JPH06102152B2 - Molecular sieve activated carbon, a method for producing the same, and a method for separating a specific gas from a mixed gas using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to activated carbon having a molecular sieving action, a method for producing the molecular sieving activated carbon, and a method for separating a specific gas from a mixed gas using the activated carbon. It is about.

Conventional technology Conventional activated carbon, which has been used for various purposes for a long time, has a very large specific surface area of 700 to 1600 m ² / g, but its pore size distribution is also very wide, and the upper limit of the distribution is up to several thousand Å. Has reached Therefore, the diameter of parallel pores is large, and it does not have the property of selectively adsorbing only a specific component by a molecular sieving action such as zeolite.

However, in recent years, research on carbon-based molecular sieves, so-called molecular sieve activated carbons, for separating them from a mixed gas containing a gas having a small kinetic gas molecular system such as oxygen and nitrogen, has been actively conducted, and some of them are commercially available. .

(A) For example, in Japanese Examined Patent Publication No. 56-28846, hard vegetable carbon is dried and then activated by an activating gas, soluble components are removed by acid and water, and dried and then reactivated by the activating gas. A method is disclosed. This method follows the conventional method for producing activated carbon and precisely adjusts the treatment conditions to produce activated carbon for adsorbing small molecules having a molecular sieving action.

Further, in Japanese Patent No. 930875 (Japanese Patent Publication No. 52-47758), polyvinylidene chloride deoxidized is pulverized,
There is disclosed a method of producing a carbon-based molecular sieve by adding a granulating agent and a sintering agent to the resulting mixture, granulating the mixture, and further performing carbonization at a high temperature. This method is a unique method using polyvinylidene chloride instead of conventional wood-based, coal-based, tar pitch-based, etc., and utilizes the fact that carbon produced by firing forms a special skeleton structure. .

(B) By the way, as a method for producing the molecular sieve activated carbon that has been reported so far, there are many methods in which a carbon material is used as a starting material and carbon is deposited on the carbon material by some method.

For example, Japanese Patent Publication No. 20322/1985 discloses that the above-mentioned Patent No. 930
As an improved method of No. 875, char obtained by dehydrochlorinating polyvinylidene chloride waste is finely pulverized, and an organic substance that produces strong coke by carbonization is mixed as a binder and adhered at room temperature. A method of granulating a mixture of an organic substance having a property and carbonizing at a high temperature is disclosed.

In addition, Japanese Patent Publication No. 49-37036 discloses a method in which a raw material for producing a phenolic resin or a furanic resin is adsorbed on activated carbon, polymerized and condensed, and then heated at a high temperature.

Japanese Patent Publication No. 52-18675 discloses a method in which a hydrocarbon that releases carbon by thermal decomposition is added to coke and treated at high temperature to deposit the released carbon in the pores of the coke. There is.

JP-A-59-45914 discloses that coconut shell charcoal powder is granulated using coal tar pitch and / or coal tar as a binder, and the carbonized carbon obtained by carbonization is washed with a dilute mineral acid aqueous solution and washed with water. After that, a method of drying and then adding coal tar pitch and / or coal tar and heat treating at high temperature is shown.

In Japanese Patent Laid-Open No. 60-171212, a microporous carbon substrate is degassed at a high temperature, then cooled to a medium temperature and then contacted with a vapor phase hydrocarbon at this temperature to bring the hydrocarbon inside. Sorbing and then degassing under reduced pressure to remove physically retained hydrocarbons from the carbon substrate, and then decomposing residual hydrocarbons that have adhered to the pores of the substrate at a higher temperature. A method of depositing pyrolytic carbon in the pores is shown.

(C) As another method, in JP-A-60-150831, a nitro group and a sulfone group are introduced into mesocarbon microbeads, and then 300 to 600 ° C. in a non-oxidizing atmosphere.
The method of heat treatment is shown. The mesocarbon microbeads are mainly composed of a condensed polycyclic aromatic compound, and the compounds are arranged in a certain direction to form a lamella (thin layer), and the lamella has a laminated structure.
This method is a method in which a functional group is previously introduced by a chemical method, a desired pore size is secured, and then the functional group is eliminated and removed.

(D) Further, JP-A-49-106982 discloses a method of reducing pores of a carbon material with an organic compound having a boiling point of 200 to 360 ° C. under normal pressure or reduced pressure. This method uses relatively high boiling organic compounds to form pores without carbonization.

Problems to be Solved by the Invention However, the method of Japanese Patent Publication No. 56-28846 described in (a) has a wide variety of steps and requires high-temperature treatment, and thus is not an economical method. Further, the method of Japanese Patent No. 930875 has a drawback that the yield of the carbon-based molecular sieve obtained from the raw material polyvinylidene chloride is low.

The method described in (b) is a method of precipitating carbon in a carbon material by some method to narrow the pores with deposited carbon to reduce the pore diameter, but a large volume reduction is observed in the carbonization step, It is difficult to effectively reduce the pore size. For this reason, it is necessary to perform the treatment a plurality of times, perform a high temperature treatment in order to reduce the entire carbon skeleton, and perform heating, cooling, and reheating, which is a problem in terms of pore size control and economy. There is.

The method described in JP-A-60-150831 described in (c) above involves complicated and diversified steps for obtaining mesocarbon microbeads as a starting material, and the yield is about 10%. There is a problem with sex.

In the method described in JP-A-49-106982 described in (d), the boiling point of the organic compound used as a pore-reducing agent is also 200 to 300 ° C.
Is. Such an organic compound is a liquid at room temperature or a liquid having a melting point of up to 216 ° C., which easily becomes a liquid and is thermally unstable. Therefore, depending on the conditions of use, such as the degree of vacuum and temperature, this organic compound may dissipate from the carbon material, and accordingly, the pore diameter also changes, so that it cannot be used stably. Further, the generated pores are very large, 0.2 to 0.6 μm.

As described above, the conventional method for producing activated carbon having molecular sieves is a method of making through many complicated steps involving high-temperature heat treatment, which is problematic in terms of controllability of pore diameter adjustment and production cost, or Although it does not require such a high temperature, the resulting molecular sieve activated carbon lacks stability and only a production method having a problem of life is presented.

The present invention is intended to solve such problems, a method for efficiently controlling the pore size adjustment while satisfying the simplification of the treatment process and energy saving, and a normally expected use condition. The present invention intends to provide a molecular sieve activated carbon which is stable to heat and pressure and has a narrow average pore size and a narrow average pore size.

Means for Solving Problems The present inventors have been researching various complex compounds as oxygen carriers having affinity with oxygen for many years, and in the course of the research, they arrived at the present invention described below. .

That is, the molecular sieve activated carbon of the present invention is characterized by having a structure in which a phthalocyanine compound is vapor-deposited on the surface of activated carbon.

The method for producing a molecular sieve activated carbon of the present invention is characterized in that the phthalocyanine compound is vapor-deposited on the surface of the activated carbon by heating and sublimating phthalocyanines at a temperature of 350 to 750 ° C. under normal pressure or reduced pressure. is there.

Furthermore, the method for separating a specific gas from the mixed gas of the present invention is a method in which a characteristic gas is separated from the mixed gas by a pressure fluctuation type adsorption separation method. It is characterized by being used.

From the IR spectrum, X-ray diffraction, etc., it was confirmed from the IR spectrum, X-ray diffraction, etc., that the activated carbon of the molecular sieve of the present invention was reduced by covering the periphery of the pores or gaps of the activated carbon with the vapor-deposited phthalocyanine compound. From the measurement of the pore size distribution and the gas adsorption property, it was found that the average pore size could be arbitrarily adjusted to 10 Å or less.

Thus, in the molecular sieve activated carbon of the present invention, the phthalocyanine-based compound is vapor-deposited on the periphery of the pores or gaps of the activated carbon, and the pores or gaps of the activated carbon are reduced by this vapor deposition with good controllability. It is suitable for the purpose of separating a specific gas, particularly for the purpose of separating oxygen and nitrogen in the air by selectively adsorbing oxygen in the air.

The phthalocyanine compound used in the present invention is thermally and chemically stable, generally sublimates at 350 to 500 ° C. under vacuum for the first time, does not melt at a temperature below this, and is resistant to acids and alkalis. It is also insoluble in most melts. Therefore, the molecular sieve activated carbon of the present invention is extremely stable and maintains its function almost permanently under normal use conditions.

The phthalocyanine compound used in the present invention,
Examples thereof include metal phthalocyanines and / or free phthalocyanines.

As the metal phthalocyanines, manganese phthalocyanine, iron phthalocyanine, cobalt phthalocyanine, nickel phthalocyanine, chromium phthalocyanine, copper phthalocyanine, tin phthalocyanine, zinc phthalocyanine,
Platinum phthalocyanine, palladium phthalocyanine and the like are exemplified, and derivatives of these chlorine-substituted compounds, sulfonic acid-substituted compounds, sulfonamide-substituted compounds, carboxylic acid-substituted compounds and the like can also be used. Other metal phthalocyanines can be used as long as they exhibit sublimability.

As the free phthalocyanines, free phthalocyanines having no metal ion as a central ion are used, and derivatives thereof such as chlorine-substituted compounds, sulfonic acid-substituted compounds, sulfonamide-substituted compounds, and carboxylic acid-substituted compounds can also be used.

As the activated carbon for depositing the phthalocyanine-based compound, wood-based, coal-based, various activated carbon such as tar pitch-based,
Those belonging to the broad category of activated carbon such as coke are used. The shape of activated carbon is powder, granular, crushed material,
Although it may be in the form of a molded product, it is preferable to use a material having a relatively uniform pore distribution and a small average pore diameter as the starting material.

Next, the method for producing the molecular sieve activated carbon of the present invention will be described in more detail.

When powdered activated carbon is used as a starting material, a finely divided powder of a phthalocyanine-based compound in a predetermined ratio is uniformly mixed with it in an atmosphere of an inert gas such as helium or nitrogen under normal pressure or reduced pressure, or inert gas. Heat sublimation is performed for a certain period of time under reduced pressure without using gas.

When the granular, crushed, or molded activated carbon is used as a starting material, the phthalocyanine-based compound is finely pulverized in advance with a ball mill or the like, and then a surfactant is used to disperse the dispersion medium such as water or alcohol (especially water). -Alcohol mixture system is preferred) to prepare a dispersion liquid having a predetermined concentration, and the activated carbon that has been sufficiently deaerated under reduced pressure is immersed in this dispersion liquid under reduced pressure for impregnation to carry out impregnation. After that, the dispersion medium is sufficiently distilled off from the activated carbon under normal pressure or reduced pressure at room temperature or under heating (for example, 50 to 150 ° C). The activated carbon having the phthalocyanine-based compound uniformly supported on the surface obtained in this manner is converted into helium in the same manner as in the case where the above-mentioned powdered activated carbon is used as a starting material.
Heat sublimation is performed for a certain period of time under an atmospheric pressure or reduced pressure in an atmosphere of an inert gas such as nitrogen, or under a reduced pressure without using an inert gas.

The heating temperature in the heat sublimation treatment is set to 350 to 750 ° C, preferably 400 to 650 ° C. Further, as the inert gas used at this time, helium is particularly preferable because of its small molecular diameter and large thermal conductivity. Further, generally, the heat sublimation treatment is often preferably performed under reduced pressure in order to accelerate the sublimation rate, but the degree of reduced pressure at that time is 50 Torr or less, more preferably 1 Torr or less, and further preferably about 10 ^-2 Torr. Or less. The time for performing the heat sublimation treatment is usually 1 to 4 hours, more preferably 2 to 3 hours.

When separating a specific gas from a mixed gas by a pressure fluctuation type adsorption separation method using the molecular sieve activated carbon produced as described above as an adsorbent, for example, the adsorption pressure is not less than atmospheric pressure and less than about 10 kg / cm ² G. And set the regeneration pressure to atmospheric pressure or below atmospheric pressure. A specific example of the pressure fluctuation type adsorption / separation device will be illustrated in Example 18 described later.

The industrial application field of the molecular sieve activated carbon of the present invention is extremely wide, for example, for separating a specific gas from a mixed gas, in particular, oxygen and nitrogen in the air are subjected to a pressure swing adsorption separation process, so-called PSA. Various chemical industries as adsorbents,
Electronics industry, food industry, agriculture and fisheries industry, heat treatment of metal, metallurgy,
Used in the field of ships, etc. In addition, by making use of its inert gas characteristics, it is often used for holding, for preventing oxidation, for suppressing breathing of living organisms, for fermentation of microorganisms, or for nitriding hardening treatment of metals, and other chemical substances. As a material for separation from a mixture, it can be widely used for analysis as a column packing for gas chromatography and separation processes of various chemical industries.

Action Since the molecular sieve activated carbon of the present invention has a narrow pore distribution and is well aligned, it is closer to the pore distribution of zeolite. Therefore, in order to separate oxygen and nitrogen well, the average pore size is reduced enough to be close enough to the dynamic molecular size of these molecules. To do. That is, in the molecular sieve activated carbon of the present invention having the pores adjusted as described above, the adsorption amount of oxygen increases almost in proportion to the adsorption pressure and the adsorption time,
While the adsorption amount tends to increase as the adsorption temperature decreases, the dependency of the adsorption amount of nitrogen on the adsorption pressure, adsorption time and adsorption temperature is small. In other words, it can be said that the activated carbon is a molecular sieve activated carbon that highly suppresses adsorption of nitrogen and selectively adsorbs oxygen. Moreover, the amount of oxygen adsorbed at this time is equal to or higher than that of the conventional molecular sieve activated carbon, and its industrial application value is extremely large.

The factors affecting the adsorption selectivity of zeolites and carbon adsorbents for oxygen and nitrogen are generally the correlation between the electric quadrupole efficiency of nitrogen and the electrochemical characteristics of the zeolite pore surface It is said that, in the carbon adsorbent without any additives other than carbon, there is no difference in the electrochemical affinity between the carbon constituting the pore surface and these oxygen and nitrogen, However, it is considered that the molecular size of these gases and the pore size of the carbon adsorbent are greatly related. Therefore,
The molecular sieve activated carbon of the present invention is a phthalocyanine-based compound which is also an oxygen carrier to reduce the pores of activated carbon so that the size of the pores or gaps involved in the separation of these gases is adjusted to, for example, around 3Å, and the pore distribution is measured. As shown in the results, the structure in which the large pores that allow the co-adsorption of the larger molecule, nitrogen, are extremely small and the pore distribution is narrow and uniform is expected to improve the adsorption selectivity. It seems to have contributed.

EXAMPLES Next, the present invention will be further described with reference to Examples.

In the following, the device shown in FIG. 8 was used as the adsorption experiment device. In the figure, (1) is a cylinder, (2) is a buffer tube, (3) is a sample tube, (4) is a vacuum pump,
(5) is a pressure gauge, (6) is a pressure sensor, (7) is a recorder, (8a), (8b) and (8c) are valves, and (9) is a sample filled in a sample tube (3) (vapor deposition). Activated carbon).

The adsorption experiment operation using this adsorption experiment apparatus was performed as follows.

In the next step, adsorption operation for oxygen gas is performed.

The sample is put in the sample tube (3), the valve (8c) is closed, the valves (8a) and (8b) are opened, and vacuum exhaust is performed.

The valves (8a) and (8b) are closed, the valve (8c) is opened, oxygen gas is introduced from the cylinder (1), and the valve (8c) is closed under a certain constant pressure.

The valve (8a) is opened and the adsorption curve is recorded by the recorder (7) through the pressure sensor (6).

Similarly, adsorption operation is performed for nitrogen gas.

Helium gas is used as a blank to determine the adsorption amount.

In the following examples, the pressure inside the buffer tube (2) was set to a constant value of 2.0 kg / cm ² G.

Example 1 A molecular sieve activated carbon was produced and an adsorption experiment using the same was performed by the following process operations.

(A) Granular activated carbon (MSC-5 manufactured by Takeda Pharmaceutical Co., Ltd.)
A) 3.0 g of powder is mixed with 0.3 g of iron phthalocyanine, and used as a sample.

(B) Pyrex or quartz glass tube (inner diameter 10 mm,
The above sample is put in a length of 150 mm), and it is evacuated at 10 ^-2 Torr for 2 hours, and then the tube is sealed.

(C) Heat in an electric furnace at a heating rate of 8 to 10 ° C / min to 450 to 500 ° C, and keep the temperature for 1 hour.

(D) After slowly cooling this, put it in a sample tube and perform an adsorption experiment, and record the adsorption curve.

The adsorption curve at this time is shown by the solid line in FIG. In the adsorption curve, the vertical axis represents the adsorption amount and the horizontal axis represents time. The curve shown by a broken line in FIG. 1 is a blank, and is a case where only the granular activated carbon MSC-5A powdered is used. (The adsorption curves shown by the broken lines in the other figures are also the case where only activated carbon is used.) The pore distribution curve of the molecular sieve activated carbon obtained above is shown by the broken lines in FIG. The pore distribution curve of only the granular activated carbon MSC-5A powder is shown by the solid line in FIG. From FIG. 2 as well, the activated carbon as a base material has a wide pore size distribution and a large average pore size, but the vapor-deposited phthalocyanine compound has a narrow pore size distribution and a small average pore size. I understand.

Comparative Example 1 The heating temperature in step (c) in Example 1 was 300 to 350 ° C.
(Lower heating temperature and constant heat retention time) or 750
Experiments were conducted in the same manner as in Example 1 except that the temperature was raised to 800 ° C (the heating temperature was raised and the heat retention time was set constant). The adsorption curve at this time is shown in FIG.

From FIGS. 1 and 3, the activated carbon used as the base material is oxygen,
Although there is no nitrogen adsorption selectivity, it can be seen that by vapor-depositing a phthalocyanine-based compound on this activated carbon, the nitrogen adsorption selectivity was suppressed and oxygen only adsorption selectivity appeared. Further, it is understood that the heating temperature, that is, the sublimation temperature of the phthalocyanine-based compound is an important factor for maximizing the adsorption selection effect of only oxygen.

Examples 2 to 5 Experiments were performed in the same manner as in Example 1 except that the type of activated carbon, the type and amount of phthalocyanine compound used, the heating temperature, and the heat retention time were variously changed.

The conditions and results are shown in Table 1.

The analysis results of the phthalocyanine compound vapor-deposited activated carbons obtained in Examples 1 to 5 were as follows.

 The average pore size is centered at 10Å or less.

From X-ray diffraction and FT-IR, there is an identification peak of the phthalocyanine compound.

Needle-like crystals, which are apparently crystals of phthalocyanine compounds, are observed by scanning electron microscopy.

From the above analysis results of, it was found that the phthalocyanine-based compound plays a role as a pore control agent. However, in addition to the identified peaks obtained by FT-IR, there may be other peaks, and peaks that are considered to be partially decomposed products or polymers having a phthalocyanine skeleton may also appear depending on heating conditions.

Example 6 Production of molecular sieve activated carbon and an adsorption experiment using the same were carried out by the following process operations.

(A) Granular activated carbon (manufactured by Takeda Pharmaceutical Co., Ltd., white eagle-
G) 3.0 g of powder is made into powder and 0.4 g of cobalt phthalocyanine is uniformly mixed to obtain a sample.

(B) Pyrex or quartz glass tube (inner diameter 10 mm,
The above sample is put into a length of 150 mm) and vacuum exhaust is performed at 10 ^-2 Torr for 2 hours.

(C) The interior is shielded from air by passing helium gas under reduced pressure, and while passing a small amount of helium gas, it is heated in an electric furnace to 700 to 750 ° C at a temperature rising rate of 8 to 10 ° C / min and kept at that temperature for 1 hour. To do.

(D) After slowly cooling this, put it in a sample tube and perform an adsorption experiment, and record the adsorption curve.

The adsorption curve at this time is shown in FIG.

Examples 7 to 10 Experiments were conducted in the same manner as in Example 6 except that the type of activated carbon, the type and amount of phthalocyanine compound used, the heating temperature, and the heat retention time were variously changed.

The conditions and results are shown in Table 2.

In Examples 6 to 10 above, vapor deposition of the phthalocyanine-based compound was carried out under normal pressure, but the adsorption amount was not much different from that in Examples 1 to 5 carried out under reduced pressure.
The analysis results of the phthalocyanine compound vapor-deposited activated carbon were also the same as those in Examples 1 to 5 described above.

Examples 11 to 15 Examples 1 to 10 were related to a homogeneous mixed system of powdered activated carbon and powdered phthalocyanine compound, but when the above-mentioned process operation was performed using granular activated carbon, vapor deposition was unsuccessful. Sufficient vapor deposition unevenness occurs.

As a countermeasure against this, Examples 11 to 15 described below employ a method of impregnating a dispersion liquid in which a phthalocyanine compound is dispersed in a dispersion medium into granular activated carbon.

In this case, the phthalocyanine compound is preferably dissolved in a solvent for impregnation, but the phthalocyanine compound is almost insoluble in the solvent but only in concentrated sulfuric acid. Therefore, in order to evenly and uniformly adhere the phthalocyanine compound to the surface of the granular activated carbon, a method of dispersing the phthalocyanine compound in the dispersion medium using a nonionic surfactant and performing vapor deposition under reduced pressure was adopted.

Example 11 A molecular sieve activated carbon was produced and an adsorption experiment using the same was performed by the following process operations.

(A) Granular activated carbon (MSC-5 manufactured by Takeda Pharmaceutical Co., Ltd.)
A) Prepare 3.0g and evacuate for 2 hours.

(B) Manganese phthalocyanine 0.30 g and nonionic surfactant (Emulgen A-90, manufactured by Kao Soap Co., Ltd.) 0.06
g is dispersed in 3.0 g of a mixed solvent having a weight ratio of water and ethanol of 10: 1, and then the activated carbon that has been evacuated under vacuum is added dropwise.

(C) After sufficiently dehydrating this, the heating rate is 8 to 8 in an electric furnace.
Heat to 500-550 ° C at 10 ° C / min and keep the temperature for 2 hours.

(D) After slowly cooling this, put it in a sample tube and perform an adsorption experiment, and record the adsorption curve.

The adsorption curve at this time is shown in FIG.

Examples 12 to 15 Experiments were performed in the same manner as in Example 11 except that the type of activated carbon, the type and amount of phthalocyanine compound, the heating temperature, and the heat retention time were variously changed.

The conditions and results are shown in Table 3.

(See Table 3) In Examples 11 to 15 above, the phthalocyanine-based compound was vapor-deposited on the granular activated carbon, and the adsorption amount was an operation relating to a homogeneous mixed system of powdered activated carbon and powdered phthalocyanine-based compound. There is not much difference from the cases of Examples 1 to 10,
The analysis results of the phthalocyanine compound vapor-deposited activated carbon were also the same as those in Examples 1 to 5 described above.

Example 16 A molecular sieve activated carbon was produced and an adsorption experiment using the same was performed by the following process operations.

(A) Prepare 3.0 g of activated carbon (Hokuetsu Carbon Co., Ltd., Y-20, crushed coal) and evacuate it for 2 hours.

(B) Copper phthalocyanine- (SO ₃ NH ₂ ) n (0 <n <1)
0.4 g and 0.06 g of nonionic surfactant (Emulgen A-90 manufactured by Kao Soap Co., Ltd.) in a weight ratio of water and ethanol of 1
After being dispersed in 3.0 g of a 0: 1 mixed solvent, it is added dropwise to the above-described evacuated activated carbon under vacuum.

(C) After sufficiently dehydrating in a vacuum, the temperature rise rate is 8 to 8
Heat at 650-700 ° C at 10 ° C / min and keep it at that temperature for 3 hours.

(D) After slowly cooling this, put it in a sample tube and perform an adsorption experiment, and record the adsorption curve.

The adsorption curve at this time is shown in FIG.

Example 17 A molecular sieve activated carbon was produced and an adsorption experiment using the same was performed by the following process operations.

(A) 1.0 kg of activated carbon (manufactured by Takeda Pharmaceutical Co., Ltd., White Eagle-G, granular) was put in a three-necked flask of 5 and 100 to 120 ° C.
And heat exhaust for 2 hours.

(B) Iron phthalocyanine 35.0 g, copper phthalocyanine 80.0 g
And 20.0 g of a nonionic surfactant (Emulgen A-90 manufactured by Kao Soap Co., Ltd.) in a weight ratio of water to ethanol of 1
Disperse using 0: 1 mixed solvent 1 (however, use a magnetic ball mill for dispersion).

(C) The above (b) is dropped into the above (a) using a dropping funnel for a sufficient time.

(D) After visually judging that there is no water on the surface,
Drain water at 120-140 ° C for 2 hours in a sand bath.

(E) With the water completely removed, transfer the attached activated carbon to a vacuum electric furnace at 10 ^-2 Torr at a heating rate of 5 to 8 ° C / min.
Heat to 530-580 ° C.

(F) Close the port of the vacuum diffusion pump to remove helium gas 20
After adding to Torr, keep the temperature at 530-580 ° C for 1 hour.

(G) Gradually increase the helium gas, open the exhaust port, and gradually cool.

The adsorption curve of 3.0 g of the sample is as shown in FIG.

Example 18 Using the pressure swing adsorption separation apparatus shown in FIG. 9, the apparatus was filled with the molecular sieve activated carbon produced in Example 11, and nitrogen was separated from air.

In FIG. 9, (10) and (10) are adsorption towers, (11) is a product tank, and (12) is a vacuum pump.

When using two adsorption towers packed with 0.58 (360 g / tower by weight) molecular activated carbon, the adsorption pressure is 4.5 kg / cm ² G, the vacuum regeneration pressure is 10 Torr, and the adsorption time is 120 seconds. The results shown in the table were obtained.

Example 19 The same operation as in Example 18 was performed using the molecular sieve activated carbon produced in Example 16. However, the adsorption time was 90 seconds.
The results are shown in Table 5.

Example 20 The same operation as in Example 18 was performed using the molecular sieve activated carbon produced in Example 17. However, the adsorption time was 60 seconds.
The results are shown in Table 6.

Example 21 Using the molecular sieve activated carbon prepared in Example 11, argon 80
Argon was separated from a mixed gas containing 20% oxygen and 20% oxygen. The apparatus and conditions were the same as in Example 18.
The results are shown in Table 7.

EFFECTS OF THE INVENTION In the molecular sieve activated carbon of the present invention, a phthalocyanine compound is vapor-deposited on the periphery of the pores or gaps of the activated carbon, and the vapor deposition reduces the pores or gaps of the activated carbon with good controllability. This average pore diameter can also be arbitrarily adjusted to 10 Å or less. Therefore, it exhibits excellent selective adsorptivity that suppresses the adsorption of nitrogen extremely and selectively adsorbs oxygen. Further, since the phthalocyanine-based compound is extremely stable both thermally and chemically, the molecular sieve activated carbon of the invention is also extremely stable,
It maintains its function almost permanently under normal use conditions.

Therefore, the molecular sieve activated carbon of the present invention separates the oxygen in the air from the nitrogen by selectively adsorbing the oxygen in the air according to the pressure swing adsorption separation process for the purpose of separating the specific gas from the mixed gas. It is suitable for the purpose and can be used for various other purposes.

Moreover, in the production of the molecular sieve activated carbon of the present invention, the treatment process is simplified and energy saving can be achieved, so that it can be said that the industrial value is also high in this respect.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows an adsorption curve in Example 1. FIG. 2 shows the pore distribution curve of the molecular sieve activated carbon obtained in Example 1 and the pore distribution curve of the activated carbon used as the base material. FIG. 3 shows the adsorption curve in Control Example 1. FIG. 4, FIG. 5, FIG. 6, and FIG. 7 show adsorption curves in Example 6, Example 11, Example 16, and Example 17, respectively. FIG. 8 shows the adsorption experimental apparatus used in each example. FIG. 9 shows the pressure fluctuation type adsorption / separation device used in the examples. (1) …… Cylinder, (2) …… Buffer tube, (3)…
… Sample tube, (4) …… Vacuum pump, (5) …… Pressure and pressure gauge, (6) …… Pressure sensor, (7) …… Recorder,
(8a), (8b), (8c) ... valve, (9) ... sample,
(10) …… Adsorption tower, (11) …… Product tank, (12) ……
Vacuum pump

Claims (8)

[Claims] 1. A molecular sieve activated carbon having a structure in which a phthalocyanine compound is vapor-deposited on the surface of activated carbon. 2. The molecular sieve activated carbon according to claim 1, wherein the average pore size after vapor deposition is 10 Å or less. 3. The molecular sieve activated carbon according to claim 1, wherein the phthalocyanine compound is a metal phthalocyanine and / or a free phthalocyanine. 4. A method for producing activated carbon of molecular sieve, which comprises subjecting a phthalocyanine compound to vapor deposition on the surface of activated carbon by heating and sublimating the phthalocyanine compound at a temperature of 350 to 750 ° C. under normal pressure or reduced pressure. 5. A method in which a fine powder of a phthalocyanine compound is uniformly mixed with powdered activated carbon and then subjected to heat sublimation treatment under atmospheric pressure or reduced pressure in an inert gas atmosphere or under reduced pressure without using an inert gas. The manufacturing method according to claim 4, characterized in that 6. A sufficiently deaerated granular, crushed or shaped activated carbon is impregnated with a dispersion liquid in which a finely ground phthalocyanine compound is dispersed in a dispersion medium, and then the dispersion medium is distilled off. Then, the sublimation treatment is carried out by heating under atmospheric pressure or reduced pressure under an inert gas atmosphere, or under reduced pressure without using an inert gas, according to claim 4. 7. When separating a specific gas from a mixed gas by a pressure fluctuation type adsorption separation method, molecular sieve activated carbon having a constitution in which a phthalocyanine compound is vapor-deposited on the surface of activated carbon is used as an adsorbent. How to separate gases. 8. The method according to claim 7, which separates oxygen and nitrogen in the air.