JP2007136280A - Microfractionating device and fractionating process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a microfractionating device which can be used by connecting it with a micro fluid device or incorporating it into a microfluid device, and to provide a fractionating process of a fine sample which is capable of treating it with a micro fluid device. <P>SOLUTION: The microfractionating device is to fractionate each component from a mixed fluid containing at least two components of which the boiling point is different and has a passage 1 for fractionation with a gas inflow port or liquid inflow port 6' and a gas outlet 5 and a liquid outlet 7. The at least two components included in the mixed solution of which the boiling point is different is fractionated by forming the gas part and the liquid part so that they are brought in gas-liquid contact with each other under countercurrent in the passage by two temperature control parts installed in the passage, which temperatures are controlled to different temperatures. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a micro rectification device for rectifying each component from a mixed fluid containing at least two types of components connected to or incorporating a so-called micro fluid device, and a method for rectifying a very small amount of sample. .

  Microfluidic devices are also called microchannel chips, microchemical chips, etc., where chemical engineering processes such as chemical and biochemical reactions, mixing and separation, components, etc. Detection and analysis. Microfluidic devices are capable of miniaturizing samples and miniaturizing devices, complying with the requirements of the times for energy saving, resource saving, and reduction of waste, improving reaction speed, and shortening experimental conditions. Since it is easy to change one after another, the time required for reaction screening and examination of optimum conditions can be greatly shortened. In addition, the temperature can be rapidly raised and lowered, the reaction can proceed at the optimum temperature, and the temperature distribution is also reduced, so that side reactions can be suppressed. Furthermore, when optimum conditions are found, the numbering-up method enables the production immediately without considering the scale-up, and it is expected as a future chemical reaction device.

  Until now, however, rectification required for many reactions could not be performed in a microfluidic device. This is because rectification is carried out by bringing the gas phase (vapor phase) rising in the vertically installed rectification tube (rectification tower) into contact with the liquid phase descending, but the diameter of the flow channel for rectification If it is thin, for example, 1 mm or less, the influence of surface tension is increased, the influence of gravity is reduced, the rectification flow path is filled with liquid, and the gas phase and the liquid phase are kept in a stable state. Could not contact in countercurrent. As one method for avoiding this difficulty, a method of applying a large gravitational acceleration by centrifugal force is conceivable, but there are many restrictions on use and it is not practical.

On the other hand, a gas-liquid contact device is known as one of micro unit operations by a microfluidic device. This is because gas is introduced from one of the inlets of the gas-liquid contact channel having two inlets at one end and two outlets at the other end, and liquid is introduced from the other, and the gas-liquid contact channel is arranged in parallel. It is made to flow in a flow and make gas-liquid contact, and flow out from each outlet (see, for example, Non-Patent Document 1 and Patent Document 1).
However, this was limited to parallel flow and could not be carried countercurrently. Therefore, it could not be applied to rectification. That is, when a liquid is introduced from one of the inlets and a gas is introduced from one of the outlets in an attempt to flow countercurrently, the liquid flows out of the other inlet and the gas flows out of the other outlet. As a result, neither liquid nor gas flowed in the gas-liquid contact channel.
Sakamoto, Goto, 5th Chemistry and Micro / Nano System Proceedings, 19 (2002) Japanese Patent Laid-Open No. 2001-137613

  The problem to be solved by the present invention is to provide a micro rectification device that can be used by being connected to or incorporated in a microfluidic device, and a method for rectifying a micro sample that can be handled by the microfluidic device. It is in. That is, an object of the present invention is to provide a method and an apparatus for performing rectification by allowing a liquid phase and a gas phase to flow in contact with each other in a minute rectification flow channel that is easily filled with a liquid phase by capillary action.

The present inventor is a micro rectification device for rectifying each component from a mixed fluid containing at least two components having different boiling points,
a) the micro rectification device has a rectification flow path having a gas inlet or liquid inlet, a gas outlet, and a liquid outlet;
b) The rectification flow path has two temperature control units that are temperature-controlled at different temperatures on the side surfaces of the flow path,
c) A low boiling point component of the mixed fluid flowing through the rectification flow channel is gasified by the first temperature control unit controlled to a high temperature among the temperature control units, and is in contact with the first temperature control unit. A gas part through which gas flows is formed,
A high boiling point component of the mixed fluid flowing through the rectification flow path is liquefied by a second temperature control unit controlled to a low temperature among the temperature control units and comes into contact with the second temperature control unit to A liquid part flows through
d) the gas part and the liquid part form a countercurrent gas-liquid contact part;
e) the gas outlet is provided downstream of the gas section;
f) Rectification using a micro rectification device for rectifying at least two kinds of components having different boiling points contained in the liquid mixture, wherein the liquid outlet is provided downstream of the liquid part. As a result, it was found that each component can be rectified, and the present invention has been achieved through intensive studies.

The inventor is also a rectifying method for rectifying each component from a mixed fluid containing at least two components having different boiling points,
a) A liquid mixed fluid is introduced from the liquid inlet of the rectification flow path, or a gaseous mixed fluid is introduced from the gas inlet,
b) Temperature control of the two temperature control units provided in the rectification flow path to different temperatures,
c) Controlling the first temperature control unit controlled to a high temperature among the temperature control units to a temperature at which the low boiling point component of the mixed fluid flowing in the rectification flow path 1 is gasified, and the gas is Forming a gas part flowing in contact with the first temperature control part;
d) Among the temperature control units, the second temperature control unit controlled to a low temperature is controlled to a temperature at which the high boiling point component of the mixed fluid flowing in the rectification flow path 1 is liquefied, so that the liquid is the second Form a liquid part that flows in contact with the temperature control part,
e) countercurrent gas-liquid contact between the liquid flowing through the liquid part in the rectification flow path of the micro rectification device and the gas flowing through the gas part;
f) outflowing gas enriched in low-boiling components from the gas outlet provided downstream of the gas section;
g) A rectification method characterized by causing a liquid having a high boiling point component to flow out from the liquid outlet provided downstream of the liquid part, and by intensively examining the rectification method. Reached.

  The present invention provides a method for rectifying a small amount of sample (that is, distillation having a theoretical plate number exceeding 1) as handled by a microfluidic device and a micro rectifying device used therefor. That is, the liquid phase and the gas phase are made to flow in a countercurrent flow in a minute rectification flow channel and brought into contact with each other, and the gas phase rich in low-boiling components and the liquid phase rich in high-boiling components are separately discharged. Can be provided.

  In addition, the present invention can construct a microreactor in which synthesis and separation are integrated by continuing with a synthesis reaction and analysis performed in a microfluidic device, and a micro total analysis system (μ-TAS). ) Can also be constructed.

  Hereinafter, the micro rectification device of the present invention will be described in detail with reference to the drawings. In each drawing used for the following description, the scale of each member is appropriately changed to make each member a recognizable size.

  The mixed fluid to be rectified according to the present invention may be a mixed fluid of three or more components. However, for the sake of simplicity, the following two components (low-boiling component and high-boiling component) unless otherwise specified. The rectification of the mixed fluid will be described as an example. The mixed fluid may be a gas phase, a liquid phase, or a supercritical fluid phase at normal temperature and pressure.

  Here, the “mixed fluid” refers to a mixed fluid to be rectified (raw fluid) or a mixture in which the composition ratio of components is changed during the rectifying treatment of the mixed fluid to be rectified. When it is necessary to clarify that the fluid is a mixed fluid (raw fluid) to be rectified, it may be referred to as “original mixed fluid”. The “(original) mixed fluid-derived gas” means a complete gasified product (steam), a partially gasified product (steam), or a residual gas (steam) partially liquefied, “Liquid derived from the (original) mixed fluid” refers to a completely liquefied product, a partially liquefied product, or a residual liquid partially gasified from the (original) mixed fluid.

[Micro rectification device]
As shown in the exploded view of FIG. 1 and the schematic view of FIG. 2, the micro rectification device 100 of the present invention has a capillary rectification flow channel 1 as an essential component, The rectification flow path 1 includes two temperature control units 10 that are temperature-controlled at different temperatures, that is, a higher temperature first temperature control unit 10a and a lower temperature second temperature control unit 10b. The temperature control mechanism 80 for controlling the temperature of the temperature control unit 10 to a predetermined temperature may be incorporated in the micro rectification device, or provided independently outside the micro rectification device 100. You may combine at the time of use.
Hereinafter, for simplification of description, the micro rectification device 100 and its components will be described in the posture shown in the side views of FIGS. 1 and 2, but the posture may be changed to an arbitrary orientation. .

  The micro rectification device 100 of the present invention may be used in combination with any other mechanism for performing rectification. For example, the micro rectification device 100 includes a fixing unit for fixing the micro rectification device 100, a temperature control mechanism 80 and a temperature control apparatus therefor, an independent pump for feeding a mixed fluid to be rectified, and a micro fluid device. It can be used in combination with a housing having a drive mechanism for a pump mechanism incorporated in the housing. By adopting such a structure, it is possible to dispose the micro rectification device 100 which is a wetted part disposable or to easily perform rectification of different liquids by replacing only the part.

The micro rectification device 100 of the present invention may be formed as an independent device that performs only rectification, or may be integrated into a microfluidic device having another mechanism such as a reaction tank or a filtration mechanism.

The external shape of the micro rectification device 100 of the present invention is arbitrary. For example, as shown in FIG. 1, the external shape of the rectification flow channel 1 is parallel to the plane of the micro rectification device 100. The provided shape is preferred. By adopting such a structure, the temperature control mechanism 80a is provided on the upper surface thereof, and the temperature control mechanism 80b is provided on the lower surface thereof, and the upper side of the separation channel 1 is adjusted to a high temperature easily and accurately. It is possible to form the liquid part 3 by adjusting the lower side of the separation channel 1 to a low temperature. That is, it is possible to form a structure in which the two temperature control units are provided on the opposing surfaces of the plate-like portions surrounding the rectification flow path. Such a structure is, for example, as shown in FIGS. 1 and 2, a plate-like or sheet-like member in which a groove to be a gas portion 2 is formed and a plate-like shape in which a groove to be a liquid portion 3 is formed. Or it can manufacture by laminating | stacking and fixing a sheet-like member. The fixing may be fixing by clamping or screwing, adhesion, fusion, adhesion, or the like.

  In the example shown in FIG. 1 and FIG. 2, the rectification flow path 1 is provided with a liquid inlet 6 ′ as an inlet for allowing the mixed fluid to flow in. Generally, as shown in FIG. As the inlet, when the mixed fluid is introduced in the liquid state, the liquid inlet 6 or the liquid inlet 6 ′ is provided, and when the mixed fluid is introduced in the gas state, the gas inlet 4 or the gas inlet is provided. 4 'is provided. The liquid inlet 6 or the liquid inlet 6 ′ is connected to the mixed fluid inlet 24 via the communication channel 14, or the gas inlet 4 or the gas inlet 4 ′ is connected via the communication channel 14. It is connected to the mixed fluid inlet 24.

Further, a gas outlet 5 is provided at one end of the rectification flow path 1, and a liquid outlet 7 is provided at the other end. The liquid outlet 7 is connected to a high boiling point component concentrate outlet 27 via a communication channel 17. The liquid inlet 6 may be connected in the middle of the rectification flow path 1 as shown in FIG. Further, the gas outlet 5 may be connected to the communication channel 15 via the porous membrane 8.
The mixed fluid inlet 24, the high-boiling component concentrate outlet 27, and the low-boiling component concentrate outlet 17 may be formed as openings to the outside of the micro rectification device 100 or outside the micro rectification device 100. A pipe (not shown) connected to the mechanism may be directly connected, or may be connected to a mechanism provided in the micro rectification device 100, such as a liquid storage tank (not shown). Further, it may be connected to another mechanism provided in the microfluidic device integrated with the micro rectification device 100, for example, a reaction tank (not shown) or a detection unit (not shown).

In the present invention, it is necessary to allow only the liquid to flow out from the liquid outlet 7 and prevent the gas from flowing out. For this purpose, the diameter of the liquid outlet 7 and the cross-sectional area of the communication channel 17 connected thereto are made smaller than the cross-sectional area of the rectification channel 1, and the inner surface of the communication channel 17 is made solvophilic. In addition, it is effective and preferable to connect a pump (not shown) to the communication channel 17 so that the fluid is taken out from the liquid outlet 7 at a predetermined speed.

  The micro rectification device 100 of the present invention is also cooled to liquefy the total amount of the mixed fluid in the middle of the communication channel 14 that guides the mixed fluid introduced into the mixed fluid inlet 24 to the liquid inlets 6 and 6 ′. It is also preferable to provide a cooling section for liquefying each rectified component or cooling it to near room temperature in the middle of the communication flow path connected to each outlet 25, 27. When the gas inlets 4 and 4 ′ are provided instead of the liquid inlets 6 and 6 ′, the mixed fluid introduced into the mixed fluid inlet 24 is guided to the gas inlets 4 and 4 ′. It is also preferable to provide a heating part in the middle of the communication channel 14 for gasifying the entire amount of the mixed fluid.

Micro rectification device 100, the thickness direction, i.e. the thermal conductivity of the second temperature control unit 10b direction from the first temperature control unit 10a is ^{preferably 10wm -1 K} -1 or ^{less, 3wm -1 K} -1 or less is more Preferably, ¹ wm ⁻¹ K ⁻¹ or less is most preferable. The lower limit of the thermal conductivity is naturally limited, but there is no inconvenience due to its small size, so there is no need to limit it. The lower limit of the thermal conductivity can be, for example, 0.01 wm ⁻¹ K ⁻¹ . By setting the thermal conductivity in the direction of permeation through the porous diaphragm of the rectification flow channel in such a range, it becomes easy to provide a temperature difference between the liquid part 3 and the gas part 2. Energy consumption can be reduced.

  As a material having the above thermal conductivity, for example, an organic polymer, glass, ceramic or the like can be preferably used. Among them, an organic polymer can be produced if a material resistant to a liquid to be distilled is selected. It is preferable because it is easy. In addition, even in the case of a material having a high thermal conductivity in bulk, a method of making the thermal conductivity in the above range by making a porous body or a composite with a low thermal conductivity material can be preferably adopted. . Examples of such a porous body include foamed glass, ceramics having bubbles, and a porous polymer. Examples of the composite with a low thermal conductivity material include mixing of microcapsules of glass or organic polymer, In the case of mixing hollow fibers, metal or glass, a laminate with an organic polymer and a laminate with the above porous body can be exemplified.

  Examples of the material having a small thermal conductivity that is the lower limit of the thermal conductivity include an organic polymer foam, and may be a vacuum heat insulating layer. In particular, in the micro rectification device 100, the member constituting the liquid portion 3 and the member constituting the gas portion 2 are fixed or fixed with a porous membrane interposed therebetween, and a part of the porous membrane is a porous diaphragm. In the case of the structure 8, the porous membrane has the same dimensions as the member sandwiching the porous membrane, and the periphery of a necessary portion in the porous membrane is sealed with resin to form the porous membrane 8. And it is also preferable to make another part function as a porous heat insulating material.

By making the thermal conductivity in the thickness direction of the rectification flow path 1 in the above range, the heat flow can be reduced while providing a large temperature difference, so that energy can be saved.

Further, by setting the thermal conductivity in the length direction of the rectification flow channel 1 to the same range as the thickness direction, it becomes easy to apply a large temperature gradient in the length direction of the rectification flow channel 1. Even in the rectification of mixed solutions with greatly different boiling points, the length of the rectification flow path can be shortened, so the rectification flow path is highly efficient, that is, has a large number of distillation stages per length of the rectification flow path. Is obtained. In addition, the first temperature control unit 10a and the second temperature control unit 10b can also provide a temperature gradient with energy saving.

  Also in this case, the material for realizing these thermal conductivities is the same as that in the thickness direction of the rectification flow channel 1.

[Rectification channel]
The rectification flow path 1 of the micro rectification device 100 of the present invention is formed as a single capillary flow path, as shown in the schematic diagram generalized in FIG. In the rectification flow path 1, the first temperature control unit 10a side is a liquid part 3 through which a liquid flows, and the second temperature control unit 10b side is a gas unit 2 through which a gas flows. The gas part 2 is an area where a gas derived from the mixed fluid flows, and the liquid part 3 is an area where a liquid derived from the mixed fluid flows. There is no boundary between the gas part 2 and the liquid part 3, and the ratio of the cross-sectional areas occupied by the liquid part 3 and the gas part 2 can be changed depending on the operating conditions. In the micro rectification device of the present invention, a liquid and a gas are brought into contact with each other in the liquid part 3 and the gas part 2 of the rectification flow channel 1 in a countercurrent manner, and gasification (evaporation) of a high-boiling component is reduced at the gas-liquid contact interface. The boiling component can be liquefied (condensed).
At this time, the state of the gas-liquid contact interface is, for example, as described in the rectification method of the present invention described later, with the first temperature control unit 10a on the upper side of the rectification flow channel 1 in FIGS. The temperature is adjusted to a temperature exceeding the boiling point to form the gas part 2, and the second temperature control unit 10 b below the rectification flow path 1 is adjusted to a temperature lower than the boiling point of the liquid and is used to form the liquid part 3. I can do it.

The length of the rectification flow path 1 is arbitrary and can be set depending on the application and purpose, but is preferably 0.5 to 20 cm, more preferably 1 to 10 cm, and most preferably 2 to 5 cm. By setting it within this range, sufficient rectification efficiency can be obtained, and operation such as temperature control becomes easy.
The rectifying flow path 1 does not necessarily need to be linear, and may be formed in an arbitrary shape such as a curved line, a zigzag shape, a spiral shape, or a spiral shape. In the micro rectification device 100 of the present invention, the rectification flow channel 1 can be installed regardless of the direction of gravity, but the liquid portion 3 side or the liquid outlet 7 on the lower side may This is preferable from the viewpoint of stabilizing the flow. .

  The cross-sectional shape of the rectification flow channel 1 is arbitrary, and may be a rectangular shape, a trapezoidal shape, a semicircular shape, or the like. However, since it can be easily incorporated into a microfluidic device and easily manufactured, the rectangular shape, the trapezoidal shape, the circular shape, or the semicircular shape A circular shape is preferred. Further, from the viewpoint of stabilizing the flow of the liquid part 3, it is preferable to have a cross-sectional shape in which the gas part 2 is wide and the liquid part 3 is narrow. For example, a shape in which a wide groove and a narrow groove are combined, for example, a convex shape (in the case of FIG. 1 and FIG. 2b, an upside down convex shape), an inverted trapezoid, and an inverted triangle Further, a shape having a plurality of small grooves provided in parallel to the rectification flow path 1 is preferable on the inner surface of the rectification flow path 1 on the second temperature control 10b portion side. The cross-sectional shape of each of the small grooves is arbitrary, and may be a rectangle, a semicircle, an inverted trapezoid, a V shape, or the like. The number of grooves is arbitrary, and is preferably 2 to 100, for example, and more preferably 3 to 10.

The distance between the first temperature control unit 10a and the second temperature control unit 10b of the rectification flow channel 1, that is, the vertical dimension in the schematic side view of FIG. May be referred to as “thickness.”) Is 3 mm or less, preferably 2 mm or less, and more preferably 1 mm or less. If this upper limit is exceeded, the amount of sample handled increases and the characteristics of the microfluidic device tend to be lost. The lower limit of the average distance is arbitrary, but is preferably 10 μm or more, more preferably 20 μm or more, and most preferably 30 μm or more. By setting this range, the pressure loss does not become excessively large, and the amount of heat flowing between the first temperature control unit 10a and the second temperature control unit 10b of the present micro rectification device does not excessively increase.

A shape in which a wide groove formed by the rectification flow path 1 and the gas part 2 and a narrow groove formed by the liquid part 3 are combined, for example, the reverse convex shape and the small grooves are provided in parallel in a plurality of rows. In the case of a shape, the upper limit of the narrow groove formed with the liquid portion 3 is preferably 300 μm or less, more preferably 200 μm or less, and most preferably 100 μm or less. When this upper limit is exceeded, mixing in the liquid phase becomes insufficient, and the efficiency of rectification decreases. Although the minimum of this thickness can be set arbitrarily, Preferably it is 3 micrometers or more, More preferably, it is 10 micrometers or more, Most preferably, it is 30 micrometers or more. By setting this range, a sufficient rectification rate can be secured.

The dimension of the rectification flow channel 1 in the direction perpendicular to the length direction and in the direction perpendicular to the thickness direction (hereinafter may be referred to as the “width” of the rectification flow channel) is also arbitrary. The average width is preferably 3 μm to 10 mm, more preferably 10 μm to 3 mm, and most preferably 30 μm to 1 mm. By making it into this range, the production becomes easy. The cross-sectional area of the flow channel 1 for rectification is also arbitrary, but it is preferably in the range of 30 μm ^{2 to 3} mm ² because it is easy to manufacture while ensuring sufficient rectification efficiency and rectification speed.

A shape in which a wide groove formed by the rectification flow path 1 and the gas part 2 and a narrow groove formed by the liquid part 3 are combined, for example, the reverse convex shape and the small grooves are provided in parallel in a plurality of rows. In the case of the shape, the width of the wide groove formed with the gas portion 2 is the same as the above-described value described as the preferred range of the rectification flow path 1. The upper limit of the width of the narrow groove and each of the small grooves formed with the liquid part 3 is less than the width of the gas part 2, and is preferably ½ or less, more preferably 1 of the width of the gas part 2. / 3 or less, most preferably 1/4 or less. By making it less than this upper limit, the effect of adopting the above structure is obtained. The lower limit of the width can be arbitrarily set, but is preferably 3 μm or more, more preferably 10 μm or more, and most preferably 30 μm or more. By setting this range, a sufficient rectification rate can be secured.

The inner surface of the rectifying flow channel 1 is the solvent-repellent (solvophobic) inner surface of the gas part 2 side (however, the “solvent” in this specification refers to the liquid flowing in the rectifying flow channel 1. In other words, including “water”, the same applies hereinafter), and the inner surface on the liquid part 3 side is solvophilic, so that the liquid is easily liquefied and the gas part 2 is less likely to be filled with the liquid. Since the gas part 2 and the liquid part 3 are clearly separated and easily flow, the number of theoretical plates is improved, which is preferable.
A method of providing the above-described solvent-repellent part and solvophilic part on the inner surface of the rectification flow path 1 is, for example, a method disclosed in Japanese Patent Application Laid-Open No. 2001-137613 filed by the present inventors. That is, it can be carried out by a method of introducing a polymer having a predetermined functional group at a predetermined position by ultraviolet graft polymerization.

  In the micro rectification device of the present invention, the liquid outlet 7 is provided at one end of the rectification flow path 1, and the gas outlet 5 is provided at the other end of the rectification flow path 1. Thus, by providing the liquid outlet 7 and the gas outlet 5 at both ends of the rectification flow path 1, the rectification device can be brought into gas-liquid contact in countercurrent. The liquid outlet 7 is preferably provided on the side wall of the rectification flow path 1 on the liquid part 3 side or the end face of the rectification flow path 1 on the liquid part 3 side, and the gas outlet 5 is preferably a rectification flow on the gas part 2 side. It is provided on the side wall of the channel 1 or the end surface of the rectification channel 1 on the gas part 2 side. By providing at this position, the flow of the liquid and gas becomes smooth, and the rectification efficiency is improved.

On the other hand, the position where each inflow port 4, 4 ', 6, 6' is provided may be as follows. Hereinafter, for simplification of explanation, one end (left side in FIG. 2) of the rectification flow channel 1 is referred to as an “A end” with respect to the rectification flow channel 1, the gas part 2, and the liquid part 3. The other end will be referred to as “B end”.
(1) First method (method of supplying mixed fluid as gas to the end of the rectification flow path 1)
In the first system, a gas inlet 4 is provided on the gas section 2 side at the A end of the rectification flow path 1 in FIG.

  In the first system, when the mixed fluid is sent as a gas from the gas inlet 4 to the rectification flow path 1, the gas flows in the gas section 2 in the direction of the gas outlet, and a part of the gas flows at the second temperature. The liquid that is liquefied in the control unit 10b and liquefied one after another sequentially pushes the previously liquefied liquid, flows through the liquid part 3 toward the A end by capillary action, contacts the gas in countercurrent, and flows out from the liquid outlet To do. Since the temperature of the first temperature control unit 10a is controlled to be higher than the boiling point of the mixed liquid, the liquid in contact with the first temperature control unit 10a is gasified and the entire rectification flow path 1 is not filled with the liquid. In addition, if the introduction flow rate and the liquid take-out flow rate are appropriately controlled, the liquid does not flow out from the gas outlet 5.

The gas flowing in the gas section 2 from the A end toward the B end and the liquid flowing from the B end toward the A end are in gas-liquid contact in a countercurrent flow in the rectification flow channel 1. The gas that has not been liquefied flows out from the gas outlet 5. When the porous diaphragm 8 is provided at the gas outlet 5, the gas passes through the diaphragm and flows out. The amount of liquid flowing from the B end toward the A end can vary depending on each part. For example, if the temperature distribution in the direction of the rectification flow path 1 of the temperature control unit 10 is adjusted so that the gas is liquefied in the vicinity of the B end and the gasification rate and the liquefaction rate are equal in other portions, The liquid amount is the same in all areas in the flow path 1.

  This method is suitable for batch rectification in which a mixed fluid is supplied as a gas. The continuous rectification is suitable for rectification of a mixed fluid that is a gas at room temperature, such as a propane / butane mixed fluid. A storage tank (not shown) for batch rectification is connected directly to the gas inlet 4 or the liquid outlet 7 in the micro rectification device or via the communication channels 14 and 17. It can also be formed, or it can be formed in another device and connected to the mixed fluid inlet 24.

(2) Second method (method of supplying a mixed fluid in the middle of the rectification flow channel 1 using gas)
The rectification flow path 1 of the second system is the same as the first system except that the gas inlet 4 ′ is provided on the gas section 2 side in the middle of the rectification flow path 1 in FIG. 3. .

  In the second system, when the mixed fluid is fed as a gas from the gas inlet 4 ′ to the gas section 2 side in the middle of the rectification flow path 1, the gas flows in the direction of the gas outlet 5 and the second temperature. A part of the liquid is liquefied in the control unit 10 b, flows in the liquid part 3 in the direction of the A end, contacts the gas in countercurrent, and flows out from the liquid outlet 7. The gas that has not been liquefied flows out from the gas outlet 5.

  On the other hand, between the gas inlet 4 ′ and the liquid outlet 7, the gas in the gas part 2 and the liquid in the liquid part 3 are in gas-liquid contact. If the gas liquefaction amount exceeds the liquid gasification amount in this range, the liquid in the liquid part 3 increases as it approaches the A end, and the gas flows in the gas part 2 from the gas inlet 4 ′ toward the A end. . On the contrary, if the gasification amount of the liquid exceeds the gas liquefaction amount in this range, the liquid in the liquid part 3 decreases as it approaches the A end, and the gas passes through the gas part 2 from the A end to the gas inlet 4 ′. Flow in the direction. The position of the gas inlet 4 'is preferably closer to the B end as the amount of low boiling point components in the mixed fluid increases.

This method is suitable for continuous rectification in which a mixed fluid is supplied as a gas, and a low-boiling component concentrated fraction with a high concentration rate and a high-boiling component concentrated fraction with a high concentration rate can be obtained simultaneously.
(3) Third method (method of supplying the mixed fluid as a liquid to the end of the rectification flow path)
In the third method, in FIG. 3, a liquid outlet 7 is provided at the A end of the rectification flow path 1, and a liquid inlet 6 and a gas outlet are provided at the B end. In this method, the liquid mixed fluid introduced from the liquid inlet 6 flows through the liquid portion 3 and flows out from the liquid outlet 7. The gas generated and gasified in the middle of flowing flows through the gas part 2 while coming into contact with the liquid in countercurrent, and flows out from the gas outlet 5.
This method can obtain a high-boiling component concentrated fraction having a high concentration rate.

(4) Fourth method (method of supplying the mixed fluid in the middle of the rectification flow path as a liquid)
The rectification flow channel 1 of the fourth system is different from the liquid flow inlet 6 in FIG. 3 except that the liquid flow inlet 6 ′ is provided on the liquid part 3 side in the middle of the rectification flow channel 1. This is the same as the third method.

  In this system, the temperature of the temperature control unit 10 is adjusted so that the gas liquefaction amount exceeds the liquid gasification amount in the vicinity of the B end. This is preferable because a liquid flow in the 6 'direction is created and the number of theoretical plates is increased. The position of the liquid inlet 6 'is preferably closer to the B end as the amount of low-boiling components in the mixed fluid increases.

This method is suitable for continuous rectification in which a mixed fluid is supplied as a liquid, and a low-boiling component concentrated fraction with a high concentration rate and a high-boiling component concentrated fraction with a high concentration rate can be obtained simultaneously.

  In any of the above systems, a communication channel (not shown) for introducing an inert gas such as nitrogen or argon as a carrier gas is provided at the A end of the rectification channel 1 or in the middle of the communication channel 14. ) May be connected.

[Porous diaphragm]
In operating the micro rectification device 100 of the present invention, it is necessary to operate so as to prevent the liquid from flowing out from the gas outlet 5 and to prevent the gas from flowing out from the liquid outlet 7. For example, if the mixed fluid introduction speed is excessively large, the liquid tends to flow out from the gas outlet 5. In order to suppress this, it is necessary to finely adjust the mixed fluid introduction speed (or mixed fluid introduction pressure) and the temperature of the temperature control unit during operation.

Such a problem can be solved by providing the porous diaphragm 8. The porous diaphragm 8 is composed of a porous film having a large number of pores penetrating the front and back surfaces. The porous diaphragm 8 functions as a diaphragm that allows gas to flow out of the gas outlet 5 and prevents liquid from flowing out of the gas outlet 5. For this reason, by attaching the porous membrane 8 to the gas outlet 5, the allowable range of the liquid introduction speed and the allowable range of the temperature of the temperature control unit 10 are widened, and the control becomes easy.

  The porous structure of the porous diaphragm 8 is arbitrary, for example, a large number of through-holes substantially perpendicular to the surface of the diaphragm, bubbles in communication with each other, gaps between aggregated particles, gaps between microfibrils, fine It can be a gap between the fibers of the nonwoven fabric, etc. The average pore diameter of the porous diaphragm 8 is smaller than the diameter of the gas outlet 5, preferably 1 nm to 10 μm, more preferably 10 nm to 1 μm, and most preferably 100 nm to 500 nm. Since the liquid can be shut off while allowing the gas to pass at a sufficient speed by setting the lower limit of this range, the liquid pressure control allowable range and the temperature control allowable range of the temperature control unit 10 are widened. It becomes easy.

  The thickness of the porous diaphragm 8 is appropriately adjusted so as to satisfy a sufficient strength and a sufficient gas permeation rate according to the material forming the porous diaphragm 8, the pore diameter, the rectification target, the rectification temperature, and the like. However, in the present invention, it is preferably in the range of 1 to 500 μm, and more preferably in the range of 5 to 100 μm. An asymmetric membrane in which a porous membrane is formed on a porous support having a larger pore size is also preferred. In such a membrane, it is preferable that the side having a small pore diameter is directed to the rectification flow channel 1 side.

  The porous diaphragm 8 is preferably a solvent-repellent one having a high contact angle with respect to the contacting liquid. When a solvent-repellent material is used for the porous diaphragm 8, the allowable range of flow rate and pressure for introducing the mixed fluid into the liquid inlets 6 and 6 'or the gas inlets 4 and 4', and the temperature of the rectification flow channel 1 The temperature control mechanism 80 for adjusting the temperature control has a wide tolerance for temperature control, and rectification is facilitated. However, even if the contact angle is low with respect to the liquid to be contacted and is wet, it can be used by keeping the temperature of the porous diaphragm 8 sufficiently higher than the boiling point of the liquid in contact therewith.

  In order to make the surface characteristics of the porous membrane 8 solvent repellent with respect to the liquid in contact with it, as a material of the porous membrane 8, for example, a fluorine-containing polymer such as polytetrafluoroethylene and its copolymer, poly It can be carried out by a method using a dimethylsiloxane group-containing polymer or the like, or a method of modifying the surface of the pores with a solvent-repellent group such as a fluorine-containing group or a dimethylsiloxane group. As the surface modification method, any method such as surface modification with a silylating agent, photochemical modification with an azide group or the like, or surface graft polymerization can be used. When the mixed fluid to be rectified is an aqueous solution, water repellent (hydrophobic) polymers such as polyolefin, polyacetal, polyphenylene sulfide and the like can be suitably used as the material for the porous diaphragm 8 in addition to the above.

The method for attaching the porous membrane 8 is arbitrary as long as the gas outlet 5 of the rectification flow channel 1 is closed. For example, as shown in FIG. 1, the micro rectification device 100 includes a member in which a groove serving as a communication channel 15 communicating with the low boiling point component concentrated fraction outlet 25 is formed on the surface, and the rectification channel 1. It is possible to preferably adopt a structure in which the porous diaphragm 8 is sandwiched and fixed with the member formed with. The member that becomes the porous diaphragm 8 may be a porous membrane that cuts out the rectification flow path 1 and the communication flow path 15 and covers the entire surface of the micro rectification device 100.
Further, as shown in FIG. 3, a porous diaphragm 8 formed at the gas outlet 5 and parallel to the thickness direction of the rectification flow path 1 may be used. Such a porous diaphragm 8 can be formed by the method disclosed in Japanese Patent Application Laid-Open No. 2000-262871 filed by the present inventors. That is, a mixed solution of an ultraviolet crosslinking polymerizable monomer and a poor solvent that dissolves the monomer but does not cause the resulting crosslinked polymer to gelate is a portion that becomes the gas outlet 5 of the rectification flow channel 1 By irradiating ultraviolet rays through the photomask only to the portion that becomes the porous diaphragm 8, the irradiated portion undergoes cross-linking polymerization and phase separation occurs, and the porous diaphragm 8 is fixedly formed.

[Temperature control unit]
The two temperature control units 10 of the micro rectification device 100 of the present invention are provided on the side surface of the rectification flow channel 1 (that is, the inner wall surface parallel to the length direction of the rectification flow channel 1), and temperature control is performed at a high temperature. The first temperature control unit 10a and the second temperature control unit 10b controlled to a low temperature. That is, the first temperature control unit 10a and the second temperature control unit 10b are provided in different portions of the side surface of the rectification flow channel 1 (different portions on the circumference in the cross section of the rectification flow channel 1). As a result, as described in the column of the rectification method of the present invention, the gas part 2 is formed on the first temperature control unit 10a side of the rectification flow path 1, and the liquid part is formed on the second temperature control unit 10b side. The

  The first temperature control unit 10a and the second temperature control unit 10b may be different portions on the side surface of the rectification flow path 1, but are preferably side surfaces facing each other. The side surfaces facing each other refer to a pair of side surfaces that come into contact with two flat surfaces when the rectifying flow channel 1 is sandwiched between two flat surfaces parallel to the rectifying flow channel 1. For example, when the cross-sectional shape of the rectifying flow channel 1 is rectangular, the side surface includes opposing sides, and when the cross-sectional shape is a circle, the side surface includes opposing points on the circumference.

  Although it is not necessary to provide the temperature control unit 10 in the entire range in the length direction of the rectification flow channel 1, rectification is substantially performed in the range in which the temperature control unit 10 is provided. It is preferable that it is all or most of 1 length direction.

  As described above, the temperature control unit of the present invention heats the lower end of the rectification tube (or the liquid storage tank connected to the part) to vaporize the mixed liquid, and cools the upper end to liquefy the vapor. This is different from the temperature control unit in the conventional rectification.

The first temperature control unit is capable of gasifying a part of the liquid flowing through the rectification flow path 1 and controlling the temperature so that the gas flows in contact with the rectification flow path 1. The controller can control the temperature at which a part of the gas flowing through the rectification flow channel 1 is liquefied. Depending on the boiling points of the two components to be separated, these may be heating parts or cooling parts. Therefore, the temperature control mechanism 80 that adjusts the temperature of the temperature control unit 10 may be a heater, a cooler, a radiator, or a combination thereof.

  The temperature control method of the temperature control mechanisms 80a and 80b is arbitrary, the temperature control mechanism 80a independently controls the temperature of the first temperature control unit 10a, and the temperature control mechanism 80b controls the second temperature control unit 10b independently. A system in which the temperature difference between the temperature control unit 10a and the second temperature control unit 10b is designed to have a specific value, and one of the temperature control mechanisms 80 has a temperature control function, the first temperature control unit 10a and the second temperature A system in which one temperature control mechanism 80 controlled in temperature is provided only on one side of the controller 10b and the other temperature control mechanism 80 adjusted to a constant temperature is provided on the other side, etc. There is. Further, for example, a temperature control mechanism 80 that is temperature-controlled is provided only on one side of the first temperature control unit 10a and the second temperature control unit 10b, and the temperature control mechanism 80 on the other side is simply a heat insulating material. Or a cover that prevents a change in airflow, and the temperature may be automatically adjusted by heat conduction from the temperature-controlled temperature control mechanism 80. The temperature control mechanism 80 may be not only a solid whose temperature is controlled but also a liquid or a gas. Although radiation such as infrared rays may be used, it is preferable to adjust the temperature of the temperature control unit 10 by a heat conduction method.

  The temperature control of the temperature control unit 10 may be a touch with the temperature control mechanism 80 adjusted to a predetermined temperature, or a temperature control mechanism by a footback from a temperature sensor provided in the vicinity of the temperature control unit 10 The temperature control may be 80, or a heating element that is automatically adjusted to an appropriate temperature using the non-linearity of electrical resistance or the like may be used.

  The temperature controller 10 preferably has a temperature gradient in the length direction of the rectification flow path 1. The gradient is preferably set to a temperature corresponding to the boiling point of the liquid at each position between the A end and the B end of the liquid portion 3. Therefore, at least the first temperature control unit of the two temperature control units has boiling points of the two components to be rectified in the length direction of the rectification flow path between the liquid outlet and the gas outlet, respectively. It is preferable to provide a temperature gradient with a temperature difference of preferably 30% to 200%, more preferably 50 to 150%, and most preferably 80 to 120%.

  Furthermore, the temperature control unit 10 preferably has a temperature curve between the A end and the B end that is a straight line or an upward convex curve (that is, the temperature at the center is higher than the straight line). The temperature control for giving such a temperature distribution to the temperature control unit 10 uses, for example, a plate-like temperature control mechanism 80 having three or more temperature-controlled heaters between the portion corresponding to the A end and the portion corresponding to the B end. Can be implemented.

  The temperature gradient of the temperature control unit 10 may be an approximate temperature gradient. If strictly observed, the temperature control unit 10 may have a swell or a step shape as long as it shows the temperature gradient as a whole. Such an approximate temperature gradient can occur when using a temperature control mechanism 80 in which three or more temperature controlled heaters are arranged. Further, even if the temperature control mechanism 80 itself has a smooth temperature gradient, a stepwise temperature gradient may be added to the rectification flow path 1. This occurs, for example, when a temperature control mechanism 80 having a temperature gradient in one direction is brought into contact with the rectification flow channel 1 formed in a zigzag pattern in the micro rectification device 100.

  The micro rectification device 100 provided with the rectification flow path 1 is plate-shaped or sheet-shaped, and the first temperature control unit 10a is formed on the side close to one surface of the micro rectification device 100, and the second When the temperature control unit 10b is formed near the back surface and provided outside the temperature control mechanism 80 micro rectification device 100, the shape has a flat surface that can be in close contact with or close to the micro rectification device 100. It is preferable that At this time, a temperature control mechanism 80b having a temperature gradient is disposed on the second temperature control unit 10b side, and the temperature control mechanism 80a having substantially no temperature gradient or the second temperature is disposed on the first temperature control unit 10a side. It is preferable to use a temperature control mechanism 80a that automatically adjusts the temperature of the control unit 10b to be higher by a certain temperature because the control becomes easy. As the temperature control mechanism 80a on the first temperature control unit 10a side, it is possible to install a transparent glass heater such as ITO vapor-deposited glass or ZnO vapor-deposited glass, or a temperature control mechanism 80a that causes a heat medium to flow between two glasses. This is preferable because the channel can be observed through the transparent glass.

  When the rectification method of the method of the present invention supplies the mixed fluid as a gas to the rectification flow channel 1, the communication flow channel 14 communicating from the mixed fluid inlet 24 to the gas inlets 4, 4 ' 1 It is preferable to have a structure that passes through the temperature control unit 10a, or to have a temperature control unit for gasification that can be adjusted to a temperature at which the mixed fluid is completely gasified.

  In the micro rectification device of the present invention, a plurality of rectification flow paths 1 may be provided in series and / or in parallel in one device. When provided in series, the gas outlet 5 is formed by connecting to the gas inlet 4 or the gas inlet 4 ′ of the next stage, or the liquid outlet 7 is connected to the liquid inlet 6 of the next stage. Alternatively, it is formed by connecting to the liquid inlet 6 ′. Thus, by providing a plurality of rectification flow paths 1 in series, three or more types of components having different boiling points can be fractionated even in continuous rectification. Further, the series connection may be formed as an integrated rectification flow path by directly connecting the outlet and the next-stage inlet without the communication flow path.

[Rectification method]
The rectification method of the present invention is a rectification method that can rectify a minute amount of fluid using the above-described micro rectification device 100, and the mixed liquid and gas portion 2 that flow to the liquid portion 3 of the rectification flow channel 1. In this method, rectification is carried out by contacting the mixed gas flowing in the gas flow countercurrently.

The mixed fluid is not particularly limited and may be an organic substance, an inorganic substance, a liquid, a gas, a supercritical fluid or the like as long as each component has a boiling point. It may be distillation. The description of the case where the mixed fluid has two components and the other terms are the same as in the description of the micro rectification device of the present invention.

[Liquid part]
A liquid derived from the fluid mixture flows from the B end to the A end in the liquid part 3 to liquefy the high boiling point component from the gas part 2 and gasify the low boiling point component from the liquid part 3 and move to the gas part 2. I will let you. Of course, in the liquefaction of the high boiling point component, the low boiling point component is also liquefied at the same time, and in the gasification of the low boiling point component, the high boiling point component is also gasified at the same time. However, as is well known, regarding the liquefaction of the gas at an arbitrary position in the length direction of the rectification flow path 1, the composition ratio of the high boiling point component liquefied from the composition ratio of the high boiling point component in the gas part 2 is better. In addition, the composition ratio of the low boiling point component that is gasified is higher than the composition ratio of the low boiling point component in the liquid portion 3.

  The liquid part 3 is kept in such a gas-liquid contact state in order to prevent the liquid flowing through the liquid part 3 from being completely gasified and lost, and to prevent the liquid from filling up to the gas part 2. The method can be implemented by adjusting the control unit 10. Such temperature control largely depends on the temperature control of the first temperature control unit 10a.

  If the temperature of the first temperature control unit 10a is too high, all the liquid is gasified in at least a part of the liquid part 3, and the liquid part is interrupted between the A end and the B end in the rectification flow path 1. When such a state occurs, simple distillation occurs and the rectification of the present invention is not performed. However, the liquid part 3 may be increased or decreased between the B end and the A end, or there may be a momentary interruption. When a fine groove serving as the liquid part 3 is formed in the rectification flow path 1 or when the surface of the liquid part 3 of the rectification flow path 1 is solvophilic, it does not boil even if the boiling point is exceeded. It is known that there are cases. In the present invention, the temperature of the first temperature control unit 10a may be set to the boiling point or higher if it does not boil.

On the other hand, if the temperature of the first temperature control unit 10a is too low, the gasification of the low boiling point components becomes insufficient, the liquefaction rate exceeds the gasification rate, and the A end and B end in the rectification flow path 1 A portion where the rectification flow path 1 is filled with the liquid is generated. When the part filled with the liquid is a part of the rectification flow path 1, the gas generated in the other part becomes a bubble and moves away from the liquid in the part to move toward the gas outlet. Although efficiency is reduced, rectification is possible and acceptable. However, when the liquid is always filled with the liquid, the rectification efficiency is remarkably lowered. When the part always filled with the liquid is the majority of the flow path for rectification 1, the rectification is impossible.

The composition of the liquid that has come into gas-liquid contact while flowing in the liquid portion 3 in the direction of the A end changes and the boiling point rises. Therefore, when the temperature of the temperature control unit is set to a constant temperature in the length direction of the rectification flow path 1, the gasification rate is relatively lowered and the liquefaction rate is increased near the A end where the boiling point of the liquid is increased. Tends to increase the amount. On the other hand, in the vicinity of the B end where the boiling point of the liquid decreases, the gasification rate relatively increases and the liquefaction rate decreases, and the amount of liquid tends to decrease. Accordingly, the temperature condition in which the liquid in the liquid part 3 is not interrupted and the gas part 2 is not filled with the liquid is narrowed over the entire rectification flow path. When the difference in boiling points of the components of the mixed fluid is large, any of the above may occur, and rectification may not be possible.

Therefore, it is preferable to provide a temperature gradient in which the A end side is high and the B end side is low in the length direction of the rectification flow channel 1. The gradient is such that the temperature difference between the two ends of the second temperature control unit 10b is preferably 30% to 200%, more preferably 50 to 150%, most preferably the difference between the boiling points of the two components to be rectified. Is preferably set to a temperature difference of 80 to 120%. Further, the curve (or straight line) of the position (horizontal axis) vs. temperature (vertical axis) in the length direction of the second temperature control unit 10b is convex upward, that is, the temperature at the midpoint of any two positions. Is preferably a curve higher than the average value of the temperatures at the two points in order to increase the rectification efficiency.

However, in practice, the A end and the B end are observed while observing the rectification flow path 1 without measuring the boiling point of the liquid existing in the rectification flow path 1 or the temperature of each part of the temperature control unit 10b as described above. In such a manner that the liquid part 3 is not interrupted and the gas part 2 is not interrupted, and the liquid amount is substantially equal at each position between the A end and the B end. Thus, the method of adjusting temperature mating is the simplest and preferable.

In the present invention, the liquid in the liquid portion 3 is moved toward the liquid outlet 7. In the moving method, the liquid in the liquid portion 3 is automatically moved toward the liquid outlet 7 by capillary action by taking out the liquid from the liquid outlet 7. The method of taking out the liquid from the liquid outlet 7 is arbitrary, for example, natural outflow due to gravity adjusting the length and height difference of the pipe connected to the high boiling point component concentrated distiller takeout part 18, quantitative takeout by the pump, decompression Suction or absorption into a porous body. In the present invention, it is necessary to prevent gas from flowing out from the outlet 7. In order to prevent the outflow of gas, it is preferable to take out the fluid at a speed at which the gas does not flow out. Among these, it is preferable to take out the fluid by a pump connected to the communication channel 17.

[Gas part]
On the other hand, the gas flows in the gas section 2 in a direction counter-current to the liquid in the liquid section 3, that is, from the A end to the B end direction, at each position in the length direction of the rectification flow path 1. In contact with the liquid in the liquid portion 3. The first temperature controller 10a adjusts the temperature to a temperature at which the gas does not liquefy. However, sometimes it is allowed that the liquid liquefied in a shape that closes a part of the gas part 2 moves in the gas moving direction so as not to lose the effect of the present invention. If the temperature of the first temperature control unit 10a is too low, the liquefied liquid fills the gas part 2 and fills the pores of the porous diaphragm 8, and the liquid flows out from the gas outlet 5 and cannot be rectified. become. On the other hand, even if the temperature of the first temperature control unit 10a is considerably high, rectification can be performed without any problem as long as the temperature of the liquid unit 3 is controlled as described above. In the present invention, the higher the temperature of the first temperature control unit 10a, the higher the tolerance, for example, it may be 50 ° C. higher than the boiling point of the liquid part.

However, if the temperature of the first temperature control unit 10a is excessively high, the liquid temperature of the liquid unit 3 is likely to be affected by heat conduction or radiation, and the temperature control of the second temperature control unit 10b tends to be inaccurate. is there. The upper limit of the temperature of the first temperature control unit 10a varies depending on the size and structure of the rectification flow path 1, the thermal conductivity of the material, etc., but it cannot be generally limited, but is preferably [the boiling point of the high boiling point component + 50 ° C.] or less, More preferably, [boiling point of high-boiling component + 30 ° C.] or less, most preferably [boiling point of high-boiling component + 20 ° C.] or less.

In the rectification method of the present invention, after the temperature of the first temperature control unit 10a is determined in advance as described above, all the liquid flowing through the liquid unit 3 is completely discharged as described in the description of the liquid unit. A method of adjusting the second temperature control unit 10b is preferable because it is easy to adjust the second temperature control unit 10b so that the gas unit 2 is not filled with liquid so that the gas unit 2 is not lost.

  While the gas flows through the gas part 2, the high boiling point component is liquefied and added to the liquid in the liquid part 3, and the low boiling point component is gasified from the liquid in the liquid part 3 and added to the gas in the gas part 2. Therefore, the liquefaction temperature of the gas flowing in the gas part 2 gradually decreases while flowing in the gas part 2 in the direction of the A end or the B end. Therefore, it is preferable that the first temperature control unit 10a also has a temperature gradient in which the temperature gradually decreases from the A end toward the B end. However, regarding the first temperature control unit 10a, as described above, since there is no problem even if the temperature is somewhat high, it is not necessary to make the whole sufficiently high and provide the temperature distribution.

  A small amount of inert gas such as nitrogen or argon may be flowed into the gas part 2 as a carrier gas. If there is a part where the temperature of the second temperature control unit 10b is excessively low or there is a time when the temperature is low, a part of the gas part 2 may be filled with liquid. And since it becomes difficult to fill the gas part 2 with the liquid, the stability and reliability of operation increase.

In this rectification method, it is necessary to prevent the liquid in the liquid part 3 from flowing out from the gas outlet 5, but the temperature of the first temperature controller 10a is sufficiently higher than the boiling point of the liquid in the part. By controlling and appropriately controlling the introduction flow rate of the mixed fluid, it is possible to immediately gasify the liquid in contact with the first temperature control unit 10 a and prevent it from flowing out from the gas outlet 5. Further, by making the inner surfaces of the gas outlet 5 and the communication channel 15 lyophobic, or by attaching the porous membrane 8 to the gas outlet 5, the allowable range of the liquid introduction speed and the temperature of the temperature control unit 10 can be reduced. The allowable range is widened and control becomes easy. At this time, the temperature of the gas outlet 5 and the porous diaphragm 8 is controlled to be preferably higher than the boiling point of the liquid in contact therewith, more preferably 5 ° C. or higher, and even more preferably 10 ° C. or higher. The upper limit is arbitrary as long as it is not higher than the decomposition temperature of the component to be rectified, but is preferably not higher than the boiling point of the liquid by 50 ° C. or more from the viewpoint of energy saving and the heat resistance of the micro rectification device. The temperature of the porous diaphragm 8 is preferably the same as that of the first temperature control unit 10a and higher.

  The site and method for introducing the mixed fluid to be rectified into the rectification flow path 1 differ depending on the rectification method, but this is as described in the section of the micro rectification device of the present invention.

[Theoretical plate number]
The rectification method of the present invention is a distillation method in which the number of theoretical plates of distillation is higher than that of simple distillation, and the number of theoretical plates of distillation is preferably 1.1 or more, more preferably 1.5 or more, and most preferably 2 or more. This is a simple distillation method. The present invention can be carried out by selecting the dimensions of each part such as the length of the rectification flow path, and controlling the rectification conditions such as the liquid and gas flow rates and temperature conditions so that the number of theoretical plates is as described above. The upper limit of the number of theoretical plates can be arbitrarily set by lengthening the rectification flow path, and is preferably 2 or more, more preferably 3 or more, and most preferably 5 or more. The upper limit is arbitrary, and can be, for example, 100 stages or 1000 stages.

[Rectification method]
Hereinafter, a rectification method in a typical rectification method of the present invention will be described.
1. Batch rectification method This rectification method uses the first type rectification flow channel 1 of the rectification flow channel, and connects the gas inlet 4 to a liquid storage tank (not shown) through a communication flow channel 14; A temperature control unit (not shown) for the liquid storage tank for heating the liquid storage tank is provided. The gas outlet 5 is connected to a low boiling point component concentrated fraction outlet 25 provided as an opening via a communication channel 15, and the liquid outlet 7 is connected to the liquid storage tank ( (Not shown).

  In this rectification method, when a mixed fluid is injected into the liquid storage tank, the mixed fluid in the liquid storage tank is heated and gasified by the temperature control unit of the liquid storage tank, and the gas is fed into the gas inlet 4 A part of the liquid returns to the liquid storage phase from the liquid outlet 7 as a liquid. At this time, as the amount of the fluid mixture in the liquid storage tank decreases, the boiling point of the liquid in each part of the liquid part 3 and the liquefaction point of the gas in each part of the gas part 2 change, so that the liquid in the liquid part 3 is not interrupted. In addition, the temperature control unit 10a is adjusted so that the gas unit 2 is not filled with liquid so as to maintain the above-described state. The end point of rectification can be known by the fact that the boiling point of the mixed fluid in the liquid storage tank rises rapidly, and gasification stops. If it does in this way, a low boiling point component will be taken out from the low boiling point component concentrated fraction taking-out port 25, and a high boiling point component will be obtained as a rectification residue.

In this rectification method, when the mixed fluid contains three or more kinds of components having different boiling points, the low boiling point components sequentially flow out from the low boiling point component concentrated fraction outlet 25 over time.
In HonseiTome scheme is an optional amount of rectification mixing fluid at a time, for example, ^{1 mm} 3 1 cm ^3, more preferably from easily rectification samples minute amount of about ^{1 mm} 3 100 mm ^3, Further, it is easy to separate and purify a mixture of three or more liquids having different boiling points.

2. Continuous rectification method of the continuous rectification process following the present invention, the processing speed of the mixed fluid to be distilled is arbitrary, for example, 100 [mu] m ³ / min ~1000mm ³ / min, more preferably wells is 1000 .mu.m ³ / min to Continuous rectification at a minute flow rate such as 100 mm ³ / min is possible. Therefore, it can be suitably incorporated into a continuous reaction microreactor. In addition, there is no restriction on the amount of liquid to be rectified, and the temperature of each part of the rectification flow path does not change with time after the steady state is reached, so that temperature adjustment is easy.

(2-1) Continuous rectification method 1 (method of supplying a gaseous mixed fluid to the end of the rectification flow path 1)
This rectification method is a rectification method using the rectification flow channel 1 of the first method 1 of the rectification flow channel, and is a mixed fluid introduction port, a low boiling point component concentrated fraction take-out port 27, a low boiling point component concentration. A micro rectification device in which the fraction outlet 25 is formed as an opening of the micro rectification device 100 can be preferably used.

In the rectification method, a gaseous mixed fluid is continuously supplied from the gas inlet 4 to the rectification flow channel 1. As a method of supplying the gaseous mixed fluid to the gas inlet 4, a method of introducing a gaseous mixed fluid at room temperature or a mixed fluid gasified by heating by pressure or the like, or a liquid mixed fluid is pumped For example, a method may be employed in which the gas is introduced into the mixed fluid introduction port 24 by heating, gasified in the communication channel 14, and continuously supplied from the gas inlet 4 to the rectification channel 1.
The gas supplied to the gas inlet 4 flows through the rectification flow path 1 in the B-end direction and flows out from the gas outlet 5. In this rectification method, the temperature of the temperature controller 10 is adjusted in the rectification flow path 1 so that the amount of gas liquefaction exceeds the amount of liquid gasification. In this way, the liquid liquefied one after another flows in the direction of the A end while contacting the liquid portion 3 in countercurrent with the gas, and flows out from the liquid outlet 7. The liquid that has flowed out is taken out from the low-boiling-component concentrated fraction take-out port 27 via the communication channel 17. At this time, if a pipe is connected to the low boiling point component concentrated fraction outlet 27 and the other end is lowered downward, the high boiling point component concentrated fraction flows out by its own weight without providing a pump mechanism. The flow rate to be taken out can be adjusted by adjusting the height difference between both ends of the pipe. Further, when a pipe is connected to the low boiling point component concentrated fraction outlet 25 and the pipe is cooled, the low boiling point component concentrated fraction flows out as a liquid. In this case, the other end of the pipe is lowered downward. In other words, the low boiling point component concentrated fraction flows out by its own weight without providing a pump mechanism. Similarly to the above, the flow rate to be taken out can be adjusted by adjusting the height difference between both ends of the pipe.
This method can obtain a low-boiling component concentrated fraction having a high concentration rate.

(2-2) Continuous rectification method 2 (method of supplying a gaseous mixed fluid in the middle of the rectification flow path 1)
This rectification method is a rectification method using the rectification flow channel 1 of the second method, and the point that the gaseous mixed fluid is supplied to the gas part 2 in the middle of the rectification flow channel 1 is the continuous rectification method. Different from rectification method 1.
In this rectification method, the continuous range is adjusted except that the range of adjusting the temperature of the temperature control unit 10 so that the gas liquefaction amount exceeds the liquid gasification amount is between the gas inlet 4 ′ and the B end. This is the same as rectification method 1. On the other hand, between the gas inlet 4 ′ and the A end, it is preferable to adjust the temperature of the temperature control unit 10 so that the gasification amount of the liquid exceeds the gas liquefaction amount. In this way, a gas flow in the direction of the gas outlet 5 is created also in the portion between the A end and the gas inlet 4 ′, and gas-liquid contact is made in countercurrent even in this range. The number of theoretical plates increases.
This method can obtain both a low-boiling component concentrated fraction having a high concentration rate and a high-boiling component concentrated fraction having a high concentration rate.

(2-3) Continuous rectification method 3 (method of supplying a liquid mixed fluid to the end of the liquid rectification flow path 1)
This rectification method is a rectification method using the third type rectification flow channel 1. In this method, a micro rectification device in which the mixed fluid introduction port, the low boiling point component concentrated fraction outlet 27 and the low boiling point component concentrated fraction outlet 25 are formed as openings of the micro rectification device 100 can be preferably used.

In this rectification method, a liquid mixture is continuously supplied from the liquid inlet 6 to the rectification flow channel 1.
When the mixed fluid is liquid at normal temperature, no special temperature operation is required in the continuous air channel 14 if the mixed fluid is sent to the mixed fluid inlet by pressure or a pump. When the mixed fluid is a gas at normal temperature, it is sent after being cooled and liquefied outside the micro rectification device in advance, or the communication channel 14 is cooled and liquefied. The temperature of the liquid supplied to the liquid inlet 6 is preferably just below the boiling point.
In this rectification method, the temperature of the temperature controller 10 is adjusted in the rectification flow channel 1 so that the gasification amount of the liquid exceeds the gas liquefaction amount. If it does in this way, the gasified one after another will flow through the gas part 2 to the B edge direction, will contact with a liquid countercurrently, and will flow out from the gas outflow port 5. FIG. Others are the same as those in the continuous rectification method 1.
This method can obtain a high-boiling component concentrated fraction having a high concentration rate.

(2-4) Continuous rectification method 4 (method of supplying a liquid mixed fluid into the rectification flow path)
This rectification method is a rectification method using the rectification flow channel 1 of the fourth type of the rectification flow channel, and a liquid mixed fluid is placed in the middle of the rectification flow channel 1 from the liquid inlet 6 ′. The supply to the liquid part 2 is different from the continuous rectification method 3.
In this rectification method, the temperature of the temperature control unit 10 is adjusted so that the gasification amount of the liquid exceeds the liquefaction amount of the gas as the entire rectification flow path 1. In the meantime, it is preferable to adjust the temperature of the temperature control unit 10 so that the gasification amount of the liquid exceeds the gas liquefaction amount. In this way, a gas flow in the direction of the B end is created in the portion between the A end and the gas inlet 4 ′, and in this range, the gas-liquid contact is made in the countercurrent direction. Will increase. Further, it is preferable to adjust the temperature of the temperature controller 10 so that the gas liquefaction amount exceeds the liquid gasification amount between the liquid inlet 6 ′ and the B end. In this way, a liquid flow from the B end to the A end direction is created in the portion between the B end and the liquid inlet 6 ′, and even in this range, gas-liquid contact is made in countercurrent. The number of steps increases. This method can obtain both a low-boiling component concentrated fraction having a high concentration rate and a high-boiling component concentrated fraction having a high concentration rate.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail using an Example, this invention is not limited to the range of a following example.

  The preparation method of the ultraviolet curable resin composition used in this example and the ultraviolet irradiation method are shown below. In the following examples, “part” and “%” represent “part by mass” and “% by mass” unless otherwise specified.

[Preparation of UV-curable composition (X1)]
18 parts of tris (acryloxyethyl) isocyanurate “Aronix M-315” manufactured by Toagosei Co., Ltd., and bis (acryloxyethyl) hydroxyethyl isocyanurate “Aronix M-215” manufactured by Toagosei Co., Ltd. 72 parts, 10 parts of 1,6-hexanediol diacrylate “New Frontier HDDA” manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and 2 parts of 1-hydroxycyclohexyl phenyl ketone “Irgacure 184” manufactured by Ciba Geigy as a photopolymerization initiator The composition (X1) was prepared by mixing.

[UV irradiation]
Using a light source unit for multi-light 250W series exposure equipment manufactured by USHIO INC., Which uses a 250W high-pressure mercury lamp as a light source, UV light with an ultraviolet intensity at 365 nm of 50 mW / cm ² is irradiated in the air at room temperature unless otherwise specified. did.

Example 1
The example of the micro rectification device of the rectification method 2-4 shown by FIG. 1, FIG. 2 is shown.
[Production of second temperature control unit side member]
The composition (X1) is applied onto a substrate 51 made of an acrylic plate having a thickness of 1 mm using a spin coater, and the coating film is irradiated with ultraviolet rays for 5 seconds, so that the polymerizable functional group still remains. A resin layer 52 in which the composition (X1) was semi-cured was formed.

  The composition (X1) is applied onto the resin layer 52 with a spin coater, and the portion other than the portion to be the liquid portion 3 of the rectification flow channel 1, the communication flow channel 14, and the communication flow channel 17 through a photomask. Is irradiated with ultraviolet rays for 5 seconds to form a resin layer 53 in which the composition (X1) is semi-cured to such an extent that the polymerizable functional group still remains, and the uncured composition (X1) in the non-irradiated portion is made of ethanol. By washing and removing, the grooves 3, 14, and 17 to be the liquid portion 3, the communication channel 14, and the communication channel 17 of the rectification channel 1 were formed. As described above, the second temperature control unit side member 92 was formed.

[Production of first temperature control unit side member]
Production of the second temperature control unit side member 92 except that a 60 μm biaxially stretched polypropylene sheet (OPP sheet) (manufactured by Nimura Chemical Co., Ltd.) was used as a temporary support (not shown) instead of the substrate 51. In the same manner as described above, a fixed body of the resin layer 57 and the resin layer 56 in which the communication channel 15 was formed was fabricated on the temporary support.
On the other hand, a porous membrane made of polytetrafluoroethylene (PTFE) having an average pore diameter of 0.2 μm (Advantech) is immersed in the composition (X1), and after reducing the pressure to a vacuum, the pressure is returned to normal pressure. The pores of the membrane were filled with composition X1. Using the OPP sheet as a temporary support (not shown), this is spread on it, and the excess composition (X1) other than the part impregnated in the pores of the porous membrane with a glass rod is scraped off. The portion other than the portion that becomes the porous diaphragm 8 through a photomask is irradiated with ultraviolet rays for 10 seconds to make the irradiated portion semi-cured, washed with n-hexane, and an uncured composition ( X1) is washed and removed, and only the porous diaphragm 8 portion is a continuous porous membrane on the temporary support, and the pores in the other portions are filled with the semi-cured composition (X1). Thus formed porous diaphragm layer 55 was formed. This was laminated on the fixed body of the resin layer 57 and the resin layer 56 at the same position, and the temporary support was peeled from the porous diaphragm layer 55.

Further, the OPP sheet is used as a temporary support (not shown), the composition (X1) is spin-coated thereon, and ultraviolet light is applied to a portion other than the portion that becomes the gas portion 2 of the rectification flow path 1 through a photomask. Is irradiated for 5 seconds to semi-cure the irradiated portion to form a resin tank 54, aligned and stacked on the resin layer 53 of the second temperature control unit side member 92, and then irradiated with ultraviolet rays for 10 seconds to be cured. Then, the temporary support was peeled from the resin layer 54.
Next, the resin tank 54 and the laminated porous film 55 are positioned at the same time as the first temperature control unit side member 91 is formed, and at the same time, is fixed to the second temperature control unit side member 92 and temporarily supported from the resin layer 57. The body was peeled off to form a micro rectification device precursor.

[Production of micro rectification device]
From the substrate 51 side of the micro-rectification device precursor, holes 64 and 67 having a diameter of 0.5 mm that reach each communication channel are drilled at the end of the communication channel 14 and the end of the communication channel 17, The mixed fluid inlet 24 and the low boiling point component concentrated fraction outlet 27 were formed, and fittings 74 and 77 for connecting pipes were bonded to the respective openings. Further, from the resin layer 57 side of the micro rectification device precursor, a hole 65 having a diameter of 0.5 mm that reaches the communication channel is opened by a drill at the end of the communication channel 15, and a low boiling point component concentrated fraction outlet is taken out. 25, and a fitting 75 for pipe connection was adhered to the opening to obtain the micro rectification device 100 shown in FIGS.

[Device structure observation]
When the device produced above was cut and the dimensions of each part of the device were measured with a scanning electron microscope, the thickness of the substrate 51 was 1 mm, the thickness of the resin layer 52, the resin layer 56, and the resin layer 57 was 100 μm, and the resin The thickness of the layer 53 and the resin layer 54 was 150 μm, and the thickness of the porous diaphragm layer 55 was about 100 μm. The cross section of the flow channel for rectification is a reverse convex shape with the gas portion 2 having a width of 500 μm and a thickness of 150 μm, and the liquid portion 3 having a width of 150 μm and a thickness of 150 μm. Was 150 μm. The length of the rectification flow path was 5 cm.

[Production of temperature control mechanism]
A 10 cm × 3 cm × 4 mm iron plate (not shown) is arranged in parallel with three electric heaters (not shown) and a 10 × 10 mm square pipe-shaped water pipe (not shown) in the longitudinal direction of the iron plate. The second temperature control mechanism 80b was fabricated by bonding the gap and embedding a sensor (not shown) in the electric heater bonding portion of the iron plate.

  On the other hand, a copper electrode (not shown) is bonded with a silver paste to the ITO coated surfaces at both ends in the longitudinal direction of a 10 cm × 3 cm × 1 mm ITO vapor-deposited glass plate (not shown), and a copper wire (not shown) is attached thereto. Glued. In addition, the first temperature control mechanism 80a was produced by bonding a thermocouple 90 to the center of the ITO vapor deposition surface with an inorganic adhesive.

[Production of rectification system]
A syringe pump (not shown) is connected to the fitting 74 of the mixed fluid inlet 24 of the micro rectification device 100, and the fitting 75 of the low boiling point component concentrated fraction outlet 25 and the low boiling point component concentrated fraction outlet 27 are connected. A PTFE tube (not shown) having an inner diameter of 200 μm was connected to the fitting 77.

  The second temperature control mechanism 80b is closely attached and fixed to the surface of the second temperature control unit side member 92 of the micro rectification device 100, and a spacer (illustrated) is attached to the surface of the first temperature control unit side member 91 of the micro rectification device 100. The first temperature control mechanism 80a was fixed with an interval of 1 mm. The rectification system was produced as described above.

It is a decomposition | disassembly sketch of the micro rectification device created in Example 1 of this invention. It is the plane schematic diagram (a) of the micro rectification device created in Example 1 of this invention, and (alpha) part cross-sectional schematic diagram (b). It is a principle figure which shows the various rectification systems of the micro rectification device of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Flow path for rectification 2 Gas part 3 Liquid part 4, 4 'Gas inlet 5 Gas outlet 6, 6' Liquid inlet 7 Liquid outlet 8 Porous diaphragm 10 Temperature control part 10a 1st temperature control part
10b Second temperature controller
14, 15, 17 Connecting flow path 24 Mixed fluid inlet 25 Low boiling point component concentrated fraction outlet 27 High boiling point component concentrated fraction outlet 51 Base material 52, 53, 54, 56, 57 Resin layer 55 Porous membrane layer 64, 65, 67 hole 74, 75, 77 fitting 80 temperature control mechanism 80a first temperature control mechanism 80b second temperature control mechanism 91 first temperature control unit side member 92 second temperature control unit side member 100 micro rectification device

Claims (11)

A micro rectification device for rectifying each component from a mixed fluid containing at least two components having different boiling points,
a) the micro rectification device has a rectification flow path having a gas inlet or liquid inlet, a gas outlet, and a liquid outlet;
b) The rectification flow path has two temperature control units that are temperature-controlled at different temperatures on the side surface of the flow path,
c) A low boiling point component of the mixed fluid flowing through the rectification flow channel is gasified by the first temperature control unit controlled to a high temperature among the temperature control units, and is in contact with the first temperature control unit. A gas part through which gas flows is formed,
A high boiling point component of the mixed fluid flowing through the rectification flow path is liquefied by a second temperature control unit controlled to a low temperature among the temperature control units and comes into contact with the second temperature control unit to A liquid part flows through
d) the gas part and the liquid part form a countercurrent gas-liquid contact part;
e) the gas outlet is provided downstream of the gas section;
f) A micro rectification device for rectifying at least two types of components having different boiling points contained in a mixed liquid, wherein the liquid outlet is provided downstream of the liquid portion. The micro rectification device according to claim 1, wherein a porous diaphragm is attached to the gas outlet. The micro rectification device according to claim 1, wherein the flow path on the side forming the liquid part has a smaller cross-sectional shape than the flow path on the side forming the gas part of the flow path for rectification. The micro rectification device is plate-shaped,
The flow channel for rectification is formed in parallel to the surface of the micro rectification device,
The micro rectification device according to claim 1, wherein the two temperature control units are provided on opposing surfaces of a plate-like portion surrounding the rectification flow path. The micro rectification device according to claim 1, wherein a cross-sectional area of the rectification flow path is 30 μm ^{2 to 3} mm ² . 2. The micro rectification device according to claim 1, wherein a distance between the wall on the liquid part side and the wall on the gas part side of the rectification flow path is 10 μm to 3 mm. The micro rectification device according to claim 1, wherein the length of the rectification flow path is 0.5 to 20 cm. Of the two temperature control units, at least the first temperature control unit has the boiling points of the two components to be rectified in the length direction of the rectification flow path between the liquid outlet and the gas outlet, respectively. The micro rectification device according to claim 1, wherein a temperature gradient of 30% to 150% of the difference can be provided. The micro rectification devices, the thermal conductivity between the two temperature control unit, micro rectification device of claim 1 wherein the 0.01~10wm ^-1 K ^-1. A rectification method for rectifying each component from a mixed fluid containing at least two components having different boiling points using the micro rectification device according to claim 1,
a) A liquid mixed fluid is introduced from the liquid inlet of the rectification flow path, or a gaseous mixed fluid is introduced from the gas inlet,
b) Temperature control of the two temperature control units provided in the rectification flow path to different temperatures,
c) Controlling the first temperature control unit controlled to a high temperature among the temperature control units to a temperature at which the low boiling point component of the mixed fluid flowing in the rectification flow path 1 is gasified, and the gas is Forming a gas part flowing in contact with the first temperature control part;
d) Among the temperature control units, the second temperature control unit controlled to a low temperature is controlled to a temperature at which the high boiling point component of the mixed fluid flowing in the rectification flow path 1 is liquefied, so that the liquid is the second Form a liquid part that flows in contact with the temperature control part,
e) countercurrent gas-liquid contact between the liquid flowing through the liquid part in the rectification flow path of the micro rectification device and the gas flowing through the gas part;
f) outflowing gas enriched in low-boiling components from the gas outlet provided downstream of the gas section;
g) A rectification method characterized by causing a liquid enriched in high-boiling components to flow out from the liquid outlet provided downstream of the liquid part. The rectification method according to claim 10, wherein a flow rate for taking out the liquid and / or liquefied gas is adjusted by adjusting a height difference between both ends of a pipe connected to the liquid outlet and / or the gas outlet.

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