosphate ion. and combinations thereof. Examples of cations that make up the electrolyte include alkali metal ions, alkaline earth metal ions, and combinations thereof, more specific examples being sodium ions, potassium ions, calcium ions, and combinations thereof. is mentioned. In the present invention, examples of electrolytes include sodium bicarbonate (sodium bicarbonate), sodium carbonate, calcium chloride, calcium hydroxide, trisodium citrate, sodium hydrogen phosphate, sodium dihydrogen phosphate, sodium chloride, and triphosphate. Sodium, as well as combinations thereof, are preferred. Sodium bicarbonate (sodium bicarbonate) is more preferable because of its versatility and easy availability.

In the present invention, the raw fats and oils, the catalyst, the alcohol, and the water are added simultaneously or in any order to the reaction tank 110 of the reaction apparatus 100 shown in FIG. A reaction liquid 116 composed of a phase 116b is formed. After that, by rotating the first flow member 123a and the second flow member 123b of the dispersion device 120 in the reaction vessel 110 through the rotation of the rotating shaft 121, the first flow member 123a is rotated as described above. and the liquid absorbing portions 124a and 124b of the second liquid member 123b, the reaction liquid thus drawn moves upward through the flow paths 126a and 126b, and flows through the first liquid member 123a and The liquid is discharged from the discharge ports 125a and 125b of the second liquid member 123b. Such movement of the reaction liquid 116 promotes agitation of the reaction liquid 116, and production of fatty acid ester as a reaction product is performed. The temperature applied inside the reaction vessel 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.

In addition, in the present invention, the rotation of the rotating shaft in the reaction device 100 does not necessarily have to be performed at a high speed (for example, 600 rpm or higher). For example, it may be set to a low speed (eg, 80 rpm or more and less than 300 rpm) or a medium speed (eg, 300 rpm or more and less than 600 rpm). Furthermore, since the reaction time varies depending on the amounts of the raw material fat, catalyst, alcohol, and water used, it is not necessarily limited and can be set arbitrarily by those skilled in the art.

After completion of the reaction, the product and reaction residue are removed from the reaction vessel 110 of the reactor 100 and separated into a layer containing the fatty acid ester and a layer containing the by-product glycerin using, for example, means well known to those skilled in the art. be done. The layer containing the fatty acid ester can then be further isolated and purified of the fatty acid ester using methods well known to those skilled in the art, if desired.

The fatty acid esters obtained as described above can be used, for example, as biodiesel fuels or constituents thereof.

100,200,300,400,500,600 Reactor 109 Bottom 110 Reaction tank 111 Inner wall 112 Reaction liquid supply port 114 Product outlet 115 Valve 116 Reaction liquid 116a Oil phase 116b Water phase 120,420,520 Dispersion device 121 Rotation Shaft 122 Mounting fixture 123a, 423a, 523a First liquid member 123b, 423b, 523b Second liquid member 124a, 124b, 424a, 424b, 524a, 524b, 624a, 624b Liquid absorption part 125a, 125b, 425a, 425b, 525a, 525b, 625a, 625b Discharge part 126a, 126b, 426a, 426b, 526a, 526b, 626a, 626b Flow path 127a, 127b, 427a, 427b, 527a, 527b, 627a, 627b Bottom end 128 Liquid level 140 Motor 210 Baffle plate 310 Jacket 320 Jacket inlet 330 Jacket outlet

Claims (5)

A rotating shaft arranged along a vertical direction, and at least one first flowing member and at least one second flowing member mounted on the rotating shaft,
Both the first flowing liquid member and the second flowing liquid member define a discharge portion positioned at an upper end, a liquid absorption portion positioned at a lower end, and a flow path extending between the discharge portion and the liquid absorption portion. prepared,
The liquid dispersion device, wherein the liquid absorbing portion of the first liquid member is positioned above the liquid absorbing portion of the second liquid member. In each of the first liquid member and the second liquid member, the liquid absorbing portion is disposed at an angle relative to the axis of the rotating shaft so that the liquid absorbing portion is located closer to the discharge portion than the discharge portion. 2. The dispersion device of claim 1, wherein the dispersion device is 3. The liquid dispersion device according to claim 1, wherein both the first flowing liquid member and the second flowing liquid member have a cylindrical shape with both ends opened. A reaction apparatus comprising a reaction tank for containing a reaction liquid, and the liquid dispersion device according to any one of claims 1 to 3 provided in the reaction tank. 5. The reactor according to claim 4, wherein said reaction liquid is composed of an oil phase and an aqueous phase.

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