JPH0716525B2 - Oxygen generation method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention elutes a sodium carbonate-hydrogen peroxide adduct (also called sodium percarbonate) packaged with a netting material into water to obtain a decomposition enzyme or decomposition catalyst. The present invention relates to an oxygen generation method in which oxygen is generated at an almost constant rate by contacting it and oxygen generation can be interrupted as appropriate.

[Conventional technology]

Conventionally, as an oxygen generation method, an oxygen cylinder itself is incorporated, or a method using liquid oxygen and hydrogen peroxide or sodium carbonate / hydrogen peroxide adduct are mixed with an inorganic catalyst such as manganese dioxide to generate oxygen by a decomposition reaction. There are known methods for generating

[Problems to be solved by the invention]

However, the one in which the oxygen cylinder is incorporated is expensive because it is a disposable system, and the one in which hydrogen peroxide or a sodium carbonate / hydrogen peroxide adduct is mixed with an inorganic catalyst to be decomposed does not react once. When it starts, there is a disadvantage that the reaction continues while hydrogen peroxide is present and cannot be interrupted.

In addition, since a granular material is used as the sodium carbonate / hydrogen peroxide addition product, dust is likely to be generated, which is difficult to handle.

The present invention has been made to solve the above-mentioned problems, and the sodium carbonate / hydrogen peroxide adduct is pre-packaged with a net material so that the sodium carbonate / hydrogen peroxide adduct is handled together with the package, for example, sealed. By laying the container sideways, pulling up the net material, and extracting liquid around the net material part,
By interrupting the contact between the liquid and the net material, oxygen generation is interrupted as appropriate,
Further, it is an object of the present invention to provide an oxygen generation method in which the oxygen generation can be restarted by bringing the liquid and the net material into contact with each other, the handling is easy, and the oxygen generation rate can be kept substantially constant. is there.

[Means and Actions for Solving Problems]

In order to achieve the above object, according to the oxygen generation method of the present invention, as shown in the drawing, powdery granular sodium carbonate / hydrogen peroxide adduct is packaged with a net material 7, and this packaging body 8 is sealed. A sodium carbonate / hydrogen peroxide adduct that is stored in a container, is brought into contact with the package 10 and the water 10 in a closed container and is eluted into water, and a decomposing enzyme or a catalyst that is previously dissolved or suspended in water. It is brought into contact with it to generate oxygen, and the package 8
The feature is that the oxygen generation is interrupted by preventing the water from contacting with the water 10. As a method for breaking the contact between the package and water, various methods such as a method of pulling up the package and a method of extracting water around the package can be used.

Instead of preliminarily dissolving or suspending the dispersed enzyme or dispersed catalyst in water, attach the degrading enzyme or degrading catalyst to paper, porous material, etc. in a place that can contact water in a closed container. It may be stored, and instead of dissolving or suspending the decomposing enzyme or decomposition catalyst in water beforehand, store the fixed decomposing enzyme or decomposition catalyst in a place where it can contact water in a closed container. In some cases.

As an enzyme for decomposing hydrogen peroxide, catalase sold as an enzyme agent in the food industry field is used.
Catalase is a substance with a molecular weight of about 225,000, which is easily crystallized and obtained in crystalline form from liver, red blood cells, bacteria, etc.

The method of using catalase is (1) preliminarily dissolving it in water in a closed container, (2) simply accommodating what is attached to paper, porous material, etc. in a cylindrical body,
(3) Examples thereof include a method of storing the immobilized enzyme immobilized by various immobilization methods in a tubular body.

Examples of the method for immobilizing the above-mentioned catalase include (1) a carrier binding method for immobilizing an insoluble carrier by covalent bond, ionic bond, physical adsorption, biochemical affinity, etc., (2) glutaraldehyde between biocatalysts. (3) Polymer gel produced by polymerizing or associating a low molecular weight compound or transferring a high molecular weight compound from a soluble state to an insoluble state (lattice type) ), Microcapsules, liposomes,
A hollow fiber (hollow fiber), an entrapping method for enclosing a biocatalyst in an ultrafiltration membrane, and (4) a composite method in which these three methods are appropriately combined are used.

As the carrier for covalent bonding in the carrier bonding method of (1), cellulose, agarose, dextran, chitin,
Collagen, amino acid polymer, polystyrene, ethylene-maleic acid copolymer, polyacrylamide, polyvinyl alcohol, nylon, 4,6-dichloro-S-triazinyl ion exchanger, ion exchange resin, glass beads, nickel silica alumina, zirconia, ceramic As a carrier for physical adsorption, sand (alkylamination) carbon, activated carbon, silica gel, alumina, molecular sieve, titania, stainless steel, calcium phosphate gel, phenoxyacetylated product, chitin, agarose gel, cellulose, Tannins,
Silicon rubber or the like is used, and carriers for ionic bonding include Amberlite and Diaion.
ion), Sephadex, cellulose, etc. are used.

Examples of the crosslinking agent in the crosslinking method (2) include glutaraldehyde, maleinimide derivatives, aryl halides, isocyanates, imide esters, and chloro-S.
-Triazines, hexamethylene diisothiocyanate, bisdiazobenzidine, etc. are used.

As the lattice type inclusion material in the inclusion method of (3),
Collagen, fibrin, albumin, casein, cellulose fiber, cellulose triacetate, agar, calcium alginate, carrageenan, agarose, polyacrylamide, poly-2-hydroxyethylmethacrylic acid, polyvinyl chloride, γ-methylpolyglutamic acid, polystyrene, polyvinylpyrrolidone, poly Dimethyl acrylamide, polyurethane, photo-crosslinkable resin, etc. are used. As encapsulating material for microcapsules, collodion, nylon, polystyrene, polyurea, ethyl cellulose, silicon derivative, phenyl siloxane, cellulose nitrate, etc. are used, and as encapsulating material for liposomes. Hydrocarbons, phospholipids and the like are used as.

As the decomposition catalyst, (1) manganese dioxide, (2)
Iron, copper, silver, nickel, cobalt, manganese, chromium,
Lead, vanadium, tungsten or the like may be used alone or as a compound.

As the net material used in the method of the present invention, a mesh cloth, a non-woven fabric, or a combination of two or more thereof is used.

As the mesh cloth, (1) 6 nylon, 6,6 nylon, 12 nylon, polypropylene, polyethylene, AB
Synthetic plastics such as S, POM, PBT, PS, (2) Silk,
Natural fibers such as wool, cotton, hemp, and cellulose, and (3) inorganic fibers such as stainless steel and ceramics are used. Nonwoven fabrics are 6 nylon, 6,6 nylon, 12
Nylon, polypropylene, polyethylene, ABS, POM,
Nonwoven fabrics such as PBT, PS and cellulose are used, and a combination of materials and a combination of pore diameters are adopted as a combination of two or more kinds.

Next, the operation of the present invention will be described.

When the closed container 1 is placed in the normal position, the sodium carbonate / hydrogen peroxide adduct 6 in the package 8 comes into contact with water 10 and gradually dissolves in water, and a decomposition enzyme or decomposition that is dissolved or suspended in water in advance. Oxygen is generated upon contact with a catalyst or a degrading enzyme or catalyst that is eluted or migrated into water.

The reaction formula at this time is as follows.

_{Na 2 CO 3 · 3 / 2H} 2 O 2 → Na 2 CO 3 + 3 / 2H 2 O + 3/40 2 ↑ (1) Hereinafter, the configuration of the present invention will be described with reference to the drawings.

1 and 2 show an example of an apparatus for carrying out the method of the present invention. Reference numeral 1 denotes a closed container, which has an opening 2 at its upper end and a lid (pillar) 3 which can be attached to and detached from this opening. The lid portion 3 can be sealed by screwing, inserting, fitting, or the like.

Under the opening 2 in the closed container 1, an inner cylinder body 5 having a porous body 4 such as a net material having a hole through which gas and liquid can freely pass in a peripheral portion and a bottom portion is housed, A package 8 in which a sodium carbonate / hydrogen peroxide adduct 6 is packaged with a net material 7 is housed in the cylinder. Therefore, the inner cylindrical body 5
As shown in FIG. 1, when a predetermined amount of water 10 is placed in the vertical normal position and a predetermined amount of water 10 is put into the closed container 1, at least a part of the package 8 comes into contact with the water 10 and the closed container When 1 is laid down sideways as shown in FIG. 2, the package 8 does not come into contact with the water 10.

In water 10, the decomposing enzyme is dissolved in advance, or the decomposition catalyst is suspended or dissolved, so that the sodium carbonate / hydrogen peroxide adduct eluted in water comes in contact with the decomposing enzyme or the decomposition catalyst. , Generate oxygen.

The generated oxygen flows into the introduction pipe 11, flows out from the air diffusing pipe 12 provided at the end of the introduction pipe, and the flush water 14 in the washing cylinder 13
After being washed by, it is sent to the oxygen inhaler 17 through the filter 15 and the hose 16. 18 is a cylinder lid, 20 is a safety valve, 21
Is a spacer, 22 is a side surface of the container, 23 is a bottom surface of the container, and 24 is oxygen gas.

Next, an example of an operation for generating oxygen using the oxygen generator shown in FIGS. 1 and 2 will be described. First wash cylinder lid 18
Open and open the lid 18 with a predetermined amount of flushing water. Next, the lid 3 of the closed container is opened, a predetermined amount of enzyme or catalyst and water are put inside, and the sodium carbonate / hydrogen peroxide adduct packaged with a net material is put inside the inner cylinder 5. The lid 3 is closed, the hose 16 of the oxygen inhaler 17 is connected to the outlet of the filter 15, and the oxygen inhaler 17 inhales the generated oxygen gas that has been washed and filtered.

When it is desired to interrupt the oxygen generation, as shown in FIG. 2, the container side 22 on the side farther from the package 8 is laid down sideways. When it is desired to restart the oxygen generation, the container bottom surface 23 is set to the bottom again as shown in FIG. When the reaction is completed, the reaction completed liquid, the package and the water for flushing are discarded.

As the net material in the method of the present invention, sodium carbonate
When the hydrogen peroxide adduct is dry, only the fine powder falls, the wet and solid one does not fall, and the one having a pore size that allows free entry and exit of water in water is used.

As the net material package, as shown in FIG. 3, a package 8a in which the sodium carbonate / hydrogen peroxide adduct 6 is packed in a single net material 7, and as shown in FIG.・
A package 8b in which the hydrogen peroxide adduct 6 is packaged in two types of net materials 7a and 7b, and as shown in FIG. 5, a package in which the sodium carbonate / hydrogen peroxide adduct 6 is packaged in the net material 7 is aluminum. A package 8c or the like is used which is packaged with a fluid impermeable material such as a laminate material 25 so as to be suitable for storage. When using this package 8c, aluminum laminate material 25
After breaking, is put into the inner cylindrical body 5. In addition, as the package 8b shown in FIG. 4, three or more kinds of net materials may be used.

The above example is a case where the decomposing enzyme or the catalyst is previously dissolved or suspended in the water in the closed container 1, but the adhering enzyme previously attached to the paper, the porous material, or the like, or fixed by various immobilization methods As shown in FIG. 6, the immobilized enzyme, the decomposing enzyme body such as the one in which the catalyst is wrapped in a net material or the catalyst body 26 is housed in the inner cylinder body 5 as shown in FIG. 6, or as shown in FIG. In some cases, it may be housed between the inner cylindrical body 5 and the container side wall 27.

〔Example〕

 Hereinafter, examples and comparative examples of the present invention will be described.

Comparative Example In a closed container 1 shown in FIG. 1, an aqueous solution prepared by dissolving 2.5 ml of catalase stock solution in water 1 having a water temperature of 13 ° C. was placed, while 100 g of powdery sodium carbonate / hydrogen peroxide adduct was added to 12 ×
A 10-mesh polyethylene net material was put into the inner cylindrical body 5 stretched around the body portion without being wrapped with the net material. The change with time of the generated oxygen flow rate was as shown in FIG.

Example 1 In a closed container 1 shown in FIG. 1, an aqueous solution prepared by dissolving 3.5 ml of catalase stock solution in 1.7 liters of water having a water temperature of 15 ° C. was placed, while 200 g of powdery sodium carbonate / hydrogen peroxide adduct was added, What was packaged with a nylon net material having an opening diameter of 185 μ × 170 μ and an opening ratio of 67% was put into the inner cylindrical body 5 of the closed container 1. The inner cylinder 5 was not covered with a mesh material having a slit width of 1 cm. The change with time of the generated oxygen flow rate was as shown in FIG.

Example 2 In a closed container 1 shown in FIG. 1, an aqueous solution prepared by dissolving 3.7 ml of catalase stock solution in 1.7 l of water having a water temperature of 15 ° C. was placed, while 200 g of powdery sodium carbonate / hydrogen peroxide adduct was added, 9th
Nylon net material used in Example 1 as shown in the figure 28
Then, the one wrapped with a net material made of polyethylene and a net material 30 of 20 × 18 mesh was placed in the inner cylinder 5 of the closed container 1. The inner cylinder 5 was the same as that of the first embodiment. The change with time of the generated oxygen flow rate was as shown in FIG.

〔The invention's effect〕

Since the present invention is configured as described above, it has the following effects.

(1) Oxygen generation can be interrupted appropriately by separating the bag containing the sodium carbonate / hydrogen peroxide adduct from the water by overturning or pulling up the closed container, pulling out the surrounding liquid, etc. By returning the bag containing the sodium carbonate / hydrogen peroxide adduct to the normal position, oxygen generation can be restarted as appropriate.

(2) At the normal position, the liquid contact part can have a structure with no opening / closing part, and the risk of liquid leakage is extremely reduced.

(3) Since the granular sodium carbonate / hydrogen peroxide adduct is handled together with the bag, dust generation is extremely reduced.

(4) As is clear from the examples, the oxygen generation rate can be kept substantially constant and can be generated for a long time.

[Brief description of drawings]

1 is an example of an oxygen generator for carrying out the oxygen generation method of the present invention, and is a cross-sectional explanatory view showing the time of oxygen generation, FIG. 2 is a cross-sectional explanatory view showing the time of interruption of oxygen generation (reaction), and FIGS. FIG. 5 is an explanatory view showing an example of packing a net material of sodium carbonate / hydrogen peroxide adduct, and FIGS. 6 and 7 are sectional explanatory views showing another example of an oxygen generator for carrying out the method of the present invention. FIG. 8 is a graph showing changes over time in the oxygen generation flow rate in Comparative Examples and Examples 1 and 2, and FIG. 9 is a front view of the package used in Example 2. 1 ... Airtight container, 2 ... Opening, 3 ... Lid part, 4 ... Porous body, 5 ...
Inner cylinder, 6 ... Sodium carbonate / hydrogen peroxide adduct, 7,
7a, 7b ... Net material, 8, 8a, 8b, 8c ... Packing body, 10 ... Water, 11 ...
Introducing pipe, 12 ... Air diffuser, 13 ... Washing cylinder, 14 ... Washing water, 15 ...
Filter, 16 ... Hose, 17 ... Oxygen inhaler, 18 ... Wash cylinder lid, 20 ... Safety valve, 21 ... Spacer, 22 ... Container side, 23 ... Container bottom, 24 ... Oxygen gas, 25 ... Aluminum laminated material, 26 ... Disassembly Enzyme body or catalyst body, 27 ... Side wall of container, 28 ...
Nylon net material, 30 ... Polyethylene net material

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-54-142896 (JP, A) JP-A-62-59503 (JP, A)

Claims (3)

[Claims] 1. A powdery granular sodium carbonate / hydrogen peroxide adduct is packaged with a net material, the package is stored in a closed container, and the package and the water in the closed container are brought into contact with each other to be eluted into water. The generated sodium carbonate / hydrogen peroxide adduct and the decomposing enzyme or decomposition catalyst previously dissolved or suspended in water are brought into contact with each other to generate oxygen, so that the package and the water do not come into contact with each other to generate oxygen. A method for generating oxygen characterized by interruption. 2. Instead of preliminarily dissolving or suspending the decomposing enzyme or decomposition catalyst in water, the decomposing enzyme or decomposition catalyst adhered to paper, a porous material or the like is contacted with water in a closed container. The oxygen generating method according to claim 1, wherein the oxygen is stored in a possible place. 3. Instead of previously dissolving or suspending the decomposing enzyme or the decomposing catalyst in water, the decomposing enzyme or the decomposing catalyst immobilized is stored in a location in a closed container where water can be contacted. Item 2. The oxygen generation method according to Item 1.