JP2001233681A - Highly selective bioreactor using porous ceramics membrane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To develop both a ceramics membrane having composite functions for holding concentrating functions of a raw material, chemical converting functions of the raw material and separating functions of the produced material from the raw material system which are ideal functions required for the ceramics membrane used in a reactor at respective high levels and a highly selective bioreactor using the ceramic membrane. SOLUTION: This porous ceramics membrane is characterized by having a structure in which a ceramics thin membrane having >=0.005 μm pore diameter, 100-1,000 m2/g specific surface area and <=0.01 mm membrane thickness is formed on a ceramics supporting membrane having 0.001-10 μm pore diameter, 1-100 m2/g specific surface area and 0.1-10 mm membrane thickness. The highly selective bioreactor comprises the above porous ceramics membrane as a chemical converting part, a raw material liquid feeding part for feeding the raw material liquid to the chemical converting part and a produced substance collecting part for collecting the produced substance from the chemical converting part.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a porous ceramic film having a structure in which a ceramic thin film is formed on a ceramic supporting film, and a highly selective bioreactor using the porous ceramic film. More specifically, the present invention relates to a highly selective bioreactor which can be suitably used for a highly durable and highly selective separation membrane, a chemical converter, and the like, and a porous ceramic membrane used for the bioreactor.

[0002]

2. Description of the Related Art Conventionally, a porous ceramic membrane has a function of separating gaseous and liquid substances by utilizing its structural characteristics.
It has been developed mainly for the function of carriers such as catalysts and enzymes, and its application to durable and selective separation membranes and chemical reactors has been studied.

As an application to a separation membrane, see, for example,
In Japanese Patent No. 239674, a porous ceramic membrane useful as a gas separation membrane having a small pressure loss and a small clogging is provided. However, this dense ceramic film pursues a function of separating gas depending on the size of pores in the film, and is not suitable for application to a chemical reactor.

Further, as an application to a chemical reactor having a separation function, for example, Japanese Patent Application Laid-Open No. 9-301789 discloses a high porosity, a large specific surface area, excellent gas permeation performance, and protein and CO ₂ gas. Excellent adsorption properties,
Ceramic membranes useful as catalyst carriers for filters, gas separation membranes, bioreactors, and the like have been provided.
However, this ceramic membrane has only a gas separation function and a catalyst carrier function. When the ceramic membrane is used in a reactor, the raw material cannot be concentrated from the raw material system, and is generated by a chemical reaction by the catalyst. The resulting product cannot be separated from the raw material system. Therefore, it is necessary to design the enrichment section and the product separation / recovery section of the raw material separately from the design of the reactor.

[0005] Manufacturing processes by a chemical reaction are roughly classified into an upstream process, a chemical reaction process (reactor), and a downstream process. In the upstream process, materials and catalysts are mainly adjusted, and in the chemical reaction process, an optimum reaction is performed. Conditions and equipment operating conditions are set, and separation and purification and quality adjustment are performed in downstream processes. Therefore, the optimization design of these entire processes is very important and requires considerable time and effort. However, if the reactors responsible for the chemical reaction process have the functions of the upstream and downstream processes at the same time, it will be very useful in designing the system of the chemical reaction process. Therefore,
In recent years, development of an ideal highly selective reactor having these combined functions has been awaited.

As described above, the ideal functions required for the ceramic membrane provided to the reactor include a function of concentrating the raw material, a function of converting the raw material chemically, and a function of separating the generated material from the raw material system. Is thought to be useful for the complex function of retaining each at a high level. However, it is difficult to develop a ceramic film having this composite function, that is, a so-called highly selective ceramic film, and at present, the highly selective ceramic film has hardly been developed.

[0007]

SUMMARY OF THE INVENTION The present invention relates to an ideal function required for a ceramic film to be provided to a reactor, a function of concentrating a raw material, a chemical conversion function of a raw material, and a raw material system of a generated material. The purpose of the present invention is to develop a ceramic membrane having a composite function of maintaining the separation function of each at a high level, and a highly selective bioreactor using the ceramic membrane.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a specific pore size,
A porous ceramic membrane having a structure in which a ceramic thin film having a specific pore diameter, a specific surface area and a thickness is formed on a ceramic support membrane having a specific surface area and a thickness is developed, and the surface of the ceramic support membrane and / or Alternatively, when the enzyme is supported on the inner surface of the pores, and the surface of the ceramic thin film and / or the inner surface of the pores are subjected to a hydrophilic or hydrophobic treatment as necessary, a ceramic film having a composite function is obtained. A completely new fact has been found that the ceramic membrane has a composite function of maintaining a high level of the function of concentrating the raw material, the function of chemically converting the raw material, and the function of separating the product from the raw material system. Furthermore, it has been found that a highly selective bioreactor can be obtained when this ceramic membrane is used, and the present invention has been completed.

That is, the present invention provides (1) a pore diameter of 0.001 to 10 μm and a specific surface area of 1 to 100 m
² / g, on a ceramic support membrane having a thickness of 0.1 to 10 mm, a pore diameter of 0.005 μm or less and a specific surface area of 100 to 1000
a porous ceramic film having a structure in which a ceramic thin film having a m ² / g and a film thickness of 0.01 mm or less is formed, (2) an enzyme is formed on the surface of the ceramic support film and / or the inner surface of the pores. The porous ceramic according to the above (1), which is carried, and the enzyme is at least one selected from the group consisting of an oxidoreductase, a transferase, a hydrolase, a removal addition enzyme, an isomerase and a synthetic enzyme. A membrane, (3) a ceramic supporting membrane having a function of concentrating the raw material from a liquid containing the raw material and a function of chemically converting the raw material by an enzyme carried on the surface and / or the inner surface of the pores. (4) The porous ceramic film according to the above (1) or (2), which has one or more functions selected from a group.
The porous ceramic film according to any one of the above (1) to (3), wherein the ceramic thin film has a function of concentrating and separating a product after the chemical conversion of the raw material from a liquid containing the raw material, and (5) a surface of the ceramic thin film. And / or the porous ceramic membrane according to any one of the above (1) to (4), wherein the inner surface of the pore is hydrophobic or hydrophilic; (6) the ceramic supporting membrane is made of glass, alumina, silica, zirconia, zeolite, The porous ceramic film according to any one of (1) to (5), which is at least one selected from the group consisting of titania, ceria, and zinc, and (7) the ceramic thin film is made of glass, alumina, silica, zirconia, zeolite, or titania. The porous cell according to any one of (1) to (6) above, which comprises at least one member selected from the group consisting of, ceria, zinca, and xerogels thereof. A mixed film, and (8) a raw material liquid supply unit for supplying the raw material liquid to the chemical conversion unit, wherein the porous ceramic film according to any one of the above (1) to (7) is a chemical conversion unit, and the chemical conversion unit The present invention relates to a highly selective bioreactor comprising a product recovery section for recovering a product from the section.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The porous ceramic film of the present invention comprises a ceramic support film and a ceramic thin film. FIG. 1 is a schematic explanatory view showing the structure of the film cross section.

As shown in FIG. 1, a ceramic thin film 2 is formed on a ceramic support film 1. The vicinity of the interface between the ceramic thin film 2 and the ceramic support film 1 is a composite system or a mixed system of both, thereby maintaining the strength of the porous ceramic film.

In the porous ceramic membrane shown in FIG. 1, reference numeral 3 denotes a supported enzyme, but the supporting position and the supporting amount are not limited to the illustrated state.

The material of the ceramic support film 1 is not particularly limited, but typical examples thereof include a clay (silicate) type,
Examples include oxide minerals, oxides, carbides, nitrides, borides, and silicides. Among them,
For example, at least one selected from the group consisting of glass, alumina, silica, zirconia, zeolite, titania, ceria, and zinca is preferable. These may be mixtures or composites.

The pore size of the ceramic support membrane 1 is 0.001 to 10 μm, preferably 0.005 to 10 μm, from the viewpoint of controlling the enzyme loading and ensuring the strength of the ceramic support membrane 1.

[0015] The specific surface area of the ceramic support layer 1, from the viewpoint of ensuring strength of carrying control and ceramics support film 1 enzyme, 1 to 100 m ² / g, preferably 5 to 100 m ² / g
It is said.

The thickness of the ceramic support film 1 is 0.1 to 10 m from the viewpoint of securing the strength of the ceramic support film 1.
m, preferably 0.2 to 10 mm.

The shape of the ceramic support film 1 is not particularly limited and is arbitrary. Examples of the shape include a tubular shape, a plate shape, a rod shape, and a fiber shape.

The ceramic support film 1 can be easily manufactured by a usual ceramic manufacturing method such as a solid phase method, a liquid phase method, and a gas phase method, and the present invention is limited by such a manufacturing method. Not something.

In consideration of cost, ease of use, ease of manufacture, chemical conversion efficiency, etc., the ceramic support film 1 is made of, for example, a ceramic tube or plate made of a material such as glass, alumina, silica, or zirconia. , Rods, fibers and the like.

The ceramic support membrane 1 has a function of concentrating the raw material from a liquid containing the raw material and a function of chemically converting the raw material by an enzyme carried on the surface and / or the inner surface of the pores. It preferably has one or more functions selected from the following. These functions can be easily imparted to the ceramic support film 1 by chemically controlling the surface and / or the inner surface of the pores in the ceramic support film 1 so as to be easily compatible with the raw material substrate, or by carrying an enzyme. it can.

An enzyme may be carried on the surface of the ceramic support film 1 and / or the inner surface of the pores. The method for supporting the enzyme is not particularly limited. As a typical example,
(1) A method in which a porous ceramic film is immersed in a liquid in which an enzyme is dispersed, and the liquid is sucked from the ceramic thin film 2 side, whereby the enzyme is supported on the ceramic support film 1. (2) The enzyme is dispersed. A method in which a porous ceramic film is immersed in a liquid, and an enzyme is supported on the ceramic support film 1 by using a chemically modified group such as a cross-linker agent attached to the ceramic support film 1 is used.

The type of the enzyme is not particularly limited. Among them, one or more selected from the group consisting of oxidoreductases, transferases, hydrolases, elimination addition enzymes, isomerases and synthases are preferred. In addition, the enzyme may be appropriately used in combination with the coenzyme.

The amount of the enzyme carried on the surface of the ceramic support membrane 1 and / or the inner surface of the pores may be determined appropriately from the viewpoint of controlling the chemical conversion.

It is preferable that the ceramic thin film 2 has a function of concentrating and separating the product after the chemical conversion of the raw material from the liquid containing the raw material from the viewpoint of reducing the concentration cost in adjusting the concentration of the raw material.

The material of the ceramic thin film 2 is not particularly limited. Typical examples thereof include clay (silicate), oxide mineral, oxide, carbide, nitride, boride, and silicide. And the like. Among them, one or more selected from the group consisting of glass, alumina, silica, zirconia, zeolite, titania, ceria, zinca and their xerogels are preferred, and glass, alumina, silica, zirconia, zeolites and their xerogels One or more selected from the group consisting of is more preferable in terms of cost, ease of use, ease of production, reaction efficiency, and the like. These may be mixtures,
Alternatively, it may be a composite.

The pore diameter of the ceramic thin film 2 is preferably 0.005 μm or less in view of the relationship between the molecular size of the product substance after chemical conversion and the molecular size of the raw material substrate.
In particular, in consideration of a substance generating an acid or an alkali having a small molecular weight, the pore diameter of the ceramic thin film 2 is preferably 0.002 μm or less.

The specific surface area of the ceramic thin film 2 is 100 to 1000 from the viewpoint of controlling the permeation of the formed material and the liquid medium molecules of the raw material.
m ² / g, and preferably from 150 ~1000m ² / g.

The thickness of the ceramic thin film 2 is set at 0.01 mm from the viewpoint of controlling the transmission of the formed substance and the liquid medium molecules of the raw material.
The following is preferred.

The ceramic thin film 2 can be easily manufactured by, for example, an ordinary ceramic manufacturing method such as a solid phase method, a liquid phase method, and a gas phase method. However, the present invention is not limited by such a manufacturing method.

The determinant of the separation ability of the ceramic thin film 2 mainly depends on the state of its surface, its pore diameter, and its inner surface. Therefore, it is desirable to control the pore size in accordance with the size of the molecule through which the product substance after chemical conversion by the enzyme passes.

The surface of the ceramic thin film 2 and / or the inner surface of the pores are not particularly limited, but are preferably hydrophobic or hydrophilic.

Examples of the hydrophobic group include chain and cyclic hydrocarbon groups, aromatic hydrocarbon groups, halogenated alkyl groups,
Examples include an organosilicon group (—Si (R) ₃ groups, R: an alkyl group), a fluorocarbon group, and the like.

Examples of the hydrophilic group include a —COOH group and a —OH
Group, -NH_TwoGroup, -NHCONH_TwoGroup,-(OCH_TwoCH _Two)_n-Group (n is an integer
Number, n ≧ 1), -SO_ThreeH group, -SO_ThreeM group (M is an alkali metal
Or ammonium group), -OSO_ThreeH group, -OSO_ThreeM group (M is
Same as above), -COOM group (M is the same as above), -N (R)_ThreeX group
(R is an alkyl group, X is a halogen) and the like.

When the surface of the ceramic thin film 2 and / or the inner surface of the pores are made hydrophobic, it is preferable to adopt a method of performing a surface treatment using a compound having a hydrophobic group such as an organosilicon compound. If it is hydrophilic,
It is preferable to employ a method of performing a normal chemical surface treatment using a compound having a hydrophilic group.

There are no particular restrictions on the types of raw materials applicable to the porous ceramic film of the present invention, and various synthetic chemicals and natural chemicals can be used. These raw materials need only be dispersed or dissolved in water, an organic solvent, oil, or the like. Note that the raw material is preferably used in a raw material liquid such as a solution or a dispersion.

When the raw material is used as the raw material liquid, the generated substance after the chemical conversion of the raw material substrate is the ceramic thin film 2
After passing through the ceramic thin film 2 after being concentrated and separated from the raw material liquid, it is obtained together with the liquid medium contained in the raw material liquid.

FIG. 2 is a schematic explanatory view showing one embodiment of the configuration of the highly selective bioreactor using the porous ceramic membrane of the present invention, but the present invention is not limited to only such an embodiment. .

As shown in FIG. 2, in the highly selective bioreactor of the present invention, a porous ceramic membrane is used as a chemical conversion section 6, a bioreactor main section 7 is used as a main section, and a raw material liquid is used as a chemical conversion section. A raw material liquid supply unit 4 for supplying the raw material liquid to the chemical conversion unit 6 and a generated material recovery unit 9 for recovering the generated material from the chemical conversion unit 6.

The raw material liquid supply section 4 stably supplies the raw material liquid to the main part 7 of the bioreactor, and may have any function as a raw material liquid storage tank and a liquid feeding function, and is not particularly limited. . Typical examples thereof include a tube pump and a line pump. It is preferable that the raw material liquid supply section 4 is provided with a constant flow control function, a stirring function, a liquid temperature control function, a pH control function, a circulating liquid receiving tank function, and the like.

The raw material liquid supply unit 4 is connected via a raw material liquid supply line 5 to a chemical conversion unit 6 mainly composed of a porous ceramic film.

The raw material liquid supply line 5 is not particularly limited as long as it can transfer the raw material liquid stably. The raw material liquid supply line 5 may be provided with a liquid temperature maintaining function, a liquid temperature / flow rate monitoring function, and the like.

The chemical conversion section 6 may be the same as the porous ceramic film, but it is preferable to use a plurality of, multiple or multiple porous ceramic films as necessary.

The type of the bioreactor main part 7 is not particularly limited. It is preferable that the bioreactor main part 7 has a built-in chemical conversion part 6 and has a monitor and control function such as a liquid temperature, a flow rate, a pH, and a stirring of a raw material liquid, a raw material circulating liquid, and a product recovery liquid.

Since the bioreactor main part 7 can be operated in a continuous, batch or semi-batch mode, it is preferable that the bioreactor has its operation control function.

The recovered liquid obtained in the main part 7 of the bioreactor is passed through a product recovery line 8 to a product recovery part 9.
Is transferred to

The product recovery line 8 is not particularly limited as long as it can stably transfer the recovery liquid. The product substance recovery line 8 may be provided with a function of maintaining a liquid temperature, a function of monitoring a liquid temperature / flow rate, and the like.

The product recovery section 9 can stably store the recovered liquid, and is not particularly limited as long as it has a recovered liquid storage tank function and a liquid receiving / sending function. Typical examples thereof include a tube pump and a line pump. It is preferable that the product recovery section 9 further has a constant flow rate control function, a stirring function, a liquid temperature control function, a pH control function, and the like.

The recovered liquid from the main part 7 of the bioreactor is supplied to the raw liquid supply section 4 through the raw liquid circulation line 10.
Is transferred to

The raw material liquid circulation line 10 is not particularly limited as long as it can transfer the recovered liquid after the raw material supply to the raw material liquid supply section 4 stably. The raw material liquid circulation line 10 may be provided with a liquid temperature maintaining function, a liquid temperature / flow rate monitoring function, and the like.

[0050]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to only these examples.

Production Example 1 [Production of Porous Ceramic Film] A solution prepared by adding 20 mol of ethanol, 0.01 mol of hydrochloric acid, and 2 mol of water to 1 mol of tetraethylsilicate.
100 mL was stirred at room temperature for 8 hours to obtain a homogeneous solution.

A porous glass tube having one end sealed (outer diameter 5 mm, inner diameter 4 mm, length 100 mm, thickness 100 mm) was added to the obtained solution.
0.5 mm, average pore diameter 4 nm, specific surface area 95 m ² / g), dip-coated at a pulling rate of 2 mm / s,
After drying at room temperature for 1 hour, the coating was dried at 150 ° C. for 2 hours at a rate of 0.5 ° C./min in order to age the obtained coating film. The same operation was repeated three times to form a xerogel thin film having a thickness of about 1 μm on the outer surface of the porous glass tube.

The physical properties of the xerogel thin film were determined by BET
As a result of using a specific surface area measuring device (nitrogen adsorption method),
It was found that the average pore diameter was about 1 nm, the specific surface area was 500 m ² / g, and the film thickness was 1.1 μm.

Next, in order to impart separability to the xerogel thin film, a hydrophobic treatment was performed on the surface of the thin film and the inner surface of the pores by using dimethyloctylchlorosilane and reducing in toluene with pyridine as an acceptor. Was given.

Next, an N-hydroxysuccinimide (NHS) active ester group for the purpose of enzyme immobilization reaction was introduced as a crosslinker agent into the porous glass support membrane. Furthermore, 10 mg of aldehyde dehydrogenase (EC 1.2.1.5), which is an enzyme extracted and purified from yeast and having a specific activity of about 20 U / mg enzyme protein, was suspended in 1 mL phosphate buffer (pH 6.5). The suspension was added to the porous glass support membrane and incubated at room temperature for 30 minutes.

After the completion of the reaction, the membrane was washed with a phosphate buffer, and this porous ceramic membrane was used as a chemical conversion section for aldehyde conversion.

Production Example 2 [Production of highly selective bioreactor] The porous ceramics membrane obtained in Production Example 2 was used as a chemical conversion part. As a raw material liquid supply unit, a combination of a 1 L flask (fixed in a thermostat) with a tube pump and a flow meter was used. As the bioreactor, a combination of a thermometer, a pH meter, and a flow meter in the chemical conversion section (fixed in a thermostat) was used. In addition, as a constant temperature product recovery part, a 500 mL flask (fixed in a constant temperature bath) combined with a tube pump was used.

A silicon tube (outer diameter: 6 mm,
Using an inner diameter of 4 mm), each component was connected so as to have the configuration shown in FIG. 2 to produce a highly selective bioreactor.

Example 1 [Production of acetic acid aqueous solution] As a raw material solution, a phosphate buffer aqueous solution containing 100 mM of acetaldehyde (pH 8.0, 100 mM NAD as a coenzyme) was used.
Use) 500mL, liquid temperature 25 ℃, liquid flow rate 1.25mL / m
Under the conditions of pH 8.0 (adjusted with sodium hydroxide), continuous steady operation was performed using the bioreactor manufactured in Production Example 2.

As a result of performing the continuous steady operation for 6 hours, a colorless and transparent liquid was obtained. About 100 mL of the liquid was collected and analyzed by gas chromatography.
M acetic acid aqueous solution was detected.

This indicates that the highly selective bioreactor obtained in Production Example 2 can easily produce an aqueous acetic acid solution from an aqueous acetaldehyde solution.

Example 2 [Production of Propionic Acid Aqueous Solution] In Production Example 1, when producing a porous ceramics membrane which is a chemical conversion part of a highly selective bioreactor, in order to impart separation ability to a xerogel thin film, Production Example 1 except that the surface of the xerogel thin film and the inner surface of the pores were subjected to a hydrophobic treatment by reducing in toluene using dimethyldodecylchlorosilane with pyridine as an acceptor.
In the same manner as described above, a porous ceramic film carrying an enzyme was produced.

A highly selective bioreactor was produced in the same manner as in Production Example 2 using the obtained porous ceramic membrane as a chemical conversion part.

As a raw material liquid, propionaldehyde was added to 10
0 mM phosphate buffer solution (pH 8.0, as coenzyme)
Using 500 mL of 100 mM NAD), a continuous steady-state operation was performed using the highly selective bioreactor under the conditions of a liquid temperature of 25 ° C., a liquid flow rate of 1.25 mL / min, and a pH of 8.0 (adjusted with sodium hydroxide). went.

As a result of continuous continuous operation for 6 hours, a colorless and transparent liquid was obtained. About 100 mL of the liquid was collected and analyzed by gas chromatography.
M aqueous propionic acid solution was detected.

From this, it is understood that the aqueous solution of propionic acid can be easily produced from the aqueous solution of acetaldehyde by the highly selective bioreactor.

Example 3 [Production of butyric acid aqueous solution] In Production Example 1, when producing a porous ceramic membrane which is a chemical conversion part of a highly selective bioreactor, xerogel was added to impart a separating ability to the xerogel thin film. Enzyme-supporting porous ceramics in the same manner as in Production Example 1, except that the surface of the thin film and the inner surface of the pores were subjected to a hydrophobic treatment using dimethylpentadecylchlorosilane using pyridine as an acceptor and reduced in toluene. A film was prepared.

Using the obtained porous ceramics membrane as a chemical conversion part, a highly selective bioreactor was produced in the same manner as in Production Example 2.

As a raw material liquid, butyric aldehyde was
0 mM phosphate buffer solution (pH 8.0, as coenzyme)
Using 500 mL of 100 mM NAD), a continuous steady operation was performed using the highly selective bioreactor under the conditions of a liquid temperature of 25 ° C., a liquid flow rate of 1.25 mL / min, and a pH of 8.0 (adjusted with NaOH). .

As a result of continuous continuous operation for 6 hours, a colorless and transparent liquid was obtained. About 100 mL of the liquid was collected and analyzed by gas chromatography.
M butyric acid aqueous solution was detected.

From this, it is understood that this highly selective bioreactor can easily produce an aqueous butyric acid solution from an aqueous butyric aldehyde solution.

[0072]

According to the highly selective bioreactor using the porous ceramic membrane of the present invention, the function of concentrating the raw material, the function of chemically converting the raw material with various supported enzymes, and the formation of the product can be obtained. With the function of separating from the liquid containing the raw material, useful chemical substances can be easily and efficiently produced from the liquid containing the raw material, so that it can be produced over a wide range from laboratory scale to industrial scale. It can respond flexibly.

[Brief description of the drawings]

FIG. 1 is a schematic explanatory view showing a cross-sectional structure of a porous ceramic film of the present invention.

FIG. 2 is a schematic explanatory view showing the configuration of a highly selective bioreactor using the porous ceramic membrane of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Ceramic support film 2 Ceramic thin film 3 Supported enzyme 4 Raw material liquid supply part 5 Raw material liquid supply line 6 Chemical conversion part 7 Main part of bioreactor 8 Produced substance recovery line 9 Produced substance recovery section 10 Raw material liquid circulation line

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[Procedure amendment]

[Submission Date] March 3, 2000 (200.3.3)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Name of invention

[Correction method] Change

[Correction contents]

[Title of the Invention The highly selective Baiori actor using a porous ceramic membrane

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Yutaka Nakazono 17 Kandoji Minamicho, Shimogyo-ku, Kyoto Inside Kansai New Technology Research Institute Co., Ltd. F term in the new technology research institute (reference) 4B033 NA01 NA23 NA25 NA26 NA34 NA35 NA37 NB04 NB15 NB22 NB24 NB25 NB26 NB27 NB64 NB68 NC03 NC12 ND02 NE05 4D006 GA02 HA21 JA02C JA53A KE02Q KE15Q KE16Q MA02 MA03 MA03 MB03 NA46 NA59 NA64 PC67 4D019 AA01 AA03 BA05 BB07 BB10 BC13 BC20 CA03 CB04 4G019 FA11 FA13 4G075 AA24 AA30 BD14 BD16 CA57 FA12 FA14 FB04 FC02

Claims (8)

[Claims] 1. A fine particle having a pore diameter of 0.001 to 10 μm and a specific surface area of 1
To 100 m ² / g, the thickness of the ceramic support layer is 0.1 to 10 mm, pore size 0.005 [mu] m or less and a specific surface area of 10
A porous ceramic film having a structure in which a ceramic thin film having a thickness of 0 to 1000 m ² / g and a thickness of 0.01 mm or less is formed. 2. An enzyme is carried on the surface of the ceramic support membrane and / or the inner surface of the pores, and the enzyme is selected from oxidoreductases, transferases, hydrolases, elimination addition enzymes, isomerases and synthases. The porous ceramic film according to claim 1, which is at least one member selected from the group consisting of: 3. The ceramic supporting film has a function of concentrating a raw material from a liquid containing the raw material,
3. The porous ceramic film according to claim 1, having at least one function selected from the group consisting of a function of chemically converting a raw material by an enzyme carried on the inner surface of the pore. 4. The porous ceramic film according to claim 1, wherein the ceramic thin film has a function of concentrating and separating a product obtained by chemical conversion of the raw material from a liquid containing the raw material. 5. The porous ceramic film according to claim 1, wherein the surface of the ceramic thin film and / or the inner surface of the pores are hydrophobic or hydrophilic. 6. The porous ceramic film according to claim 1, wherein the ceramic support film is made of at least one selected from the group consisting of glass, alumina, silica, zirconia, zeolite, titania, ceria, and zinc. 7. The porous film according to claim 1, wherein the ceramic thin film is made of at least one selected from the group consisting of glass, alumina, silica, zirconia, zeolite, titania, ceria, zinca, and xerogels thereof. Ceramics film. 8. A raw material liquid supply unit for supplying the raw material liquid to the chemical conversion unit using the porous ceramic film according to claim 1 as a chemical conversion unit, and a substance produced from the chemical conversion unit. Highly selective bioreactor consisting of a product recovery section for recovering biomass.