KR20030032775A - Manufacturing Method of Silica-Titania Composit Material with Nano sized pore for Protein Immobillization - Google Patents

Abstract

PURPOSE: A fabrication method of silica-titania composite material with nano sized pore for protein immobilization is provided. CONSTITUTION: The method comprises the steps of inputting sodium silicate (SiO2 28.8%, Na2O 0.95%) into a raw material tank(2); inputting solution mixture of TiOCl2 and 18% sulfuric acid into the raw material tank(2); transferring the sodium silicate and the solution mixture to a reaction hopper(4) through a metering pump(3); causing reaction between the sodium silicate and solution mixture in the reaction hopper(4); keeping the reactant in ambient temperature for 6 hours, thereby converting silica-titania sol to hydrogel; crushing the hydrogel to have a size of 2-6 mm; and rinsing the crushed hydrogel using water with pH 3.8 at 23°C for 10 hours.

Description

Manufacturing Method of Silica-Titania Composit Material with Nano sized pore for Protein Immobillization

The present invention relates to a method for preparing a composite material for a silica-titania biocatalyst carrier having a nanoporous structure, and more particularly, to prepare TiOCl ₂ from TiCl ₄ , H ₂ O, and HCl, to prepare a mixed solution with sulfuric acid, The sol obtained by reacting with an aqueous alkali solution was gelled at a temperature of about 20-80 ° C., and the obtained hydrogel was washed with water at a pH of about 3-9.5, washed with acid, alkali or neutral distilled water, and the surface area of the composite material and After controlling the pore volume, it is dried in the range of 150-250 ° C. and then pulverized to prepare a silica-titania composite material for a biocatalyst carrier of coarse or fine powder.

In addition, the present invention is characterized by a method capable of synthesizing a porous composite material having a nanoporous structure using a relatively inexpensive raw material. The method for producing the silica-titania composite material of the present invention provides a uniform porous inorganic material as compared to the material by the particle filling method currently used as a biocatalyst carrier, the sol-gel method as an expensive starting material, the porous body produced by the sponge, and the like. The carrier material according to the present invention can be used as a ceramic carrier for wastewater treatment, an immobilized carrier for aerobic and anaerobic microorganisms, a biological carrier for wastewater purification, and a ceramic porous high surface area carrier for photocatalysts.

As described above, the silica-titania composite material is used for various purposes, and in particular, it is widely used as a lightweight filler for additive printing paper, an additive, a catalyst of petrochemical industry (some titania supporting method), and the like. However, there have been many inventions related to the preparation of catalyst carriers using silica alone, but a method synthesized by inexpensive silicate and sol-gel reaction using a mixed inorganic acid, in particular, an inorganic acid mixture (TiOCl ₂ + H ₂ SO ₄ ) and silicate The production of biocatalyst carriers by sol-gel reaction with is not reported.

As a prior art, Japanese Patent No. 6-298520 (1994) discloses a method of preparing ultrafine particles of silica-titanium oxide by dispersing ultrafine titanium oxide particles into silica colloids, then gelling the colloids and then grinding them. By using the ultrafine particles of titanium, it is impossible to control uniform pore of the composite material of silica-titanium oxide. Because titanium oxide made of powder is in the form of fine particles, it cannot be hydrogel, and in the sol-gel reaction, there is a problem in that the pores cannot be controlled by polymerization conditions. This is because pore control is impossible from the Xerogel phase powder which has become a network structure.

In addition, Japanese Patent 3-296435 (1991) synthesizes a matrix of silica having a specific surface area of 30-800 m 3 / g, pore volume of 0.3-2.0 ml / g, and an average pore diameter of 80-1000 mm 3, and then titanium oxide is deposited on the surface thereof. By supporting it, it can be seen that silica and titania are not uniformly made of a composite material.

Bio-conversion system using enzymes can suppress the generation of pollutants in an environment-friendly way compared to chemical methods, and research is being conducted at home and abroad due to various beneficial effects such as simplifying the manufacturing method and reducing costs in production. As a material required for this study, a porous ceramic carrier is needed. Here, there are various conditions for the ceramic carrier, but control of surface area, pore, pore volume, oil absorption, etc. is important, and an invention satisfying these conditions is required.

Currently used porous ceramic support for immobilization has the following types and features, but is not made of a composite material to be achieved in the present invention.

Manufacturing method Characteristic General physical properties Particle Filling Method Simple manufacturing process, processing size is influenced by the size of raw material particles, economical, high temperature sintering furnace, poor processing and poor porosity control · Porosity within 40% · Formation of pore size · Pore size is adjusted to the size of the pterosaur particle Sol-gel method High homogeneity and high purity of raw materials, high cost of raw materials, complicated manufacturing process, and handling of organic solvents 50-60% porosity Precursor or sponge method · Simple process and economical · Easy pore formation but low strength of final product · Pore characteristics depend on type of combustible material · Porosity of around 70% · Pore size is controlled by kinds of strong substance (several tens to hundreds of ㎛) Foam Easy to adjust porosity and pore size Representative porous body manufacturing method -Porosity of around 80%, Pore size can be adjusted by the type of additive (tens-hundreds of ㎛) Polymer Sponge Method Complex manufacturing and manufacturing process of reticulated ceramics Porosity 85% or more Pore size nm

As can be seen from the above, there are no carriers of composite materials having fine pores of about 3-80 nm in pore size and are currently produced and researched for biocatalytic porous carriers. There is a need for the invention of a composite inorganic material having a pore distribution on the order of 3-80 nm, which is required in the wastewater treatment industry, environmental industry, medicine, pharmaceutical industry, and bio-related industries.

Therefore, the present invention is used as a bio-immobilized carrier by physically trapping the cells in the porous carrier or by treating a functional group such as hydroxyl group (-OH group) on the surface with a chemical agent such as cyanide bromide (CNBr), or having an amine group on the inorganic porous carrier. Used by treating with silane. However, various carriers which have been used as inorganic porous carriers until now have to satisfy the following conditions, but until now, porous carriers satisfying the following contents have not been invented and only partially satisfy their physical properties.

1. How porosity does the material have?

2. Does the porous material have a morphology that allows enough organisms to immobilize, such as enzymes, into the porosity?

3. Do the carrier materials used have sufficient durability against acids, alkalis, atmospheres with high concentrations of salts, organic solvents, etc.?

4. Is the carrier material convenient for use?

5. Does the carrier material have high compressive strength?

6. Can I carry enough biological material such as enzymes per unit volume?

7. Is the carrier material able to withstand the maximum pressure loss?

8. Do these factors affect the particle size and shape of the carrier?

9. Is the supply and storage of carrier material easy?

However, there is currently no material that can satisfy all of the above factors.

The present invention has been made to solve the above-mentioned problems of the prior art and to produce a material that can satisfy all of the various factors described above. It is to provide a manufacturing method of a composite material showing alkali resistance in the region.

The present invention also relates to a method for using a low-cost inorganic salt as a starting material in order to increase alkali resistance among the conventional problems.

In addition, as an alternative to organic and various types of carriers used as biocatalyst carriers, the properties of amorphous silica-titania composites in the synthesis of silica-titania composites are about 60-800㎡ / g and the pore volume is 0.3-2.0ml / It aims at providing the manufacturing method of the composite material which has g and an average pore diameter of 30-100 nm. In general, in the case of a biocatalyst carrier, when the specific surface area is too large, there is a problem in that the pores are too small, and in the case where the pores are too large, there is a problem in that the supporting efficiency per unit area is lowered. Therefore, the present invention synthesizes a silica-titania composite having a pore size of about 3-60 nm to immobilize enzymes in biological industry, fermentation industry, food industry, wastewater treatment industry, environmental industry, medicine, pharmaceutical industry, bio-related industry, etc. It is an object to provide a carrier.

1 is a view showing a schematic configuration of a manufacturing reaction mechanism of the present invention

2 is a measurement rate table by the FT-IR spectrometer

Figure 3 is an electron micrograph of the silica-titania composite of the present invention

<Explanation of symbols for main parts of drawing>

One: TiOCl₂+ H₂SO₄Mixed acid tank

2: Sodium Silicate or Potassium Silicate Mixture Tank

3: metering pump

4: Reactor

5: silica-titania (TiO₂/ SiO₂Composite reactant

The present invention for achieving the above object will be described in detail.

In the present invention, TiOCl ₂ is prepared from TiCl ₄ , H ₂ O, and HCl, and then a mixed solution with sulfuric acid is prepared, and the sol obtained by reacting it with an aqueous alkali silicate solution is gelled at a temperature of about 20-80 ° C. Water-treated under the condition of -9.5, washed with acid, alkali or neutral distilled water to control the surface area and pore volume of the composite material, dried in the range of 150-250 ° C, and then pulverized for biocatalyst carrier A method for producing a silica-titania composite is characterized.

Basic concept of enzyme immobilization, which is a field using a porous biocatalyst carrier prepared by the present invention, relates to a technique for utilizing enzymes in a biochemical process using enzymes, and a technique for improving the biological activity of enzymes and stabilizing its activity. The former has been developed in the field of genetic engineering, while the latter has been developed around immobilization.

An important purpose of immobilizing the enzyme is to improve the economics of the enzyme reaction process because the enzyme can be easily recovered and reused, and the reaction mode can be variously applied in batch or continuous mode. Therefore, in order to effectively use natural enzymes in biochemical processes, the enzymes must be immobilized. The immobilization methods include adsorption, covalent bonding, and polymer confinement. Immobilization by adsorption is to adsorb the enzyme to the carrier, and the structural characteristics of the carrier should be high in adsorption content to the enzyme, small in pore diffusion resistance, and large in binding force to the enzyme, thereby not freeing the enzyme. Immobilization by covalent bonds is a method of covalently bonding the surface of the carrier and the enzyme with a binder or a pier to surface-treat the carrier or to introduce functional groups into the enzyme, and to prevent the active enzymes of the supported enzyme from being blocked.

At present, commercial production has been carried out in such a manner, and the usefulness of porous silica in the type of carrier has already been verified. However, the production of silica-titania composites as inorganic porous carriers used for bioenzyme immobilization has not been reported.

Therefore, in the present invention, a nano-sized pore structure as a biocatalyst carrier material in which an organic or inorganic carrier is used by making a mixed solution of TiOCl ₂ + H ₂ SO ₄ and reacting the mixed solution with an inexpensive inorganic salt (sodium silicate, potassium silicate, etc.) It is to provide a method for producing a silica-titania composite having a.

Hereinafter, the manufacturing method of the present invention will be described in detail.

The present invention prepares TiOCl ₂ from TiCl ₄ , H ₂ O, HCl. This is a method for stabilizing at room temperature as a precursor of TiO ₂ because TiCl ₄ has unstable properties at room temperature. The titania precursor prepared in this manner and sulfuric acid are mixed to prepare the necessary titania precursor mixed material. This is an alternative to the problem that the silica and titania components are not uniformly distributed in the catalyst carrier prepared by conventional silica fine powder or fine powder of titania after forming by binder or other method. 1) is uniformly mixed by the sol-gel process to produce a composite material, so that the distribution of two components of the composite material can be uniformly controlled.

The present invention is a gelling time that can sufficiently control the physical properties during the gelation process of the silica-titania composite material after the reaction by reacting the prepared acid and inorganic salts (sodium silicate, potassium silicate) in an excess acid atmosphere of 0.1N or more. Adjustment can be made arbitrarily. In the sol-gel method, this prevents the silica-titania primary particles from rapidly gelling due to the polymerization reaction in the alkali region, thereby controlling the surface area, the pore volume, the pore diameter, and the like of the target properties.

The silica-titania composite material having a nanostructure prepared in the present invention may be selectively selected from about 1 μm to 5 mm in size, and the surface area is 50-850 m 2 / g, the pore volume is 0.3-2.0 ml / g, and the like. Range. Also, the titania to silica ratio (TiO ₂ / SiO ₂ ) is usually 0.1-28 wt%, most ideally 10-25 wt%.

In the present invention, first, a TiOCl ₂ solution is prepared by mixing TiCl ₄ , H ₂ O, and HCl, and sulfuric acid is mixed therein to react the mixture with an aqueous alkali silicate solution. The aqueous alkali silicate solution used herein is usually sodium silicate or Potassium silicate is used. Its aqueous solution is, for example, 5-28 wt%. The amount of TiOCl ₂ used is determined by the titania ratio (TiO ₂ / SiO ₂ ) to silica of the silica-titania composite material to be prepared. In addition, the concentration of sulfuric acid is about 5-12N. This reaction was usually carried out by dropping a mixed acid in a predetermined amount of alkali silicate aqueous solution in a reactor equipped with a stirring device, but in the present invention, by using a reactor having a structure as shown in FIG. The reaction was carried out in a way that can control the reaction rate to gel in the sol region. At this time, the temperature of the reaction tank passing through the reactor port is 10-60 ℃, the best is to perform at room temperature. Gelation time is related to the concentration of excess acid and the concentration of silica-titania but usually takes at least 6 hours at room temperature. In this reaction, the silica and titania primary particles are uniformly dispersed with each other to obtain a silica-titania sol, and the gelation proceeds slowly to the next step to form a silica-titania hydrogel composite material in about 6 hours. The formed gel-like substance ln ^{_{Na +, Cl -, SO 4}} 2- ion, etc. are present, and by adjusting the temperature and pH of the distilled water by the alkaline or neutral pH approximately 3-5 or acidic pH 8-9.5 area of the silica- It removes ionic materials other than titania and controls pore volume and surface area. The volume, size and surface area of the pores produced in this process were controlled to 200-850 m 2 / g, pore volume of 0.3-2.0 ml / g and the like. In addition, the silica-titania composite prepared for hydrothermal synthesis was heat treated with water in a pressure vessel of 150 ° C. or more to control the surface area of about 50-500 m 2 / gr.

The silica-titania composite material obtained in the present invention is absolutely stable in an acidic atmosphere, and is stable in an alkaline pH range. In addition, the surface area, pore volume, pore volume, and the like can be arbitrarily controlled within the above ranges, so that a predetermined physical property value can be obtained, and thus it can be used as a biocatalyst carrier. In addition, the static durability test was conducted in 1% NaOH aqueous solution compared to the existing porous silica carrier, and it was 1.5mg / m2 / 16hr for silica, while 0.8mg / m2 / 16hr for silica-titania composite material was 1% NaOH. Alkali resistance in aqueous solution was shown to be twice as durable as conventional porous silica.

Hereinafter, various embodiments according to the present invention will be described.

Example 1.

Commercially available sodium silicate No. 3 (molar ratio SiO₂28.8%, Na₂9.5%) is placed in the silicate raw material tank 2 of FIG. TiOCl₂Mixed acid with 18% sulfuric acid is placed in the mixed acid tank (1) of FIG. The control gauge of the homogeneous metering pump (2) (3) was turned through the silicate and mixed acid continuous reactor of FIG. 1 to pump the mixed acid excessively under the conditions of the silicate and mixed acid reaction, and the concentration of the solution after the reaction was 1.2 N. Adjust the metering pump (3) to the excess acid of the reaction hopper (4), the amount required in the reaction hopper (4), and left for 6 hours at room temperature so that the silica-titania sol becomes a hydrogel (hydrogel). After confirming that the gel is completely formed, the gel is crushed to about 2-6mm. A mesh net is installed at the bottom of the tank to flush the ionic material inside the gel by flushing the water from the top to the bottom while preventing loss of fine powder. At this time, the water temperature of 23 ℃, pH 3.8, time washed with water about 10 hours and dried to synthesize a product (5) having various physical properties.

Example 2.

Commercially available sodium silicate (molar ratio SiO ₂ 24.3%, Na ₂ O 6.5%) is placed in the silicate raw material tank 2 of FIG. The mixed acid of TiOCl ₂ and 18% sulfuric acid is placed in the mixed acid tank 1 of FIG. 1. Through the silicate and mixed acid continuous reactor of FIG. 1, the control gauge of the uniform metering pump is turned to pump the mixed acid excessively under the conditions of the silicate and mixed acid reaction so that the concentration of the solution after the reaction becomes an excess acid of 0.7N. Adjust (3) to react as required in the reaction hopper (4), and let stand for 6 hours at room temperature so that the silica-titania sol becomes a hydrogel. After confirming that the gel is completely formed, the gel is crushed to about 2-6mm. A mesh net is installed at the bottom of the tank to flush the ionic material inside the gel by flushing the water from the top to the bottom while preventing loss of fine powder. At this time, the water temperature of 23 ℃, pH 3.8, time washed with water about 10 hours and dried to synthesize a product (5) having various physical properties.

Example 3.

Commercially available sodium silicate No. 4 (molar ratio SiO ₂ 24.3%, Na ₂ O 6.5%) is placed in the silicate raw material tank 2 of FIG. The mixed acid of TiOCl ₂ and 18% sulfuric acid is placed in the mixed acid tank 1 of FIG. 1. The control gauge of the homogeneous metering pump 3 is turned through the silicate and mixed acid continuous reactor of FIG. 1 to pump the mixed acid excessively under the conditions of the silicate and mixed acid reaction so that the concentration of the solution after the reaction becomes 1N excess acid. The metering pump is adjusted to react as required in the reaction hopper (4), which is allowed to stand for about 6 hours at room temperature so that the silica-titania sol becomes a hydrogel. After confirming that the gel is completely formed, the gel is crushed to about 2-6mm. A mesh net is installed at the bottom of the tank to flush the ionic material inside the gel by flushing the water from the top to the bottom while preventing loss of fine powder. At this time, the water temperature of 23 ℃, pH 3.8, time washed with water about 10 hours and dried to synthesize a product (5) having various physical properties.

Example 4.

Commercially available sodium silicate No. 4 (molar ratio SiO ₂ 24.3%, Na ₂ O 6.5%) is placed in the silicate raw material tank 2 of FIG. The mixed acid of TiOCl ₂ and 18% sulfuric acid is placed in the mixed acid tank (1) of Figure 1. The control gauge of the homogeneous metering pump 3 is turned through the silicate and mixed acid continuous reactor of FIG. The metering pump is adjusted to react as required in the reaction hopper (4), which is allowed to stand for about 6 hours at room temperature so that the silica-titania sol becomes a hydrogel. After confirming that the gel is completely formed, the gel is crushed to about 2-6mm. A mesh net is installed at the bottom of the tank to flush the ionic material inside the gel by flushing the water from the top to the bottom while preventing loss of fine powder. At this time, the water temperature of 60 ℃, pH 8.5, time washed with water for about 17 hours and dried to synthesize a product (5) having various physical properties.

Example 5.

Commercially available sodium silicate (molar ratio SiO ₂ 24.3%, Na ₂ O 6.5%) is placed in the silicate raw material tank 2 of FIG. The mixed acid of TiOCl ₂ and 18% sulfuric acid is placed in the mixed acid tank 1 of FIG. 1. The control gauge of the homogeneous metering pump 3 was turned through the silicate and mixed acid continuous reactor of FIG. Adjust the metering pump so that the reaction hopper 4 is reacted with the required amount. The mixture is allowed to stand at room temperature for about 6 hours so that the silica-titania sol becomes a hydrogel. After confirming that the gel is completely formed, the gel is crushed to about 2-6mm. A mesh net is installed at the bottom of the tank to flush the ionic material inside the gel by flushing the water from the top to the bottom while preventing loss of fine powder. At this time, the water temperature of 60 ℃, pH 8.5, time washed with water for about 18 hours and dried to synthesize a product (5) having various physical properties.

Example 6.

Commercially available sodium silicate 3 (molar ratio SiO ₂ 28.8%, Na ₂ O 9.5%) is placed in the silicate raw material tank 2 of FIG. The mixed acid of TiOCl ₂ and 18% sulfuric acid is placed in the mixed acid tank 1 of FIG. 1. The control gauge of the homogeneous metering pump 3 is turned through the silicate and mixed acid continuous reactor of FIG. 1 to pump the mixed acid excessively under the conditions of the silicate and mixed acid reaction, and the concentration of the solution after the reaction is 1.2N. Adjust the metering pump so that the reaction hopper 4 is reacted with the required amount. The mixture is allowed to stand at room temperature for about 6 hours so that the silica-titania sol becomes a hydrogel. After confirming that the gel is completely formed, the gel is crushed to about 2-6mm. A mesh net is installed at the bottom of the tank to flush the ionic material inside the gel by flushing the water from the top to the bottom while preventing loss of fine powder. At this time, the water temperature of 80 ℃, pH 8.5, time washed with water about 17 hours and dried to synthesize a product (5) having various physical properties.

Example 7.

Commercially available sodium silicate No. 4 (molar ratio SiO ₂ 24.3%, Na ₂ O 6.5%) is placed in the silicate raw material tank 2 of FIG. The mixed acid of TiOCl ₂ and 18% sulfuric acid is placed in the mixed acid tank 1 of FIG. 1. The control gauge of the homogeneous metering pump 3 is turned through the silicate and mixed acid continuous reactor of FIG. 1 to pump the mixed acid excessively under the conditions of the silicate and mixed acid reaction so that the concentration of the solution after the reaction becomes 1N excess acid. The metering pump is adjusted to react as required in the reaction hopper (4), which is allowed to stand for about 6 hours at room temperature so that the silica-titania sol becomes a hydrogel. After confirming that the gel is completely formed, the gel is crushed to about 2-6mm. A mesh net is installed at the bottom of the tank to flush the ionic material inside the gel by flushing the water from the top to the bottom while preventing loss of fine powder. At this time, the water temperature of 80 ℃, pH 9.0, time washed with water for about 25 hours and dried to synthesize a product (5) having various physical properties.

Example 8.

Commercially available sodium silicate (molar ratio SiO ₂ 24.3%, Na ₂ O 6.5%) is placed in the silicate raw material tank 2 of FIG. The mixed acid of TiOCl ₂ and 18% sulfuric acid is placed in the mixed acid tank 1 of FIG. 1. The control gauge of the homogeneous metering pump 3 was turned through the silicate and mixed acid continuous reactor of FIG. 1 to pump the mixed acid excessively under the conditions of the silicate and mixed acid reaction, and the concentration of the solution after the reaction was 0.7 N. Adjust the metering pump so that the reaction hopper 4 is reacted with the required amount. The mixture is allowed to stand at room temperature for about 6 hours so that the silica-titania sol becomes a hydrogel. After confirming that the gel is completely formed, the gel is crushed to about 2-6mm. A mesh net is installed at the bottom of the tank to flush the ionic material inside the gel by flushing the water from the top to the bottom while preventing loss of fine powder. At this time, the water temperature of 80 ℃, pH 9.0, time washed with water for about 28 hours and dried to synthesize a product (5) having various physical properties.

Example 9.

Commercially available sodium silicate 3 (molar ratio SiO ₂ 28.8%, Na ₂ O 9.5%) is placed in the silicate raw material tank 2 of FIG. The mixed acid of TiOCl ₂ and 18% sulfuric acid is placed in the mixed acid tank 1 of FIG. 1. The control gauge of the homogeneous metering pump 3 is turned through the silicate and mixed acid continuous reactor of FIG. 1 to pump the mixed acid excessively under the conditions of the silicate and mixed acid reaction, and the concentration of the solution after the reaction is 1.2N. Adjust the metering pump so that the reaction hopper 4 is reacted with the required amount. The mixture is allowed to stand at room temperature for about 6 hours so that the silica-titania sol becomes a hydrogel. After confirming that the gel is completely formed, the gel is crushed to about 2-6mm. A mesh net is installed at the bottom of the tank to flush the ionic material inside the gel by flushing the water from the top to the bottom while preventing loss of fine powder. At this time, the water temperature was 85 ℃, pH 9.0, time washed with water for about 25 hours and dried to synthesize a product (5) having various physical properties.

Results comparison table according to each example Example TiO ₂ / SiO ₂ wt% Specific Surface Area㎡ / g Oil absorption ml / 100g Average pore area ml / g Average pore diameter mm Average thin process mm after hydrothermal synthesis Example 1 27/73 750 100 0.15 2.4 12 Example 2 25/75 800 90 0.4 2.0 9 Example 3 25/75 820 85 0.38 1.85 8 Example 4 25/75 510 170 0.79 6.19 27 Example 5 25/75 500 165 0.8 6.4 29 Example 6 25/75 480 160 0.85 7.0 31 Actual practice7 25/75 310 285 1.2 15.5 80 Example 8 25/75 280 305 1.3 18.5 83 Example 9 25/75 300 300 1.25 16.7 81

The present invention as described above,

1. By providing a functional bio-catalyst carrier that is environmentally friendly and reusable, it has the effect of suppressing malignant wastewater or chemicals,

2. Silica-titania composite is more durable than silica alone in alkali-resistant atmosphere,

3. As a silica-titania composite material, it manufactures a composite material with a surface area of 50-800㎡ / g, pore diameter of 5-100nm and oil absorption of 50-300ml / 100g, so that the biological industry, fermentation industry, food industry, wastewater treatment industry and environmental industry It can be supplied to the pharmaceutical, pharmaceutical, and bio-related industries.

In addition, using a silica-titania composite material carrier having a nanoporous structure prepared according to the present invention after the treatment of the silane having an amine group on the surface after reacting with glutaraldehyde and immobilized acylase, the immobilization efficiency of 100Unit or more per unit Indicated.

Claims (5)

The primary particle size is 3-100nm, the pore volume is 0.3-1.3ml / g, the specific surface area is 50-850㎡ / g, the ratio of TiO _{2 in} the silica-titania composite, using a mixed acid of silicate, sulfuric acid and TiOCl ₂ Silica-Titania porous composite for biocatalyst immobilization having 0.5-28% Silica-titania porous composite pore volume for biocatalyst immobilization Using a carrier of 3-60 nm, specific surface area 250-850 m2 / g, pore diameter by hydrothermal synthesis under conditions of temperature 150-300 ° C and pressure 10-30kg / cm2 Silica-Titania porous composite method of 5-100nm, specific surface area 50-600㎡ / g After synthesis of the TiO ₂ Seed by the hydrolysis of TiCl ₄ , the size of the primary particles was 3-100nm, the pore volume was 0.3-1.3ml / g, the specific surface area was 50-850㎡ / g, Method of preparing silica-titania porous composite for biocatalyst immobilization in which the ratio of TiO _{2 in} the silica-titania composite is 0.5-28% After synthesis of Seed of SiO ₂ using TEOS, the synthesized Seed and TiCl ₄ were reacted to obtain primary particles with a size of 3-100 nm, pore volume of 0.3-1.3ml / g, specific surface area of 50-850㎡ / g, silica Method for preparing silica-titania porous composite for biocatalyst immobilization in which the ratio of TiO _{2 in} the titania composite is 0.5-28% After synthesis of SiO ₂ Seed by ion exchange method or reverse osmosis (R / O) membrane method using silicate, the synthesized Seed and TiCl ₄ were reacted to make the primary particles 3-100nm in size and 0.3-1.3ml / g pore volume. , Silica-titania porous composite for biocatalyst immobilization having a specific surface area of 50-850 m2 / g and a TiO ₂ ratio of 0.5-28% in the silica-titania composite