JP2012143188A - Method for producing immobilized catalyst membrane, immobilized catalyst membrane and transmembrane reaction method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an immobilized catalyst membrane which can produce a homogeneous immobilized enzyme membrane.SOLUTION: The method for producing the immobilized catalyst membrane 100 is provided with a preparation process and a production process. In the preparation process, a first solution is prepared. In the first solution, at least a catalyst 200, a polycationic compound 310, a polyanionic compound 320 and a polyionic complex-formation inhibitor are dissolved in the solvent. In the membrane formation process, the first solution is supplied onto a membrane and the polyionic complex-formation inhibitor in the first solution and the solvent are selectively permeated through the membrane to form the immobilized catalyst membrane on the membrane. In the immobilized catalyst membrane, the catalyst is immobilized in the polyionic complex comprising the polycationic compound and a polyanionic compound.

Description

  The present invention relates to an immobilized catalyst membrane, a method for producing the immobilized catalyst membrane, and a membrane permeation reaction method using the immobilized catalyst membrane.

  In fields such as food, medicine and analysis, expensive and valuable enzymes are sometimes used as catalysts. In order to repeatedly use this enzyme, the enzyme is immobilized on a carrier by a covalent bond method, an ion bond method, a physical adsorption method, a crosslinking method, a comprehensive method, or the like. The enzyme immobilized on this carrier is referred to as an immobilized enzyme.

  For example, Patent Document 1 discloses an enzyme immobilization method in which an enzyme is immobilized on a carrier by a combined method combining an ion binding method and a comprehensive method. In this enzyme immobilization method, an aqueous solution in which a polycation compound is dissolved and an aqueous solution in which a polyanion compound is dissolved are mixed to precipitate a polyion complex, and the enzyme is immobilized in the polyion complex. In this enzyme immobilization method, since the enzyme is immobilized in an aqueous solution system, a decrease in enzyme activity can be suppressed.

JP 2006-127957 A

  However, it is extremely difficult to produce a homogeneous immobilized enzyme membrane by the above-described enzyme immobilization method.

  An object of the present invention is to provide a method for producing an immobilized catalyst membrane capable of producing a homogeneous immobilized enzyme membrane.

(1)
The method for producing an immobilized catalyst membrane according to the present invention includes a first preparation step and a membrane formation step. In the first preparation step, a first solution is prepared. In the first solution, at least a catalyst, a polycation compound, a polyanion compound, and a polyion complex formation inhibitor are dissolved in a solvent. In the membrane forming step, the first solution is supplied to the membrane, and the polyion complex formation inhibitor and the solvent in the first solution are selectively permeated to form an immobilized catalyst membrane on the membrane. In this immobilized catalyst membrane, the catalyst is immobilized in a polyion complex composed of a polycation compound and a polyion compound. As a membrane permeation method, it is preferable to employ a gas pressurization method in which the primary side (first solution supply side) is pressurized with a gas such as an inert gas. The solvent may be a buffer solution.

  In this method for producing an immobilized catalyst membrane, the first solution is supplied to the membrane, and the polyion complex formation inhibitor and the solvent in the first solution are selectively permeated to form an immobilized catalyst membrane on the membrane. The For this reason, if this method for producing an immobilized catalyst membrane is used, a homogeneous immobilized enzyme membrane can be produced on the membrane.

(2)
In the method for producing an immobilized catalyst membrane of (1) described above, it is preferable that a plurality of first solutions containing different kinds of catalysts are prepared in the first preparation step. In the film formation step, after the formation of the nth immobilized catalyst layer, the first solution is supplied onto the nth immobilized catalyst layer, and the polyion complex formation inhibitor and the solvent in the first solution are selectively selected. Through the membrane, the (n + 1) th immobilized catalyst layer is formed on the nth immobilized catalyst layer to form a multilayered immobilized catalyst membrane. Here, n is an integer of 1 or more. Also, here, the product produced by the immobilized catalyst present in the nth immobilized catalyst layer can be decomposed by the immobilized catalyst present in the (n + 1) th immobilized catalyst layer, Alternatively, it is preferable to dispose different types of catalysts in the n and (n + 1) th immobilized catalyst layers so that a new compound can be synthesized by reacting with another compound. The product generated by the immobilized catalyst existing in the (n + 1) th immobilized catalyst layer can be decomposed by the immobilized catalyst present in the nth immobilized catalyst layer, or other Different catalysts may be arranged in the n and (n + 1) th immobilized catalyst layers so that a new compound can be synthesized by reacting with the above compound (in this case, the immobilized catalyst membrane is Placed upside down).

  For this reason, if this method for producing an immobilized catalyst membrane is used, a homogeneous immobilized catalyst membrane having a multilayer structure can be obtained, and, for example, an immobilization existing in the nth immobilized catalyst layer can be obtained. The product produced by the catalyst can be decomposed by the immobilized catalyst existing in the (n + 1) th immobilized catalyst layer, or reacted with another compound to synthesize a new compound.

(3)
In the immobilized catalyst membrane according to the present invention, the catalyst is immobilized on the polyion complex so that the catalyst is ubiquitous in the polyion complex. When this immobilized catalyst membrane has a multilayer structure, the catalyst is immobilized on each polyion complex so that the catalyst is ubiquitous in at least two layers of the polyion complex.

  For this reason, when a substrate is supplied into the immobilized catalyst membrane, at least one of decomposition of the substrate and synthesis of the compound is uniformly promoted. Further, with such an immobilized catalyst membrane, the final product can be continuously discharged out of the immobilized catalyst membrane, and the product and the catalyst can be easily separated. Therefore, with such an immobilized catalyst membrane, the final product can be produced continuously and efficiently.

(4)
The immobilized catalyst membrane of (3) above preferably has a multilayer structure. In this immobilized catalyst membrane, different types of catalysts are immobilized in at least two layers of polyion complexes. Here, the product produced by the immobilized catalyst present in the upstream layer in the solvent flow direction can be decomposed by the immobilized catalyst present in the downstream layer in the solvent flow direction, or It is preferable to arrange a different type of catalyst so that a new compound can be synthesized by reacting with another compound.

  For this reason, in this fixed catalyst membrane, a plurality of different decomposition reactions or synthesis reactions can be executed continuously. Therefore, with this immobilized catalyst membrane, the final product can be obtained efficiently.

(5)
The membrane permeation reaction method according to the present invention includes a second preparation step and a first membrane permeation reaction step. In the second preparation step, a second solution is prepared. This second solution contains at least one substrate. In the first membrane permeation reaction step, the second product is supplied into the immobilized catalyst membrane of (3) above, and at least one of decomposition of the compound (including the substrate) and synthesis of the compound is performed, It is discharged out of the immobilized catalyst membrane.

  For this reason, in this membrane permeation reaction method, at least one of the decomposition of the compound (including the substrate) and the synthesis of the compound is uniformly promoted. Further, in this membrane permeation reaction method, the final product can be continuously discharged out of the immobilized catalyst membrane, and the product and the catalyst can be easily separated. Therefore, if this membrane permeation reaction method is used, the final product can be obtained continuously and efficiently.

(6)
The membrane permeation reaction method according to the present invention includes a third preparation step and a second membrane permeation reaction step. In the third preparation step, a third solution is prepared. This third solution contains at least one substrate. In the first membrane permeation reaction step, the third solution is supplied into the immobilized catalyst membrane described in (4) above, and the final product is immobilized while the compound (including the substrate) is decomposed or synthesized in each layer. Discharged outside the catalyst membrane.

  For this reason, in this membrane permeation reaction method, a plurality of different decomposition reactions or synthesis reactions can be continuously performed. Therefore, if this membrane permeation reaction method is used, the final product can be obtained efficiently.

By using the method for producing an immobilized catalyst membrane according to the present invention, a homogeneous immobilized enzyme membrane can be produced.
In addition, if the immobilized enzyme membrane obtained by the method for producing an immobilized catalyst membrane according to the present invention is used, at least one of decomposition of the compound and synthesis of the compound is promoted uniformly, and the final product is continuously immobilized. It can be discharged out of the catalyst membrane, and the product and the catalyst can be easily separated. Therefore, with such an immobilized catalyst membrane, the final product can be obtained continuously and efficiently.

It is sectional drawing of the fixed catalyst membrane which concerns on 1st Embodiment of this invention. It is sectional drawing which showed the state which ultrafiltered the mixed solution. It is sectional drawing which showed the state which completed the ultrafiltration of the mixed solution. It is sectional drawing of the fixed catalyst membrane which concerns on 2nd Embodiment of this invention. It is sectional drawing which showed the state which is pressing the mixed solution against the 1st layer. It is sectional drawing which showed the state which finished pressing the mixed solution on the 1st layer. It is sectional drawing of the fixed catalyst membrane which concerns on the modification of 2nd Embodiment of this invention. It is sectional drawing which showed the state which is pressing the mixed solution against the 2nd layer. It is sectional drawing which showed the state which finished pressing the mixed solution on the 2nd layer. FIG. 3 is a cross-sectional view showing a state where a substrate solution is being supplied into an immobilized catalyst membrane according to Example 1. FIG. 3 is a graph showing the change over time of the conversion rate of the product produced from the substrate according to Example 1. It is a graph which shows the time-dependent change of the conversion rate of the product produced | generated from the substrate which concerns on the reference example 1. FIG. 6 is a cross-sectional view showing a state where a substrate solution is supplied to an immobilized catalyst membrane according to Example 2. FIG. It is a graph which shows a time-dependent change of the conversion rate of the product produced | generated from the substrate which concerns on Example 2. FIG. It is a graph which shows the time-dependent change of the conversion rate of the product produced | generated from the substrate which concerns on the reference example 2. FIG. 6 is a cross-sectional view showing a state where a substrate solution is supplied to an immobilized catalyst membrane according to Example 3. FIG. It is a graph which shows a time-dependent change of the conversion rate of the product produced | generated from the substrate which concerns on Example 3. FIG. It is a graph which shows the time-dependent change of the conversion rate of the product produced | generated from the substrate which concerns on the reference example 3. FIG. 6 is a cross-sectional view showing a state in which a substrate solution is supplied to an immobilized catalyst membrane according to Example 4. FIG. It is a graph which shows a time-dependent change of the conversion rate of the product produced | generated from the substrate which concerns on Example 4. FIG. 6 is a cross-sectional view showing a state where a substrate solution is supplied to an immobilized catalyst membrane according to Example 5. FIG. It is a graph which shows a time-dependent change of the conversion rate of the product produced | generated from the substrate which concerns on Example 5. FIG. 10 is a cross-sectional view showing a state where a substrate solution is supplied to an immobilized catalyst membrane according to Example 6. FIG. It is a graph which shows a time-dependent change of the conversion rate of the product produced | generated from the substrate which concerns on Example 6. FIG.

-First embodiment-
The immobilized catalyst membrane 100 according to the first embodiment of the present invention is mainly composed of a catalyst 200 and a polyion complex 300, as shown in FIG. In this immobilized catalyst membrane 100, the catalyst 200 is immobilized on the polyion complex 300 so that the catalyst 200 is ubiquitous in the polyion complex 300. The polyion complex 300 is formed by an ionic bond between the polycation compound 310 and the polyanion compound 320.

As the catalyst 200, for example, a biocatalyst such as an enzyme or yeast is used.
Examples of the enzyme include oxidoreductase, transferase, hydrolase, lyase, isomerase, ligase and the like. More specifically, examples of the enzyme include amylase, cellulase, maltase, catechol oxidase (tyrosinase), tryptophanase, fumarase, urease and the like. Examples of yeast include baker's yeast, wine yeast, and beer yeast.

  Examples of the polycation compound 310 include a chitosan salt, a quaternized chitosan salt (chitosan salt in which an amino group is quaternary ammonium ionized), a polyvinyl pyridine salt, and a quaternized polyvinyl pyridine salt (an amino group is quaternary). Ammonium ionized polyvinylpyridine salt), poly-L-lysine salt, polyallylamine salt, polyvinylimidazole salt, polyethyleneimine salt, polyvinylpyrrolidone salt, and the like are used. As the polyanion compound 320, for example, carboxymethyl cellulose salt, polyacrylic acid salt, polymethacrylic acid salt, polyfluorosulfonic acid salt, polyalginate, polystyrene sulfonic acid salt, polyethylene sulfonic acid salt and the like are used.

<Method for producing immobilized catalyst membrane>
A first aqueous solution in which the polycation compound 310 and the polyion complex formation inhibitor are dissolved in a buffer solution and a second aqueous solution in which the polyanion compound 320 and the polyion complex formation inhibitor are dissolved in a buffer solution are prepared. As the polyion complex formation inhibitor, for example, alkali metal or alkaline earth metal halides are used. Specifically, sodium chloride, potassium chloride, lithium chloride, sodium bromide, potassium bromide, sodium iodide, potassium iodide and the like are listed as polyion complex formation inhibitors. The polyion complex formation inhibitor of the first aqueous solution is preferably the same type of salt as the polyion complex formation inhibitor of the second aqueous solution, but may be a different type of salt.

  When sodium chloride, potassium chloride, lithium chloride, sodium bromide, or potassium bromide is used as the polyion complex formation inhibitor, the concentration of the polyion complex formation inhibitor is 9.5% by weight or more based on the entire aqueous solution. It is preferable that (in such a case, about 1% by weight of a polycation compound or a polyanion compound is added to the aqueous solution). When sodium iodide or potassium iodide is used as the polyion complex formation inhibitor, the concentration of the polyion complex formation inhibitor is preferably 20% by weight or more based on the entire aqueous solution (in this case, the aqueous solution 1% by weight of polycationic compound or polyanionic compound is added). In addition, the density | concentration of the said polyion complex formation inhibitor is only a standard to the last. An appropriate concentration of the polyion complex formation inhibitor can be easily determined by a person skilled in the art by performing a simple experiment.

  After mixing the first aqueous solution and the second aqueous solution, the catalyst 200 is added to the aqueous solution to prepare a mixed solution 400. At this time, in the mixed solution 400, a polyion complex is not formed from the polycation compound 310 and the polyanion compound 320 by the polyion complex formation inhibitor. That is, the polycation compound 310 and the polyanion compound 320 are dissolved in the mixed solution 400. In addition, in this mixed solution 400, the addition amount of the polycation compound 310 may be the same amount as the addition amount of the polyanion compound 320, or may be a different amount. The ratio of the amount of addition greatly affects the network structure of the polyion complex.

  As shown in FIG. 2, the mixed solution 400 is put into an ultrafiltration device 500 in which an ultrafiltration membrane 600 is set. The ultrafiltration membrane 600 is a porous membrane that selectively permeates the polyion complex formation inhibitor and water in the mixed solution 400. FIG. 2 shows a flat ultrafiltration membrane 600, but a tubular ultrafiltration membrane, a hollow fiber fibrous ultrafiltration membrane, or the like may be employed as the ultrafiltration membrane. Good. In such a case, it is necessary to prepare an ultrafiltration device suitable for each shape of ultrafiltration membrane. In the ultrafiltration device 500, when an inert gas is supplied to the upper space of the mixed solution 400, the mixed solution 400 is pressed toward the ultrafiltration membrane 600, and the mixed solution 400 is ultrafiltered. At this time, the filtrate 410 is separated from the mixed solution 400. The filtrate 410 mainly contains a polyion complex formation inhibitor and water.

  When the ultrafiltration is completed, an immobilized catalyst membrane 100 is formed on the filtration membrane 600 as shown in FIG. In the immobilized catalyst membrane 100, the catalyst 200 is included in a homogeneous polyion complex 300. Thereafter, the buffer solution is put into the ultrafiltration device 500. When an inert gas is supplied to the upper space of the buffer solution, the buffer solution is pressed toward the immobilized catalyst membrane 100, and the buffer solution passes through the immobilized catalyst membrane 100. By this treatment, the polyion complex formation inhibitor is washed out from the immobilized catalyst membrane 100. In this way, the immobilized catalyst membrane 100 is obtained. As the buffer, for example, an acetic acid-based or phosphoric acid-based buffer is used.

  Here, an ultrafiltration membrane is used to form the immobilized catalyst membrane 100, but the membrane is a membrane that selectively permeates the polyion complex formation inhibitor and the solvent in the mixed solution 400. Of course, a dense polymer membrane may be used instead of the ultrafiltration membrane.

<Usage method of immobilized catalyst membrane>
The immobilized catalyst membrane 100 is set in the ultrafiltration device 500, and the substrate solution containing the substrate is put into the ultrafiltration device 500. Next, when an inert gas is supplied to the upper space of the substrate solution and the substrate solution is pressed against the immobilized catalyst membrane 100, the substrate solution penetrates into the immobilized catalyst membrane 100. When the substrate solution permeates the immobilized catalyst membrane 100, the substrate in the substrate solution comes into contact with the catalyst 200 in the immobilized catalyst membrane 100. As a result, the catalyst 200 promotes a “substrate decomposition reaction” and a “synthesis reaction using the substrate as a raw material”. The product generated by the catalyst 200 permeates the immobilized catalyst membrane 100 along the flow of the solvent (buffer solution) and is discharged out of the system of the immobilized catalyst membrane 100.

  Examples of the reaction to decompose the substrate include a reaction in which starch (substrate) is decomposed into maltose by amylase (catalyst), a reaction in which maltose (substrate) is decomposed into glucose by maltase (catalyst), and glucose (substrate) is converted into chymase (catalyst). ) To decompose ethanol into ethanol, a reaction to decompose sucrose (substrate) into glucose with invertase (catalyst), and a reaction to decompose urea (substrate) into carbon dioxide and ammonia with urease (catalyst).

  As a reaction for synthesizing a compound, for example, a reaction for synthesizing phenol, pyruvic acid and ammonia (substrate) into L-tyrosine by β-tyrosinase (catalyst), and indole, pyruvic acid and ammonia (substrate) for tryptophanase (catalyst) ) And a reaction of synthesizing fumaric acid and water (substrate) into L-malic acid by fumarase (catalyst).

<Method for Producing Immobilized Catalyst Membrane and Immobilized Catalyst Membrane According to Present Embodiment>
(1)
In the method for producing an immobilized catalyst membrane according to the present embodiment, the mixed solution 400 is supplied to the ultrafiltration membrane 600, and the polyion complex formation inhibitor and water in the mixed solution 400 are selectively permeated to the ultrafiltration membrane 600. An immobilized catalyst membrane 100 is formed on the filtration membrane 600. For this reason, if this method for producing an immobilized catalyst membrane is used, a homogeneous immobilized enzyme membrane 100 can be produced on the ultrafiltration membrane 600.

(2)
In the method for producing an immobilized catalyst membrane according to this embodiment, water is used as the solvent of the mixed solution 400. For this reason, it can suppress that the activity of the enzyme which is a biocatalyst, or yeast falls.

(3)
If the method for producing an immobilized catalyst membrane according to this embodiment is used, the immobilized catalyst membrane 100 in which the catalyst 200 is ubiquitous in the polyion complex 300 can be obtained. For this reason, when a substrate is supplied into the immobilized catalyst membrane 100, at least one of decomposition of the substrate and synthesis of the compound is promoted uniformly. Further, in such an immobilized catalyst membrane 100, the final product can be continuously discharged out of the immobilized catalyst membrane 100, and the product and the catalyst 200 can be easily separated. Therefore, with such an immobilized catalyst membrane 100, the final product can be produced continuously and efficiently.

-Second Embodiment-
A catalyst film 101 according to a second embodiment of the present invention will be described. The immobilized catalyst film 100 according to the first embodiment has a single-layer structure, but the immobilized catalyst film 101 according to the second embodiment has a multilayer structure. In the second embodiment, the same components as those in the first embodiment are denoted by the same reference numerals as those in the first embodiment, and description thereof is omitted as appropriate.

  The immobilized catalyst film 101 according to the second embodiment includes a first layer 110 and a second layer 120, as shown in FIG. The first layer 110 is mainly composed of the catalyst 200 and the polyion complex 300. The second layer 120 is mainly composed of the catalyst 210 and the polyion complex 300. In the present embodiment, the catalyst 210 is preferably a different type of catalyst from the catalyst 200. However, the catalyst 210 may be the same type of catalyst as the catalyst 200 for the purpose of extending the reaction time. The polyion complex 300 in the second layer 120 may be formed from the same polycation compound 310 and polyanion compound 320 as the polyion complex 300 in the first layer 110, or the polyion complex 300 in the first layer 110. May be formed from different polycationic compounds and polyanionic compounds.

<Method for producing catalyst membrane>
First, the 1st layer 110 is obtained by the method similar to the catalyst film 100 of said 1st Embodiment (refer FIG. 2, 3). At this stage, the polyion complex formation inhibitor may or may not be washed out from the first layer 110 with a buffer solution.

  Next, in order to obtain the second layer 120, the first aqueous solution in which the polycation compound 310 and the polyion complex formation inhibitor are dissolved in the buffer solution, and the polyanion compound 320 and the polyion complex formation inhibitor are dissolved in the buffer solution. A second aqueous solution is prepared. The polyion complex formation inhibitor of the first aqueous solution is preferably the same type of salt as the polyion complex formation inhibitor of the second aqueous solution, but may be a different type of salt. The polyion complex formation inhibitor in the mixed solution for forming the second layer 120 may be the same type as the polyion complex formation inhibitor in the mixed solution for forming the first layer 110, or the first A different type from the polyion complex formation inhibitor in the mixed solution for forming the layer 110 may be used.

  After mixing the first aqueous solution and the second aqueous solution, the catalyst 210 is added to the aqueous solution to prepare a mixed solution 401. At this time, in the mixed solution 401, a polyion complex is not formed from the polycation compound 310 and the polyanion compound 320 by the polyion complex formation inhibitor. That is, the polycation compound 310 and the polyanion compound 320 are dissolved in the mixed solution 401. In addition, in this mixed solution 401, the addition amount of the polycation compound 310 may be the same as the addition amount of the polyanion compound 320, or may be a different amount. The ratio of the amount of addition greatly affects the network structure of the polyion complex.

  As shown in FIG. 5, after the first layer 110 is formed on the ultrafiltration membrane 600, the mixed solution 401 is put into the ultrafiltration device 500. In the ultrafiltration device 500, when the inert gas is supplied to the upper space of the mixed solution 401, the mixed solution 401 is pressed toward the first layer 110. At this time, the permeate 411 is separated from the mixed solution 401. The permeate 411 mainly contains a polyion complex formation inhibitor and water.

  When the above process is completed, the second layer 120 is formed on the first layer 110 as shown in FIG. In the second layer 120, similar to the first layer 110, the catalyst 210 is included in the homogeneous polyion complex 300. The second layer 120 is in close contact with the first layer 110. Thereafter, the buffer solution is put into the ultrafiltration device 500. When an inert gas is supplied to the upper space of the buffer solution, the buffer solution is pressed toward the second layer 120, and the buffer solution passes through the layers 110 and 120. By this treatment, the polyion complex formation inhibitor is washed out from each of the layers 110 and 120. In this way, the immobilized catalyst membrane 101 having a two-layer structure is obtained. As the buffer, for example, an acetic acid-based or phosphoric acid-based buffer is used.

<Usage of catalyst membrane>
The immobilized catalyst membrane 101 is set in the ultrafiltration device 500, and the substrate solution containing the substrate is put into the ultrafiltration device 500. Next, when an inert gas is supplied to the upper space of the substrate solution and the substrate solution is pressed against the immobilized catalyst membrane 101, the substrate solution penetrates into the immobilized catalyst membrane 101. When the substrate solution permeates the immobilized catalyst film 101, the substrate in the substrate solution comes into contact with the catalyst 210 in the second layer 120. As a result, the catalyst 210 promotes the “decomposition reaction of the substrate” and the “synthesis reaction using the substrate as a raw material” to generate a compound different from the substrate. The compound then contacts the catalyst 200 in the first layer 110. As a result, the catalyst 200 promotes a “decomposition reaction of the compound” and a “synthesis reaction using the compound as a raw material”, and further different compounds are generated. That is, in the immobilized catalyst film 101, the decomposition reaction and the synthesis reaction occur in two stages. Then, the product generated by the catalyst 200 permeates the first layer 110 of the immobilized catalyst film 101 along the flow of the solvent (buffer solution) and is discharged out of the system of the immobilized catalyst film 100. .

<Effect in this embodiment>
(1)
By using the method for producing an immobilized catalyst membrane according to this embodiment, a homogeneous immobilized catalyst membrane having a multilayer structure can be obtained.

(2)
The immobilized catalyst film 101 according to this embodiment is a multilayer structure having a first layer 110 and a second layer 120. In the immobilized catalyst film 101, different types of catalysts 200 and 210 are immobilized in the polyion complex 300 of the layers 110 and 120, respectively. For this reason, in this immobilized catalyst film 101, the product produced by the catalyst 210 present in the second layer 120 is decomposed by the catalyst 200 present in the first layer 110, or other compounds and New compounds can be synthesized by reaction.

<Modification>
(A)
As shown in FIG. 7, the immobilized catalyst film 102 may have a third layer 130 in addition to the first layer 110 and the second layer 120 described above. In FIG. 7, the third layer 130 is formed on the second layer 110. The immobilized catalyst film 102 may be a multilayer structure having four or more layers.

  The third layer 130 is mainly composed of the catalyst 220 and the polyion complex 300. In this variation, the catalyst 220 is preferably a different type of catalyst from the catalyst 200 and the catalyst 210. However, the catalyst 220 may be the same type of catalyst as at least one of the catalyst 200 and the catalyst 210 for the purpose of extending the reaction time. The polyion complex 300 of the third layer 130 may be formed of the same polycation compound 310 and polyanion compound 320 as the polyion complex 300 of each layer 110 and 120, or a different polyion complex 300 from the polyion complex 300 of each layer 110 and 120. The cation compound 310 and the polyanion compound 320 may be formed.

<Method for producing immobilized catalyst membrane>
First, the first layer 110 and the second layer 120 are obtained by the same method as the immobilized catalyst film 101 of the second embodiment (see FIGS. 2, 3, 5 and 6). At this stage, the polyion complex formation inhibitor in the first layer 110 and the second layer 120 may or may not be washed out with a buffer solution.

  Next, in order to obtain the third layer 130, the first aqueous solution in which the polycation compound 310 and the polyion complex formation inhibitor are dissolved in the buffer solution, and the polyanion compound 320 and the polyion complex formation inhibitor are dissolved in the buffer solution. A second aqueous solution is prepared. The polyion complex formation inhibitor of the second aqueous solution is preferably the same type of salt as the polyion complex formation inhibitor of the first aqueous solution, but may be a different type of salt. Further, the polyion complex formation inhibitor in the mixed solution for forming the third layer 130 is contained in at least one of the mixed solution for forming the first layer 110 and the mixed solution for forming the second layer 120. It may be the same type as the polyion complex formation inhibitor or may be a different type from the polyion complex formation inhibitor in the mixed solution for forming the first layer 110 and the mixed solution for forming the second layer 120. Good.

  After mixing the first aqueous solution and the second aqueous solution, the catalyst 220 is added to the aqueous solution to prepare a mixed solution 402. At this time, in the mixed solution 402, a polyion complex is not formed from the polycation compound 310 and the polyanion compound 320 by the polyion complex formation inhibitor. That is, the polycation compound 310 and the polyanion compound 320 are dissolved in the mixed solution 402. In addition, in this mixed solution 402, the addition amount of the polycation compound 310 may be the same as the addition amount of the polyanion compound 320, or may be a different amount. The ratio of the amount of addition greatly affects the network structure of the polyion complex.

  As shown in FIG. 8, after the first layer 110 and the second layer 120 are formed on the ultrafiltration membrane 600, the mixed solution 402 is put into the ultrafiltration device 500. In the ultrafiltration device 500, when the inert gas is supplied to the upper space of the mixed solution 402, the mixed solution 402 is pressed toward the second layer 120. At this time, the permeate 412 is separated from the mixed solution 402. The permeate 412 mainly contains a polyion complex formation inhibitor and water.

  When the above process is completed, a third layer 130 is formed on the second layer 120 as shown in FIG. In the third layer 130, as in the first layer 110 and the second layer 120, the catalyst 220 is included in the homogeneous polyion complex 300. The third layer 130 is in close contact with the second layer 120. Thereafter, the buffer solution is put into the ultrafiltration device 500. When an inert gas is supplied to the upper space of the buffer solution, the buffer solution is pressed toward the third layer 130, and the buffer solution passes through each layer 110, 120, 130. By this treatment, the polyion complex formation inhibitor is washed out from each layer 110, 120, 130. In this way, a fixed catalyst membrane 102 having a three-layer structure is obtained. As the buffer, for example, an acetic acid-based or phosphoric acid-based buffer is used.

<Usage of catalyst membrane>
The immobilized catalyst membrane 102 is set on the ultrafiltration device 500, and a substrate solution containing the substrate is put into the ultrafiltration device 500. Next, when an inert gas is supplied to the upper space of the substrate solution and the substrate solution is pressed against the immobilized catalyst membrane 102, the substrate solution penetrates into the immobilized catalyst membrane 101. When the substrate solution permeates the immobilized catalyst membrane 102, the substrate in the substrate solution comes into contact with the catalyst 220 in the third layer 130. As a result, the catalyst 220 promotes the “decomposition reaction of the substrate” and the “synthesis reaction using the substrate as a raw material” to generate a compound different from the substrate. The compound then contacts the catalyst 210 in the second layer 120. As a result, the catalyst 210 promotes a “compound decomposition reaction” and a “synthesis reaction using a compound as a raw material”, and further different compounds are generated. The compound then contacts the catalyst 200 in the first layer 110. As a result, the catalyst 200 promotes a “decomposition reaction of the compound” and a “synthesis reaction using the compound as a raw material”, and further different compounds are generated. That is, in the immobilized catalyst film 102, the decomposition reaction and the synthesis reaction occur in three stages. Then, the product generated by the catalyst 200 permeates the first layer 110 of the immobilized catalyst membrane 102 along the flow of the solvent (buffer solution) and is discharged out of the system of the immobilized catalyst membrane 100. .

(B)
In the method for producing an immobilized catalyst membrane according to the previous embodiment, the first layer 110 and the second layer 120 were continuously formed. However, the first layer 110 and the second layer 120 were produced separately. It does not matter. In such a case, the same function as that of the immobilized catalyst film 101 can be expressed by stacking and using the first layer 110 and the second layer 120 in a wet state.

(C)
In the method for producing an immobilized catalyst film according to the previous embodiment, the immobilized catalyst film 101 is formed so that the first layer 110 and the second layer 120 are in close contact with each other. A layer made of only a polyion complex (that is, a catalyst-free layer) may be formed between the two layers 120.

  Next, the immobilized catalyst membranes 100, 101, and 102 according to the above embodiment will be described in more detail with reference to examples. In addition, this invention is not limited at all by the following Example.

<Preparation of immobilized catalyst membrane>
Quaternized chitosan (polycation compound 310) (1.01 g of chitosan manufactured by Nihon Suisan Co., Ltd., quaternary ammonium ionized by a known method) and sodium bromide (pure Wako Jun), a polyion complex formation inhibitor A first aqueous solution was prepared by dissolving 11.2 g of a first grade reagent (manufactured by Yakuhin Kogyo Co., Ltd.) in 100 g of acetate buffer (pH 5.9). Further, 1.01 g of sodium carboxymethyl cellulose (primary reagent manufactured by Wako Pure Chemical Industries, Ltd.) which is a polyanion compound 320, and sodium bromide (primary reagent manufactured by Wako Pure Chemical Industries, Ltd.) 11 which is a polyion complex formation inhibitor 11 A second aqueous solution prepared by dissolving 2 g in 100 g acetate buffer (pH 5.9) was prepared. Then, 0.03 g of α-amylase (manufactured by MP Biomedicals Co., Ltd., first grade reagent) as the catalyst 200 is added to the aqueous solution obtained by mixing the first aqueous solution and the second aqueous solution to prepare a mixed solution 400. did.

  As shown in FIG. 2, after the mixed solution 400 is put into an ultrafiltration device (advantech Toyo Co., Ltd., product name: stirring ultra holder) 500 in which the ultrafiltration membrane 600 is set, the upper part of the mixed solution 400 Nitrogen gas was supplied to the space, the mixed solution 400 was pressed toward the ultrafiltration membrane 600, and the mixed solution 400 was ultrafiltered.

  After completion of the ultrafiltration, as shown in FIG. 3, the immobilized catalyst membrane 100 was formed on the ultrafiltration membrane 600. Next, 20 g of an acetate buffer solution is charged into the ultrafiltration device 500, then nitrogen gas is supplied to the upper space of the acetate buffer solution, and the acetate buffer solution is pressed toward the immobilized catalyst membrane 100 to thereby immobilize the immobilized catalyst membrane. 100 was permeated with acetate buffer. The immobilized catalyst membrane 100 was used in a wet state without being dried.

<Decomposition of substrate using immobilized catalyst membrane>
As shown in FIG. 10, the immobilized catalyst membrane 100 was set in an ultrafiltration device (manufactured by Advantech Toyo Co., Ltd., product name: stirring type ultra holder) 500. Moreover, the starch aqueous solution 700 of pH 5.9 was prepared. The substrate starch (Wako Pure Chemical Industries, Ltd., first grade reagent) 710 was added to 1% by weight with respect to the whole starch aqueous solution. The starch aqueous solution 700 is put into the ultrafiltration device 500, nitrogen gas is supplied to the upper space of the starch aqueous solution 700, the starch aqueous solution 700 is pressed against the immobilized catalyst membrane 100 at a pressure of 0.2 MPa, and the starch aqueous solution 700 is fixed. The catalyst catalyst 100 was permeated. At this time, the temperature of the starch aqueous solution 700 was adjusted to 30 ° C. As a result, starch 710 was decomposed by α-amylase in the immobilized catalyst membrane 100, and maltose 711 and glucose 712 were generated (see FIG. 11).

The concentrations of maltose 711 and glucose 712 in the secondary side (solvent permeation side) solution of the immobilized catalyst 100 were quantified by a calibration curve method using high performance liquid chromatography (manufactured by Shimadzu Corporation). The measurement conditions were as follows.
・ Liquid feeding unit: LC-10AD VP
Column oven: CTO-10A VP
・ Degasser: DGV-12A
-Differential refractometer detector: RID-10A
Column name: Asahipak NH2P-50 4E (manufactured by Showa Denko KK)
・ Mobile phase: 75 wt% acetonitrile aqueous solution ・ Mobile phase speed: 1 mL / min ・ Ambient temperature: 30 ° C.

(Reference Example 1)
A starch aqueous solution having a pH of 5.9 was prepared. Starch as a substrate (manufactured by Wako Pure Chemical Industries, Ltd., first grade reagent) was added to 1% by weight with respect to the whole starch aqueous solution. Then, α-amylase (manufactured by MP Biomedicals Co., Ltd., first grade reagent) was added to the aqueous starch solution, and the aqueous starch solution was allowed to stand at 30 ° C. As a result, starch was decomposed by α-amylase to produce maltose and glucose (see FIG. 12).

  An immobilized catalyst membrane 100a was obtained in the same manner as in Example 1 except that the catalyst 200 was replaced with maltase (manufactured by Tokyo Chemical Industry Co., Ltd., first grade reagent). Moreover, the maltose aqueous solution 701 of pH 5.9 was prepared. The substrate, maltose (manufactured by Wako Pure Chemical Industries, Ltd., first grade reagent) 711 was added to 1% by weight with respect to the entire maltose aqueous solution. And as FIG. 13 showed, it carried out similarly to Example 1, and the maltose aqueous solution 701 was osmose | permeated the fixed catalyst membrane 100a. As a result, maltose 711 was decomposed by maltase in the immobilized catalyst membrane 100a to produce glucose 712 (see FIG. 14).

(Reference Example 2)
An aqueous maltose solution was obtained in the same manner as in Reference Example 1 except that the substrate was changed to maltose (manufactured by Wako Pure Chemical Industries, Ltd., first grade reagent). Then, 0.05 g of maltase (manufactured by Tokyo Chemical Industry Co., Ltd., primary reagent) was added to the maltose aqueous solution, and the maltose aqueous solution was allowed to stand at 30 ° C. as in Reference Example 1. As a result, maltose was decomposed by maltase to produce glucose (see FIG. 15).

  An immobilized catalyst membrane 100b was obtained in the same manner as in Example 1 except that the catalyst 200 was replaced with baker's yeast (made by Oriental Yeast Co., Ltd.). Moreover, pH 5.9 glucose aqueous solution 702 and pH 5.0 glucose aqueous solution 702 were prepared. In addition, glucose (Wako Pure Chemical Industries, Ltd., a primary reagent) 712 which is a substrate was added so that it might become 1 weight% with respect to the whole glucose aqueous solution. And as FIG. 16 shows, it carried out similarly to Example 1, and made the said 2 types of glucose aqueous solution 702 osmose | permeate each in separate fixed catalyst membrane 100b. As a result, glucose 712 was decomposed by baker's yeast in the immobilized catalyst membrane 100b, and ethanol 713 was generated (see FIG. 17).

In addition, the density | concentration of ethanol 713 in the liquid of the secondary side (solvent permeation | transmission side) of the fixed catalyst film | membrane 100b was quantified by the calibration curve method using gas chromatography (Shimadzu Corporation GC-14A). The measurement conditions were as follows.
Column name: Thermon-3000 5% SHIN CARBON A 60-80 (manufactured by Shinwa Processing Co., Ltd.)
-Mobile phase: hydrogen, helium-Mobile phase speed: 0.5 kg / cm ²
・ Detector: Thermal conductivity type ・ Ambient temperature: 50 ℃

(Reference Example 3)
A glucose aqueous solution was obtained in the same manner as in Reference Example 1 except that the substrate was replaced with glucose (Wako Pure Chemical Industries, Ltd., first grade reagent). Then, 0.5 g of baker's yeast (manufactured by Oriental Yeast Co., Ltd.) was added to the aqueous glucose solution, and the aqueous glucose solution was allowed to stand at 30 ° C. as in Reference Example 1. As a result, glucose was decomposed to produce ethanol (see FIG. 18).

<Method for producing immobilized catalyst membrane>
(1) Preparation of first layer 1.01 g of quaternized chitosan (polysulfur compound made by Nippon Suisan Co., Ltd. obtained by quaternary ammonium ionization by a known method) and inhibition of polyion complex formation A first aqueous solution in which 11.2 g of sodium bromide (manufactured by Wako Pure Chemical Industries, Ltd., first grade reagent) as an agent was dissolved in 100 g of acetate buffer (pH 5.9) was prepared. Further, 1.01 g of sodium carboxymethyl cellulose (primary reagent manufactured by Wako Pure Chemical Industries, Ltd.) which is a polyanion compound 320, and sodium bromide (primary reagent manufactured by Wako Pure Chemical Industries, Ltd.) 11 which is a polyion complex formation inhibitor 11 A second aqueous solution prepared by dissolving 2 g in 100 g acetate buffer (pH 5.9) was prepared. Then, 0.05 g of maltase (manufactured by Tokyo Chemical Industry Co., Ltd.), which is the catalyst 200, was added to the aqueous solution obtained by mixing the first aqueous solution and the second aqueous solution to prepare a mixed solution 400.

  As shown in FIG. 2, after the mixed solution 400 is put into an ultrafiltration device (advantech Toyo Co., Ltd., product name: stirring ultra holder) 500 in which the ultrafiltration membrane 600 is set, the upper part of the mixed solution 400 Nitrogen gas was supplied to the space, the mixed solution 400 was pressed toward the ultrafiltration membrane 600, and the mixed solution 400 was ultrafiltered.

  After completion of ultrafiltration, the first layer 110 was formed on the ultrafiltration membrane 600 as shown in FIG.

(2) Production of second layer In the same manner as described above, 1.01 g of quaternized chitosan which is polycation compound 310 (a product obtained by ionizing quaternary ammonium ion of chitosan manufactured by Nihon Suisan Co., Ltd. by a known method) And a first aqueous solution prepared by dissolving 11.2 g of sodium bromide (primary reagent, manufactured by Wako Pure Chemical Industries, Ltd.), a polyion complex formation inhibitor, in 100 g of acetate buffer (pH 5.9). . Further, 1.01 g of sodium carboxymethyl cellulose (primary reagent manufactured by Wako Pure Chemical Industries, Ltd.) which is a polyanion compound 320, and sodium bromide (primary reagent manufactured by Wako Pure Chemical Industries, Ltd.) 11 which is a polyion complex formation inhibitor 11 A second aqueous solution prepared by dissolving 2 g in 100 g acetate buffer (pH 5.9) was prepared. Then, α-amylase (primary reagent, manufactured by MP Biomedicals), which is the catalyst 210, was added to the aqueous solution obtained by mixing the first aqueous solution and the second aqueous solution to prepare a mixed solution 401.

  As shown in FIG. 5, after the mixed solution 401 is put into an ultrafiltration apparatus (product name: stirring ultra holder) 500 in which the first layer 110 is formed, the upper portion of the mixed solution 401 Nitrogen gas was supplied to the space, and the mixed solution 401 was pressed toward the first layer 110.

  After the above processing was completed, the second layer 120 was formed on the first layer 110 as shown in FIG. Next, 20 g of acetate buffer solution is charged into the ultrafiltration device 500, then nitrogen gas is supplied to the upper space of the acetate buffer solution, and the acetate buffer solution is pressed toward the second layer 120 to form the first layer. The acetate buffer was permeated through 110 and the second layer 120. As a result, an immobilized catalyst film 101 having a two-layer structure was obtained. The immobilized catalyst membrane 101 was used in a wet state without being dried.

<Decomposition of substrate using immobilized catalyst membrane>
As shown in FIG. 19, the immobilized catalyst membrane 101 was set in an ultrafiltration device (manufactured by Advantech Toyo Co., Ltd., product name: stirring type ultra holder) 500. Moreover, the starch aqueous solution 700 of pH 5.9 was prepared. Starch (Wako Pure Chemical Industries, Ltd., first grade reagent) 710 as a substrate was added to 10% by weight with respect to the whole starch aqueous solution. The starch aqueous solution 700 is put into the ultrafiltration device 500, and nitrogen gas is supplied to the upper space of the starch aqueous solution 700, whereby the starch aqueous solution 700 is pressed against the immobilized catalyst membrane 101 at a pressure of 0.2 MPa to fix the starch aqueous solution 700. The catalyst catalyst 101 was permeated. At this time, the temperature of the starch aqueous solution 700 was adjusted to 30 ° C. As a result, starch 710 is decomposed by α-amylase in the second layer 120 to generate maltose 711 and glucose 712, and the maltose 711 is partially decomposed by maltase in the first layer 110 to generate glucose 712. (See FIG. 20).

  Immobilized catalyst membrane 101a was obtained in the same manner as in Example 4 except that catalyst 200 was replaced with baker's yeast (manufactured by Oriental Yeast Co., Ltd.) and catalyst 210 was replaced with maltase (manufactured by Tokyo Chemical Industry Co., Ltd.). Moreover, the maltose aqueous solution 701 of pH 5.9 was prepared. The substrate, maltose (manufactured by Wako Pure Chemical Industries, Ltd., first grade reagent) 711 was added to 1% by weight with respect to the entire maltose aqueous solution. Then, as shown in FIG. 21, the maltose solution 701 was permeated into the immobilized catalyst membrane 101a in the same manner as in Example 4. As a result, maltose 711 is decomposed by maltose in the second layer 120 to generate glucose 712, and the glucose 712 is decomposed by baker's yeast in the first layer 110a to generate ethanol 713 (see FIG. 22). ).

<Method for producing immobilized catalyst membrane>
(1) Preparation of first layer 1.01 g of quaternized chitosan (polysulfur compound made by Nippon Suisan Co., Ltd. obtained by quaternary ammonium ionization by a known method) and inhibition of polyion complex formation A first aqueous solution in which 11.2 g of sodium bromide (manufactured by Wako Pure Chemical Industries, Ltd., first grade reagent) as an agent was dissolved in 100 g of acetate buffer (pH 5.9) was prepared. Further, 1.01 g of sodium carboxymethyl cellulose (primary reagent manufactured by Wako Pure Chemical Industries, Ltd.) which is a polyanion compound 320, and sodium bromide (primary reagent manufactured by Wako Pure Chemical Industries, Ltd.) 11 which is a polyion complex formation inhibitor 11 A second aqueous solution prepared by dissolving 2 g in 100 g acetate buffer (pH 5.9) was prepared. And the baker's yeast (made by Oriental Yeast Co., Ltd.) which is the catalyst 200 was added to the aqueous solution which mixed the 1st aqueous solution and the 2nd aqueous solution, and the mixed solution 400 was prepared.

  As shown in FIG. 2, after the mixed solution 400 is put into an ultrafiltration device (advantech Toyo Co., Ltd., product name: stirring ultra holder) 500 in which the ultrafiltration membrane 600 is set, the upper part of the mixed solution 400 Nitrogen gas was supplied to the space, the mixed solution 400 was pressed toward the ultrafiltration membrane 600, and the mixed solution 400 was ultrafiltered.

  After completion of ultrafiltration, the first layer 110 was formed on the ultrafiltration membrane 600 as shown in FIG.

(2) Production of second layer In the same manner as described above, 1.01 g of quaternized chitosan which is polycation compound 310 (a product obtained by ionizing quaternary ammonium ion of chitosan manufactured by Nihon Suisan Co., Ltd. by a known method) And a first aqueous solution prepared by dissolving 11.2 g of sodium bromide (primary reagent, manufactured by Wako Pure Chemical Industries, Ltd.), a polyion complex formation inhibitor, in 100 g of acetate buffer (pH 5.9). . Further, 1.01 g of sodium carboxymethyl cellulose (primary reagent manufactured by Wako Pure Chemical Industries, Ltd.) which is a polyanion compound 320, and sodium bromide (primary reagent manufactured by Wako Pure Chemical Industries, Ltd.) 11 which is a polyion complex formation inhibitor 11 A second aqueous solution prepared by dissolving 2 g in 100 g acetate buffer (pH 5.9) was prepared. Then, a mixed solution 401 was prepared by adding maltase (manufactured by Tokyo Chemical Industry Co., Ltd., first grade reagent) as the catalyst 210 to the aqueous solution obtained by mixing the first aqueous solution and the second aqueous solution.

  As shown in FIG. 5, after the mixed solution 401 is put into the ultrafiltration device 500 in which the first layer 110 is formed, nitrogen gas is supplied to the upper space of the mixed solution 401, and the mixed solution 401 is Pressed towards layer 1 of 110.

  After the above processing was completed, the second layer 120 was formed on the first layer 110 as shown in FIG.

(3) Production of third layer In the same manner as above, quaternized chitosan which is polycation compound 310 (a product obtained by ionizing quaternary ammonium ion of chitosan manufactured by Nihon Suisan Co., Ltd. by a known method) 1.01 g And a first aqueous solution prepared by dissolving 11.2 g of sodium bromide (primary reagent, manufactured by Wako Pure Chemical Industries, Ltd.), a polyion complex formation inhibitor, in 100 g of acetate buffer (pH 5.9). . Further, 1.01 g of sodium carboxymethyl cellulose (primary reagent manufactured by Wako Pure Chemical Industries, Ltd.) which is a polyanion compound 320, and sodium bromide (primary reagent manufactured by Wako Pure Chemical Industries, Ltd.) 11 which is a polyion complex formation inhibitor 11 A second aqueous solution prepared by dissolving 2 g in 100 g acetate buffer (pH 5.9) was prepared. Then, α-amylase (primary reagent, manufactured by MP Biomedicals), which is the catalyst 220, was added to the aqueous solution obtained by mixing the first aqueous solution and the second aqueous solution to prepare a mixed solution 402.

  As shown in FIG. 8, after the mixed solution 402 is put into an ultrafiltration device (made by Advantech Toyo Co., Ltd., product name: stirring type ultra holder) 500 in which the second layer 120 is formed, the upper portion of the mixed solution 402 Nitrogen gas was supplied to the space, and the mixed solution 402 was pressed toward the second layer 120.

  After the completion of the processing, a third layer 130 was formed on the second layer 120 as shown in FIG. Next, 20 g of acetate buffer solution is charged into the ultrafiltration device 500, then nitrogen gas is supplied to the upper space of the acetate buffer solution, and the acetate buffer solution is pressed toward the third layer 130 to form the first layer. 110, the second layer 120, and the third layer 130 were permeated with acetate buffer. As a result, a fixed catalyst membrane 102 having a three-layer structure was obtained. The immobilized catalyst membrane 102 was used in a wet state without being dried.

<Decomposition of substrate using immobilized catalyst membrane>
As shown in FIG. 23, the immobilized catalyst membrane 102 was set in an ultrafiltration device (manufactured by Advantech Toyo Co., Ltd., product name: stirring type ultra holder) 500. Moreover, the starch aqueous solution 700 of pH 5.9 was prepared. Starch (Wako Pure Chemical Industries, Ltd., first grade reagent) 710 as a substrate was added to 10% by weight with respect to the whole starch aqueous solution. The starch aqueous solution 700 is put into the ultrafiltration device 500, and nitrogen gas is supplied to the upper space of the starch aqueous solution 700 to press the starch aqueous solution 700 against the immobilized catalyst membrane 102 at a pressure of 0.2 MPa, thereby fixing the starch aqueous solution 700. The catalyst catalyst 101 was permeated. At this time, the temperature of the starch aqueous solution 700 was adjusted to 30 ° C. As a result, starch 710 is decomposed by α-amylase in the third layer 130 to generate maltose 711 and glucose 712, and maltose 711 is decomposed by maltase in the second layer 120 to generate glucose 712. The glucose was decomposed by baker's yeast in the first layer 110 to produce ethanol (see FIG. 24).

  An immobilized catalyst membrane was obtained in the same manner as in Example 1 except that the catalyst 200 was replaced with urease (Funakoshi Co., Ltd., first grade reagent). Moreover, 0.15 weight% urea aqueous solution (pH 7.4) was prepared. And as FIG. 13 shows, it carried out similarly to Example 1, and the urea aqueous solution was osmose | permeated to the fixed catalyst membrane. As a result, urea was decomposed by urease in the immobilized catalyst membrane, and carbon dioxide and ammonia were generated.

In addition, the ammonia concentration in the liquid on the secondary side (solvent permeation side) of the immobilized catalyst membrane was quantified by a calibration curve method using high performance liquid chromatography (manufactured by Shimadzu Corporation). The measurement conditions were as follows.
・ Liquid feeding unit: LC-10AD VP
Column oven: CTO-10A VP
・ Degasser: DGV-12A
-Differential refractometer detector: RID-10A
Column name: Asahipak NH2P-50 4E (manufactured by Showa Denko KK)
・ Mobile phase: 75 wt% acetonitrile aqueous solution ・ Mobile phase speed: 1 mL / min ・ Ambient temperature: 30 ° C.

(Reference Example 4)
A urea aqueous solution was obtained in the same manner as in Reference Example 1 except that the substrate was changed to urea (manufactured by Wako Pure Chemical Industries, Ltd., first grade reagent). Then, urease (manufactured by Funakoshi Co., Ltd.) was added to the urea aqueous solution, and the urea aqueous solution was left at 30 ° C. as in Reference Example 1. As a result, urea was decomposed by urease to generate carbon dioxide and ammonia.

100, 100a, 100b, 101, 101a, 102 Immobilized catalyst membrane 200, 210, 220 Catalyst 300 Polyion complex 310 Polycation compound 320 Polyanion compound 400, 401, 402 Mixed solution (first solution, second solution, third solution )
600 Ultrafiltration membrane (membrane)
710 Starch (substrate)

Claims (6)

A first preparation step of preparing a first solution in which at least a catalyst, a polycation compound, a polyanion compound, and a polyion complex formation inhibitor are dissolved in a solvent;
The first solution is supplied to the membrane, the polyion complex formation inhibitor and the solvent in the first solution are selectively permeated through the membrane, and the polycation compound and the polyion compound comprising the polyion compound are formed on the membrane. And a membrane forming step of forming an immobilized catalyst membrane in which the catalyst is immobilized in a complex. In the first preparation step, a plurality of the first solutions containing different kinds of the catalysts are prepared,
In the film forming step, after the formation of the nth immobilized catalyst layer, the first solution is supplied onto the nth immobilized catalyst layer, and the polyion complex formation inhibitor in the first solution and The solvent is selectively permeated to form an (n + 1) th immobilized catalyst layer on the nth immobilized catalyst layer, thereby forming a multilayered immobilized catalyst membrane. 2. The method for producing an immobilized catalyst membrane according to 1. An immobilized catalyst membrane in which the catalyst is immobilized on the polyion complex so that the catalyst is ubiquitous in the polyion complex. The immobilized catalyst membrane according to claim 3, which has a multilayer structure, and the different kinds of catalysts are immobilized in the polyion complex of at least two layers. A second preparation step of preparing a second solution containing at least one substrate;
A first membrane permeation for discharging the final product out of the immobilized catalyst membrane while supplying at least one of decomposition of the compound and synthesis of the compound by supplying the second solution into the immobilized catalyst membrane according to claim 3. A membrane permeation reaction method comprising a reaction step. A third preparation step of preparing a third solution containing at least one kind of substrate;
A second product is discharged to the outside of the immobilized catalyst membrane while supplying the third solution into the immobilized catalyst membrane according to claim 4 and continuously decomposing or synthesizing the compound in each layer. A membrane permeation reaction method comprising a membrane permeation reaction step.

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