JP4992655B2 - Reactor - Google Patents

Description

  The present invention relates to a reaction apparatus, and more particularly to a reaction apparatus having a porous body in a flow path.

Conventionally, porous bodies such as filters have been used in various reaction apparatuses. In addition, the elements constituting the microfluidic system (microreactor device) include microfluidic elements such as microfluidic control elements such as micropumps and microvalves, filters, sample injectors, mixing / reactors, and separators (non-reactive). Patent Document 1).
Among these, regarding the filter, it is inevitable that “clogging” will occur in the mesh type filter if filtering is performed.
As a means for avoiding clogging of the filter, an apparatus that detects clogging and backwashes the filter with washing water to perform cleaning has been reported (see Patent Document 1).

JP-A-9-122411 Shoichi Shoko, “Microfluidic devices / elements and application trends to microsystems”, Measurement and Control, December 2003, Vol. 42, No. 12, p. 1005-1008

  An object of this invention is to improve performance maintainability in the reaction apparatus which has a porous body in a flow path.

The present invention has been solved by the means described in <1> below. It is described below together with <2> to <4> which are preferred embodiments.
<1> A reaction having a flow path for sending a fluid, comprising a porous body through which the fluid passes, and the contact area between the porous body and the fluid being adjustable. apparatus,
<2> The reaction apparatus according to <1>, wherein the contact area between the porous body and the fluid increases or decreases with a change in fluid resistance.
<3> The inner wall near the porous body of the flow path is formed by a cantilever part, and the cantilever part has a space on the side opposite to the inner wall of the flow path. The reaction apparatus according to
<4> The reaction apparatus according to any one of <1> to <3> above, comprising a window part for visually recognizing the arrangement part of the porous body.

According to the invention described in the above <1>, a reactor having high performance maintainability can be provided by increasing or decreasing the contact area between the porous body provided in the flow path and the fluid.
According to the invention described in <2> above, the contact area between the porous body and the fluid changes with a change in the resistance between the porous body and the fluid. Thus, the flow rate can be kept within a certain range.
According to the invention described in <3> above, the contact area between the porous body and the fluid can be increased or decreased by a simpler means.
According to the invention described in <4> above, the contact area between the porous body and the fluid can be observed by visually recognizing the arrangement portion of the porous body.

The reaction apparatus of the present invention has a flow path for sending a fluid, includes a porous body through which the fluid passes, and the contact area between the porous body and the fluid can be increased or decreased. Features.
Conventionally, in order to eliminate clogging of a porous body such as a filter, an apparatus provided with a means for actively washing, such as a technique of backflowing washing water, has been reported (see Patent Document 1). However, the application of such an active cleaning means is problematic in terms of structural complexity and cost. When the channel diameter is small, and when the channel is a minute channel, it is difficult to apply active cleaning means.
In the present invention, by increasing / decreasing the contact area between the porous body and the fluid, the reaction can be used stably over a longer period of time as compared with a reaction apparatus that does not have such means for increasing / decreasing the contact area. A device is provided.
In the present invention, the “reaction apparatus” is not limited to an apparatus used for a chemical reaction, and is not particularly limited as long as it is a reaction apparatus using a porous material, and widely includes a filtration apparatus. It is.

<Flow path>
In the present invention, the shape and width of the flow path are not particularly limited and are preferably selected according to the purpose, but are preferably used for a flow path having a small flow path diameter to which it is difficult to apply active cleaning means. can do.
Specifically, it is suitable for a channel having a channel diameter of 10 cm or less, more preferably 5 cm or less, further preferably 2 cm or less, and particularly preferably 1 cm or less.

In the present invention, a microchannel can also be suitably used as the channel.
In the present invention, the micro channel refers to a channel having a channel diameter of 5,000 μm or less. The channel diameter is an equivalent circle diameter (diameter) obtained from the cross-sectional area of the channel.
In the present invention, a reactor having a channel diameter of several to several thousand μm (hereinafter, a reactor having a microchannel is also referred to as a microreactor device or simply a microreactor) is preferably used as the microchannel. The channel diameter of the microchannel of the microreactor device is preferably 50 to 1,000 μm, more preferably 50 to 500 μm. The microreactor apparatus used in the present invention is a reaction apparatus having a plurality of microscale flow paths (channels). Since the flow path of the microreactor device is microscale, both the dimensions and flow velocity are small, and the Reynolds number is 2,300 or less. Therefore, the reaction apparatus having a micro flow channel is not a turbulent flow control like a normal reaction apparatus but a laminar flow control apparatus unless stirring, vibration application, baffle plate formation, or the like is performed.
Here, the Reynolds number (Re) is expressed by the following formula, and when it is 2,300 or less, the laminar flow is dominant.
Re = uL / ν
(U: flow velocity, L: representative length, ν: kinematic viscosity coefficient)

<Fluid>
In the present invention, the fluid to be sent may be either liquid or gas, but is preferably liquid. The fluid may contain a solid (for example, fine particles) and is not particularly limited. By selecting the fluid and the porous body, it is possible to perform filtration of impurities in the fluid, removal of fine particles, treatment of the fluid (for example, chemical reaction), and the like.
Examples of the fluid suitable for the present invention include water, hydrophilic organic solvents such as ethanol, and lipophilic organic solvents such as toluene. From the viewpoint of pressure loss, a solution having a viscosity of 100 cP or less is preferable.

<Porous body>
In the present invention, the porous body can be selected from known porous bodies. Any material such as glass, metal, resin, or porous silicon may be used.
Examples of the porous body include a porous alumina foil, a woodpile structure, a wire mesh, and a membrane filter, but are not particularly limited.
It is preferable to select the hole diameter, strength, etc. according to the desired application.

Preferred examples of the woodpile structure include the woodpile structure described in Takayuki Yamada et al, '3D MICROFLUIDIC DEVICE FABRICATED BY USING SURFACE-ACTIVATED BONDING OF ELECTROPLATED Ni PATTERNS' IEEE Transducers, 2005, p.1485.
Moreover, as a metal mesh, the fine mesh by electroforming etc. can be illustrated.

  In the present invention, a mesoporous body such as a silica porous body, a porous body made of a fluororesin, various nonwoven fabric filters, woven fabric filters, membrane filters, and the like can be used. Specific examples of the fluororesin porous material include a tetrafluoroethylene resin (PTFE) filter.

  In addition, although the said porous body can also be used as a membrane filter, since strength is requested | required of a porous body in this invention, it is preferable to select the porous body which does not produce a deformation | transformation by use.

  The porous body can also be used as a filtration device that removes particles, foreign matters, and the like in the fluid. Further, the reaction or treatment can be performed by allowing the fluid to pass through the porous body by supporting the catalyst on the porous body or forming the porous body with the catalyst.

<Contact area between porous body and fluid>
In the present invention, the contact area between the porous body and the fluid can be increased or decreased. Here, the contact area between the porous body and the fluid means the contact area between the fluid to be sent and the outer surface of the porous body, and does not mean the contact area between the fluid and the fluid inside the porous body. . In addition, it does not exclude that the contact area with the fluid inside the porous body increases or decreases.

  The porous body is “clogged” by use, but when such clogging occurs, the pressure loss increases and the flow rate decreases. Further, if the flow rate is kept constant, a burden on a pump or the like for feeding fluid increases. By increasing or decreasing the contact area, the flow rate can be kept constant and the burden on the liquid delivery device can be reduced.

In addition, the contact area is preferably increased or decreased with changes in fluid resistance. In particular, it is preferable that the contact area increases as the fluid resistance increases. When clogging occurs in the porous body, the fluid resistance increases with an increase in pressure loss. If the contact area between the porous body and the fluid is increased as the fluid resistance increases, the flow rate of the fluid can be increased. Therefore, even if clogging occurs, a decrease in flow rate can be suppressed and fluid can be sent stably.
On the other hand, when the contact area between the porous body and the fluid is increased from the beginning of the flow of the fluid, the flow path diameter increases in the flow area of the porous body, so the flow rate becomes slower and the porous body is more easily clogged. Become. In addition, it is difficult to form a stable laminar flow.
In the present invention, it is preferable to increase the contact area after clogging, whereby a stable flow rate can be maintained.

Any means may be used as a means for increasing / decreasing the contact area between the porous body and the fluid, but the inner wall near the porous body of the flow path is formed by a cantilever part, and the cantilever part is It is preferable to have a space on the side opposite to the inner wall of the flow path.
Hereinafter, description will be given with reference to the drawings. In the present invention, the same reference numerals indicate the same objects.
FIG. 1 is a schematic perspective view showing an example of the reaction apparatus of this example. 2 and 3 are partial enlarged views of a schematic plan view observed from above through the lid when the lid in FIG. 1 is transparent.
In FIG. 1, the reaction apparatus 100 has a flow path 102 through which a fluid L is sent. In FIG. 1, a flow path 102 is provided in a base body 120 and a lid body 122 is joined.

The method for producing the reactor of this example is not particularly limited, and can be produced by appropriately selecting from known production methods.
When the reaction apparatus of this embodiment is a microreactor apparatus in particular, a micro flow path is formed on a substrate by using a lithography technique such as dry etching, wet etching, laser processing, beam processing, or by injection molding. For example, it can be produced by joining a lid to the lid.
In addition, the reactor of this embodiment can also be formed by stacking thin film patterns. Examples of a method for producing a reaction device using a thin film pattern, particularly a microreactor device, include the production methods described in JP-A Nos. 2006-187855 and 2006-187684.

  The channel 102 includes a porous body 110 through which the fluid L passes. As described above, the porous body may be appropriately selected depending on the required pore diameter, strength, and the like. The porous body may be a filter, a porous body carrying a catalyst, or a porous body formed of a catalyst.

<Cantilever part>
In FIG. 2, the upstream inner wall in the vicinity of the porous body of the flow path is formed by the cantilever part 135, and the downstream inner wall in the vicinity of the porous body of the flow path is formed by the cantilever part 136. Yes. The cantilever portions 135 and 136 have spaces 150 and 151 on the side opposite to the inner wall.
The cantilever portion is preferably provided at least in the vicinity of the porous body of the flow path, and the entire inner surface of the porous body can be formed by the cantilever portion, or a part of the cantilever portion cantilevered. It can also be formed by a part. For example, in the case of a channel having a rectangular cross section, all of the upper surface, the lower surface, and both side surfaces can be formed by cantilever portions, or any surface such as the upper surface, the lower surface, or both side surfaces can be cantilever portions. It can also be formed. Among these, when the flow path cross section is rectangular, the inner walls in the vicinity of the porous body on the two opposing surfaces (upper and lower surfaces or both side surfaces) are formed by the cantilever portion because of the ease of holding the porous body. The cantilever portion preferably has a space on the side opposite to the inner wall of the flow path.
Further, the cantilever portion can be formed on one of the upstream side or the downstream side, but is preferably formed on both sides.
The ends of the cantilever portions 135 and 136 on the porous body side are preferably contactable with the porous body 110. However, as shown in FIG. Is not required to be in contact with the porous body.

  The cantilever portion 135 is preferably formed of an elastic body, and the type of the elastic body is preferably selected in consideration of the type of fluid, the required Young's modulus of the elastic body, and the like. Examples of the elastic body include various types of elastic resins, such as various general-purpose rubbers, epoxy resins, silicon rubbers, butyl rubbers, polyimide resins, and fluororubbers. Among these, silicon rubber is preferable.

  In FIG. 2, the entire porous body holding portion 130 of the flow path 102 is formed of an elastic body, but only the cantilever portion may be formed of an elastic body. In FIG. 2, the porous body holding part 130 is fitted into the notch part 140 provided in the base body 120. In FIG. 2, silicon rubber is used as the elastic body.

FIG. 3 is a partial enlarged view of a schematic plan view of the reaction apparatus 100 having the porous body 110 in which clogging has occurred, observed from above through the transparent lid in FIG.
As the fluid L passes through the porous body 110, the porous body may become clogged. When the porous body 110 is clogged 172, the fluid L becomes difficult to flow. Therefore, when the porous body 110 is sent at the same pressure, the fluid pressure at the upstream portion 170 of the fluid becomes high. As a result, the pressure of the fluid going to the outside of the flow path increases.
Thereby, the cantilever part 135 is pushed to an outer edge, and the contact area of a porous body and a fluid increases. In FIG. 1, the contact area between the porous body and the fluid is represented by the width B of the flow path × the height H of the flow path (see FIG. 1). On the other hand, in FIG. 3, the contact area between the porous body and the fluid is increased by the cantilever portion that spreads outward, and in FIG. 3, D × flow path height H.

In the present invention, the degree of extension of the porous body can be adjusted by the amount of deformation of the cantilever portion.
For example, in FIG. 2, A = B (channel width) + 2 × C is established.
Here, assuming that the channel width is 500 μm, C is 300 μm, and the thickness of the cantilever portion is 100 μm, the maximum surface area of the porous body can be obtained by the following equation as shown in the following formula: This is 1.8 times (180%) of the contact area between the body and the fluid.
{(300-100) × 2 + 500} /500=1.8
If it is considered that the lifetime (usable period) of the porous body depends only on the contact area between the porous body and the fluid, the usable period is 1.8 times that of the conventional microreactor apparatus.

Further, in the present invention, when the clogging of the porous body is eliminated, the fluid pressure is reduced. Therefore, the cantilever portion is preferably returned to the state shown in FIG. Thereby, the contact area of a porous body and a fluid reduces.
As a means for eliminating the clogging of the porous body, after filtering the fine particles contained in the fluid, a fluid capable of dissolving the fine particles trapped in the porous body is flowed to clog the porous body. Examples of the method include eliminating the clogging by dissolving the fine particles by changing the temperature or changing the temperature.

In the present invention, the porous body is preferably exchangeable. By making the porous body exchangeable, the apparatus can be used by exchanging only the porous body without making the entire reaction apparatus disposable. In addition, it is also preferable that the porous body and the porous holding portion be exchangeable.
Specifically, there can be exemplified a method in which the upper cover member of the substrate can be opened and closed, and the porous body or the porous body and the porous body holding portion provided in the flow path are exchanged together.
2 and 3, the porous body 110 is a slide type that can be inserted from above, and can be replaced depending on the degree of clogging.

  In the present invention, it is also preferable that the reaction apparatus includes a window portion through which the arrangement portion of the porous body can be visually recognized. Here, it is preferable that the arrangement | positioning part of a porous body is a window part which can visually recognize the contact surface of a porous body and fluid at least. The visual recognition is not limited to the naked eye but also includes visual recognition with a magnifying glass or the like. The visual recognition includes observation with a CCD camera, an optical sensor, a video camera, or the like.

Providing the window portion is preferable because the contact area between the microchannel and the porous body can be confirmed, and the degree of clogging of the porous body can be grasped from the outside.
Specifically, a method of forming the substrate of the arrangement part provided with the porous body with a resin having transparency such as polymethyl methacrylate resin can be exemplified. Moreover, you may form with inorganic glass, a tempered glass, another organic glass etc., and if it can achieve the intensity | strength requested | required of a reaction apparatus, it will not specifically limit.

Other preferred embodiments of the present invention are described below.
FIG. 4 is a schematic view showing an example of a reaction apparatus having a cantilever portion made of a photoresponsive gel. FIG. 4A shows a plan view of the porous body arrangement portion observed from above, and FIG. 4B shows the same portion observed when the entire lid is transparent. In this embodiment, the above-mentioned cantilever part is made of a photosensitive gel. In this case, the lid portion of the base is manufactured from a transparent resin or the like, and actively irradiated from the outside by irradiating light from the outside toward the cantilever portion (that is, regardless of internal conditions such as pressure loss). The contact area between the porous body and the fluid can be increased or decreased. That is, the contact area between the porous body and the fluid can be reduced by irradiating light of a wavelength to which the cantilever part responds from the window part 180 shown in FIG. 4A and contracting or expanding the cantilever part. It can be increased or decreased.
In FIG. 4, only the cantilever portions 135 and 136 are made of a photoresponsive gel.
When a gel that swells due to light absorption is used as the light-responsive gel, the light-responsive gel in the light-irradiated part absorbs the liquid and swells when irradiated with light from the window. The contact area of the body can be reduced.

As the photoresponsive gel, a cross-linked product of a hydrophilic polymer compound having a group that is ionically dissociated by light, such as a triarylmethane derivative or a spirobenzopyran derivative, is preferable. For example, a vinyl-substituted triarylmethane leuco derivative and ( Examples thereof include a crosslinked product of a copolymer with (meth) acrylamide.
The photoresponsive gel is preferably a crosslinked product of a polymer compound having a group that causes cis-trans isomerization by light, such as a compound having an azo group (particularly an azobenzene structure). Examples thereof include a crosslinked product of a copolymer of (meth) acryloyl group-containing azobenzene and (meth) acrylamide.

In addition, in this invention, the cantilever part is produced with stimulus responsive gels other than light, and the stimulus which a stimulus responsive gel responds from the outside can also be provided. Examples of the stimulus applied to the gel include a magnetic field, a current or electric field, and heat.
Examples of the stimuli-responsive gel that responds to a stimulus by applying a magnetic field include cross-linked polyvinyl alcohol containing ferromagnetic particles and a magnetic fluid, but the gel itself is particularly suitable if it is a gel that responds to a magnetic field stimulus. It is not limited, and any material may be used as long as it is included in the category of gel.

  As a stimulus-responsive gel that responds to a stimulus by applying an electric current or an electric field, a CT complex (charge transfer complex) of a cationic polymer gel and an electron-accepting compound is preferable, and amino-substituted (meta) such as dimethylaminopropyl (meth) acrylamide is used. ) Crosslinked product of acrylamide; Crosslinked product of amino-substituted alkyl ester of (meth) acrylic acid such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and dimethylaminopropyl acrylate; Crosslinked product of polystyrene; Crosslinked product of polyvinylpyridine A crosslinked product of polyvinyl carbazole; a crosslinked product of polydimethylaminostyrene, and in particular, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate Over DOO, dialkylaminoalkyl such as diethylaminoethyl (meth) acrylate (meth) acrylate-based polymer is preferable. These may be used in combination with electron accepting compounds such as benzoquinone, 7,7,8,8-tetracyanoquinodimethane (TCNQ), tetracyanoethylene, chloranil, trinitrobenzene, maleic anhydride and iodine. it can.

As a stimulus-responsive gel that responds to a stimulus by heat (temperature change), a polymer with LCST (lower critical eutectic temperature) that has the property of aggregating by a hydrophobic interaction and precipitating from an aqueous solution above a certain temperature. Cross-linked body, cross-linked body of polymer having UCST (upper critical eutectic temperature), polymer gel having polymer chain hydrogen-bonded to each other, or two-component polymer IPN body to hydrogen-bond to each other (interpenetration) Network structure) and polymer gels having cohesive side chains such as crystallinity are preferred. Among these, LCST gel using hydrophobic interaction is particularly preferable. The LCST gel shrinks at high temperature, and the UCST gel, IPN gel, and crystalline gel have a characteristic of swelling at high temperature.
Specific examples of gels that shrink at high temperatures include cross-linked N-alkyl-substituted (meth) acrylamides such as poly-N-isopropylacrylamide, N-alkyl-substituted (meth) acrylamide and (meth) acrylic acid and salts thereof, Or a crosslinked product of a copolymer of two or more components such as (meth) acrylamide or (meth) acrylic acid alkyl ester, a crosslinked product of polyvinyl methyl ether, a crosslinked product of an alkyl-substituted cellulose derivative such as methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, etc. Etc. Among these, poly N-isopropyl (meth) acrylamide is preferable.

On the other hand, specific compounds of gels that swell at high temperatures include IPN bodies composed of crosslinked poly (meth) acrylamide and crosslinked poly (meth) acrylic acid, and partially neutralized bodies thereof (partially acrylic acid units). And an IPN body composed of a cross-linked copolymer of poly (meth) acrylamide as a main component and a cross-linked body of poly (meth) acrylic acid, and a partially neutralized body thereof. More preferably, a crosslinked product of poly N-alkyl-substituted alkylamide, an IPN product of a crosslinked product of poly (meth) acrylamide and a crosslinked product of poly (meth) acrylic acid, and a partially neutralized product thereof.
In addition, as the crystalline gel, a crosslinked product of a copolymer of (meth) acrylic acid ester and (meth) acrylic acid having a long-chain alkyl group such as octyl group, decyl group, lauryl group, stearyl group, or the like Salt. The temperature (phase transition temperature) showing the volume change of the thermoresponsive polymer gel can be variously designed depending on the structure and composition of the polymer gel. The preferred phase transition temperature is preferably within the boiling point or freezing point of the solvent, more preferably in the range of -30 to 300 ° C, still more preferably in the range of -10 to 150 ° C, particularly preferably 0 to 0. The range is 60 ° C.

  In addition to the specific examples illustrated above, a gel showing a plurality of phase transition points in accordance with temperature changes can be suitably used as the stimulus-responsive gel that responds to a stimulus by heat. Specific examples include an IPN form of a cross-linked product of polyalkyl-substituted (meth) acrylamide such as poly-N-isopropyl (meth) acrylamide and a cross-linked product of poly (meth) acrylic acid. These gels are known to exhibit two phase transition points of swelling-shrinking-swelling with increasing temperature.

  It is also preferable to include an ionic functional group in the polymer gel for the purpose of increasing the volume change amount of the stimulus-responsive gel that responds to the stimulus by heat. Examples of the ionic functional group include carboxylic acid, sulfonic acid, ammonium group, and phosphoric acid group. The ionic functional group copolymerizes monomers having these functional groups when preparing the gel, and impregnates the synthesized stimuli-responsive gel with the monomer to form an IPN (interpenetrating network structure) body. The functional group in the stimulus-responsive gel can be partially contained by a method such as conversion by a chemical reaction such as hydrolysis or oxidation.

<Cantilever design>
An example is given and demonstrated about the design of a cantilever part.
The design procedure in this example is “determining the porous structure”, “calculating the pressure loss change when the porous material is blocked by a predetermined amount”, and “calculating the deflection amount of the cantilever with respect to the pressure loss change amount”. There are three stages.
In this example, first, the porous structure was determined to be the woodpile structure shown in FIG.
The woodpile structure is a porous shape composed of one cycle of four layers, and is a structure used for an optical element using Bragg reflection in addition to the microfilter as in this embodiment. In this example, the opening of the porous body is 750 μm × 300 μm (that is, the height and width of the rectangular channel cross section at the start of use), the thickness of the entire porous body is 400 μm, and the lattice pitch of the wood pile is 100 μm ( The opening is 25 μm, the rib is 75 μm, and the thickness of one layer is 25 μm). This device is formed of 16 layers (4 cycles), and the ratio of porous cross-sectional area: porous sidewall required for determining pressure loss is 1:56.

Next, calculate the Reynolds number, flow velocity, hydraulic diameter, pipe friction coefficient, and pressure loss of the porous material from the assumed flow rate, solution temperature and viscosity, and porous shape. To do. The pressure loss approximates each porous hole to a cylindrical tube with the equivalent friction coefficient (the diameter of the cylinder is the hydraulic diameter), and the relationship of the pipe friction coefficient varies depending on the Reynolds number. , Can be determined uniquely.
In the case of a laminar flow field (Reynolds number: Re ≦ 2,300), the pressure loss (ΔP) is determined by the following equations 1 to 4, and can be finally obtained from equation 5.

In the case of the porous body of this example, the Reynolds number when the flow rate is 25 ml / min is about 400, and the liquid passing through the porous body is sent as a laminar flow. Moreover, the hydraulic diameter calculated | required from a structure is about 30 micrometers, and is determined by 64 / Re as shown in Formula 2 under laminar flow.
In addition, when a porous body is this filter structure, according to the calculated value, a laminar flow field can be maintained to about 150 ml / min.

Next, each parameter when 30% of the filters are blocked is calculated similarly. The difference in pressure loss thus obtained becomes a driving force that increases the cross-sectional area of the flow path when the flow path is closed.
In this embodiment, a pressure loss difference of about 0.0024 MPa is generated. The obtained results are shown in Table 1 below.

Finally, the deformation of the opening (cantilever near the porous membrane) is calculated when the opening is clogged and a pressure loss difference (about 0.002 MPa) occurs.
Assuming that the hinge portion formed of polyimide resin is a cantilever portion formed of an elastic body, the deformation amount when a uniform load (pressure loss difference of about 0.002 MPa) is applied is calculated.
In this example,
Cantilever length L (= 800μm)
Section modulus (Z = bD ² /0.0005)
(Where b = beam width = 100 μm, D = beam height = porous height = 300 μm)
The second moment (Ix = bD ³ /12=0.000025)
When the Young's modulus of the polyimide resin is 4.7 MPa, the amount of deflection is about 240 μm in total for the beams on both sides.
Since the porous width is 750 μm, 240 μm is about 30% of this, and as a result, an opening (contact area between the porous body and the fluid) equivalent to the amount of clogging is newly obtained. Become. Therefore, the contact area fall with the fluid of the porous body by clogging can be suppressed.
This design is not limited to the one based on the above calculation, and it is desirable to design using a calculation such as fluid simulation (CFD) or finite element method (FEM).

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.

Example 1
This will be described below with reference to FIG.
FIG. 5 is a conceptual schematic diagram showing the configuration of the reaction apparatus used in Example 1, and is an example of a microreactor apparatus using a cooling water filter as a porous body.
A microreactor device 500 shown in FIG. 5 is a stacked microreactor device, and a first layer is shown in FIG. 5A and a second layer is shown in FIG. 5B. The microreactor apparatus of the present embodiment is an apparatus for dilute sulfuric acid by diluting concentrated sulfuric acid with pure water. The first layer is provided with an inlet 501 for concentrated sulfuric acid S and an inlet 502 for pure water (pure water for dilution) W, which are sent to the introduction channels 505 and 506, respectively.
The introduction flow path merges downstream thereof, and concentrated sulfuric acid and pure water are fed in a laminar flow through one merge flow path 508. In the merging channel 508, concentrated sulfuric acid and pure water gradually diffuse at the interface, gradually become uniform diluted sulfuric acid, and are discharged from the discharge port 509.

When concentrated sulfuric acid and pure water are mixed, heat of dilution is generated. In some cases, bumping or the like may occur in the microreactor apparatus.
In this embodiment, the cooling water C is sent to the second layer to cool the merging channel and the internal fluid. In a region corresponding to the confluence channel of the second layer, a meandering minute channel 550 is provided, and cooling water is introduced from the inlet 503 of the cooling water C provided in the first layer, and is provided in the second layer. The cooling water is sent to the micro flow path 550 through the inlet 503 ′ of the cooling water C thus obtained. Further, the cooling water C is discharged from a discharge port 504 ′ provided in the first layer through a discharge port 504 provided in the second layer.
In the present embodiment, a filter 510 that is a porous body is provided on the upstream side of the micro flow channel that sends cooling water. As the cooling water, it is preferable to use inexpensive tap water. However, if scale accumulates in the flow path or fine particles in the tap water are clogged in the micro flow path, the cooling water is supplied to a pump or the like that sends the cooling water. The load increases. Further, if the cooling water does not flow, the microreactor may be damaged by excessive heating, or bumping of the mixed solution may occur, which is not preferable.
In the present embodiment, the clogging of the micro flow path is suppressed by disposing a filter formed of a porous body on the upstream side of the cooling region of the second layer.
Also, when the filter is clogged, similar problems such as increased load on the pump and excessive heating of the microreactor occur. In the present embodiment, the inner walls in the vicinity of the upstream and downstream of the filter are formed by cantilever portions 535 and 536, and when the filter is clogged due to the filtration of tap water, the fluid pressure increases as shown in FIG. As shown in FIG. 3, the cantilever portion spreads outward, and the contact area between the filter and the cooling water increases. A space is provided on the side opposite to the inner wall of the flow path of the cantilever portions 535 and 536.

By such an increase in the contact area, tap water can be stably fed. In addition, the life of the filter is extended and it can be used for a long time.
On the other hand, when the filter is not provided, there may be a problem of clogging of the micro flow path of the microreactor device, and when the filter area does not increase, the filter life is short.

(Example 2)
Example 2 is an example of another reaction apparatus of the present invention, which is an example of catalytic reforming using a microreactor apparatus or a centimeter-order chemical reaction apparatus.
Catalytic reforming is a process in which the octane number of a gasoline fraction obtained by distilling crude oil in petroleum refining is increased by a catalytic reaction, and is also referred to as reforming.
The heavy naphtha fraction obtained by distilling crude oil is mainly composed of paraffin and cycloalkane having a low octane number, and the octane number is about 40 to 50, which is not suitable for gasoline fuel. Therefore, the above heavy naphtha fraction is subjected to hydrodesulfurization treatment to remove impurities such as sulfur, nitrogen and metal in the naphtha which becomes a catalyst poison of the catalytic reforming catalyst, and then supplied to the catalytic reforming apparatus.

As a catalytic reforming catalyst, a catalyst in which chlorine is added to a platinum or rhenium noble metal catalyst using a calcined zeolite, which is a kind of solid acid, as a carrier has been used as a mainstream.
The conventional reforming reaction is performed at about 500 ° C. in the presence of hydrogen. The reaction mechanism is considered as follows.
(1) A straight chain alkane is dehydrogenated by a noble metal and converted into an alkene.
(2) A carbocation is generated by supplying a proton to the generated alkene from the catalyst.
(3) Carbocation causes rearrangement of hydrogen atom or alkyl group or cyclization. In this rearrangement reaction, a highly stable carbocation having a large number of substituted alkyl groups is likely to be formed, so that many branched alkenes are obtained. A part of the cyclized product is further dehydrogenated to become an aromatic hydrocarbon.
(4) The produced branched alkene is hydrogenated again with a noble metal to become a branched alkane.
By the above reaction, reformed gasoline mainly composed of aromatic hydrocarbons, hydrogen, and C4 or lower hydrocarbons as cracked products are generated.

FIG. 6 is a conceptual schematic diagram showing the configuration of the reaction apparatus used in Example 2.
In this example, an inverted gas-liquid cylindrical reactor was used. The reactor 600 used in Example 2 has a raw material oil reforming unit 610 and a cooling / separating unit 650.
The straight-run or cracked gasoline O, which is a raw material oil, is adjusted to an appropriate boiling point range by a pre-distillation tower (not shown) and then introduced from the raw material oil inlet 601. Further, a gas containing hydrogen (indicated by H ₂ in FIG. 6) is introduced from the gas inlet 602, and the feedstock oil is pressurized (for example, 50 atmospheres) in the feedstock oil heating furnace 612 together with the gas containing hydrogen. Be heated to. In FIG. 6, bubbling with a gas containing hydrogen is performed in the bubbling unit 614 in the raw material oil heating furnace 612, and thereafter, the gas is sent to the first porous body 620 to the third porous body 622 in this order.

In this example, a filter structure in which platinum rhenium is supported on porous zeolite is used as the first to third porous bodies.
The raw material oil undergoes modification as it passes through the porous body.
Since the reforming reaction is an endothermic reaction, the temperature of the system is lowered, so the heater 630 is provided to keep the temperature constant.
In this embodiment, three stages of reforming are performed. However, the present invention is not limited to this, and the number of stages may be changed until a desired degree of reforming is obtained. In the present embodiment, by using multiple stages, reforming can be performed efficiently with a single flow.

  The inner walls in the upstream and downstream of the porous bodies 620 to 622 are formed by cantilever portions 635, and the cantilever portions have a space on the side opposite to the inner wall of the flow path. In the present embodiment, the reforming process is performed under heating, so that the cantilever portion 635 is formed of a polyimide resin having high heat resistance.

The reformed raw material oil is then sent to the cooling / separation unit 650, where it is cooled and gas is separated to be separated into reformed crude oil and product gas. It is discharged from the product gas discharge port 682. The product gas contains hydrogen, methane to butane (C4 or less hydrocarbon). In addition, the modified crude oil has an increased aromatic content as compared with the raw material oil.
In the present embodiment, a cooling system similar to that used in the first embodiment is employed as the cooling device. That is, tap water is used as the cooling water C, and is fed from the cooling water inlet 651. In addition, a filter 670 having a front surface and a back surface supported by a cantilever portion 660 is provided at an upstream portion of the micro flow path through which the cooling water C is sent. The cooling water C is discharged from the discharge port 657.
Since fine particles, scales, etc. existing in the cooling water can be removed by the filter, clogging of the fine flow path can be suppressed. Further, when clogging occurs in the filter 670, the cantilever portion 660 spreads to the outside as shown in FIG. 6, and the contact area between the cooling water and the filter increases, so that the filter has a longer life and is stable. The cooling water was able to be sent.

  In this embodiment, the heating temperature in the reforming process is 375 ° C. in a system using a microreactor device. Conventionally, heating at about 500 ° C. was necessary, but since the reforming process is performed using a micro flow path, high catalytic activity can be obtained and the heating temperature can be lowered to 375 ° C. It was. Further, in order to obtain a large amount of reaction in one reactor, even when a reactor of the centimeter order is used, the heating can be lowered to 450 to 480 ° C., which is effective in reducing environmental load.

  On the catalyst, carbonaceous coke is gradually deposited along with the reforming reaction, causing a decrease in the catalytic activity. In the present embodiment, when coke is deposited on the catalyst, the pressure loss of the raw material oil increases, so that the cantilever portion 635 spreads outward as shown in FIG. 6, and a new catalyst surface is exposed. Therefore, the durability of the catalytic effect was improved.

(Example 3)
Example 3 is another example using the reaction apparatus of the present invention and is a synthesis example of triarylamine using a catalytic reaction.
Triarylamine compounds have attracted much attention in recent years as organic electronics materials such as organic EL.
FIG. 7 is a conceptual schematic diagram showing the configuration of the reactor used in this example.
In FIG. 7, the liquid A shown in Table 2 below was fed to the reaction apparatus 700 from the inlet 701 at 0.05 ml / min with a syringe pump. On the other hand, nitrogen gas (N ₂ ) was introduced from the inlet 702, the solution A and nitrogen gas were mixed in the mixing channel 710, and further heated to 110 ° C. by the heater 715. In this embodiment, nitrogen gas (N ₂ ) is used. However, it is important that the liquid A is an inert gas atmosphere, and other inert gases can also be used.
The mixing channel 710 is provided with a separation channel 720 for removing excess nitrogen gas (N ₂ ) and a nitrogen gas (N ₂ ) outlet 722. It is more desirable to stir the introduced nitrogen gas with an ultrasonic element (not shown) or the like.

The solution A from which excess nitrogen gas was removed was passed through a copper porous body 730 while being heated. Copper acts as a catalyst, and ditrinaphthylamine which is a reaction product is produced in the solution A by passing through the copper porous body. This method is an Ullmann reaction using copper as a catalyst.
In the present embodiment, the upstream and downstream inner walls of the copper porous body 730 are formed by two cantilever portions 735 and 736 facing each other, and the contact area between the porous body and the solution A can be increased or decreased. . Further, a space is provided on the side opposite to the inner walls of the cantilever portions 735 and 736.

Next, the solution that passed through the copper porous body was cooled to 40 ° C. by a cooling fan 740.
In this embodiment, the cooling fan 740 is used for cooling. However, a cooling water supply layer may be disposed downstream of the porous body 730 to cool the porous body 730 as in the first embodiment. .

After cooling, distilled water (H ₂ O) was introduced from the distilled water inlet 750 through the introduction flow path 751. The solution A (organic phase) and distilled water (aqueous phase) after the reaction were sent to the merge channel 760 in a laminar state.
While being fed through the merge channel, diffusion occurs between the organic phase and the aqueous phase, and the hydrophilic raw material moves to distilled water. As a result, the product ditrinaphthylamine is relatively contained in the organic phase.
Thereafter, the organic phase (indicated by B in FIG. 7) is recovered from the discharge port 780 via the separation channel 770, and the aqueous phase (indicated by H ₂ O in FIG. 7) is separated. It was recovered from the discharge port 781 via the passage 771.

  Toluene is volatilized from the organic phase (solution B) recovered from the discharge port 780 by batch processing, and methanol is added dropwise to the concentrated solution and recrystallized to obtain 2.35 parts by weight of the desired ditolylnaphthylamine. Got. The yield was 66%.

In this example, it is inferred that such a good yield could be obtained because the Ullmann reaction proceeded efficiently by the porous catalyst body supported in the microreactor apparatus.
Further, conventionally, when the introduced nitrogen gas reaches the porous body, there is a problem that the porous body is clogged. Nitrogen gas introduced by bubbling needs to be separated (gas-liquid separation) upstream of the porous body, but since solution A is an organic solvent (organic phase), separation of gas-liquid by hydrophilic / water-repellent treatment is not possible. There is a problem that the introduced nitrogen gas is clogged by the introduced nitrogen gas.
In this example, even if a small amount of nitrogen gas reaches the porous body, since the cantilever portion is provided in the vicinity of the porous body, the contact area between the porous body and the solution A increases. It is inferred that a good yield was obtained.

It is a typical perspective view which shows an example of the reaction apparatus of a present Example. It is the elements on larger scale of the typical top view observed from the upper part through the transparent cover body in FIG. It is the elements on larger scale of the typical top view observed from the upper part through the transparent cover body in FIG. It is a schematic diagram which shows an example of the reaction apparatus which has the cantilever part produced with the photoresponsive gel. 1 is a conceptual schematic diagram showing the configuration of a reaction apparatus used in Example 1. FIG. 3 is a conceptual schematic diagram showing the configuration of a reaction apparatus used in Example 2. FIG. 3 is a conceptual schematic diagram showing the configuration of a reaction apparatus used in Example 3. FIG. It is a perspective view which shows a woodpile structure.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100 Reaction apparatus 102 Flow path 110 Porous body 120 Base body 122 Cover body 130 Porous body holding | maintenance part 135, 136 Cantilever part 140 Notch part 170 Porous body upstream part 172 Clogging 500 Microreactor apparatus 501 Concentrated sulfuric acid inlet 502 Pure water inlets 503, 503 ′ Cooling water inlets 504, 504 ′ outlet 505 Concentrated sulfuric acid introduction channel 506 Pure water introduction channel 508 Merge channel 509 Discharge port 510 Filter 535, 536 Cantilever part 550 Microchannel 600 Reactor 601 Raw material oil inlet 602 Gas inlet 612 Raw material oil heating furnace 614 Bubbling portion 620, 621, 622 Porous body 630 Heater 635 Cantilever portion 650 Cooling / separation portion 651 Cooling water inlet 655 Micro channel 657 Discharge port 660 Cantilever 670 Filter 680 Reformed crude oil discharge port 6 2 Product gas outlet 700 Reactors 701 and 702 Inlet 710 Mixing channel 715 Heater 720 Separation channel 722 Exhaust port 730 Porous body 735 and 736 Cantilever 740 Cooling fan 750 Distilled water inlet 751 Inlet channel 760 Junction channel 770, 771 Separation channel 780, 781 Discharge port H Height of minute channel L Fluid

Claims (3)

Having a flow path for fluid flow;
A porous body through which fluid passes in the flow path;
The channel diameter of the channel is 50 to 1,000 μm,
The inner wall near the porous body of the flow path is formed by a cantilever part,
The cantilever portion has a space on the side opposite to the inner wall of the flow path,
The free end of the cantilever portion is formed so as to contact the porous body,
The free end of the cantilever portion curves into the space towards the outside of the flow path,
A reaction device characterized in that the contact area between the porous body and the fluid increases or decreases as the fluid resistance changes. The reaction apparatus according to claim 1, wherein a contact area between the porous body and the fluid increases with an increase in fluid pressure accompanying an increase in fluid resistance of the porous body.   The reaction apparatus of Claim 1 or 2 provided with the window part which visually recognizes the arrangement | positioning part of a porous body.

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