WO2013157798A1

WO2013157798A1 - Subcritical reactor and subcritical reaction method using same

Info

Publication number: WO2013157798A1
Application number: PCT/KR2013/003156
Authority: WO
Inventors: 마승진
Original assignee: 목포대학교산학협력단
Priority date: 2012-04-16
Filing date: 2013-04-15
Publication date: 2013-10-24

Abstract

The present invention provides a subcritical reactor and, more particularly, to a high-temperature and high-pressure reactor provided with a reaction chamber for providing a reaction space and a stirrer including a stirring shaft, wherein the reactor comprises: a reactive outer wall in which a fluid-moving path through which a fluid introduced from the outside can flow is formed in at least one internal area thereof, and which partitions the reaction space; a heat supply unit which is formed on at least a partial outer side of the reactive outer wall, and which includes a heating means; and a cover body which seals the reaction space in connection with the outer wall of the reaction chamber during the reaction, and which has a first penetration path through which the stirring shaft of the stirrer can penetrate and rotate, wherein an internal state of the reaction space can be converted into the pressure and temperature of a subcritical state.

Description

Subcritical reaction apparatus and subcritical reaction method using the same

The present technology relates to a high temperature and high pressure reaction apparatus, and more particularly, to a subcritical reaction apparatus that can be utilized as an extraction apparatus.

In general, subcritical water extraction is often used to extract specific ingredients in agricultural products or other organic substances. The subcritical water extraction method is used as an extraction solvent for organic matters by mixing the organic substance to be extracted with a fluid such as water and processing it to a temperature and pressure state below the critical point where water liquid and gaseous coexist. This is how you do it. This subcritical water extraction method requires continuous agitation inside the processing vessel in the process of converting to a subcritical state. For this purpose, the stirring shaft is inserted into the processing vessel from the outside, and then rotates the internal processing object while rotating. However, since the inside of the processing vessel is a high pressure state, when the stirring shaft is rotated in the state directly inserted into the processing vessel, fine clearance is formed at the penetration point for smooth rotation. This has a problem that arises.

In addition, since the conventional subcritical extraction apparatus cools down to room temperature depending on the natural cooling method after reaching the subcritical state, it is difficult to adjust the cooling rate or the temperature holding time according to the intention of the operator. It was difficult to organically derive various experimental data according to temperature variables. In addition, in the case of the conventional cooling method by the cooling water may cause problems of durability degradation, such as the occurrence of cracks in the outer wall of the reactor due to rapid cooling.

The present invention has been made to overcome the problems of the prior art as described above, and an object thereof is to provide a subcritical reaction apparatus capable of experimenting at various angles after the subcritical state is reached without internal pressure loss. .

Another object of the present invention is to provide a subcritical reaction method capable of performing multi-degree experimental design after reaching the subcritical using the subcritical reaction device.

Subcritical reaction apparatus according to an embodiment of the present invention is a high temperature and high pressure reaction apparatus having a stirrer including a reaction chamber and a stirring shaft to provide a reaction space, the fluid flow path through which the fluid flowing from the outside can flow A reaction outer wall formed in at least one region of the reaction space and partitioning the reaction space, a heat supply part formed on at least a part of the outer surface of the reaction outer wall and including a heating means, and engaged with the outer wall of the reaction chamber during the reaction to react the reaction. The space is sealed and includes a cover body in which a stirring shaft of the stirrer is formed with a first passageway for penetrating and rotating, and converting the reaction space internal state into a subcritical pressure and temperature. The fluid flow path may include a curved surface.

The subcritical reaction device blocks fluid inflow into the fluid flow path until the interior of the reaction space reaches a subcritical state and allows the fluid to enter after reaching the subcritical state.

On the other hand, the subcritical reaction device may be provided outside the reaction chamber, it may further include a temperature control means for adjusting the temperature of the fluid flowing into the fluid inlet.

One region of the reaction outer wall may include a plurality of fluid inlets through which fluid may be introduced into the fluid flow path.

An insulation member may be disposed in at least one region of the outer surface of the heat supply unit.

The cover body may include a gas discharge pipe and a gas discharge port for discharging the pressure inside the reaction space to the outside. The subcritical reaction device is fastened to an upper surface of the cover body, and extends from the first through passage and provides a second through passage as a through and rotating space of the stirring shaft and a rotating space for rotating the head of the stirrer. It may further include a head body is formed. The head body is directly fastened and fixed to the upper surface of the cover body and is spaced apart from the head portion of the stirrer to surround the head portion of the stirrer, at least one opening is formed in at least one region facing the stirrer head portion And a second head body disposed on an outer surface of the first head body and capable of rotating by receiving rotational power from the outside. The second head body includes a second magnetic body protruding toward the opening side in at least one region corresponding to the opening, and the agitator head portion includes a first magnetic body corresponding to the second magnetic body on at least one surface of the agitator head portion. It may include.

The subcritical reaction device may further include a plurality of power supply means disposed outside the reaction chamber and supplying power to the heat supply unit.

In the subcritical reaction method according to an embodiment of the present invention, the step of introducing a reactant into the reaction space of the above-described subcritical reaction device, the subcritical reaction to boost and raise the subcritical reaction space to the pressure and temperature of the subcritical state And a cooling step of reducing the pressure in the reaction space and introducing the first fluid into the fluid flow path of the subcritical reaction device to cool the reaction space.

The temperature of the first fluid may be adjusted to change during the cooling step, and in the cooling step, after the inflow of the first fluid, a second fluid different from the first fluid may be introduced into the fluid flow path. have.

According to the subcritical reaction device of the present invention, even though the stirrer protrudes out of the reaction chamber, the outermost structure of the reaction device is fixed so that no leakage of internal gas occurs even when the stirrer is rotated, thereby thoroughly reducing the pressure loss of the reaction device. You can block.

In addition, the reaction apparatus can intentionally adjust the temperature change in the cooling process after reaching the subcritical state, and can experimentally utilize various state changes after the subcritical reaction, which is designed to take into account the various variables. It can be very useful to researchers. Furthermore, since the cooling method of the device is not a simple left cooling method or a rapid cooling method using coolant, it does not cause durability problems such as cracking of the chamber that may occur during the cooling process.

According to the subcritical reaction method according to the present invention, the temperature change after reaching the subcritical state can be variously designed according to the intention of the operator, and if necessary, when a fluid having a higher boiling point than water is used, 100 ° C. during the cooling process. The above relatively high cooling temperature can be maintained for a certain time as desired.

1 is a cross-sectional view for explaining the chamber region of the subcritical reaction apparatus according to an embodiment of the present invention.

FIG. 2 is a cross-sectional view illustrating a shape according to another exemplary embodiment of part 'A' of FIG. 1.

3 is a cross-sectional view illustrating a state according to still another embodiment of portion 'A' of FIG. 1.

4 is a cross-sectional view for explaining the upper region of the subcritical reaction apparatus according to an embodiment of the present invention.

5 is a graph showing the temperature change after reaching the subcritical state according to an embodiment of the present invention.

6 is a graph showing the temperature change after reaching the subcritical state according to another embodiment of the present invention.

Hereinafter, the structure of the subcritical reaction apparatus according to the present invention with reference to the accompanying drawings to be described in detail. However, the following descriptions are merely illustrative of the present invention, and the technical idea of the present invention is not limited by the following description, which is defined by the claims to be described later.

On the other hand, the names of the components used below are merely exemplary, and the technical features of the present invention are not limited by the concept of such names.

Referring to FIG. 1, the subcritical reaction apparatus 1000 includes a reaction chamber 100 securing a reaction space 70 partitioned by the reaction outer wall 110. The subcritical reaction device 1000 is a device for performing a reaction such as extracting a reaction target material introduced into the reaction space 70 of the reaction chamber 100 by using a solvent in a subcritical state. That is, the subcritical reaction device 1000 is a device for converting the internal pressure and temperature into a high pressure and high temperature environment below a critical point.

The reaction outer wall 110 includes a fluid flow path 120 which is an empty space formed in one region of the inside. The fluid flow path 120 may be formed entirely on the three-dimensional surface of the reaction outer wall 110 or may be selectively formed only in a partial region, but in order to ensure cooling efficiency or temperature control ease, the front surface of the reaction outer wall 110 ( It is preferable to be formed along the entire surface.

Until the inside of the reaction chamber 100 reaches a subcritical state, fluid inflow is blocked so that no fluid flows into the fluid flow path 120. The fluid flows into the fluid flow path 120 from the end of the reaction, that is, after the inside of the reaction chamber 100 reaches a subcritical state. The fluid flow path 120 is spatially connected to the fluid flow part 121 and the fluid flow part 121, which are hollow areas inside the reaction outer wall 110, and penetrates the reaction outer wall 110. The fluid inlet 123 and the fluid flow part 121 that are spatially connected to each other, and flow through the reaction outer wall 110 to discharge the fluid to the outside after the fluid flow part 121 flows. And a fluid outlet 125 formed. The fluid inlet 123 is formed below the reaction chamber 100, and the fluid outlet 125 is formed above the reaction chamber 100. Meanwhile, the fluid introduced into the fluid flow path 120 may be continuously reused in a circulation structure. In addition, the fluid inlet 123 and the fluid outlet 125 are provided with fluid inlet and out adjusting means such as a valve that can control the entry and exit of the fluid.

The position of the fluid inlet 123 and the fluid outlet 125 is not particularly limited, but it is advantageous in terms of thermal efficiency to flow from the bottom to the top.

The subcritical reaction device 1000 includes a fluid temperature control means 50 disposed outside the reaction chamber 100 and connected to the fluid inlet 123. The fluid temperature regulating means 50 may variably control the temperature of the fluid flowing into the fluid flow path 120, so that the temperature environment of the cooling step after the reaction is changed in various degrees. By the temperature control means 50, the experimenter can design the experiment in consideration of various temperature variables after the subcritical state ends.

The temperature of the fluid flowing into the fluid flow path 120 may be 80 to 90 ℃. However, depending on the experimenter, it may be intended to introduce a fluid of 100 ℃ or more, in this case, an organic solvent having a boiling point higher than water may be used as the fluid. For example, so-called heat medium oil and the like can be used.

Meanwhile, in the present exemplary embodiment, the number of fluid inlets 123 through which fluid is introduced into the fluid flow unit 121 is described as being singular. Alternatively, the fluid inlets 123 may be designed in plural numbers. Therefore, heterogeneous fluids having different boiling points along the plurality of fluid inlets 123 may be introduced into the fluid flow path 120 sequentially or simultaneously. Through the design parameters of the fluid inlet 123 may be more experimental design of multiple angles.

A heat supply unit 130 including heating means is disposed on an outer circumferential surface of the reaction outer wall 120. The heat supply unit 130 serves to supply a heat source to the reaction space 70 such that the inside of the reaction space 70 becomes a subcritical temperature condition. The heat source generated from the heat supply unit 130 is transferred to the reaction space 70 using air inside the fluid flow unit 121 of the reaction outer wall 110 as a heat transfer medium. The volume or width of the fluid flow portion 121 may be determined in consideration of such heat transfer efficiency.

For example, a band heater or the like may be used as the heat supply unit 130. The heat supply unit 130 receives power from an external power supply means P to convert electricity into heat. As the power supply means P, two or more powers P ₁ and P ₂ may be used, and after the subcritical state is reached, the internal cooling rate is easily diversified by sequentially shutting down the power without collectively shutting down the power. To adjust. This also serves to provide the experimenter with various experimental design factors.

A first heat insulating member 140 is disposed on an outer wall of the heat supply unit 130 to prevent heat loss inside as an outermost portion of the reaction chamber 100. The material of the first heat insulating member 140 is not particularly limited, and various heat insulating materials known to those skilled in the art may be used.

In the reaction space 70, a stirrer 30 for agitating the reactants is inserted and disposed for uniform reaction of the reactants. The stirrer 30 includes a stirring shaft 31 and the stirring blade (32).

The upper portion of the reaction outer wall 110 is formed with a fastening groove 113 that can be fastened to the cover body 200 to be described later. The cover body 200 is firmly fastened with the reaction outer wall 110 during the reaction, and is separated from the reaction outer wall 110 before the reaction ends or before the reaction. That is, the cover body 200 is a means for tightly sealing the reaction space 70, and the opening and closing means of the reaction chamber 100.

The cover body 200 surrounds the cover member 210 and the cover member 210 in which the protrusion 212 that can be fastened to the fastening groove 113 and the second heat insulation to prevent internal heat loss. The member 220 is included.

In the central portion of the cover member 210, a first through passage 215 is provided to provide a rotation space in which the stirring shaft 31 of the stirrer 30 is inserted and rotated.

As will be described later, the stirrer 30 is not an accessory of the reaction chamber 100 but an accessory of the head body (see 300 of FIG. 4) that is fastened to the cover body 200 and the cover body 200. Therefore, when the cover body 200 is separated from the reaction chamber 100, the cover body 200 is separated from the reaction chamber 100 along the reaction chamber 100.

FIG. 2 is a cross-sectional view illustrating a shape according to another exemplary embodiment of part 'A' of FIG. 1. 3 is a cross-sectional view illustrating a state according to still another embodiment of portion 'A' of FIG. 1.

2, a fluid flow part 461 is formed inside the reaction outer wall 450 according to the present embodiment, and the fluid flow part 461 includes a curved surface. The aspect of the curved surface is not particularly limited but may have a regular curved structure for uniform supply of heat or uniform cooling, and an inner surface of the fluid flow portion 461 may have a wavy structure, for example. Can have As such, since the fluid flow portion 461 includes a curved surface, heat inflow efficiency may be improved by increasing the contact area of heat transfer or cooling. The heat supply part 470 and the heat insulation member 480 are sequentially arranged outside the reaction outer wall 450. Since the heat supply unit 470 and the heat insulating member 480 have already been described, a detailed description thereof will be omitted.

Referring to FIG. 3, a fluid flow part 561 is formed inside the reaction outer wall 550 according to the present embodiment, and the fluid flow part 561 includes an inclined structure that gradually narrows upward. The inclination angle θ of the inclined structure is not particularly limited, but is preferably about 5 m or less. Since the fluid flow portion 561 has an inclined structure that becomes thinner toward the top, the cooling efficiency of the lower region where the sediment may be concentrated may be relatively enhanced. The heat supply part 570 and the heat insulating member 580 are sequentially arranged outside the reaction outer wall 550. Since the heat supply unit 570 and the heat insulating member 580 have already been described, a detailed description thereof will be omitted.

In the above description, the

fluid flow portions

461 and 561 including the curved structure or the inclined structure have been described, but the three-dimensional shape of the fluid flow portion may be appropriately designed and manufactured according to the operator's experimental environment.

As described above, the reaction outer wall 110 and the cover body 200 by the fastening of the fastening groove 113 of the reaction outer wall 110 and the protrusion 212 of the cover body 200 and other precise fastenings. ) Is fastened so as not to allow minute spacing. The cover member 210 of the cover body 200 is formed with at least one gas discharge pipe 216 formed for the discharge of the gas generated from the reaction chamber 100 described above, the gas discharge pipe 216 to the outside The end 218 of the exposed gas discharge pipe 216 is provided with a means such as a valve that can block or allow the discharge of gas. A gas outlet 222 is formed in a corresponding region of the second heat insulating member 220 corresponding to the end 218 of the gas discharge pipe.

The extension part 211 formed to extend from the protrusion 212 into the cover member 210 may have a structure integrated with the cover member 210, or alternatively inserted into the cover member 210 to be assembled. It may be a structure. The upper surface of the cover body 200 is fastened with the head body 300 and extends along the longitudinal direction of the stirring shaft 31 of the stirrer 30 and a rotating space for the rotation of the stirring shaft 31 ( 92, a second through hole) is formed in the opening hole 230 in the upper surface.

The head body 300 is inserted into the opening hole 230 of the cover body 200 and is firmly coupled to the cover body 200. The coupling portion B of the cover body 200 and the head body 300 may be introduced into a variety of fastening grooves or coupling means that can be considered at the level of those skilled in the art.

As such, the stirring shaft 31 extends along the space 92 completely enclosed by the cover body 200 and the head body 300.

The head body 300 includes a cylindrical first head body 310 and second head body 320 each having an outer circumferential surface.

The first head body 310 is a portion which is directly coupled to the cover body 200, the first passage of the fastening body 200 for smooth rotation of the stirring shaft 31 (215 of FIG. 1). And a second passageway 92 formed extending from).

A stirring head 34 integrated with the stirring shaft is formed at an upper end of the stirring shaft 31, and the stirring head 34 is recessed inside the stirring head 40. The stirring head 34 and the stirring head 40 may have an integrated structure for efficient transmission of rotational force.

An upper portion of the first head body 310 accommodates the stirring head portion 40 corresponding to the shape of the stirring head portion 40 and is spaced apart from the stirring head portion 40. That is, the first head body 310 is formed with a rotary cavity 94 which is a space for accommodating the stirring head portion 40. At least one opening 312 is formed in at least one region of the outer circumferential surface of the first head body 310.

The second head body 320 is disposed to surround the outer circumferential surface and the upper portion of the upper portion of the first head body 310. Since the second head body 310 is not coupled to the first head body 310, the second head body 310 may rotate along the outer circumferential surface of the first head body 310.

A second magnetic body 322 is formed in an area of the second head body 320 facing the opening 312. Meanwhile, a first magnetic body 42 is formed in an area of the stirring head 40 that faces the opening 312. The first magnetic body 42 and the second magnetic body 322 are firmly attached or recessed to one region of the second head body 320 and the stirring head 40, respectively.

The durability of the

magnetic bodies

42 and 322 is, after all, very important as a factor in determining the rotational durability of the stirrer 30. Therefore, it is important to arrange the

magnetic bodies

42 and 322 to ensure maximum durability.

The first magnetic body 42 and the second magnetic body 322 are magnetically attracted to each other through the opening 312 (M) acts to rotate the second head body 320 in accordance with the stirring head portion ( 40) will rotate. The rotational force of the stirring head portion 40 is transmitted to the stirring shaft 31 as it is.

The second head body 320 may be connected to an external rotational power transmission device (not shown) and the belt 5 to receive a rotational force.

As a result, the head body 300 according to the embodiment of the present invention has a boundary surface between the first head body 310 and the second head body 320, which is a boundary surface R from which the second head body 320 is separated from each other. It has a structural feature that can rotate along R).

In summary, the first head body 310 is firmly fastened and fixed to the cover body 200, and the second head body 320 is free to rotate by being supplied with external rotational force. Has a structure. Therefore, the subcritical reaction apparatus 1000 according to the present invention can sufficiently prevent the loss of the internal gas pressure by easily transmitting the rotational force through the magnetic force while ensuring sufficient internal airtightness.

Subcritical reaction method according to an embodiment of the present invention is based on the above-described subcritical reaction apparatus (1000). The method includes a subcritical reaction step of introducing the injected reactant into the reaction space 70 and raising and raising the pressure and temperature to a subcritical pressure and temperature. When the subcritical reaction is completed, a fluid is introduced into the fluid flow path 120 to undergo a cooling step of cooling the reaction space.

Using the above-described subcritical reaction apparatus 1000, it is possible to vary the tendency of the internal temperature decrease during the cooling step by adjusting the temperature of the incoming fluid. In addition, by using heterogeneous fluids, it is possible to diversify the variables of the experimental design, and in some cases, by using a fluid having a high boiling point of 100 ° C or higher, the environment of 100 ° C or higher can be sufficiently experienced during cooling.

5 is a graph showing the temperature change after reaching the subcritical state according to an embodiment of the present invention. 6 is a graph showing the temperature change after reaching the subcritical state according to another embodiment of the present invention.

Referring to FIG. 5, as an example, the use of the same fluid (first fluid) during the cooling process may also change the slope on the cooling curve by inducing a temperature change of the first fluid. Alternatively, as shown in FIG. 5, two fluids (first fluid and second fluid) may be sequentially used to change the slope on the cooling curve.

Referring to FIG. 6, after the first cooling using the first fluid, the third fluid having a high boiling point may be continuously used and the temperature may be prevented from being lowered, thereby maintaining a constant environment of 100 ° C. or higher, which is a relatively high temperature during the cooling process. have.

5 and 6 are merely illustrative of an exemplary cooling process, the experimental designer can utilize the external temperature control means (50 in FIG. 1), selective shutdown of the power supply means (P ₁ , P _{2 in} Figure 1, boiling point Through the use of a plurality of different fluids, experimental variables after reaching the subcritical state (after completion of the reaction) can be diversified and various experimental designs can be envisioned.

Claims

In the high temperature and high pressure reaction device having a stirrer including a reaction chamber and a stirring shaft for providing a reaction space,

A reaction outer wall having a fluid flow path through which a fluid flowing from the outside flows and formed in at least one region therein and partitioning the reaction space;

A heat supply unit formed on at least a part of an outer surface of the reaction outer wall and including heating means; And

When the reaction is coupled to the outer wall of the reaction chamber to seal the reaction space, the stirring shaft of the stirrer includes a cover body formed with a first through passage for penetrating and rotating,

A subcritical reaction device capable of converting the state inside the reaction space into the pressure and temperature of the subcritical state.
The method of claim 1,

And the fluid flow path comprises a curved surface.
The method of claim 1,

Subcritical reaction device, characterized in that to block the flow of fluid into the fluid flow path until the interior of the reaction space reaches a subcritical state, and to allow the flow of the fluid after reaching the subcritical state.
The method of claim 1,

Subcritical reaction apparatus is provided outside the reaction chamber, the temperature control means for adjusting the temperature of the fluid flowing into the fluid inlet.
The method of claim 1,

And a plurality of fluid inlets for introducing fluid into the fluid flow path in one region of the reaction outer wall.
The method of claim 1,

Subcritical reaction apparatus, characterized in that the heat insulating member is disposed in at least one region of the outer surface of the heat supply.
The method of claim 1,

The cover body subcritical reactor, characterized in that it comprises a gas discharge pipe and a gas discharge port for discharging the pressure inside the reaction space to the outside.
The method of claim 1,

It is fastened to the upper surface of the cover body, and is formed with a rotary cavity extending from the first through passage and providing a second through passage as the through and rotating space of the stirring shaft and the rotating space of the head portion of the stirrer. Subcritical reaction device further comprises a head body.
The method of claim 8,

The head body is directly fastened and fixed to the upper surface of the cover body and is spaced apart from the head portion of the stirrer to surround the head portion of the stirrer, at least one opening is formed in at least one region facing the stirrer head portion A first head body; And

And a second head body disposed on an outer surface of the first head body and capable of rotating by receiving rotational power from the outside.
The method of claim 9,

The second head body includes a second magnetic body protruding toward the opening portion in at least one region corresponding to the opening portion,

And the stirrer head portion includes a first magnetic body corresponding to the second magnetic body on at least one surface of the stirrer head portion.
The method of claim 1,

And a plurality of power supply means disposed outside the reaction chamber and supplying power to the heat supply unit.
Injecting a reactant into the reaction space of the subcritical reaction apparatus of claim 1;

A subcritical reaction step of elevating and raising the reaction space to be a subcritical pressure and temperature; And

And a cooling step of reducing the pressure in the reaction space and introducing the first fluid into the fluid flow path of claim 1 to cool the reaction space.
The method of claim 12,

And the temperature of the first fluid is adjusted to vary during the cooling step.
The method of claim 12,

In the cooling step, the subcritical reaction method, characterized in that the second fluid having a boiling point different from the first fluid after the introduction of the first fluid to the fluid flow path.