JPS63229122A - Preparation of gas permeable membrane - Google Patents

Abstract

PURPOSE:To increase pressure resistance of a gas permeable membrane by piling a specific sheet A to be used as a carrier of a reactive layer and a specific sheet B to be used as a gas permeable membrane, bringing into contact, and hot-pressing after drying and heat treating. CONSTITUTION:Fine particles used as a catalyst carrier, fine particles for a binder material and a fluid lubricant are kneaded to prepare a paste of kneaded substance, and a sheet 1 used as a carrier of a reactive layer is prepared by pressurizing the kneaded substance. On the other hand, electrically conductive fine particles, fine particles for the binder material and a liquid lubricant are kneaded to prepare a paste of kneaded substance, and a sheet 2 used as a gas permeable layer is prepared by pressurizing and molding said kneaded substance into a sheet-shaped mold. Then, after said sheets 1 and 2 are piled, brought into contact, bonded and turned into a thin sheet, the drying treatment and the heat treatment are carried out successively, said sheet being pressed to be thinner, and a gas permeable membrane is prepared.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a pattern having gas permeability that is suitably used as an electrode of an aqueous solution electrolyzer.

"Conventional technology 6 and its problems" Conventionally, an electrolysis device used for electrolysis of an aqueous solution, etc. has a container in which the solution is stored, a cathode and an anode provided in this container, and a It consisted of a diaphragm provided between the two electrodes to prevent mixing of electrolyzed products.

The diaphragm of this type of electrolytic device is generally made of compression molded material such as asbestos.

However, problems such as asbestos being carcinogenic have been pointed out, and the installation of electrolyzers equipped with such diaphragms has been dissatisfied with various restrictions.

In order to deal with these problems, it has been proposed to use a membrane that has both gas permeability and electrical conductivity.

However, when manufacturing this type of membrane using conventional manufacturing methods, there has been a dissatisfaction that when attempting to impart good gas permeability and conductivity to the membrane, the pressure resistance strength of the membrane is significantly reduced.

``Object of the Invention'' The present invention was made in view of the above circumstances, and an object thereof is to provide a manufacturing method capable of manufacturing a gas permeable membrane that has good gas permeability and conductivity, and has excellent pressure resistance. shall be.

"Means for Solving the Problems" In the manufacturing method of the present invention, a gas permeable membrane is created through the following steps.

■ Create a paste-like mixture by kneading fine particles that will serve as a carrier for the catalyst, fine particles of a binder material, and a liquid lubricant, and pressurize this mixture to form a sheet to form a sheet that will serve as a carrier for the reaction layer. create.

At the same time, conductive fine particles, binder material fine particles, and liquid lubricant are kneaded to create a paste-like mixture, which is then pressurized and formed into a sheet. Sheet B becomes the gas permeable layer. Create.

■ These sheets A and B are overlapped and pressed together, and the thickness is reduced while being joined.

■ Next, this material is subjected to a drying process.

■ Next, this material is further subjected to heat treatment.

■ Hot press these roe to make them even thinner.

FIG. 1 shows an example of a gas permeable membrane manufactured by the gas permeable membrane manufacturing method of the present invention, in which reference numeral 1 represents a reaction layer and reference numeral 2 represents a gas permeable layer.

The reaction layer 1 is formed by supporting and fixing a catalyst on a carrier, and the carrier for this reaction 11 is formed from the sheet A described above. Further, the gas permeable layer 2 is formed from the sheet B described above.

Alumina (Ai
Various types of particles can be used, such as fine particles made of ceramics such as 2*Os) and silica (Sift), fine particles made of organic polymer compounds, and fine particles made of conductive materials. Among them, conductive fine particles have a reaction T! It is preferably used because it can reduce the electrical resistance of J1. Such conductive particles include iron, aluminum, silver, copper,
Metals such as gold, amorphous carbon, carbon such as graphite, zirconia ceramics, β-alumina ceramics, conductive ceramics such as boron compounds [lanthanum polide (La[3s), titanium polide ('r iB z)], etc. I can list the following. Among them, carbon is preferably used because it has excellent water repellency and corrosion resistance, and the resulting gas permeable membrane has a long life and good chemical resistance.

As the conductive fine particles, those having a particle size of 0.5 μl or less are preferably used. If the particle size exceeds 0.5 μm, there will be an inconvenience that large pores will be formed in the reaction layer l of the gas permeable membrane.

Further, as the binder material used to create the sheet A, various materials having a binder function such as low melting point metals and organic polymer compounds can be used, but organic polymer compounds are usually preferably used.

As suitable organic polymer compounds, various synthetic resin materials such as fluororesin, silicone resin, polyethylene, polypropylene, polyacrylonitrile, polyvinyl chloride, polycarbonate, and polyethylene terephthalate can be used. Among them, polytetrafluoroethylene (PT)
Fluororesins such as FE), polychlorotrifluoroethylene, polyvinylidene fluoride, and tetrafluoroethylene-hexafluoropropylene copolymer are suitable. Among them, PTFE is particularly preferably used because it has excellent corrosion resistance that is not attacked by acids or alkalis, and has excellent water repellency, and the resulting gas permeable membrane has a long life and chemical resistance. It will be done.

It is desirable that the reaction WIt formed from the sheet A has a structure in which hydrophilic portions and water-repellent portions are finely distributed in a network so that it can appropriately contact the aqueous solution. The reaction of such a structure r! In order to form It, hydrophilic fine particles and water-repellent fine particles are mixed and used when producing the sheet A.

Such fine particles include, for example, general carbon black as a water-repellent particle, and Vulc as a hydrophilic particle.
anX C-72n Cm aqueous carbon (trade name: manufactured by Vulcan Cabot), and the like.

As the liquid lubricant used when kneading the fine particles that serve as the catalyst carrier and the fine particles that serve as the binder, various solvents can be used as long as they do not dissolve these fine particles, but organic solvents such as naphtha are preferably used.

The mixture consisting of these fine particles and liquid lubricant is pressure-formed to form sheet A, and the thickness of sheet A is as follows:
It is set considerably thicker than the reaction 5t thickness of the target gas permeable membrane.

The above gas permeation r? The conductive fine particles used to create sheet B forming sheet 12 have a reaction T! Examples of the material for creating sheet A, which is il, include the same conductive particles as those mentioned above, that is, particles made of metals such as silver, copper, and gold, and carbon such as amorphous carbon and graphite.

The conductive fine particles used in preparing this sheet B preferably have a particle size of 0.1 μm or less. Particle size is 0.1μ!
If it exceeds this, a problem arises in that large-diameter pores are formed in the gas permeable layer 2.

Further, as the binder material used when creating the sheet B, an organic polymer compound is suitably used.

As such an organic polymer compound, those similar to those listed for Sheet A above can be used.

When using an organic polymer compound as a binder material in this way, the amount of the organic polymer compound to be added is usually determined by the following: The weight ratio of PTFE to the total amount is approximately 10% to Gθ%. If the amount of the organic polymer compound added exceeds 60%, the electrical resistance of the gas permeable layer 2 to be formed will increase, and the gas permeability of the gas permeable layer 2 will deteriorate. Moreover, if the amount added is less than 10%, the bonding of the conductive fine particles becomes insufficient, and the strength of the gas permeable layer 2 decreases.

The liquid lubricant used when kneading the conductive fine particles and the fine particles that will become the binder includes, as in the case of the sheet,
Organic solvents such as naphtha are preferably used.

The mixture consisting of these fine particles and liquid lubricant is pressure-molded to form sheet B, and the thickness of sheet B is as follows:
The thickness is set to be considerably thicker than the thickness of the gas permeable layer 2 of the target gas permeable membrane.

After the sheets A and 13 created as described above are overlapped, they are pressed together by a roller or the like to be integrated and thinned.

Thereafter, the joined sheets A and B are subjected to a drying process to remove the liquid lubricant.

Next, this dried material is subjected to heat treatment at a temperature slightly lower than the melting temperature of the binder fine particles, or higher than the gelling temperature for fluororesins such as P71' F E. This is done at a slightly lower temperature. Specifically, when P T F I'' is used as a binder, it is desirable that the temperature is about 280°C.

After the heat treatment has been completed, the sheet is further thinned by hot pressing. The temperature applied during hot pressing is
This is carried out at a temperature higher than the temperature at which the binder fine particles melt, and at a temperature higher than the temperature at which the fluororesin such as PTFE gels. Specifically, when PTFE is used as a binder, it is desirable that the temperature is about 380°C.

In the manufacturing method of the present invention, there is no particular limitation on where the step of supporting the catalyst on the portion formed by the sheet 8 is carried out, but it is usually carried out after the hot pressing step.

A simple method for supporting the catalyst is to apply or spray a solution in which the catalyst is dissolved (catalyst solution) onto the surface of the sheet and allow it to penetrate into the sheet, and then dry it. In this way, the catalyst is supported even inside the reaction layer 1.

The catalysts used include iron group elements such as nickel (Ni), cobalt (CO), and iron (Fe), which promote chemical reactions such as electrolysis, or platinum (Pt) and ruthenium.

(Ilu), gold (A u), silver (Δg), copper (Cu),
Chromium (Cr) Manganese (M n), Palladium (r'
Various catalysts such as catalysts made of noble metal elements such as d), their oxides, or alloys thereof can be used.

Among them, 6. For electrolysis of aqueous solutions, etc., Ni, r't,
A catalyst made of flu or the like is preferably used since it can significantly improve electrolysis efficiency.

Since the carrier of the reaction layer 1 of the gas permeable membrane manufactured by the above process is porous, it has the advantage of being able to support a large amount of catalyst. The pore diameter of this carrier is 0.5 μJI to 0.01 μl
It is desirable that the

When the diameter of the reaction layer 1 exceeds 0.5 μl, the strength of the reaction layer I decreases. Furthermore, if the diameter is less than 0.01R1, it becomes difficult for the solution to penetrate into the reaction layer 1, and only the surface of the reaction layer 1 contributes to reactions such as electrolysis, resulting in a disadvantage that the reaction efficiency decreases.

Further, the porosity of the reaction layer I is preferably about 40% to 80%.

If the porosity of the carrier exceeds 80% without the weight of the reaction layer, the resulting reaction layer will have insufficient compressive strength, which is not preferable. If the porosity is less than 40%, a sufficient amount of catalyst cannot be supported, which is not preferable.

Another reactive layer! The thickness is about 1. It is desirable that the thickness be formed to be less than Oxm. When the thickness of this reaction layer 1 exceeds 1, Oxm, the reaction layer! This makes it difficult for the gas generated to permeate into the gas permeable layer 2, resulting in a disadvantage that the gas permeability of the gas permeable membrane is impaired.

The gas permeable H2 of the gas permeable membrane manufactured by the manufacturing method of the present invention is a porous and conductive layer in which conductive fine particles are bound together via a binder or by sintering or the like.

The hole formed in this gas permeation 71212 has a diameter of 0.5
It is desirable that the pores are continuous and have a diameter of less than μ, preferably less than 800 Å. If the diameter of the pores exceeds 0.5 μl, the gas permeable layer 2 will be able to permeate not only gaseous molecules but also liquid molecules, resulting in a disadvantage that the gas-liquid separation function will deteriorate.

Further, the porosity of the gas permeable layer 2 is preferably about 40% to 80%. Gas penetration r! J2 porosity is 80%
If the porosity exceeds 40%, the resulting gas permeable membrane will have insufficient pressure resistance, and if the porosity is less than 40%, the gas permeation rate of the gas permeable layer 2 will decrease and the decomposition product gas will not be released efficiently. I also don't like it.

This gas permeable layer 2 is desirably formed to have a thickness of about 0.3xz to 2xx. The thickness of this gas permeable layer 2 is 2
If it exceeds m shoulder, the gas permeation rate of the gas permeation layer 2 will decrease, and if it becomes less than 0.3x shoulder, the gas permeation rate will decrease.
This would cause the inconvenience of lowering the strength of m2.

"Example" Hereinafter, the method for manufacturing the gas permeable membrane of the present invention will be explained in detail.
1) The explanation is about the organic polymer compound as a binder.
A gas permeable membrane using FE and carbon black as conductive particles will be used as an example.

First, to create sheet A, the average particle size is 0.042.
μl of carbon black 70 parts by weight and average particle size 0.25
Mixture A1 obtained by sufficiently mixing 30 parts by weight of PTFE with μ shoulder and VulcanX C-7 having hydrophilic properties.
2R, 70fffffl part and P with average particle size 0.25μl
A mixture B was prepared by thoroughly mixing the mixture with TFE. These mixtures A1B were then mixed in a ratio of A:n=4:6, an organic solvent (naphtha) was added, and the mixture was uniformly kneaded. This was pressurized to form a sheet 8 with a thickness of 0.4 ytx.

Separately, in order to create sheet B, an average grain size of 0.
042 μl of carbon black 70 parts by weight and average particle size 0
．． Mixture C was prepared by thoroughly mixing 25 μl of 30 parts by weight of PTFE. Next, an organic solvent (naphtha) was added to this to form a paste, and the mixture was mixed sufficiently to become uniform. This material was pressurized to form a sheet B with a thickness of 2.5xz.7 The two types of sheets A113 formed in this way were overlaid and pressed together with a roller to join them together and form a sheet B with a thickness of 0.
．． It was made into a 9 mm sheet. This product was dried to volatilize the solvent used, and then heat-treated in a heating oven at 280°C. Next, this product was hot pressed at 380° C. for a predetermined time to form a sheet with a thickness of 0.8 xx.

Next, a solution in which a catalyst was dissolved (catalyst solution) was applied to the portion formed by the sheet A and permeated into the sheet, and then dried to support the catalyst.

Note that the method for manufacturing a gas permeable membrane of the present invention is not limited to the above embodiments. For example, a metal mesh may be pasted on the gas permeable membrane to be created, if necessary. When pasting a metal net, its position is on the surface of the gas permeable layer 2, on the surface of the reaction layer 1.
, or between the gas permeable layer 2 and the reaction El. As this metal net, one made of a metal with good electrical conductivity such as copper is suitably used. In addition, it is desirable that the mesh size of the metal net is about 30 to 100,
The metal fiber that makes Gold 171#14 has a diameter of 100 μm to 50 μm.
About 0 μl is preferably used.

The pasting of such a metal net is carried out, for example, by setting the metal net at an appropriate position when overlapping the sheets Δ and B, and hot-pressing the metal net.

"Experimental Example 1" The properties of the gas permeable membrane produced by the production method of the present invention were investigated.

First, the relationship between the gas permeation rate of the gas permeable layer 2 and the composition of the gas permeable layer 2 was investigated.

First, a film corresponding to gas permeable layer 2 was created using I'TFE and carbon black. Various types of this membrane were prepared by changing the proportion of PTFE. For P'rFE, one having an average particle size of 0.25 μl was used, and for carbon black, one having an average particle size of 0.042 μl was used, and these PTFE and carbon were combined to 100w1%.

The membrane used in this experiment was manufactured as follows.

First, carbon black and PTFE were sufficiently mixed to create a mixture. Naphtha was added to this and thoroughly kneaded, and then this was formed by a roll method at room temperature to a thickness of 1.
0JII sheet B.

Sheet B thus formed was dried to volatilize the solvent used, and then heat-treated in a heating furnace at 280°C. Next, I hot pressed this thing 19 at a time, and the area was 12.56 CI! ', and was fired while being formed into a sheet with a thickness of 1 degree. The hot pressing conditions were a temperature of 380° C., a pressure of 600 kg/ax”, and a time of 3 seconds.

In addition, when the diameter of the pores formed in the obtained membrane was examined using a mercury porosimeter, the diameter was 800 to 200 in all cases.

In this gas permeation experiment, a membrane was set in the center of a sealed container, the container was airtightly partitioned into two chambers, and one chamber had a gauge pressure of 1
This was carried out by introducing hydrogen gas at 7 am'' and measuring the amount of hydrogen gas that permeated into the other chamber maintained at atmospheric pressure.

As can be seen from FIG. 2, the gas permeable layer 2 obtained by the method for producing a gas permeable membrane of the present invention has 1) 'r F
The lower the proportion of E, the higher the gas permeation rate.

Experimental Example 2J It was investigated how the gas permeation rate of the gas permeation layer 2 created by the manufacturing method of the present invention changes depending on the differential pressure.

The membrane used in this experiment was made of PTF with an average particle size of 0.25 μl.
Carbon 70 with E30wt% and average particle size 0.042μm
wt%, the film thickness was "■", and the diameter of the pores formed was 700 to 200. The film was created by the same method as in Experimental Example 1. Ta.

In the experiment, a membrane was set in the center of a closed container to airtightly partition the container into two chambers, one chamber was maintained at atmospheric pressure, and the pressure difference between the other chamber and the first chamber was 0 and 5. aLm,
While introducing hydrogen gas or oxygen gas so that OaLl"' It was done by

The results are shown in Figure 3.

From FIG. 3, it was confirmed that the gas permeation rate of the gas permeation 52 produced by the gas permeation membrane manufacturing method of the present invention is proportional to the differential pressure. It was also confirmed that the permeation rate is faster for hydrogen than for oxygen, and that the thinner the gas permeable layer 2 of the gas permeable membrane obtained by the manufacturing method of the present invention is, the higher the permeation rate is.

"Experimental Example 3" In the method for manufacturing a gas permeable membrane of the present invention, the gas permeable layer 2
It was investigated how the porosity of the PTFE changes depending on the press pressure used to form the gas permeable layer 2 and the pretreatment applied to the PTFE.

First, a membrane corresponding to the gas permeable layer 2 was created in the same manner as in Experimental Example 1. At that time, the 11 three powers of the pot press are 10~
It was varied between 600 kg/ax''. PTP used
F: has an average particle size of 0.25 μl, and this 1'TFE
70 parts by weight of carbon having an average particle size of 0.042 μm was mixed into 30 parts by weight. This mixture was subjected to the following 3MM treatments, namely: ■Freeze drying treatment, ■Freezing treatment,
We decided to perform alcohol immersion treatment.

Each 1.0 g portion of the mixture subjected to these treatments was molded. The molding temperature during hot pressing was 380° C. in terms of material temperature. The average diameter of the pores in the formed membrane is 500.
It was about 1 Angstrom.

Mercury was injected into the molded membrane to measure the pores m of the membrane.

The results are shown in Figure 4.

From FIG. 4, it was confirmed that the higher the press pressure was used, the lower the porosity was. Also, P'r I? It was confirmed that by soaking a mixture of E and carbon in alcohol, a gas permeable membrane with high porosity could be created.

"Experimental Example 4" It was investigated how the porosity of the gas permeable layer 2 created by the method for manufacturing a gas permeable membrane of the present invention changes depending on the proportion of PTFE.

A membrane corresponding to gas permeable layer 2 was created in the same manner as in Experimental Example 4. PTFE that has been subjected to freezing treatment is used, and P
The cases where TFE: carbon black = 30 parts by weight, near 0 parts by weight, and 40 parts by weight = 60 parts by weight were investigated. The diameter of the pores in the membranes formed was approximately 500 on average.

Mercury was injected into the formed membrane to measure the pores m of the membrane.

The results are shown in Figure 5.

From FIG. 5, it was confirmed that the porosity was lower when the proportion of PTPE was higher. Furthermore, it was confirmed that when the press pressure was increased, the porosity of the material with a high proportion of PTl-1 decreased rapidly.

"Experimental Example 5" The relationship between the porosity and water pressure resistance of the gas permeable layer 2 produced by the method for producing a gas permeable membrane of the present invention was described.

The membrane prepared in Experimental Example 3 was attached liquid-tightly to the side wall of the container having an opening, and water was poured into the container. The water pressure of the tank was checked and the water pressure was determined to be resistant.

The results are shown in Figure 6.

From FIG. 6, it was confirmed that the lower the porosity of the gas permeable layer 2 produced by the gas permeable membrane manufacturing method of the present invention, the higher the water pressure resistance.

"Experimental Example 6" It was investigated how the water pressure resistance of the gas permeable membrane 52 produced by the gas permeable membrane manufacturing method of the present invention changes depending on the proportion of PTFE.

The experiment was conducted by attaching the membrane prepared in Experimental Example 4 in a liquid-tight manner to the side wall of a container having an opening, and applying pressure by injecting water into the container.

The results are shown in FIG.

From Figure 7, it can be seen that the amount of PTr'E is 30 wt% and 40 wt%.
It was confirmed that there was no significant difference in the water pressure resistance of the gas permeable layer 2 between the gas permeable layer 2 and the gas permeable layer 2.

"Experimental Example 7" The membrane produced in Experimental Example 3 regarding the water pressure resistance of the gas permeable layer 2 produced by the gas permeable membrane production method of the present invention and the press pressure during production was liquid-tightly attached to the side wall of a container having an opening. Attach to,
The water pressure resistance of the membrane was examined by injecting water into the container.

The results are shown in FIG.

From FIG. 8, it was confirmed that the gas permeable layer 2 of the gas permeable membrane manufactured by the manufacturing method of the present invention has better water pressure resistance as the gas permeable layer 2 is manufactured at a higher press pressure.

"Experimental Example 8" It was investigated how the water pressure resistance of the gas permeable layer 2 produced by the method for manufacturing a gas permeable membrane of the present invention changes depending on the proportion of I'TFE.

The experiment was carried out by attaching the membrane prepared in Experimental Example 4 in a liquid-tight manner to the side wall of a container having an IJfJ opening, and applying pressure by injecting water into the container.

The results are shown in Figure 9.

From FIG. 9, it can be seen that the gas permeable FrJ2 produced by the gas permeable membrane manufacturing method of the present invention has a higher water pressure resistance as the proportion of PTF'E increases and as the press pressure during manufacturing increases. This was confirmed.

“Experiment Example 9” Using the gas permeable membrane manufactured by the manufacturing method of the present invention,
A prototype gas separation and purification device 3 was manufactured to separate oxygen from air.

FIG. 10 shows a schematic configuration of a prototype gas separation and purification device 3. This device consists of a raw material gas chamber 4 and a solution flow a.
A chamber 5 and a gas recovery chamber 6 are provided in parallel,
A gas permeable membrane A is provided between the raw material gas chamber 4 and the solution distribution chamber 5.
A gas permeable membrane B separates the gas recovery chamber 6 and the solution distribution chamber 5 from each other. Further, the gas permeable membranes A1B are installed such that the reaction layer 1.1 is located on the solution distribution chamber 5 side. The distance between the membranes Δ, 8 is set to IJIjI.

The specifications of the gas permeable membrane A used in this experiment are as follows.

■) Gas permeable membrane A Structure: Reaction layer 1 with thickness O, La+x and gas permeable T with thickness 0.5 mm! A three-layer trench structure in which j2 and copper mesh are laminated in sequence.

Area: 900CI" a) Reaction layer 1 Composition: 70 parts by weight of carbon, average particle size 0.038μ11
) Parts by weight of TFE3G, average particle size 0.25 μl Catalyst: Platinum type, average particle size 50 b) Gas permeation layer 2 Composition: 70 mm parts carbon, average particle size 0.042711
1 PTFE 70 parts by weight, average particle size 0.25 μ Shoulder porosity =
65% Pore diameter: average 450 ■) Gas permeable membrane B Structure: Fl-SaQ, 1xxcD reaction layer 1 and thickness 0.5x
x(1): // 3-layer structure in which 7° infiltrated FeI2 and copper mesh are sequentially laminated.

Area: 900 ci' a) Reaction layer I Composition: 30 parts by weight of carbon, average particle size 0. Q48μlP
T F E3G parts by weight, average particle size 0.25 μl catalyst:
Nickel-based, average particle size aOO b) Gas permeation layer 2 Composition: 65 parts by weight of carbon, average particle size 0.042 μz 1
'TFFL: 35 parts by weight, average particle size 0.25 μx porosity = 65% Hole diameter: 450 people on average , potassium hydroxide (
Kol-I) 20wt% solution at 0.1212/min, 2
, 2 kg, 7 am".G (gauge pressure). Furthermore, air of 0.01 ky/ax".G was supplied to the raw material gas chamber 4 at a rate of 80 Q/min. Then, the gas permeable membrane is used as a cathode, the gas permeable membrane B is used as an anode, and a voltage of 0, which is lower than the voltage (1.25 V) required for water electrolysis, is applied between the gas permeable membranes A and I1.
．． 96V and a current of 450A were applied.

When the apparatus was operated under the above conditions, the purity of 99.99% and the pressure of 2 kg/ax''・G (approximately 3
atm) of oxygen was obtained at a rate of 1.5612 (standard @) per minute.

Then, instead of the above potassium hydroxide solution, 20wt
When a similar experiment was conducted using a % sodium hydroxide solution, it was possible to separate 1.5512/min of oxygen (purity 99.99%) from air under standard conditions.

Since the gas permeable membrane produced by the manufacturing method of the present invention has a strong pressure resistance (approximately 20 kg/ax" or more), the gas separation and purification device 3 equipped with the gas permeable membrane of the present invention can be used in the solution distribution chamber 5. This makes it possible to maintain high pressure.

In this device, a gas having a pressure approximately equal to the pressure in the solution distribution chamber 5 can be obtained, so by increasing the pressure in the solution distribution chamber 5, a large amount of high-pressure oxygen can be produced.

“Experimental Example 10J Hydrogen gas was purified using the same gas separation and purification device y13 as in Experimental Example 9.

The specifications of the gas permeable membrane A113 used in this fruit pod are as follows.

■) Gas permeable membrane A Structure: Three-layer structure in which a reaction layer I with a thickness of O, Lxm, a gas permeable layer 2 with a thickness of 0.5xg, and a copper net are laminated in sequence.

Area: 000cz" a) Reaction layer 1 Composition: 0ffi parts of carbon, average particle size 0.038μ
lr'Tr;"30 parts by weight of E, average particle size 0.25μ Shoulder catalyst: Platinum-based, particle size 50 b) Gas permeation layer 2 Composition: 70 parts by weight of carbon, average particle size 0.042μ order P
TI? E30fflff 1 part, average particle size 0.25μx porosity 264% Pore diameter: average 440 people'') Gas permeable membrane B Structure: Thickness O, 1IIJF reaction layer l and thickness 0.5xx
A three-layer structure in which a gas permeable layer 2 and a copper mesh are sequentially laminated.

Area: 900CJII' a) Reaction if Composition: 70 parts by weight of carbon, average particle size 0.038 μIP
T F E 30 parts by weight, average particle size 0.25 μl Catalyst: Platinum based, particle size 50 b) Gas penetration T! J2 Composition: Force-yi! 770ffim N, average grain 11
0.042 μx PTF'E 30 parts by weight, average particle size 0.2
5μ Porosity: 64% Hole diameter: 440 people on average A 5% by weight diluted sulfuric acid solution was added to the solution distribution chamber 5 of the gas separation and purification device 3 equipped with such gas permeable membranes Δ and B.
．． It was supplied at a rate of 212/min, 2.2 kg/ax"-Q. In addition, the raw material gas chamber 4 was supplied with a purity of 99% containing oxygen and nitrogen.
of hydrogen gas to 0.01 97cm”・G.

It was fed at a rate of 812/min. Then, the gas permeable membrane A is used as an anode,
Gas permeable membrane B is used as the cathode, and the voltage between gas permeable rtXA and B is 0.2V (this value is the minimum voltage required for water electrolysis of 1.2V).
(lower than 5 V) and a current of 900 A was applied.

When the apparatus was operated under the following conditions, hydrogen gas with a purity of 99.999% and a pressure of 2 kg/cm"-c was obtained from the gas recovery chamber 6 at a rate of 6.2 G (l) per minute in terms of standard conditions. Ta.

In this apparatus, the energy required to purify 1 m' of hydrogen gas under standard conditions was 0.48 KW·hr. On the other hand, in the case of conventional hydrogen purification using a palladium slag, it is 1, OKW-hr/ff3, and in the case of cryogenic hydrogen purification, it is 1,2 KW-hr/z'. It was confirmed that the gas separation and purification device 3 equipped with the created gas permeable membrane could efficiently purify hydrogen gas.

Further, in this device 3, it is considered that energy efficiency can be further improved by further increasing the distance between the membranes A and B.

Experimental Example 11J A gas generator 7 using the gas permeable membrane produced by the production method of the present invention was prototyped to produce hydrogen gas and oxygen gas.

FIG. 11 does not show the schematic configuration of the experimentally manufactured gas generator 7. This device consists of a generated gas recovery chamber 9 and IO provided on both sides of a solution distribution chamber 8, and the solution distribution chamber 8 and generated gas recovery chamber 9 and IO are separated by gas permeable membranes A and B, respectively. It is being The gas permeable membranes A and B are each attached so that the reaction B 112 faces the solution distribution chamber 8 side, and the distance between GA and 111 is set to f ax.

The specifications of the gas permeable membranes A and B used in this experiment are as follows.

[) Gas permeable membrane A Structure: 3-layer structure in which a reaction layer 1 with a thickness of 0.1 mm, a gas permeable layer 2 with a thickness of 0.5 zx, and a copper net are laminated in sequence.

Area + 900ca + @ a) Reaction layer! Composition: 65 parts by weight of carbon, average particle size 0.042μ11
) TFE 35 parts by weight, average particle size 0.25Bm catalyst: 1
1 uOt system, particle size 100 b) Gas permeation layer 2 Composition J) - E: z 70fflfL5J, average particle size 0, 042 μz PTFE 30 parts by weight, average particle size Q
, 25 μz porosity = 65% Pore diameter: average 460 + 1 > Gas permeable membrane B Structure: Reaction layer 1 with a thickness of 0.1xx, gas permeable layer 2 with a thickness of 0, 5xm, and copper mesh are laminated in sequence. Three-layer structure.

Area: 900 cz” a) Reaction Ji!1 Composition: 70 parts by weight of carbon, average particle size 0.038μ Shoulder P
'l' FE 30 parts by weight, average particle size 0.25 μx Catalyst: Platinum type, particle size 50 b) Gas penetration P! 2 Composition: 70 parts by weight of carbon, average particle size 0.042μlP
'r F E 30fflff1 part, average particle size 0.2
5 B
．． While supplying at 1212/min, 2,2 kg/ax”-G, a voltage of 1.8 VS current 9 was applied between the gas permeable membranes A and 8.
00A was applied. At this time, gas permeable membrane A was used as an anode, and gas permeable membrane B was used as an anode.

When the device was operated under the above conditions, the generated gas recovery chamber 9
3.1312 per minute (under standard conditions) of oxygen gas from the generated gas recovery chamber! 0 to 6.2512 hydrogen gas per minute (under standard conditions).

Then, instead of the sulfuric acid solution, an alkaline solution (25
When similar experiments were conducted using a neutral solution (wt% potassium hydroxide solution), a neutral solution (20wL% sodium sulfate solution), etc., oxygen gas and hydrogen gas could be similarly produced efficiently.

In addition, when one of the permeable membranes A and I'3 was replaced with the electrode of a conventional electrolyzer and the gas generator 7 was operated,
Oxygen gas and hydrogen gas were also obtained in the same way. When the apparatus 7 was operated in this manner, the life of the membrane could be extended.

"Experimental Example 12" Carbon dioxide gas and hydrogen gas were produced using the gas generator 7 of Experimental Example II.

The specifications of the gas permeable membranes A and B used in this experiment are as follows.

■) Gas permeable membrane A (11 Hikozo: Reaction layer with thickness 0.1xtx! and thickness 0.5
A three-layer structure in which m-shoulder gas-permeable Fr32 and copper mesh are sequentially laminated.

a) Reaction layer! Composition: 70 parts by weight of carbon, average particle size 0.042μlP
'rFE 30 parts by weight, average particle size 0.25 μm catalyst, platinum-based catalyst with 5 particle sizes, and particle size 100 N u O-based catalyst b) Gas permeation layer 2 Composition: carbon flow heavy part ffi, average particle size Diameter 0.042μ
1 PTFE 30 parts by weight, average particle size 0.25μz Porosity:
65% Pore diameter: 450 people on average ■) Gas permeable membrane B Structure: Thickness 0Axx reaction JF! It has a three-layer structure in which violet, gas permeation 52 with a thickness of 0.5xx, and copper mesh are laminated in sequence.

Area: 900cm” a) Reaction layer! Composition: 70ffl parts of carbon, average particle size 0.038μ
Next P T F 930 mm part, average particle size 0.25 μm Catalyst: Platinum type, particle size 50 b) Gas penetration report 2 Composition: Carho 77Otlff m part, average 1elO,0
42 μ x 30 parts by weight of PTFE, average particle size 0.25 μ Shoulder porosity = 65% Pore drilling: Average of 450 people First, add 1 part of methanol to 0.5 mol# dilute sulfuric acid solution.
A raw material solution containing 0vo1% mixture was created. Then, while supplying this raw material solution to the solution distribution chamber 8 of the gas generator 7 at a rate of 2.0 kg/ax''·G for 0.LU, a voltage of 0.6 to 0.0 kg was applied between the gas permeable membranes Δ and 8. 7 V and a current of 450 A were applied.At this time, the gas permeable membrane was connected to the anode, and the gas permeable membrane B
was used as the cathode. Further, the temperature of the raw material solution was 65°C.

When the device was operated under the above conditions, the generated gas recovery chamber 9
purity 99.9%, pressure I, 5 ky/am'
-G carbon dioxide gas per minute converted to standard state is 1.0312
, purity 99.9%, pressure 1 from the generated gas recovery chamber 10,
It was possible to obtain hydrogen gas of 5 kg/Cm''·G at a rate of 6.24Q per minute when converted to standard conditions.

In this device, since methanol has a depolarizing effect, it was possible to significantly reduce power consumption.

Here, the characteristics of the gas separation and purification device 3 and the gas generation device 7, which are equipped with the gas permeable membrane produced by the manufacturing method of the present invention, will be listed.

Furthermore, by using the gas permeable membrane created by the manufacturing method of the present invention, it is possible to manufacture a device that can produce and purify six types of gases, including not only oxygen gas and hydrogen gas but also chlorine gas, as long as they can be ionized. be able to.

``Effects of the Invention'' As explained above, the method for manufacturing a gas permeable membrane of the present invention is as follows: First, a paste-like mixture is prepared from fine particles serving as a catalyst carrier, fine particles of a binder material, and a liquid lubricant. A material is pressurized and formed into a sheet to create Sheet A. At the same time, a paste-like mixture is created from conductive fine particles, binder material fine particles, and liquid lubricant, and this material is pressurized to form a sheet. Form it into a shape to create sheet B,
■Next, these sheets A and B are piled up and pressure-welded to make the thickness thinner while bonding.■Next, this sheet is sequentially subjected to drying treatment and heat treatment.■The gas permeable membrane is formed by hot pressing and further thinning. It's manufacturing. Therefore, according to the manufacturing method of the present invention, it is possible to manufacture a gas permeable membrane that has good gas permeability and conductivity, and also has excellent pressure resistance (20 kv/ax” or more). According to the gas permeable membrane produced by the manufacturing method of the invention, the pressure of the solution distribution chamber partitioned by the gas permeable membrane can be set high, and a small gas separation and purification device or gas can be produced that can purify or produce a large amount of high-pressure gas. A generator can be configured.

In addition, the gas permeable membrane produced by the manufacturing method of the present invention has excellent pressure resistance, so gas separation and purification equipment and gas generation equipment using this membrane can apply pressure to the electrolyte. . Therefore, according to the gas permeable membrane produced by the manufacturing method of the present invention, it is possible to provide an apparatus that also has the function of pressurizing gas, which can obtain high-pressure gas from each electrode without mixing.

Furthermore, since the gas permeable membrane produced by the manufacturing method of the present invention has a good gas-liquid separation function, gas separation and purification equipment and gas generation equipment equipped with this membrane have high purity (9.
9,999% or more) gas can be obtained.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view showing an example of a gas permeable membrane produced by the manufacturing method of the present invention, and FIGS. 2 to 9 each show the results of experiments. A graph showing the relationship between velocity and the composition of the gas permeable layer. Figure 3 is a graph showing the relationship between the gas permeation rate and differential pressure of the gas permeable layer. Figure 4 shows the porosity of the gas permeable layer and the composition at the time of manufacture. A graph showing the relationship between press pressure and pretreatment applied to PTFE,
Figure 5 is a graph showing the relationship between the porosity of the gas permeable layer and the press pressure during manufacturing and the proportion of PTFE. Figure 6 is a graph showing the relationship between the porosity of the gas permeable layer and water pressure resistance. The figure is a graph showing the relationship between the water pressure resistance of the gas permeable layer and the proportion of PTFE. Figure 8 is a graph showing the relationship between the water pressure resistance of the gas permeation layer and the press pressure during manufacturing. Figure 9 is the graph showing the relationship between the water pressure resistance of the gas permeation layer and the press pressure during manufacturing. and PTF
Graph showing the relationship between the proportions of E, Figure 10 and Figure 1! Each figure is a schematic configuration diagram showing a gas generator using the gas permeable membrane of the present invention. I... Reactive stone, 2... Gas permeable membrane.

Claims (2)

[Claims] (1) A method for producing a gas permeable membrane, in which a reaction layer in which a catalyst is supported on a carrier formed by bonding fine particles is laminated on a porous gas permeable layer formed by bonding conductive fine particles. First, fine particles that will serve as a carrier for the catalyst, fine particles of a binder material, and a liquid lubricant are kneaded to create a paste-like mixture, and this mixture is pressurized and formed into a sheet to form sheet A that will be a carrier for the reaction layer. At the same time, conductive fine particles, binder material fine particles, and liquid lubricant are kneaded to create a paste-like mixture, which is then pressurized and formed into a sheet to form sheet B, which becomes the gas permeable layer. The above-mentioned sheets A and B are then piled up and pressure-welded to bond them and thinned, and then this sheet is sequentially subjected to drying treatment and heat treatment, and then this sheet is hot-pressed to further thin the sheet. A method for producing a gas permeable membrane. (2) The method for producing a gas permeable membrane according to claim 1, characterized in that the fine particles forming the sheet A include both water-repellent particles and hydrophilic particles.