JPS62202804A - Method for generating excited oxygen molecule o2 (1delta) - Google Patents

Abstract

PURPOSE:To generate an excited oxygen molecule in high generation ratio, by reacting a mixed aqueous solution of an alkali aqueous solution and hydrogen peroxide with a molecular chlorine-containing gas in a layer of a hydrophilic material having gas permeability. CONSTITUTION:Hollow pipes 16 of a hydrophilic, gas-permeable material is set in a reactor 10. Then, a mixed aqueous solution of an alkali aqueous solution and hydrogen peroxide is fed from a feed opening 12 attached to the reactor 10 to the reactor 10, discharged from an outlet 20 and penetrated to the whole surface part of the pipes 16 by capillary phenomena. Simultaneously a molecular chlorine-containing gas is fed from gas feed openings 22 to hollow parts of the pipes 16, transported through fine pores of the pipes 16 to the surface parts of the pipes 16, brought into contact with and reacted with the mixed aqueous solution of an alkali aqueous solution and hydrogen peroxide to generate an excited oxygen molecule, which is discharged from the outlet 20 and recovered.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for generating singlet delta oxygen. Specifically, the present invention provides excited oxygen molecules (molecular OXygen) through a reaction between a liquid and a gas.
in the eXCited 5inlJlet-
delta electronicC5tate) 02
(+Δ).

(Prior Art) Excited oxygen molecules 02 (1Δ) are mainly used as a raw material for chemically excited iodine lasers.

A chemically excited iodine laser is a transition between an excited iodine atom 1 (2P, /2) generated by energy transfer from 02 (1Δ) generated by a chemical reaction and an iodine atom I (2P2/3) in the ground state. It is a laser that oscillates at This 02 (1Δ) is generated by reacting an aqueous hydrogen peroxide solution (H202) with chlorine gas in an alkaline aqueous solution such as sodium hydroxide. The reaction formula is
It can be summarized as follows.

H202+2Na01-l+cN-+ 02 (1△) +2NaOH+21-120 Conventionally, such a reaction method involved injecting chlorine gas in the form of bubbles into a mixture of H2O2 and an aqueous sodium hydroxide solution [U.S. 4,461.756, 4.246.252, 4.310.502 and 4,342,116, Journal of Applied Physics (J, Aρp1, Phys,
) 52(8), August issue (1981), Applied
Physical Letter (8pp, Phl/S, Le
tt, > 45 (10).

15 November issue (1984) and Applied Physical Letters (8pp1.phys, Left, >
41 (1), July @ (1982)].

(Problem to be solved by the invention) However, in such a method, 02
(1Δ) has to pass through the solution, so the rate of deactivation of 02 (1Δ) in the solution is very high, so the actually obtained generation rate [02(1Δ) partial pressure] The ratio to the total oxygen pressure is only about 40 to 60%.

In addition, these methods do not increase the amount of chlorine gas and generate a large amount of bubbles due to the reaction heat, which hinders the reaction.
There was a drawback that half of (1△) was limited.

It is therefore an object of the present invention to provide a new method for singlet delta oxygen generation.

Another object of the present invention is to provide a method for generating excited oxygen molecules 02 (1△) at an extremely high generation rate through a reaction between a liquid and a gas.

(Means for Solving Problems) The purpose of these developments is to infiltrate the surface of a material that is hydrophilic and gas permeable with a mixed aqueous solution of an alkaline aqueous solution and hydrogen peroxide. A molecular chlorine-containing gas is passed through from the opposite side of the surface of the layer, and when the gas passes through the material, it reacts with the mixed aqueous solution that has penetrated into the surface of the material, releasing excited oxygen molecules 02 (IΔ) onto the surface of the layer. This is achieved by a method for generating excited oxygen molecules, which is characterized in that the excited oxygen molecules are generated from the side of the aqueous solution permeation section.

(Function) In order to cause the above reaction, the system according to the present invention uses an alkaline aqueous solution, for example, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, etc. A mixed aqueous solution of an aqueous solution of an alkaline earth metal hydroxide, etc. and a highly concentrated hydrogen peroxide solution is applied to the surface of a layer of a gas-permeable material that is hydrophilic and has homogeneous and fine pores. Penetration takes full advantage of capillary force. On the other hand, when a molecular chlorine-containing gas is permeated from the opposite side of the surface of the layer, when the gas permeates through the material, the mixed aqueous solution that has permeated the surface of the material and chlorine come into contact and react, Excited oxygen molecule 02 (1Δ
) is generated from the aqueous solution permeation portion side of the surface of the layer.

According to the present invention, by pressurizing the molecular chlorine-containing gas from the opposite side of the mixed liquid permeation section, the gas permeates through the material layer and the aqueous solution and chlorine come into contact and react, causing excited oxygen molecules. 02 (1Δ) is generated in the space on the opposite side of the material from the surface of the aqueous solution. In other words, since the reaction between this aqueous solution and chlorine occurs in an extremely thin layer on the surface of the material layer, the generated excited oxygen molecules 02 (1△) immediately leave the aqueous solution surface and enter another space where the gas flows. Move to. Therefore, the probability that the degenerated excited oxygen molecules are deactivated by collision with other molecules in the aqueous solution is extremely small.

As the alkaline aqueous solution, an aqueous solution of an alkali metal hydroxide is preferable, and an aqueous solution of potassium hydroxide and sodium hydroxide is particularly preferable. 911 in mixed aqueous solution is 7
．． 5-14, preferably 8-11. Further, the concentration of hydrogen peroxide in the mixed aqueous solution is usually 30 to 90%,
Preferably it is 50 to 80% by weight.

Examples of materials having hydrophilicity and gas permeability include porous ceramics, porous glass, porous metals, porous organic materials (for example, hydrophilized polypropylene, polyvinyl chloride resin, fluororesin, etc.), Its average pore size is between 1 and 20 μm, preferably between 3 and 7 μm.

Its porosity is 20-85%, preferably 35-85%. That is, if it is less than 20%, the transparency is poor;
This is because if it exceeds 5%, it is difficult to maintain strength.

However, it is preferable that the porosity is as high as possible. Roughly,
The integral pore diameter distribution is 9 times the maximum length of the pores.
It is 0% or more, preferably 95% or more, and the length up to 172 times is 10% or less, preferably 5% or less. The shape of the material may be any shape, such as a film or sheet, a hollow body such as a hollow pipe, or a hollow fiber. The thickness of the material layer is usually 0.01 to 20III, preferably 1 to 5111111.

In addition to chlorine gas 111, the molecular chlorine-containing gas includes a mixed gas of chlorine gas and an inert gas (for example, nitrogen, helium, argon, etc.). The supply amount is 1 to 100 m mol/7-111 to the material layer as CΩ2.
in, preferably 2 to 20 mIIIO1/d・min
It is. The chlorine gas concentration in the mixed gas is 5 volume M% or more, preferably 100 volume d%. Therefore, the atmosphere on the side where incidental oxygen molecules are generated is usually 0°1 to 100 TOrr,
Preferably, the pressure is maintained at a reduced pressure of 3 to 10 rorr.

Next, the present invention will be roughly described in detail with reference to the drawings.

As shown in FIGS. 1 to 3, a mixed aqueous solution of an alkaline aqueous solution and a hydrogen peroxide solution is supplied to the lower part of the reaction vessel 10 through a mixed aqueous solution supply port 12 so as to be in contact with the liquid surface of an aqueous solution layer 14 formed. At least one hollow pipe 16 is provided, and a space 18 above the aqueous solution layer 14 is provided with an oxygen gas outlet 20 connected to the pipe (not shown). In order to maintain a constant level of
A lachrymal solution outlet 26 is provided if necessary. The hollow pipe 16 used in this device has an average pore diameter of 5, for example.
It is made of ceramics with microscopic pores.

In such an apparatus, by supplying a mixed aqueous solution of an alkaline aqueous solution and a hydrogen peroxide solution through the supply port 12 and discharging it through the discharge port 20, the mixed aqueous solution in the reaction vessel 10 is maintained at a constant temperature of 1.

In this case, the hydrogen peroxide solution is preferably highly concentrated;
0 to 90% by weight, for example 90% by weight, is used. The alkaline aqueous solution used is 10 to 50% by weight, for example 25% by weight. The hydrogen peroxide solution and the alkaline aqueous solution should have a volume ratio of about 5:1.

As a result, the hydrogen peroxide concentration in the mixed aqueous solution is 32 to 82% by weight, and the alkali concentration is 3 to 25% by weight. These famous waters) d liquid may be separately supplied to the reaction vessel 10,
It is desirable to supply it to the reaction vessel as a uniform mixed aqueous solution. It is desirable to reduce the pressure of the reaction vessel 10 to 10 m orr or less using a vacuum pump before supplying the mixed aqueous solution. The amount of the mixed aqueous solution supplied is such that the pipe 16 sinks 0.5 to 4 mm, preferably 1 to 2 mm, below the surface of the aqueous solution. The aqueous solution permeates the entire surface of the pipe 16 from the lowest point in contact with the pipe 16 due to capillary action. The molecular chlorine-containing gas supplied from the gas supply port 22 passes through the fine pores of the pipe and reaches its surface due to the pressure difference with the outside of the pipe, contacts and reacts with the mixed aqueous solution, and excites oxygen molecules 02 (1 △) is generated and is discharged to the outside of the yarn from the oxygen gas discharge port 20. The flow layer of molecular chlorine-containing gas is 1 to 100 mm0/cd-min per unit outer peripheral area of the ceramic pipe as CΩ2,
For example, H-111 inch at 5 m NOV.

FIG. 4 shows another embodiment of the present invention, in which a middle part of the reaction vessel 30 (a gas supply chamber 46 and a gas discharge chamber 40 facing the gas supply chamber are provided, and the gas supply chamber 4
6 (on the side of the gas discharge chamber), a thin plate or thin film 36 made of a material layer having hydrophilicity and gas permeability is attached vertically or diagonally. A mixed aqueous solution 34 of a hydrogen peroxide solution and an alkaline aqueous solution is stored in the upper part of both chambers 46 and 40, and when this is dripped from the upper part, the thin plate or thin film made of the material is wetted with the mixed aqueous solution. When molecular chlorine-containing gas is supplied to the gas supply chamber 46 after depressurizing the gas discharge chamber 40 and the reaction vessel 30 in advance, the chlorine gas passes through the thin plate or thin film 36 and comes into contact with the mixed aqueous solution to react. , excited oxygen molecules 0
2 (1△) is generated and is discharged from the gas outlet 40 to the outside of the system. The mixed aqueous solution that has flown down the thin plate or film forms a liquid layer 44 that accumulates at the bottom of the reaction vessel 30, but is discharged outside the system if necessary.

5 and 6 show roughly other embodiments of the present invention, which are similar in principle to the case shown in FIG. A cylindrical gas supply chamber 56 made of a permeable material layer and a mixed aqueous solution supply device 68 are provided substantially obliquely above the gas supply chamber. After reducing the pressure in the reaction container 50 in advance, the mixed aqueous solution supply device 68
When the mixed aqueous solution is dripped from the lower drip hole or Surin 1~, the aqueous solution flows down while wetting the surface of the cylindrical gas supply chamber 56. On the other hand, after reducing the pressure in the reaction vessel 50 in advance, when a molecular chlorine-containing gas is supplied from the gas supply port 62, the chlorine gas passes from the gas supply chamber 56 into the reaction vessel 50 due to the pressure difference, and the mixed aqueous solution. Upon contact and reaction, excited oxygen molecules 02 (1Δ) are generated and are discharged from the gas outlet 60 to the outside of the system. The mixed aqueous solution that has flowed down the surface of the cylindrical gas supply chamber 56 forms a liquid tank 64 that accumulates at the bottom of the reaction vessel 50, but is discharged outside the thread if necessary. Note that the cylindrical gas supply chamber 56 may be rotated if necessary.

7 and 8 show another embodiment of the present invention, in which an apparatus similar to that shown in FIGS. The cylindrical gas supply chamber 76 of the layer is provided with a central axis (rotary shafts 84a and 84b, and is rotatably supported by bearings 86a and 86b. When the reaction vessel 70 is immersed in the liquid and rotated, its outer surface becomes wet.When molecular chlorine-containing gas is supplied from the gas supply port 82 after reducing the pressure inside the reaction vessel 70, the chlorine gas permeates through the material layer and mixes. Upon contact with the aqueous solution and reacting, excited oxygen molecules 02 (1Δ) are generated and are discharged from the system through the gas outlet 80.
The mixed aqueous solution is supplied from the liquid supply lower 2 and discharged from the liquid outlet 88, so that the concentration can be kept constant.

FIG. 9 is a sectional view showing an example of a cylindrical gas supply chamber made of a hydrophilic and gas permeable material used in the present invention.

(Example) Examples 1 to 4 In one device shown in Figs. 1 to 3 (however, there is one gas supply chamber 16), the average pore diameter is 4 to 5 μm, the outer diameter is 10 mm, the length is 623 QntmJ3, and the thickness is 1 m. A cylindrical pipe made of ceramics is used as the gas supply chamber 16, and 50% hydrogen peroxide solution containing 90% by weight of hydrogen peroxide solution is placed in the reaction vessel 10.
m and a sodium hydroxide aqueous solution with a concentration of 43% by weight and 50%
After supplying a mixed aqueous solution of 0d (p (about 10)), the pressure inside the reaction vessel was reduced to 5mTorr, and the gas supply chamber
When chlorine gas was supplied into the chamber, the results shown in Table 1 were obtained. The measurement was performed from a point approximately 500 mm away from the cylindrical gas supply chamber 16, after cooling a 600 mm pipe to 195 K with a mixture of dry ice and alcohol to remove moisture, and then The distance from ff1B is 60Q
The absolute amount of 02 (lΔ) was measured using a PbS detector at a point of mm, and unreacted chlorine was also measured using a gas analyzer. The product gas was sucked at 3001 iter/min and cooled with liquid nitrogen at 77°C to remove unused chlorine (see Figure 10A). The result is the first
Shown in the table.

Examples 5 to 10 Experiments were conducted using the apparatus shown in FIGS. 10A and 108. In the reaction vessel '110, the average pore size was 4 to 5 μm.
A ceramic cylindrical pipe with an outer diameter of 10 mm, a length of 230 mm, and a thickness of 11 II m is used as the gas supply chamber 116, and is connected to a mixing chamber 112 equipped with a hydrogen peroxide solution supply port 112a and an alkaline aqueous solution supply port 112b. Ta8! A dropping tube (diameter Q, equipped with 5 holes of 3 mm) 114 is installed in the reaction vessel 10 above the peroxy acid gas supply chamber 116 with a hydrogen peroxide concentration of 90% by weight, and chlorine is supplied from the gas supply port 122. A gas was supplied, and a mixed aqueous solution similar to that in Example 1 was dropped from the droplet tube at a rate of 2.5 mff1/Sec to cause a reaction, and the aqueous solution after the reaction was discharged from the liquid outlet 124. The excited oxygen molecules 02 (1Δ) generated on the outer surface of the cylindrical gas supply chamber 116 are
After cooling the pipe 130 of 600 mm from a point approximately 500 mm away from 6 to 195 K with a mixture of dry ice and alcohol to remove 1 minute of water, PbS was detected at a point where the distance 1fSltB from the outlet was 60Qm111. The absolute amount of O2 ('△) in the vessel 132 was measured, and the amount of unreacted chlorine was also measured using a gas analyzer. The produced gas was sucked in at 3001 iter/l1lin and cooled with liquid nitrogen at 77°C in a cooler 134 to remove unused chlorine. The results are shown in Table 1.

Comparative Examples 1 to 4 A glass filter having an average pore diameter of 100 μm, a thickness of 10III11, and a diameter of 12CI11 is placed in a relatively lower part of a vertical cylindrical reaction vessel, and the glass filter is formed by the upper surface of the glass filter and the inner surface of the reaction vessel. Example 1 in space
The same u-containing solution as in Example 5 was supplied, and chlorine gas was supplied to the space formed by the lower surface of the glass filter and the inner surface of the reaction vessel, and the solution was allowed to pass through the glass filter under the same conditions as in Example 5. 02(lΔ)102, and 02/CΩ2
The yield was measured in the same manner as in Example 5. The results are shown in Table 1.

When the data in Table 1 is plotted, it is as shown in FIG. In the figure, ○ marks represent Examples 5 to 10, and Δ marks represent Comparative Examples 1 to 4.

[Brief explanation of drawings]

FIG. 1 is a partially cutaway schematic perspective view showing an embodiment of the excited oxygen molecule generation system according to the present invention, and FIG.
A cross-sectional view taken along the line I-II, FIG. 3 is the section III in FIG.
4 is a sectional view showing another embodiment of the present invention, FIG. 5 is a sectional view showing still another embodiment of the present invention, and FIG. 6 is a sectional view of FIG. 7 is a sectional view showing another embodiment of the present invention; FIG. 8 is a sectional view taken along line Vllll-■ in FIG. 7; FIG. FIG. 10A is a cross-sectional view showing an example of the shape of a material layer having hydrophilicity and gas permeability, and FIG. 10A is a schematic diagram showing measurement points of the system of the present invention, and FIG.
11A is a sectional view taken along the line XIA-XIA in FIG. 11A, and FIG. 11 is a graph showing the relationship between 02 pressure and 02 (snow Δ) 102. Procedure rli positive limit (method) June 4, 1985 Director General of the Patent Office U N Tsu Department 1, Indication of the case 1986 Patent application No. 71.196 @ 2, Name of the invention Excited oxygen molecule 02 (1Δ ) generation method 3, relationship with the person making the amendment f4 Patent Applicant Address: 2663-9 Naruse, Machida City, Tokyo Name: Jiyu Abe Address: Saitama-based 11-10 Sayamagahara, Iruma City Name: Mitsui Grinding Whetstone Co., Ltd. Representative: Akio Matsumoto 4, Agent Address: Dia Palace Niban-cho, 11-9 Niban-cho, Chiyoda-ku, Tokyo May 6, 1986 (Shipping date: May 20, 1986) 6. Amendment Target "drawings" and "power of attorney" 7. Contents of amendment Cleaning of the drawings attached to the application As shown in the attached sheet (no change in content) is the formal document (method) % formula % 1. Indication of the case 1985 Patent Application No. 71.196 2, Title of the Invention "V" Method of Generating Super Oxygen Molecule 02 (1Δ) 3, Relationship with the Amendment Case Patent Applicant Address 2663-9 Naruse, Machida City, Tokyo Name Free Fatabe Address Saitama-based Ningen City Oaza Sayamagahara 11-10 Name Mitsui Grinding Tool 6 Co., Ltd. Representative Akio Matsumoto 4, Agent XXl - This is a cross-sectional view along the line from [- 10B
The figure is a sectional view taken along the line X-XA in Figure 10A.
and correct it. Procedure Yu 1 Masakichi August 6, 1986 Commissioner of the Patent Office Black 1) Yu Akira Spontaneous amendment 6, subject of amendment "Figure 10 of the drawings"

Claims (3)

[Claims] (1) A mixed aqueous solution of an alkaline aqueous solution and hydrogen peroxide is infiltrated into the surface of a layer of a hydrophilic and gas permeable material, and molecular chlorine-containing gas is permeated from the opposite side of the surface of the layer. When the gas passes through the material, it reacts with the mixed aqueous solution that has penetrated the surface of the material, and excited oxygen molecules O_
2(^1Δ) is generated from the aqueous solution permeation part side of the surface of the layer. (2) Claim 1, wherein the material having hydrophilicity and gas permeability is at least one selected from the group consisting of porous ceramics, porous glass, porous metals, and porous organic materials. The method described in. (3) The method according to claim 1, wherein the material has an average pore diameter of 1 to 20 μm.