JP5013513B2 - MICRO REACTOR, MANUFACTURING METHOD THEREOF, INTEGRATED MICRO REACTION MODULE, AND METHOD FOR PURIFYING ORGANIC AREAS - Google Patents

Description

  The present invention relates to a microreaction apparatus capable of performing a chemical reaction, separation, etc. in a fine channel, a method for producing the same, an integrated microreaction module, and a method for purifying organic arsenic contaminated water using the integrated microreaction module About.

The microreactor is a reactor that performs chemical reaction, separation, and the like in a fine flow channel having a diameter of several μm to several hundred μm, and has many advantages over the conventional batch system.
In particular, in photochemical reactions, the irradiated light is absorbed and scattered in the reaction field, so in the case of a batch system in which the reaction is carried out by suspending the photocatalyst in the reaction vessel, the entire reaction vessel is irradiated with sufficient light. However, there are problems that the utilization efficiency of light used in the reaction cannot be increased, and that the operation of separating the catalyst after the reaction is necessary, and thus the operation is complicated.

  In order to solve the above problem, Patent Document 1 discloses a photochemical reaction in which a liquid containing a reactive molecule is circulated in a fine reaction channel provided with a photocatalyst, and the reactive molecule contained in the liquid can be photochemically reacted. A device has been proposed. In the photochemical reaction device used in Patent Document 1, a hollow through-hole that reaches from the one end surface of the reactor formed of quartz or borosilicate glass to the other end surface facing is provided as a fine channel. Yes.

Further, in Patent Document 2, a groove that forms a fine flow path is formed in a glass plate, a photocatalyst is supported in the groove, and a plate holder provided with a reaction raw material supply port and a reaction liquid extraction port is joined. The microreactor formed by is used.
Patent Document 3 discloses a microreactor formed by laminating a plurality of thin plates including a thin plate provided with a reaction part (reaction channel).
JP 2005-279595 A JP 2006-239640 A Japanese Patent Laid-Open No. 2006-18785

  However, as in Patent Document 1, if a hollow through hole is provided in a reactor formed of quartz or borosilicate glass or the like to form a fine flow path, the processing is difficult and costly, and a complicated shape is required. The flow path cannot be formed.

  In addition, in the microreactor of Patent Document 2, a glass plate in which a groove forming a reaction channel is formed and a plate holder (which is also a plate made of glass) joined to the upper surface thereof, such as a bolt and a nut. Since the glass is pressed and joined by the member, a gap is generated between the glasses, and the loss of pressure for introducing the reaction raw material into the reaction channel is increased due to the influence of the gap. In particular, as the reaction flow path becomes finer, the influence of the pressure loss becomes larger, and the introduction of the reaction raw material becomes impossible. Therefore, there is a limit to miniaturization of the reaction flow path by this method. In addition, when the reaction channel diameter is such that the reaction raw material can be introduced, there is a possibility that the reaction raw material flowing through the reaction channel leaks.

  In order to seal this gap, it is possible to heat the stacked glass plates and weld the glass plates together, but in the case of borosilicate glass, it is 500 to 600 ° C., in the case of quartz, 1100 ° C. or more. Heating is required. Here, it is known that titanium dioxide, which is a typical example of a photocatalyst, has a crystal structure that changes from anatase type to rutile type at around 650 ° C., and the photocatalytic activity decreases. Further, even if heating at a lower temperature (300 to 500 ° C.), the activity may be reduced due to the modification of the catalyst and the like, and the influence on the crystal structure starts to occur from the transition temperature or lower (300 to 400 ° C.). When a photocatalyst such as titanium dioxide is supported on the flow path, the glass plate cannot be pressure-bonded at a high temperature.

  Further, in the microreactor of Patent Document 3, when a glass substrate or a quartz substrate is used as the thin plate, the formation of the reaction part (reaction channel) on the thin plate is performed by a semiconductor process, which increases the cost.

  In view of such problems, the inventors have developed a microreactor in which a fine channel with high hermeticity is formed without forming a through hole or a groove in glass or quartz, which causes an increase in cost. Developed. An object of the present invention is to provide a microreaction apparatus that can easily form a fine flow path with high hermeticity and can also carry a catalyst such as a photocatalyst, a manufacturing method thereof, and an integrated microreaction module. There is to do.

  In order to solve the above problems, a microreaction apparatus according to a first aspect of the present invention includes an adhesive resin film, a slit-like through-hole provided in the adhesive resin film, and the adhesive resin film. A first substrate bonded to one surface, and a second substrate bonded to the other surface of the adhesive resin film, the inner surface of the first substrate, the second substrate and the through hole, A fine reaction channel is formed. Here, the “adhesive resin film” refers to a resin film having self-adhesive properties at room temperature or by heating.

  According to the present invention, the inner surface of the slit-shaped through-hole provided in the adhesive resin film, the first substrate bonded to one surface of the adhesive resin film, and the other of the adhesive resin film Since the fine reaction channel is formed by the second substrate bonded to the surface, it is possible to provide the slit-like through hole by excision of the adhesive resin film or notch formation. Therefore, it is easier than etching processing or processing by a semiconductor process such as quartz or borosilicate glass to form a fine reaction channel, and processing can be performed at low cost. In addition, the adhesiveness of the adhesive resin film enhances the tightness of the fine reaction channel and reduces pressure loss when introducing the reaction raw material into the fine reaction channel. The formed reaction channel can be formed. In addition, it is possible to prevent leakage of reaction raw materials and the like flowing through the reaction channel.

  The microreaction apparatus according to the second aspect of the present invention includes a plurality of adhesive resin films disposed on the same plane, and an end of an adjacent adhesive resin film among the plurality of adhesive resin films. One surface of the plane formed by the slit formed by the sides being arranged so as to maintain a predetermined distance in the normal direction from each point on the end side, and the plurality of adhesive resin films A first substrate bonded to the second substrate, and a second substrate bonded to the other surface of the plane formed by the plurality of adhesive resin films, the first substrate, the second substrate, and the slit A minute reaction flow path is formed by the inner surface of. According to the present invention, the same effect as that of the first aspect can be obtained.

  The microreaction apparatus according to a third aspect of the present invention is characterized in that, in the first aspect or the second aspect, the material constituting the adhesive resin film is an adhesive fluororesin. Here, the “adhesive fluororesin” is non-adhesive at normal temperature but exhibits adhesiveness at a temperature of a relatively low melting point or higher, and has chemical stability as a fluororesin at normal temperature.

  According to the present invention, in addition to the same effect as the first aspect or the second aspect, reaction raw materials such as organic solvents and halides are circulated in the reaction flow path due to the high chemical resistance of the adhesive fluororesin. Therefore, a micro reaction apparatus that can be used for various reactions can be obtained.

  The microreaction apparatus according to a fourth aspect of the present invention is the microreaction apparatus according to any one of the first to third aspects, wherein the first substrate and / or the second substrate is bonded to the adhesive resin film. The surface is provided with a catalyst. According to the present invention, the microreaction apparatus according to any one of the first to third aspects can be used for the catalytic reaction.

  The microreaction apparatus according to a fifth aspect of the present invention is characterized in that, in the fourth aspect, the catalyst is a photocatalyst. According to the present invention, the microreaction apparatus according to the fourth aspect can be used for the photocatalytic reaction. In particular, since the reaction channel of the microreactor of this embodiment is not etched, the surface of the reaction channel is high on the first substrate and the second substrate formed of quartz, borosilicate glass, or the like. Since the light transmittance is maintained, the light irradiated from the outside of the micro reactor can be used effectively.

  The method for producing a microreaction apparatus according to the sixth aspect of the present invention includes a step of providing a slit-like through hole in an adhesive resin film, and one of the adhesive resin film provided with the slit-like through hole. The first substrate is bonded to the surface based on the adhesive property of the adhesive resin film, and the second substrate is bonded to the other surface based on the adhesive property of the adhesive resin film. And a step of forming a fine reaction channel by the substrate and the inner surface of the through hole.

  According to the present invention, a microreaction apparatus having a fine reaction channel can be easily manufactured at low cost, and a fine channel having a high sealing property is provided by the adhesiveness of the adhesive resin film. A microreactor.

  In the method for manufacturing a microreaction apparatus according to the seventh aspect of the present invention, a plurality of adhesive resin films are disposed on the same plane on the first substrate, and the edges of the adjacent adhesive resin films are further aligned. Are arranged so as to maintain a predetermined distance in the normal direction from each point on the edge, and a slit is formed, and a first surface is formed on one surface of the adhesive resin film in which the slit is formed. The substrate is bonded based on the adhesive property of the adhesive resin film, and the second substrate is bonded to the other surface based on the adhesive property of the adhesive resin film, and the first substrate, the second substrate, and the fine substrate are bonded. And a step of forming a fine reaction channel by the inner surface of the gap. According to the present invention, the same effect as that of the sixth aspect can be obtained.

  The method for manufacturing a microreaction apparatus according to an eighth aspect of the present invention is characterized in that, in the sixth aspect or the seventh aspect, the material constituting the adhesive resin film is an adhesive fluororesin. It is. According to the present invention, it is possible to manufacture a microreactor that exhibits the same effects as the third aspect.

  According to a ninth aspect of the present invention, there is provided the method for manufacturing a microreaction apparatus according to any one of the sixth to eighth aspects, wherein the first substrate and the second substrate are bonded to an adhesive resin film. Before, it has the process of providing a catalyst in the joint surface with the said adhesive resin film of said 1st board | substrate and / or said 2nd board | substrate, It is characterized by the above-mentioned. According to the present invention, it is possible to manufacture a microreaction apparatus that exhibits the same effects as the fourth aspect.

  An integrated microreaction module according to a tenth aspect of the present invention includes an adhesive resin film, a plurality of slit-like through holes provided in the adhesive resin film, and one surface of the adhesive resin film. And a second substrate bonded to the other surface of the adhesive resin film, and the first substrate, the second substrate, and the inner surface of the through-holes, An integrated micro reaction module in which a reaction flow path portion having various reaction flow paths is formed, and the reaction flow path portion includes an integrated flow path portion in which a plurality of fine reaction flow paths are arranged in parallel. A plurality of fine reaction channels, and a common channel part formed so as to merge with a common fluid inlet and a common fluid outlet, the first substrate and / or the second A catalyst is applied to the bonding surface of the substrate with the adhesive resin film. It is characterized in that that example.

  According to the present invention, in addition to the same effect as the first aspect, the reaction raw material is introduced into a plurality of integrated fine reaction flow paths by introducing the reaction raw material into one fluid inlet. Therefore, a large volume of catalytic reaction can be performed. Furthermore, the reactants discharged from each reaction channel are merged again and discharged from one fluid outlet, so that the recovery is easy.

  Furthermore, since the adhesive resin film is laminated between the first substrate and the second substrate when the capacity of the microreactor is increased by integrating a plurality of fine reaction channels, it is manufactured. It can be easily integrated with high accuracy.

  An integrated microreaction module according to an eleventh aspect of the present invention is the integrated microreaction module according to the tenth aspect, wherein the fluid and the integrated flow introduced into the integrated flow path between the integrated flow path and the common flow path. It is characterized by having a common wide channel part for making the conditions of the fluid discharged from the channel part uniform. “Conditions” of the fluid introduced into the integrated flow path section and the fluid discharged from the integrated flow path section include, for example, the introduction pressure, the concentration of raw materials and reaction products contained in the fluid, and the like.

  According to the present invention, the common fluid introduction port and the integration channel are provided by providing the common wide channel unit between the common channel unit and the integration channel unit on the common fluid introduction port side. The difference in the introduction pressure of the reaction raw material into each fine reaction channel due to the difference in the positional relationship with each fine reaction channel of the part can be made uniform.

  In addition, since the common wide flow channel portion is provided between the common flow channel portion on the common fluid discharge port side and the integrated flow channel portion, the difference in reactivity in each fine reaction flow channel The concentration difference of the reaction product due to can be made uniform.

  An integrated micro reaction module according to a twelfth aspect of the present invention is the integrated microreaction module according to the eleventh aspect, wherein the common wide channel portion is constituted by a recess formed in the first substrate and / or the second substrate. It is characterized by being. According to the present invention, the same effect as that of the eleventh aspect can be obtained with a simple structure.

  According to a thirteenth aspect of the present invention, there is provided a method for purifying organic arsenic-contaminated water, wherein the organic arsenic-contaminated water is purified using any one of the integrated micro reaction modules according to the tenth to twelfth aspects. It is characterized by.

  According to the present invention, the inner surface of the slit-shaped through-hole provided in the adhesive resin film, the first substrate bonded to one surface of the adhesive resin film, and the other of the adhesive resin film Since the fine reaction flow path is formed by the second substrate bonded to the surface, it is easy to form a fine flow path with high hermeticity and can be processed at low cost.

[Example 1]
Hereinafter, an embodiment of the microreaction apparatus according to the present invention will be described. 1 is a perspective view of a first substrate, an adhesive resin film, and a second substrate constituting the microreaction apparatus according to Example 1, and FIG. 2 is a first substrate, an adhesive resin film, and a second substrate of FIG. FIG. 3 is a perspective view of the microreactor formed by joining together. FIG. 3 is a view taken along the line III-III in FIG.

  The microreaction apparatus 1 according to Example 1 is bonded to an adhesive resin film 3, a slit-like through hole 5 provided in the adhesive resin film 3, and one surface 6 of the adhesive resin film 3. A first substrate 2 and a second substrate 4 joined to the other surface 7 of the adhesive resin film 3, and the first substrate 2, the second substrate 3, and the inner surface 10 of the through-hole. Thus, a fine reaction channel 11 is formed and configured.

  That is, the width and length of the slit-like through-hole 5 provided in the adhesive resin film 3 become the width and length of the fine reaction channel 11. Moreover, the thickness of the adhesive resin film 3 after joining becomes the depth of the fine reaction flow path 11.

  The adhesive resin film 3 is a resin film having self-adhesive properties at room temperature or by heating, and examples thereof include a fluororesin, an epoxy resin, and a silicone resin. Since the fluororesin has high chemical resistance, it is particularly preferable as a material for forming the reaction channel 11.

  As the adhesive resin film 3, a commercially available sheet-like resin film can be used. For example, in the case of a fluororesin, Daikin Industries, Ltd., NEOFRON (registered trademark) EFEP RP-4020 or RP-5000 may be used. Since the melting point of RP-4020 is about 160 ° C. which is lower than that of a general fluororesin (for example, ETFE, melting point 265 ° C.), the modification of the catalyst is performed as in the case where a catalyst is provided in the reaction channel 11 described later. In addition to being usable when there is a bonding temperature limitation due to temperature, it is non-tacky at room temperature and has chemical stability and chemical resistance as a fluororesin. The adhesive resin film 3 is particularly suitable.

  In addition, when there is no limitation on the bonding temperature and when it is desired to set the use temperature of the formed microreactor 1 high, the adhesive resin film 3 bonded at a higher temperature can be selected. In addition, when the catalyst provided in the reaction channel 11 is a photocatalyst, it is desirable to use a transparent resin with high light transmittance in order to effectively use the light to be irradiated.

  Furthermore, the depth of the reaction channel 11 of the microreaction apparatus 1 is preferably 25 μm to 1000 μm. When the adhesive resin film 3 is fused by heating, the depth of the reaction channel 11 formed by the fusion becomes thinner than the sheet thickness of the adhesive resin film 3 before the fusion. Therefore, according to the resin property of the adhesive resin film 3, a sheet thickness is selected so that the thickness of the adhesive resin film 3 after joining becomes the desired depth of the reaction flow path 11.

  The adhesive resin film 3 is provided with a slit-like through hole 5. The slit-like through-hole 5 can be provided using a known technique such as excision of the adhesive resin film 3 or formation of a notch. Since the adhesive resin film 3 is a resin and is very thin (several tens to several hundreds μm), the processing is easier than etching processing such as quartz or borosilicate glass. It is preferable that the width of the slit-like through-hole 5 which becomes the channel width of the fine reaction channel is 50 to 5000 μm.

  4 (A), 4 (B), and 4 (C) are diagrams showing examples of fine reaction channels formed by slit-like through holes formed in the adhesive resin film. FIG. 4A shows a reaction flow path 11a composed of straight slit-like through holes. Further, as shown in FIG. 4B, a structure in which a plurality of raw materials can be introduced and reactants can be separated as in the reaction channel 11b by a slit-like through hole having a branched structure. . In FIG. 4C, a long reaction channel 11c can also be formed by a slit-like through hole provided with a gentle turning point.

Next, the first substrate 2 and the second substrate 4 will be described. The first substrate 2 and the second substrate 4 are respectively joined to one surface 6 and the other surface 7 of the adhesive resin film 3 to form the top and bottom surfaces of the reaction channel 11 of the microreactor 1. It is.
The first substrate 2 and the second substrate 4 are preferably transparent plate materials having high visibility and light transmittance in the reaction channel, for example, plate materials such as quartz, borosilicate glass, and acrylic. In particular, from the viewpoint of chemical resistance, quartz or borosilicate glass is preferable.

The first substrate 2 has a fluid inlet 8 for introducing a reaction raw material into the reaction channel 11 at a position corresponding to the start point 12 and the end point 13 of the reaction channel 11 , and a reaction that has passed through the reaction channel 3. A fluid discharge port 9 through which an object is taken out is formed. Either one or both of the fluid introduction port 8 and the fluid discharge port 9 may be provided on the second substrate 4.

  Moreover, a catalyst can be provided on the bonding surfaces 14 and 15 of the first substrate 2 and the second substrate 4 or both of the adhesive resin films 3. Thus, the catalyst 16 is provided on one or both of the top surface and the bottom surface of the reaction channel 11, and various catalytic reactions can be performed while the reaction raw material passes through the reaction channel 11.

Thus, the bonding surface 14 of the first substrate 2 with the adhesive resin film 3 and the adhesive resin film 3 of the second substrate 4, which form the top and bottom surfaces of the reaction flow path 11 of the microreactor 1, mating surface 15, i.e., pre-catalyst 16 is provided, the first substrate 2 and the second junction surface 14, 15 of the substrate 4 bonded to the adhesive resin film 3 on a flat surface not subjected to etching processing or the like If the reaction channel 11 is formed, the catalyst 16 can be easily formed.

  In particular, when the catalyst 16 is a photocatalyst, the light transmittance of the first substrate 2 or the second substrate 4 is important. When quartz, borosilicate glass, or the like is etched, the etched surface is rubbed white to form a glass, and light transmittance is reduced. By using a catalyst on the surface of the first and second substrates that are made of quartz, borosilicate glass, etc. and maintaining high light transmission, the light emitted from the outside of the microreactor can be used effectively. can do. The catalyst 16 is desirably provided on the entire surface of the joint surface with the adhesive resin film 3, but can be provided only on a portion constituting the reaction flow path.

The catalyst 16 may be any material that can be fixed to the first substrate 2 or the second substrate 4, and examples thereof include a photocatalyst, a metal catalyst, and an enzyme. Here, it is known that the photocatalyst and the enzyme are denatured (deactivated) at a relatively low heating temperature. Among the photocatalysts, titanium dioxide (TiO ₂ ) has its crystal structure changed from anatase type to rutile type at about 650 ° C., and the photocatalytic activity becomes low. Further, even when heating at a lower temperature (300 to 500 ° C.), the activity may be reduced due to the modification of the catalyst. Enzymes are proteins, and their denaturation temperature is much lower and many enzymes are inactivated at 100 ° C. or lower. In such a case, the adhesive resin film 3 that can be bonded at a temperature lower than the modification temperature of the catalyst used is selected.

  Thus, the inner surface 10 of the slit-shaped through-hole 5 provided in the adhesive resin film 3, the first substrate 2 bonded to one surface 6 of the adhesive resin film, and the adhesive resin film Since the minute reaction flow path 11 is formed by the second substrate 4 bonded to the other surface 7 of the third, the production of the microreaction apparatus 1 is easy and inexpensive. Furthermore, the tightness of the fine reaction channel 11 is enhanced by the adhesiveness of the adhesive resin film 3, and the loss of pressure when the reaction raw material is introduced into the fine reaction channel 11 can be reduced. It is possible to form a reaction channel 11 that is finely divided. Further, it is possible to prevent the reaction raw materials flowing through the reaction flow path 11 from leaking.

[Example 2]
Next, another embodiment of the microreaction apparatus according to the present invention will be described. 5 is a perspective view of a first substrate, an adhesive resin film, and a second substrate constituting the microreaction apparatus according to Example 2, and FIG. 6 is a first substrate, an adhesive resin film, and a second substrate of FIG. 7 is a perspective view of a microreactor formed by joining together, and FIG. 7 is a view taken in the direction of arrows VII-VII in FIG.

  The microreaction apparatus 21 according to Example 2 includes a plurality of adhesive resin films 23a and 23b arranged on the same plane on the first substrate 22 (in FIG. 5, in order to facilitate understanding, the adhesive resin film 23a and 23b show a state before being disposed on the first substrate 22.) Among the plurality of adhesive resin films 23a and 23b, the end sides 32a of the adjacent adhesive resin films 23a and 23b are shown. , 32b are formed with a slit 25 formed so as to be kept at a predetermined distance in the normal direction from each point on the edge, and the plurality of adhesive resin films 23a, 23b are formed. A first substrate 22 bonded to one surface 26 of the plane, and a second substrate 24 bonded to the other surface 27 of the plane formed by the plurality of adhesive resin films 23a, 23b, The first substrate 22 and the The inner surface 30 of second substrate 24 and the slit 25 is configured fine reaction flow channel 31 is formed.

  That is, the adhesive resin films 23 a and 23 b are arranged at an interval corresponding to the channel width of the fine reaction channel 31 to form the slit 25. Further, the lengths of the end sides 32a and 32b become the channel length, and the thickness of the adhesive resin film 23 after joining becomes the depth of the fine reaction channel 11.

  In this embodiment, the first substrate 22, the adhesive resin films 23a and 23b, and the second substrate 24 are joined based on the adhesive property of the adhesive resin film, and formed on the side surface of the formed microreactor. Since the opening can be used as a fluid inlet 28 for introducing a reaction raw material into the reaction channel 31 and a fluid outlet 29 from which a reactant passing through the reaction channel 31 is taken out, the first substrate 22 or The second substrate 24 may be configured not to be provided with holes as the fluid introduction port 28 and the fluid discharge port 29.

  FIG. 8A and FIG. 8B are examples of fine reaction flow paths constituted by slits formed by arranging a plurality of adhesive resin films. FIG. 8A shows a reaction channel 31a composed of linear slits formed by two adhesive resin films 23a and 23b. Further, as shown in FIG. 8B, introduction of a plurality of raw materials such as the reaction channel 31b is performed by a slit having a branched structure formed by four adhesive resin films 23c, 23d, 23e, and 23f. And it can be set as the structure which can isolate | separate a reactant.

  The simple shapes such as the adhesive resin films 23a to 23f can be formed by cutting the adhesive resin sheet with a cutter or the like, so that the simple shapes as shown in FIGS. 8A and 8B are used. This is suitable for the case where a micro reaction apparatus having a configuration is to be easily created at the laboratory level. Of course, a precise microreactor can be manufactured by a cutting method capable of forming a dense cut surface.

[Example 3]
Next, an embodiment of the integrated micro reaction module according to the present invention will be described. 9 is a perspective view of a first substrate, an adhesive resin film, and a second substrate constituting the microreaction apparatus according to Example 3, and FIG. 10 is a first substrate, an adhesive resin film, and a second substrate of FIG. FIG. 11 is a XI-XI arrow view of FIG. 10.

  In the integrated micro reaction module according to Example 3, the through-hole provided in the adhesive resin film 43 is a plurality of slit-like through-holes 45 and is bonded to one surface 46 of the adhesive resin film 43. Reaction channel having a plurality of fine reaction channels formed by the first substrate 42, the second substrate 44 bonded to the other surface 47 of the adhesive resin film 43, and the inner surface 50 of the through hole 45. The part 51 is formed.

  In this embodiment, the material of the adhesive resin film 43, the first substrate 42 and the second substrate 44 and the method of forming the plurality of slit-like through holes 45 are the same as those of the microreactor 1 of the first embodiment. Therefore, the description is omitted.

  Next, the reaction channel portion 51 will be described. 12A, FIG. 12B, FIG. 12C, and FIG. 22 show the configuration of the reaction channel section 51 having a plurality of fine reaction channels of the integrated micro reaction module according to the third embodiment. It is an example.

  The reaction channel 51 includes an integrated channel 56 in which a plurality of fine reaction channels are arranged in parallel, and a common fluid inlet and a common fluid outlet for the plurality of minute reaction channels. And a common flow path portion 57 formed so as to merge with each other.

  FIG. 12A shows a reaction channel portion 51a formed such that a plurality of fine reaction channels merge with one common fluid inlet 52a and one common fluid outlet 53a.

  By introducing the reaction raw material into one common fluid introduction port 52a, the reaction raw material is fed into a plurality of integrated fine reaction flow paths, so that a large-capacity catalytic reaction can be performed. Furthermore, the reactants discharged from each reaction channel are joined again and discharged from one fluid discharge port 53a, so that the recovery is easy.

  FIG. 12B shows a reaction channel portion formed such that a plurality of fine reaction channels merge with two common fluid inlets 52b1 and 52b2 and two common fluid outlets 53b1 and 53b2. 51b.

  The common fluid inlets 52b1 and 52b2 and the fluid outlets 53b1 and 53b2 can be appropriately increased according to the number of the plurality of fine reaction channels. By adopting a configuration in which several reaction channels are joined, the number of raw material introduction pumps and the like can be reduced, which leads to cost reduction.

  FIG. 12C shows that the conditions of the fluid introduced into the integrated flow channel portion 56 and the fluid discharged from the integrated flow channel portion 56 are made uniform between the integrated flow channel portion 56 and the common flow channel portion 57. It is the reaction flow path part 51c provided with the common wide flow path part 58 for this.

  The common wide flow channel portion 58 is provided between the common flow channel portion 57 and the collective flow channel portion 56 on the common fluid introduction port 52c side, so that the common fluid introduction port 52c and the collective flow channel portion are provided. The difference in the introduction pressure of the reaction raw material to each fine reaction channel due to the difference in the positional relationship with each of the 56 minute reaction channels can be made uniform.

  Further, by providing the common wide flow channel portion 58 between the common flow channel portion 57 and the integrated flow channel portion 56 on the common fluid discharge port 53c side, The concentration difference of the reaction product due to the difference in reactivity can be made uniform and discharged from the common fluid outlet 53c.

  Furthermore, as shown in FIG. 22, the common wide flow path portion 58 has a shape (a fan shape that requires the common flow path portion 57) that radiates from the common flow path portion 57 toward the accumulation flow path portion 56. Is preferred. By adopting such a shape, the introduction pressure of the reaction raw material from the common flow path portion 57 to the accumulation flow path portion 56 is made uniform, and the concentration of the reaction product sent from the accumulation flow passage portion 56 is made uniform. Can be efficiently performed.

  Also in the present embodiment, a catalyst (not shown) can be provided on the bonding surfaces 44 and 45 of the first and second substrates 42 and 44 with the adhesive resin film 43. As a result, a catalyst (not shown) is provided on one or both of the top surface and the bottom surface of the reaction channel 51, and various catalytic reactions are performed while the reaction raw material passes through the reaction channel 41. be able to.

[Example 4]
13 to 17 are diagrams showing another embodiment of the integrated micro reaction module. 13 is a plan view of the integrated micro reaction module according to Example 4, FIG. 14 is a view taken along arrow XIV-XIV in FIG. 13, FIG. 15 is a view taken along arrow XV-XV in FIG. 14, and FIG. FIG. 17 is a view taken in the direction of arrow XVI and FIG. 17 is a view taken in the direction of arrow XVII-XVII in FIG. FIG. 23 is a diagram illustrating another example of the shape of the recess 79 provided in the second substrate.

  In the present embodiment, the common wide channel portion formed by the through hole provided in the adhesive resin film 43 in the configuration of FIG. The integrated micro reaction module 61 includes an adhesive resin film 63 provided with a plurality of slit-like through holes 65 as in the fourth embodiment, and a first substrate 62 bonded to one surface of the adhesive resin film. And a second substrate 64 bonded to the other surface of the adhesive resin film, and a plurality of fine reactions are caused by the first substrate 62, the second substrate 64, and the inner surface 70 of the through-hole 65. A flow path portion 71 is formed. A catalyst 66 is provided on the joint surface of the first substrate 62 to be joined to the adhesive resin film 63.

  In the adhesive resin film 63, independent slit-like through holes 65 are formed in parallel as shown in FIG. The independent slit-like through holes 65 form an accumulation reaction channel portion 76 (FIG. 17). A common wide channel portion 78 that joins the integrated reaction channel portion 76 formed by the independent slit-like through-holes 65 to the bonding surface of the second substrate 64 bonded to the adhesive resin film 63. The recessed part 79 which comprises is provided in the position corresponding to the both ends of the said slit-shaped through-hole 65 (FIG. 16).

  In this embodiment, the joint surface of the second substrate 64 further serves as a common flow path portion serving as a common fluid introduction port to the integrated reaction flow channel portion 76 and a common fluid discharge port from the integrated reaction flow channel portion. 77 is provided. The common flow path portion 77 can also be formed by providing the recess 80 on the second substrate 64 in this way, but the adhesive resin film 63 has a through hole different from the independent slit-like through hole 65. It is also possible to provide it.

  Further, as shown in FIG. 23, the concave portion 79 forming the common wide flow path portion 78 has a shape that radiates from the concave portion 80 that forms the common flow path portion 77 (a fan shape that requires the concave portion 80 that forms the common flow path portion 77). ). Thus, the introduction pressure of the reaction raw material from the common flow channel portion 77 to the integrated reaction flow channel portion 76 is made uniform, and the concentration of the reaction product sent from the integrated flow channel portion 76 is made uniform efficiently. be able to.

  By bonding the first substrate 62, the adhesive resin film 63, and the second substrate 64 having such a configuration, a reaction channel portion 71 having a common wide channel portion 78 as shown in FIGS. 14 and 17 is configured. can do. In this embodiment, the adhesive resin film 63 is provided with independent slit-like through-holes 65 arranged in parallel, so that the adhesive resin film after the formation of the through-hole 65 is a single sheet. It is a continuous sheet and is easy to handle and can be easily bonded to the first substrate 62 and the second substrate 64.

  By using the integrated micro reaction module 61 as a unit and combining the integrated micro reaction module 61, it is possible to perform a micro reaction performed in a fine reaction channel with a large volume.

[Example 5]
In this example, a UV diode element module is provided on the upper side of the first substrate 62 of the integrated micro reaction module of Example 4, and it is possible to perform photocatalytic reaction by irradiating ultraviolet rays from the upper surface of a fine reaction channel. This is an integrated micro reaction module for photocatalytic reaction.

  18 to 20 are diagrams showing an embodiment of the integrated micro reaction module for photocatalytic reaction, FIG. 18 is a plan view of the integrated micro reaction module for photocatalytic reaction of Embodiment 5, and FIG. FIG. 20 is a cross-sectional view taken along the line XX-XX in FIG. 21A to 21C are diagrams showing the configuration of the UV diode element module, where FIG. 21A is a plan view of the UV diode element module, FIG. 21B is a bottom view of the UV diode element module, and FIG. FIG. 22 is a view on arrow cc in FIG.

  First, the UV diode element module 91 mounted on the integrated micro reaction module 61 will be described. As shown in FIG. 21C, the UV diode element module 91 includes a UV diode unit 92 and a module cooling unit 93. The UV diode unit 92 is a known ultraviolet light emitting diode (UV-LED). The module cooling unit 93 cools the heat generated by the UV diode unit 92 and is configured to distribute cooling water through the cooling water flow path 94.

  In this embodiment, since the UV diode element module 91 is disposed along the reaction channel portion 71 of the integrated micro reaction module 61 (FIG. 20), all the channel lengths of the reaction channel portion 71 are ultraviolet rays. Are arranged in series [FIG. 21 (B)]. The length of the module cooling unit 93 is determined according to the length of the UV diode units 92 arranged in series. The arranged UV diode part 92 and module cooling part 93 are integrated by a casing metal frame 95 to form one UV diode element module 91.

  Such a UV diode element module 91 is disposed on an integrated micro reaction module 61 having the same configuration as that of the fourth embodiment. As shown in FIG. 18 and FIG. 19, the UV diode element module 91 is provided in all the channels depending on the number of integrated fine reaction channels, that is, the range in which the reaction channels are provided. A number of UV diode element modules 91 capable of irradiating ultraviolet rays are arranged in parallel.

  Although the UV diode element module 91 can be directly provided on the first substrate 62, as shown in FIGS. 19 and 20, the module spacer 96 is used to form the UV diode element module 91 and the integrated micro reaction module 61. It is preferable to provide a space between them.

  The UV diode element module 91, the module spacer 96, and the integrated micro reaction module 61 can be integrated with the presser fitting 97 and the fixing bolt 98 to be used as the integrated micro reaction module 101 for photocatalytic reaction.

[Organic arsenic decomposition reaction experiment]
Next, a micro reaction experiment using the micro reaction apparatus according to the present invention will be described. This experiment is a decomposition reaction experiment of diphenylarsinic acid (hereinafter referred to as DPAA) using a microreactor.

  DPAA is a causative substance of organic arsenic compound contamination of groundwater in Kamisu-cho, Ibaraki Prefecture, and the establishment of a treatment method is urgently needed. On the other hand, as a method for treating contaminated water containing an inorganic arsenic compound, an iron salt addition coagulation precipitation method has been put into practical use. However, since DPAA is a relatively stable compound and has a benzene ring (phenyl group), it has been difficult to achieve the water quality standard required by the iron salt-added aggregation precipitation method.

  Further, an iron salt-added coagulating sedimentation method in which photodegradation with an ultraviolet lamp (batch type in a storage tank) is performed as a pretreatment has been studied, but DPAA is hardly decomposable with respect to photolysis and has a high content exceeding 10 ppm. Since it took a long time to treat the concentration-contaminated raw water, it was difficult to realize in terms of cost.

  In this experiment, due to the adhesiveness of the adhesive resin film, the tightness of the fine reaction channel is high, and it is possible to prevent leakage of contaminated water containing a highly toxic arsenic compound and to support a photocatalyst. If the photoreaction of DPAA is efficiently performed by using the microreactor according to the present invention that can be integrated to treat large volumes of contaminated water, photolysis can be used for treating organic arsenic compound contaminated water. It was done with the idea that the possibilities could be increased.

In this experiment, a microreactor having the same configuration as that of the microreactor 1 of Example 1 and FIG. 1 was used. As the adhesive resin film 3, an adhesive fluororesin film having a melting point around 180 ° C. was used. The first substrate 2 and the second substrate 4 is made of synthetic quartz, the TiO ₂ as a photocatalyst on the joint surface 15 of the adhesive resin film 3 of the second substrate 4 Sol - used was carried by gel method.

  The reaction channel 11 was formed with a channel width of 2 mm and a channel length of 50 mm. The flow path depth is formed around 40 μm by welding the adhesive resin film 3 of 45 μm around 200 ° C. Moreover, UV-LED (wavelength 365nm) was used as a light source for performing a photocatalytic reaction. A light source (not shown) was arranged on the upper side of the first substrate 2 along the reaction flow path 11 and irradiated with ultraviolet light from the upper surface of the bonding surface 15 of the second substrate 4 provided with a photocatalyst. Using this microreactor 1, a photolysis experiment was conducted for DPAA. The results are shown in Table 1.

  The total arsenic concentration was analyzed by inductively coupled plasma mass spectrometry (ICP / MS). Inorganic arsenic compounds [trivalent: As (III), pentavalent: As (V)] and organic arsenic compounds [monomethylarsonic acid (MMAA), dimethylarsonic acid (DMAA), diphenylarsinic acid (DPAA), phenylarsonic acid ( PAA), methylphenylarsinic acid (PMAA), trimethylarsine oxide (TMAO)] were analyzed by liquid chromatography-inductively coupled plasma mass spectrometry (LC-ICP / MS).

上記マイクロ反応装置を用いてＴｉＯ_２触媒によるＤＰＡＡの光分解を行うと、１０秒で７７．３％、２１秒で８２．５％の高効率でＤＰＡＡが分解され、三価の無機ヒ素化合物が生じていることが分かる。無機ヒ素化合物にまで分解されれば、従来の鉄塩添加凝集沈殿法を用いた処理を行うことができる。尚、分解後の各化合物のヒ素濃度の合計が総ヒ素濃度よりも低い値となっているのは、ＤＰＡＡの光分解によって、今回の測定対象以外の形態のヒ素化合物に分解されているためであると考えられる。

When the photo-decomposition of DPAA using a TiO ₂ catalyst is carried out using the above microreactor, DPAA is decomposed with high efficiency of 77.3% in 10 seconds and 82.5% in 21 seconds, and trivalent inorganic arsenic compounds are converted. You can see that it has occurred. If it decomposes | disassembles even to an inorganic arsenic compound, the process using the conventional iron salt addition coagulation precipitation method can be performed. Note that the total arsenic concentration of each compound after decomposition is lower than the total arsenic concentration because it is decomposed into arsenic compounds in a form other than the current measurement object by the photolysis of DPAA. It is believed that there is.

  In this experiment, the decomposition reaction seems to converge at a decomposition rate of about 80%. By optimizing the reaction conditions (reaction channel depth, specific surface area, reaction temperature, etc.), the decomposition rate It is thought that it can raise.

  Modeling a continuous-flow photocatalytic microreactor using fine reaction channels in the CFD numerical analysis program, and referring to the results of numerical analysis of phenol photolysis reaction, the reaction channel depth is further reduced. It is expected that the decomposition rate may be improved to 95 to 99% or more by forming and using a reaction channel having a depth of 25 to 40 μm.

  In addition, by using a microreactor, decomposition from an organic arsenic compound (DPAA) to an inorganic arsenic compound can be performed with high efficiency. Therefore, by applying the integrated microreaction module described in Example 5, A practical purification device for organic arsenic-contaminated water can be realized.

  The present invention relates to a microreaction apparatus capable of performing a chemical reaction, separation, etc. in a fine flow path, a manufacturing method thereof, an integrated microreaction module, and purification of organic arsenic contaminated water using the integrated microreaction module It can be used as a method.

It is a perspective view of the 1st substrate which constitutes the micro reaction device concerning Example 1, an adhesive resin film, and the 2nd substrate. It is a perspective view of the micro reaction device formed by joining the 1st substrate of Drawing 1, an adhesive resin film, and the 2nd substrate. It is the III-III arrow line view of FIG. It is a figure which shows the example of the fine reaction flow path formed by the slit-shaped through-hole formed in an adhesive resin film, (A) is a linear reaction flow path, (B) is branched in the shape of a branch (C) is a reaction channel provided with a gentle turning point. 6 is a perspective view of a first substrate, an adhesive resin film, and a second substrate that constitute a microreaction apparatus according to Example 2. FIG. FIG. 6 is a perspective view of a micro reaction device formed by joining the first substrate, the adhesive resin film, and the second substrate of FIG. 5. It is a VII-VII arrow line view of FIG. It is an example of the fine reaction flow path comprised by the slit formed by arrange | positioning several adhesive resin film, (A) is the reaction flow path 31A which consists of a linear slit, (B) is branched This is a reaction channel 31C having a structure. 6 is a perspective view of a first substrate, an adhesive resin film, and a second substrate that constitute a microreaction apparatus according to Example 3. FIG. FIG. 10 is a perspective view of a microreaction apparatus formed by joining the first substrate, the adhesive resin film, and the second substrate of FIG. 9. It is a XI-XI arrow line view of FIG. It is a structural example of the reaction flow path part which has a some fine reaction flow path, (A) is a plurality of fine reaction flow paths in one common fluid introduction port and one common fluid discharge port. The reaction channel portion formed so as to merge, (B) is formed such that a plurality of fine reaction channels merge into two common fluid inlets and two common fluid outlets. The reaction channel part (C) is for uniformizing the conditions of the fluid introduced into the integrated channel part and the fluid discharged from the integrated channel part between the integrated channel part and the common channel part. It is a reaction channel part provided with the common wide channel part. 7 is a plan view of an integrated micro reaction module for photocatalytic reaction according to Example 4. FIG. It is a XIV-XIV arrow line view of FIG. It is a XV-XV arrow line view of FIG. It is a XVI-XVI arrow line view of FIG. It is a XVII-XVII arrow line view of FIG. 7 is a plan view of an integrated micro reaction module of Example 5. FIG. It is the XIX-XIX arrow line view of FIG. It is XX-XX sectional drawing of FIG. It is a figure which shows the structure of a UV diode element module, (A) is a top view of a UV diode element module, (B) is a bottom view of a UV diode element module, (C) is cc arrow of FIG. 21 (A). FIG. 7 is a configuration example of a reaction channel unit having a plurality of fine reaction channels of an integrated micro reaction module according to Example 3. FIG. It is a figure which shows the other example of the shape of the recessed part 79 in Example 4. FIG.

Explanation of symbols

1 micro reactor, 2 first substrate, 3 adhesive resin film,
4 second substrate, 5 slit-like through hole,
8 fluid inlet, 9 fluid outlet, 10 inner surface of through hole,
11, 11a, 11b, 11c Fine reaction flow path,
14 Bonding surface of first substrate with adhesive resin film,
15 Bonding surface of second substrate with adhesive resin film, 16 catalyst,
21 microreactor, 22 first substrate,
23, 23a, 23b, 23c, 23d, 23e, 23f Adhesive resin film,
24 second substrate, 25 slit, 28 fluid inlet,
29 fluid outlet, 30 inner surface of the slit,
31, 31a, 31b Fine reaction flow path,
41 integrated microreaction module, 42 first substrate,
43 adhesive resin film, 44 second substrate,
45 through hole, 50 inner surface of the through hole,
51, 51a, 51b, 51c, 51d reaction channel part,
52, 52a, 52b1, 52b2, 52c, 52d fluid inlet,
53, 53a, 53b1, 53b2, 53c, 53d Fluid outlet,
56 integrated flow channel portions, 57 common flow channel portions, 58 common wide flow channel portions,
61 integrated micro reaction module, 62 first substrate,
63 adhesive resin film, 64 second substrate,
65 a plurality of slit-like through holes, 66 catalyst,
70 inner surface of the slit-shaped through hole, 71 reaction channel portion,
76 integrated reaction channel part, 77 common channel part, 78 common wide channel part,
79, 80 recess,
91 UV diode element module,
92 UV diode section, 93 module cooling section,
101 Integrated micro reaction module for photocatalytic reaction

Claims (9)

An adhesive resin film;
A slit-like through-hole provided in the adhesive resin film;
It is made of a light-transmitting material and is composed of a flat surface that has not been processed to reduce the light transmittance, such as etching, and one surface of the adhesive resin film is bonded to the flat surface. A first substrate,
It is made of a light transmissive material and is composed of a flat surface plate that has not been processed to reduce the light transmittance such as etching, and the other surface of the adhesive resin film is formed on the flat surface. A second substrate bonded,
The flat surface of the first substrate and / or the second substrate is bonded to the adhesive resin film, and is preliminarily provided in a region before the bonding at least in a region corresponding to the through hole. Equipped with a photocatalyst,
The adhesive resin film is an adhesive fluororesin that is non-tacky at room temperature, is fused to the substrate by heating, and has a melting point lower than the modification temperature of the photocatalyst,
A microreaction apparatus in which a fine reaction channel for performing a photocatalytic reaction is formed by the first substrate, the second substrate, and the inner surface of the through hole. A plurality of adhesive resin films disposed on the same plane;
Among the plurality of adhesive resin films, the ends of adjacent adhesive resin films are arranged and formed so as to maintain a predetermined distance in the normal direction from each point on the end sides. Gap
A flat surface formed of a light-transmitting material and formed of a flat surface that is not subjected to processing that reduces the light transmittance such as etching, and the plurality of adhesive resin films are formed on the flat surface. A first substrate on which one of the surfaces is bonded,
A flat surface formed of a light-transmitting material and formed of a flat surface that is not subjected to processing that reduces the light transmittance such as etching, and the plurality of adhesive resin films are formed on the flat surface. A second substrate bonded to the other surface of
The flat surface of the first substrate and / or the second substrate is bonded to the adhesive resin film, and is preliminarily provided in a region before the bonding at least in a region corresponding to the slit. Equipped with a photocatalyst
The adhesive resin film is an adhesive fluororesin that is non-tacky at room temperature, is fused to the substrate by heating, and has a melting point lower than the modification temperature of the photocatalyst,
A microreaction apparatus in which a fine reaction channel for performing a photocatalytic reaction is formed by the first substrate, the second substrate, and the inner surface of the slit. Providing a slit-like through-hole in the adhesive resin film;
A first surface is formed of a light transmissive material and is not subjected to a process for reducing the light transmittance such as etching, and the adhesive resin film is bonded to the flat surface. A bonding surface of the second substrate to which the adhesive resin film is bonded to the substrate and / or the flat surface to the adhesive resin film , and at least in a region corresponding to the through-hole before the bonding Providing a photocatalyst in advance,
The adhesive having the slit-like through-holes, which is non-adhesive at normal temperature, is fused to the substrate by heating, and is an adhesive fluororesin having a melting point lower than the modification temperature of the photocatalyst. The first substrate is bonded to one surface of the resin film by the heat fusion of the adhesive resin film, and the second substrate is bonded to the other surface by the heat fusion of the adhesive resin film, Forming a fine reaction flow path for performing a photocatalytic reaction by the first substrate, the second substrate, and the inner surface of the through-hole. A plurality of adhesive resin films are arranged on the same plane on the first substrate, and the end sides of the adjacent adhesive resin films are separated from each point on the end sides by a predetermined distance in the normal direction. Forming a slit by arranging to keep the
It is formed of a flat surface that is formed of a light transmissive material and has not been subjected to a process that reduces the light transmittance such as etching, and the adhesive resin film is bonded to the flat surface. A bonding surface of the second substrate to which the adhesive resin film is bonded to one substrate and / or the flat surface, to the adhesive resin film , at least in a region corresponding to the slit before the bonding A step of providing a photocatalyst in advance at the stage;
One of the adhesive resin films in which the slit is formed, which is non-adhesive at normal temperature, is fused to the substrate by heating, and is an adhesive fluororesin having a melting point lower than the modification temperature of the photocatalyst. The first substrate is bonded to the surface by the heat fusion of the adhesive resin film, and the second substrate is bonded to the other surface by the heat fusion of the adhesive resin film, and the first substrate and the And a step of forming a fine reaction channel for carrying out a photocatalytic reaction by the second substrate and the inner surface of the slit. An adhesive resin film;
A plurality of slit-shaped through holes provided in the adhesive resin film;
It is made of a light-transmitting material and is composed of a flat surface that has not been processed to reduce the light transmittance, such as etching, and one surface of the adhesive resin film is bonded to the flat surface. A first substrate,
It is made of a light transmissive material and is composed of a flat surface plate that has not been processed to reduce the light transmittance such as etching, and the other surface of the adhesive resin film is formed on the flat surface. A second substrate bonded,
An integrated micro reaction module in which a reaction channel portion having a plurality of fine reaction channels is formed by the first substrate, the second substrate, and the inner surface of the through hole,
The reaction channel part is an integrated channel part in which a plurality of fine reaction channels are arranged in parallel;
A plurality of fine reaction flow paths, a common flow path portion formed so as to merge with a common fluid introduction port and a common fluid discharge port,
The flat surface of the first substrate and / or the second substrate is bonded to the adhesive resin film, and is preliminarily provided in a region before the bonding at least in a region corresponding to the through hole. Equipped with a photocatalyst
The adhesive resin film is non-adhesive at normal temperature, is fused to the substrate by heating, and is an adhesive fluororesin having a melting point lower than the modification temperature of the photocatalyst, Integrated micro reaction module.   6. The integrated micro reaction module according to claim 5, wherein the condition of the fluid introduced into the integrated flow path section and the fluid discharged from the integrated flow path section is between the integrated flow path section and the common flow path section. An integrated microreaction module comprising a common wide flow path portion for uniformizing the flow rate.   7. The integrated micro reaction module according to claim 6, wherein the common wide channel portion is formed in a fan-like shape that requires the common channel portion. . 8. The integrated micro reaction module according to claim 6, wherein a concave portion is formed on the flat surface of the first substrate and / or the flat surface of the second substrate, and the common wide flow path is formed. A part of the part is constituted by the concave part, and is an integrated micro reaction module.   A method for purifying organic arsenic-contaminated water, comprising purifying organic arsenic-contaminated water using the integrated micro reaction module according to any one of claims 5 to 8.

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