JPH082293B2 - Reactor - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reactor used for analysis, quantification, production of useful substances or decomposition and removal of environmental pollutants. More specifically, the present invention relates to a reactor capable of realizing a highly efficient reaction and capable of contributing to a reaction in the state where a functional material such as a catalyst does not deteriorate in function.

[0002]

2. Description of the Related Art Conventionally, since a sheet catalyst has better moldability than a particle catalyst and is easy to handle, a reactor using a sheet catalyst has been developed. For example, an enzyme was immobilized. Attempts have been made to produce useful substances by filling a disc-shaped container such as a membrane holder with paper and continuously passing the substrate to bring the substrate into contact with the catalyst.
"H. I Chijo, et al., SEN-I GA.
KKAISHI, Vo1.42, T-636 to T-
642 (1986) ”In this reactor, the substrate is arranged to pass in the thickness direction with respect to the sheet surface, and there is a shortcoming that the distance that the substrate moves in the catalyst layer is short and the reaction efficiency is poor. there were. Improve the contact between the substrate and the catalyst,
In order to increase the reaction efficiency, it was necessary to increase the contact time by forming a dense sheet structure or by stacking sheets in multiple layers to increase the layer length. However, if the structure is made fine, there is a problem that the liquid passage resistance becomes large and the production rate is reduced.

On the other hand, in the field of analysis and measurement, the purpose is often to treat a large number of specimens. When a large reaction vessel is used, a large amount of substrate (fluid to be treated) and catalyst are required, and the treatment is performed. Since it takes a long time and is very uneconomical, it was necessary to use a small amount of fluid to be treated and a minute reaction vessel. However, it is practically difficult to manufacture a minute reaction vessel by stacking sheet catalysts in multiple layers, and thus it is necessary to create a new reaction vessel.

Further, there is a catalyst sensor provided with a reaction section in which glass beads or chitosan beads on which a biocatalyst is immobilized are packed in a tubular column. In this sensor, a substrate is continuously sent to the reaction section to cause a reaction. It is supposed to be done. However, with this sensor,
Since beads are packed in a tubular column having a small diameter of about 2 mm, the operation of immobilizing the biocatalyst is difficult,
It was extremely complicated. Also, with this sensor, once air bubbles enter the column, it is difficult to remove them.
For this reason, the column must always be kept in a wet state,
Conditioning was difficult. Further, when the inside of the column was always kept in a wet state, it was apt to be affected by foreign matters in water and the activity of the catalyst was apt to decrease, so that it could not be stored for a long period of time. Furthermore, impurities such as proteins and bacteria in the fluid to be treated during the measurement tend to cause clogging, resulting in deterioration of the catalytic function.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and it is possible to realize a highly efficient reaction, and it is possible to process even a small amount of a fluid to be processed and a catalyst. It is an object of the present invention to provide a reactor capable of contributing to a reaction in a state in which a functional material such as does not cause functional deterioration.

[0006]

In order to achieve the above object, in the invention according to claim 1, " continuous
A catalyst on the surface of the constituent material of a sheet having a three-dimensional porous structure
Equipped with a functional sheet carrying functional materials such as
One longitudinal end side of the functional sheet with inlet portion the substrate is forced into are provided, the outflow portion is provided with the reactants to the other end of the functional sheet to flow out,
In the course of substrates to which the sent into function the sheet moves through the functional sheet in the longitudinal direction, the reactor, characterized in that the substrate and the functional material is configured to contact and react "
Was the gist.

According to the second aspect of the invention, the "functional system
A carrier is provided on one end side in the longitudinal direction of the carriage to carry it.
The fluid is forced into the functional sheet.
To create a flow from one end of the functional sheet to the other
Along the flow of this carrier fluid.
The substrate sent into the inside of the functional sheet from the one end side to the other
Reaction characterized by being configured to move to the edge
Vessel "is the gist.

According to the invention of claim 3 , the " machine "
The gist is “reactor characterized in that the Noh sheet is a nonwoven fabric in which a catalyst is entrapped and fixed in a silk fibroin layer formed on the surface of the constituent fibers”.

The reactor of the present invention will be described in detail below.
The reactor of the present invention has a continuous three-dimensional porous structure.
A functional material such as a catalyst is supported on the surface of the components of the sheet.
Is the functional sheet is used, the substrate forcibly fed into the functional sheet, by moving the function in the seat in the longitudinal direction, is characterized in that the reaction is carried out by contacting the substrate and catalyst.

Functional sheets include non-woven fabrics, felts, woven fabrics,
The synthetic resin sheet having a fiber sheet or a continuous three-dimensional porous structure with a knitted or continuous three-dimensional porous structures such as these complexes as a carrier, these fiber sheet
Surface of synthetic resin sheet, that is, fiber sheet,
A functional material such as a catalyst is supported on the surface of fibers or synthetic resin forming a synthetic resin sheet . As the functional material, a metal catalyst such as platinum, a biocatalyst such as an enzyme, a microbial cell, an organelle, or a tissue piece of a plant, which has a catalytic function, and a reagent such as a color former can be used. In particular, since the biocatalyst has high selectivity and high sensitivity, it is possible to react a specific substrate contained in a trace amount from a mixture containing a plurality of substances. When a biocatalyst containing multiple catalysts (enzymes) inside, such as a microbial cell, an organelle, or a tissue piece of a plant, is used, it is possible to carry out multi-step or multiple types of catalytic reactions at once with one sheet. There is an advantage. It should be noted that the functional sheet may carry a plurality of types of functional materials, and in this case, a multi-step or a plurality of types of reactions can be caused in the functional sheet as in the case of microbial cells and organelles. As a method of fixing the functional material to the functional sheet, there are a method of using a binder and a method of kneading a functional material such as a catalyst into a constituent (for example, fiber) of the functional sheet. Among them, as a method for immobilizing biocatalyst such as enzyme, covalent bond to carrier, ionic bond, physical adsorption, carrier binding method for immobilizing catalyst itself by biochemical affinity, silk fibroin with network structure, etc. An immobilization method such as an encapsulation method in which the catalyst is confined and immobilized in the lattice of the molecular gel or in the resin film can be applied. In particular, silk fibroin is desirable as a means for immobilizing a biocatalyst because it has a property that it does not allow large molecules such as proteins to pass but small molecules such as substrates. An inflow portion into which the substrate is forcibly fed is provided on one end side in the longitudinal direction of the functional sheet thus configured.

A liquid passage means such as a pump or an injector is arranged on one end side in the longitudinal direction of the functional sheet,
The carrier fluid is forced into the functional sheet through the inlet of the reactor. The carrier fluid is a fluid such as a buffer solution such as a phosphate buffer solution or a borate buffer solution or an inert gas, and the carrier fluid is fed from one end side in the longitudinal direction of the functional sheet through the inflow portion by the liquid passing means to function. through the inside sheet in the longitudinal direction and flows out to the other longitudinal end side of the functional sheet, flow extending from one longitudinal end of the functional Sea <br/> bets to the other is made.

The flow velocity of the carrier fluid is not particularly limited, but between the flow velocity of the carrier fluid and the volume of the functional sheet and the space velocity, space velocity = carrier velocity / machine
It is related that the volume of the capacity sheet, in that setting the size of the functional sheet, the reaction rate of the functional material, it is necessary to consider and peak intensity of the substrate response curve. If the carrier flow rate is 0.5 ml / min, the functional sheet has a width of 0.3 to 1.0 cm, a length of 2 to 10 cm, and a thickness of 0.1 to 1.5 mm. Is desirable.
This is because the peak intensity of the substrate response curve is high, the response speed is fast, and the space velocity condition is 30 to 3000 / h ^-1 ,
This is because it is preferably 200 to 400 / h ⁻¹ .

From the inlet of the reactor, the substrate as well as the carrier fluid is fed into the functional sheet by the liquid passing means. Here, when a substrate and a functional material that reacts with the substrate are exemplified, glucose-glucose oxidase, ethanol-alcohol oxidase, uric acid-uricase, L-amino acid-L amino acid oxidase, L-asparagine-asparaginase,
Urea-urease, cholesterol-cholesterol esterase, neutral fat-lipase, glucose-Pseudomonas florescens (Pseudomonas f)
luorescens), ammonia-digesting bacteria, BOD
-Trichosporon Cataneum (Trichosporo)
n cutaneum) and the like.

The substrate fed into the functional sheet through the inlet of the reactor, along with the flow of carrier fluid,
The functional sheet moves from one end side to the other end side in the longitudinal direction. In the process of this movement, the surface of the functional sheet components
The functional material carried by the and the substrate come into contact with each other, and the reaction occurs there. It should be noted that a predetermined amount of the substrate and the carrier fluid are mixed in advance, and this is mixed with an injector or the like.
It can also be sent to a function sheet.

The reaction product generated on the functional sheet, that is, the reaction product or the reaction consumer, flows out from the outflow portion provided on the other end side in the longitudinal direction of the functional sheet. Purifiers, detectors, etc. are connected to this outflow section for the purpose of production, analysis, quantification of useful substances or decomposition and removal of environmental pollutants, and the reaction products are processed. There is.

As a concrete example of the reactor, in FIGS. 1 and 2, a silicone sheet is filled as a spacer 7 between two acrylic plates 6 and 6 to function between the acrylic plates 6 and 6. A plastic cell 1 in which a storage part 4 for storing a sheet 5 is formed, a carrier fluid / substrate inflow part 2 is provided at one end side in the longitudinal direction of the storage part 4, and an outflow part 3 is provided at the other end side. Using the storage part 4 of this cell 1.
It is shown that the functional sheet 5 is housed in the longitudinal direction. According to this reactor, the carrier fluid and the substrate flow into the cell 1 through the inflow portion 2 of the plastic cell 1, and the carrier fluid and the substrate flow in the functional sheet 5 of the storage portion 4 provided in the cell 1 in the longitudinal direction. Go to, functioning <br/> substrate and functional sheet 5 configuration material surface in contact with the supported functional material in the reaction is going on over preparative within 5, of the reactants also cell 1 according to the reaction It is designed to flow out through the outflow portion 3. As another aspect of the reactor, as shown in FIG. 3, a container having an inflow part 2 and an outflow part 3 on both side walls is a plastic cell 1 and the inside of this cell 1 is a machine.
It is also possible to cite a Noh sheet 5 stored in the longitudinal direction.

The functional sheet of the reactor will be described in more detail with a suitable example. For example, using a non-woven fabric mainly composed of hydrophilic fibers such as rayon and three-dimensionally entangled by hydroentangling, a silk fibroin gel layer is formed on the surface of the constituent fibers of the non-woven fabric, and the silk fibroin layer is formed on the silk fibroin layer. A functional sheet in which the catalyst is comprehensively fixed is preferable. In this functional sheet, the silk fibroin gel layer has a heterogeneous structure with a concentrated crystal structure region on the surface and a small number of this region inside, so that the catalyst molecules such as enzymes are large. Although it cannot easily come out of the gel layer, it can freely come in and out of low molecular weight substrates and reactants.
In addition, since the degree of freedom of the catalyst such as the enzyme is large in the gel layer, it is in a state where it is easy to react. Therefore, the activity of the catalyst in the layer is high, and it is easy to contact the specific chemical substance with the catalyst. can do. Furthermore, since the gel layer of silk fibroin is formed on the surface of the constituent fibers of the non-woven fabric composed mainly of hydrophilic fibers, the affinity between the fibers and the gel layer is high,
The gel layer does not easily fall off the fiber surface. The functional sheet is obtained by impregnating a hydro-entangled nonwoven fabric composed mainly of hydrophilic fibers with an aqueous silk fibroin solution containing a catalyst to adhere silk fibroin to the surface of the constituent fibers of the nonwoven fabric, which is dried and then insolubilized with alcohol. It can be obtained in the process.

[0018]

[Examples] Example A fibrous web made of silkworm scouring silk was entangled by a hydroentangling method to have a thickness of 0.5 mm and an apparent density of 0.18 g / cm ^3.
Of non-woven fabric. On the other hand, a 3% silk fibroin aqueous solution was prepared, and glucose oxidase (EC.1.1.3.4) as a biocatalyst was added to the silk fibroin in an amount of 3%.
A solution added at a ratio of% was prepared. The above nonwoven fabric was impregnated with this solution, air-dried at 20 ° C. and a relative temperature of 50% for 2 hours, and then immersed in an 80% methanol aqueous solution for 30 seconds to insolubilize silk fibroin. As shown in FIGS. 1 and 2, this functional sheet was cut into a rectangle having a width of 5 mm and a length of 50 mm, and a thickness of 0.
A 5 mm silicone sheet was filled as a spacer 7 to produce a flat plastic cell 1. This cell 1
A carrier fluid / substrate inflow portion 2 is provided on one end side in the longitudinal direction of the functional sheet 5 housed in the pump. Further, a pump 8 and an injector 9 for forcibly feeding the carrier fluid and substrate into the reactor are provided in the inflow portion 2. Arranged. On the other hand, the enzyme electrode 10 was installed on the other end side of the functional sheet 5 in the longitudinal direction to manufacture a biosensor.

A phosphate buffer solution having a pH of 7 as a carrier fluid was fed into the functional sheet at a rate of 0.5 ml / min by a double plunger type pump, and 10 μl as a substrate.
An aqueous solution of glucose (glucose) was forcibly fed into the carrier fluid flow by a loop injector to cause catalytic reaction with glucose oxidase in the functional sheet of the reactor, and the dissolved oxygen concentration was measured by the oxygen electrode at the outlet of the reactor. . The measurement of the dissolved oxygen concentration is based on the fact that glucose oxidase consumes oxygen when it oxidizes glucose.

This measured value is obtained as a substrate response curve,
The curve showed a peak shape. Glucose concentration 0.05 ~
The measurement was performed while changing the range of 2.00%, and the reciprocal of glucose concentration and the reciprocal of peak intensity were plotted.
A linear calibration curve showing a proportional relationship was obtained. Therefore, according to the biosensor of this example, the concentration of glucose contained in an unknown sample can be measured using this calibration curve.

Comparative Example A disc-shaped cell designed to allow a carrier fluid to flow in a direction perpendicular to a sheet surface was fitted with a disc-shaped disc having a diameter of 22 mm obtained by punching out the functional sheet obtained in the example. , The reactor part was produced.

The dissolved oxygen concentration was measured in the same manner as in Example except that the reactor section was changed to the above-mentioned reactor section. As a result, the substrate responsiveness was extremely low and the peak intensity was 10% of the intensity detected in the Example. In the following, the sensitivity was low and it could not be used.

[0023]

According to the present invention, the above-mentioned structure is provided.
In the described reactor, a continuous three-dimensional porous structure
A functional material such as a catalyst is placed on the surface of the constituent material of the sheet
Substrate is fed into the functional sheet being carried, since the reaction of the substrate with functional sheet inside in the process of moving in the longitudinal direction with the substrate and the functional material is to be carried out, high in functionality sheet Efficient reaction can be realized, and the amount of substrate and functional material can be minimized. Also, in this reactor, the substrate is fed continuously from one longitudinal end of the functional Sea <br/> bets, to react in the functioning <br/> over preparative is continuously performed Therefore, it is possible to efficiently perform processing such as analysis, quantification, production of useful substances or decomposition and removal of environmental pollutants. Further, in this reactor , a sheet having a continuous three-dimensional porous structure is used.
A functional material such as a catalyst is supported on the surface of the component
Since it is provided with a functional sheet, it is easy to remove air bubbles, it is not necessary to make it wet, and conditioning can be performed by flowing the carrier fluid for several minutes. Further, since it can be stored in a dry state, it is less likely to be affected by contaminants in water, and the contaminants are less likely to reduce the activity of the catalyst, which enables long-term storage. In addition, in this reactor, the functional sheet has a tertiary
Since it has an original porous structure, clogging is less likely to occur due to contaminants such as proteins and microorganisms, and deterioration of the catalytic function due to clogging of the functional sheet can be prevented.

Further , in the reactor according to claim 2,
Carrier fluid flow from one end of the performance sheet to the other.
The substrate fed into the function sheet along the row is
To move inside the Noh seat from one end to the other
The substrate can move smoothly in the function sheet.
Therefore, a more efficient reaction can be realized.

Further, in the reactor according to claim 3, the silk fibroin gel layer formed on the surface of the constituent fibers of the non-woven fabric used as the functional sheet is easily formed from the gel layer because the catalyst molecules such as enzymes are large. It has the property that low molecular weight substrates and reactants can freely move in and out, whereas this gel layer has a high degree of freedom in the catalyst. The reaction can be realized.

[Brief description of drawings]

FIG. 1 is a front view schematically showing a reactor according to claim 1.

FIG. 2 is an enlarged cross-sectional view of a plastic cell and a functional sheet as seen from the front.

FIG. 3 is an enlarged cross-sectional view showing another example of the reactor.

[Explanation of symbols] 1 ... plastic cell 2 ... inflow part 3 ...
Outflow section 4 ... Storage section 5 ... Functional sheet

Claims (3)

[Claims] 1. A system having a continuous three-dimensional porous structure.
A functional material such as a catalyst is supported on the surface of the component
A function sheet are, substrate in the longitudinal direction of the one end side of the functional sheet, together with inlet part which is forced into is provided, and the outflow part is provided reactants to the other end of the functional sheet flows out cage, reactor in the process of substrate fed to the function the sheet moves through the functional sheet in the longitudinal direction, characterized in that the substrate and the functional material is configured to contact and react. 2. Provided to one end side in the longitudinal direction of the functional sheet
Carrier fluid inside the functional sheet
By being forcibly fed, from one end side of the function sheet
The flow to the other end is created and the carrier fluid flow is
The substrate fed into the function sheet along the row is
It is configured to move from one end to the other end in the Noh seat.
The reactor according to claim 1, characterized in that 3. A functional sheet is, the reactor according to claim 1 or 2, wherein the catalyst silk fibroin layer formed on the constituent fibers surface is entrapped and immobilized nonwoven.