KR0186157B1 - Deodorant and preparing method of the same - Google Patents

Abstract

The present invention carbonized the carbonaceous raw material and activated in an atmosphere having a water content of 15% by volume or less, and then activated carbon produced by cooling to 300 ° C or less while maintaining the water vapor content in the gas composition as it is or activated carbon produced by a conventional method. The metal phthalocyanine compound and / or the metal in the activated carbon produced by heat-treatment at 500 ° C. or higher in an atmosphere substantially free of oxygen and water, and then cooling to 300 ° C. or lower in an atmosphere substantially free of oxygen and water vapor in the gas composition. A deodorant carrying an oxide and a method for producing the same.

Description

Deodorant Using Heat Treated Activated Carbon And Manufacturing Method Thereof

The present invention relates to a deodorizing agent having an oxidative catalytic activity and antimicrobial activity and a method for producing the same, and more particularly, to a deodorant in which a metal oxide and / or a metal phthalocyanine compound is supported or bonded to a heat treated activated carbon and a method for producing the same.

In particular, the deodorant of the present invention can effectively remove a low concentration of malodorous gas, for example, methylmethane or trimethylamine.

In addition, the deodorant of the present invention has an antimicrobial activity against pathogens such as E. coli and Staphylococcus aureus.

The deodorant of the present invention can be used in various air conditioners because of its excellent catalytic activity even at low temperatures, and is particularly preferred as a deodorant for refrigerators.

In order to remove odors, it is known to use an adsorbent such as activated carbon, an adsorbent in which an alkaline or acidic substance is supported on a porous body, or a catalyst in which a metal phthalocyanine compound is bonded to ceramics.

However, deodorants using metal oxidants or metal phthalocyanine compounds reported to date have short lifespan and low deodorant performance. In addition, the method using other catalysts has low deodorizing performance, and many side reactions often produce odorous substances harmful to the human body, and have a difficulty in effectively removing odorous gases because of their short lifespan and frequent replacement.

In particular, when there is a low concentration of malodorous gases such as methylmethane and trimethylamine in a low temperature environment such as in a refrigerator. In order to effectively remove the malodorous gas, a catalyst having a high catalytic activity for oxidizing the malodorous gas, less generation of by-products, and a long lifetime are required.

Furthermore, in various air conditioners including refrigerators, it is necessary to suppress germ reproduction as well as to remove odors. Many kinds of bacteria are floating around or inside the air conditioner. When these floating various bacteria are attached to the deodorant, the deodorant may be a breeding ground of the fungus. Therefore, the development of a deodorant having antibacterial activity as well as deodorant activity is required.

In order to improve the above problems, the present invention is to increase the deodorizing activity and / or antimicrobial activity of the catalyst using the activated carbon produced by treating the carbonaceous raw material under specific conditions, or the activated carbon obtained by heat treatment of the conventional activated carbon under specific conditions It relates to a deodorant and a method for producing the same.

It is an object of the present invention to provide a deodorant which can effectively remove odors and which can effectively remove odor gases, such as methylmultantan and trimethylamine, which are present at low concentrations, and a method for producing the same.

Still another object of the present invention is to provide a deodorant having antibacterial activity against pathogenic bacteria such as Escherichia coli and Staphylococcus aureus and a method for producing the same.

It is still another object of the present invention to provide a deodorant with low pressure loss and a method for producing the same.

The activated carbon heat treated in the present invention carbonizes carbonaceous raw materials, such as coal or palm charcoal, and is activated in an atmosphere having a water content of 15% by volume (hereinafter simply expressed as%), and then maintains the water vapor content in the gas composition as it is. It can manufacture by cooling to 300 degrees C or less while making it.

In addition, the activated carbon heat treated in the present invention, a carbonaceous raw material produced by a conventional method, for example, activated carbon is heat-treated at 500 ° C or more in an atmosphere substantially free of oxygen or water vapor, for example, nitrogen gas or carbon gas. Then, it can manufacture by cooling to 300 degrees C or less in the atmosphere which does not contain oxygen or water vapor substantially.

Here, "substantially free of oxygen or water vapor" refers to an atmosphere in which oxygen atoms bonded to the surface of activated carbon are not present in the heat treatment of activated carbon, and refers to a state in which oxygen and water vapor are 1 to 2% by volume or less.

The activated carbon treated according to the present invention not only has excellent supporting ability but also excellent oxidation catalyst activity itself, and also improves the catalytic activity of the supported catalytically active component.

Deodorants of the present invention may include catalytically active ingredients supported or bonded to the carbonaceous raw material treated as described above, ie metal oxides, metal phthalocyanine compounds or both.

In the present invention, the metal oxide imparts an oxidation catalytic activity and is an oxide of at least one metal selected from the group consisting of iron, chromium, nickel, cobalt, manganese, zinc, copper, magnesium and calcium, and the form of the metal oxide is completely It does not need to be an oxide and some may be in the form of salts. The amount of metal oxide is about 0.1 to 10% by weight based on the total amount of deodorant.

In the present invention, the metal phthalocyanine imparts an oxidation catalyst activity and particularly an antibacterial activity, and a phthalocyanine compound of a metal selected from the group consisting of iron, cobalt, copper, nickel, manganese, osmium, titanium, molybdenum and tungsten may be used. The amount of metal phthalocyanine compound is about 0.01 to 2.0% by weight relative to the total amount of deodorant.

The deodorant of the present invention consists of a metal oxide and / or a metal phthalocyanine compound supported on a carbonaceous raw material treated as described above.

As one example, the deodorant of the present invention consists of a metal phthalocyanine compound supported on activated carbon treated according to the method of the present invention, and has an antibacterial activity that kills bacteria such as Escherichia coli, antistaining staphylococci, as well as deodorizing activity.

As another example, the deodorizing agent of the present invention consists of a metal oxide supported or separately supported on the heat-treated carbonaceous raw material, the metal phthalocyanine compound, present in a low concentration of less than about 100ppm at 0 ~ 40 ℃, eg For example, methylmultantan and trimethylamine can be removed sufficiently, and no harmful odorous substances are generated by side reactions.

When a metal phthalocyanine compound is used together with a metal oxide, the performance of the oxidation catalyst by the said metal oxide is further improved.

Hereinafter, the present invention will be described in detail.

Activated carbon used in the present invention is obtained by carbonizing carbonaceous raw materials such as palm coal and coal, activating in an atmosphere having a water content of 15% by volume or less, and cooling to 300 ° C or less while maintaining the water vapor content in the gas composition as it is. In general, carbonization is carried out by heat treatment at 600 to 900 ° C., and carbonaceous raw materials may be molded before carbonization if necessary.

The activating gas of the present invention may contain other gases such as carbon dioxide and nitrogen in addition to water vapor or oxygen, and the content of water vapor should be maintained at 15% by volume or less.

In the commonly used activated carbon activation gas, the water vapor content is 40 to 60% by volume, which is much higher than the water vapor content in the activation gas in the present invention, which is activated because the carbonaceous activation rate by water vapor is significantly slowed down by carbon dioxide gas. This is because the partial pressure of water vapor of the gas is set as high as possible. Therefore, the activation condition according to the present invention significantly slows down the activation rate compared to the conventional activated carbon activation method.

As can be seen from Tables 7 and 8 (Example 5 and Comparative Example 6), when the carbonaceous raw material is activated under conditions of high water vapor content, oxidative degradability of odorous gases such as metal methane and trimethylamine is significantly lowered. do.

Although the activation conditions with low water vapor content are not well known for the detailed mechanism of improving the oxidation catalyst activity of activated carbon, it is pointed out that oxygen atoms bound to the surface of the treated activated carbon are not present.

The activated carbon is cooled to 300 ° C. or lower and discharged out of the system under the condition of maintaining the water vapor content in the gas composition.

The atmosphere at the time of cooling is not necessarily the same composition as the gas used for the activation gas and the gas at the time of cooling, as long as the composition of the gas used for the activation step is 15% by volume or less.

Activated carbon according to the conditions of the present invention and then activated carbon produced by leaving it in an atmosphere containing a large amount of water vapor, hydrogen gas, air or oxygen gas by discharging it out of the system at high temperature without undergoing a cooling step of cooling to 300 ° C. or lower. When the deodorant is used to prepare a deodorant, the activity of the catalyst is significantly lowered.

Even when the cooling step after activation is performed at 300 ° C. or higher, the activity as a catalyst, that is, the oxidation catalyst capacity and the antimicrobial activity are significantly reduced.

In addition, activated carbon used in the present invention is activated carbon produced by contacting with air or the like and the oxidation catalyst activity is lowered, for example, activated carbon produced by a conventional method at 500 ° C. or higher in an atmosphere substantially free of oxygen or water vapor. After heat treatment, it can also be produced by cooling to 300 ° C. or lower in an atmosphere substantially free of oxygen or water vapor.

The composition of the gas used in the cooling step need not be the same as the gas used in the heat treatment.

Conventional activated carbon to which the heat treatment-cooling step can be applied may be obtained from any raw material such as coal and palm coal, and the shape thereof is not limited. Therefore, any of activated carbons such as granular, honeycomb, plate and the like produced by a conventional method can be used in the oxidation catalyst production of the present invention by treating them by the above method.

Although the heat treatment time varies depending on the temperature, for example, at 500 ° C., about 20 to 180 minutes is good, and at 800 ° C., the effect is sufficiently obtained by treatment of water.

Although the specific surface area of the activated carbon of this invention is not specifically limited, 500 m <2> / g or more is preferable and it is more preferable if it is 800 m <2> / g or more.

Conventional activated carbon is produced by activating carbonaceous raw material shaped into granular form, honeycomb form, etc. with water vapor, combustion gas, etc. and then discharging it with air vapor, but such activated carbon does not exhibit sufficient oxidation catalytic activity when used in the present invention. can not do it. The effect of the present invention is first obtained by using activated carbon produced by activating at a specific gas composition and temperature as described above and then cooling to 300 ° C. or lower in a specific atmosphere.

The activated carbon catalyst having the oxidation catalyst activity and the antimicrobial activity of the present invention comprises a metal oxide and / or a gold phthalocyanine compound supported on the activated carbon prepared as described above.

The method for supporting a specific metal oxide and / or metal phthalocyanine compound on the activated carbon produced according to the present invention is described below.

The method for supporting a specific metal oxide on the activated carbon produced according to the present invention is as follows.

The activated carbon according to the present invention is added to an aqueous solution of a water-soluble metal salt and stirred to sufficiently adsorb the metal salt to the activated carbon. After drying the activated carbon to which the metal salt is adsorbed by filtration, the metal compound can be supported on the activated carbon by oxidizing the metal salt into a metal oxide, for example, by thermal decomposition.

Optionally, the aqueous metal salt solution can be sprayed onto the activated carbon to adsorb the metal salt to the activated carbon and (thermally) dried, and if necessary, the desired metal compound can be supported on the activated carbon by oxidizing the metal salt to a metal oxide, for example, by pyrolysis. have.

After supporting the metal salt on the activated carbon, drying is preferably performed at 150 ° C or less.

The supported amount of the metal oxide is in the range of 0.1 to 10% by weight, but more preferably about 0.5 to 5% by weight.

When the supported amount of the metal oxide is 0.1% by weight or less, the catalytic activity is insufficient. When the supported amount of the metal oxide is 10% by weight or more, the catalytic activity is not improved as compared with the larger the supported amount, and the adsorption performance of the activated carbon itself is impaired.

The carrying amount adjustment of the metal oxide can be controlled by changing the ratio of the metal salt concentration in the aqueous metal salt solution to the activated carbon. Usually, metal salts in solution are almost completely adsorbed to activated carbon.

As the metal salt, inorganic acid salts such as nitrates, hydrochlorides, active salts and carbonates, organic acid salts and hydroxides such as acetates, oxalates and phosphates can be used, and mixtures of these salts can also be used. Moreover, it is also possible to use the aqueous solution which added acid, such as hydrochloric acid, nitric acid, acetic acid, and formic acid.

When metal salts or oxides such as iron, chromium, nickel, cobalt, manganese, zinc, copper, magnesium and calcium are used, the catalytic function of activated carbon is particularly excellent, and these metal salts or metal oxides can be used together in two or more kinds.

When oxidizing metal salts supported on activated carbon to metal oxides, not all metal salts need to be completely oxidized to metal oxides, and even when some metal salt forms are present, oxidation catalyst activity is exerted when metal oxides are present. For example, in the case of using nitrate, formate, acetate, etc., it is presumed that a substantial portion remains in the salt state even after the heat treatment.

In addition, the activated carbon catalyst of the present invention contains a metal phthalocyanine compound 0.01 to 2.0% by weight together with or separately from the metal oxide. An example of a method of supporting a metal phthalocyanine compound on activated carbon is as follows.

First, activated carbon is added to a basic solution of pH. 9 to 13 containing a predetermined amount of a metal phthalocyanine compound and stirred to sufficiently adsorb the metal phthalocyanine compound to the activated carbon, and then an acid is added to make the solution to pH 6 to 8. The solution is left for a certain time and then filtered to dry the activated carbon carrying the metal phthalocyanine compound.

Optionally, the metal phthalocyanine can be supported on the activated carbon by spraying an aqueous solution of metal phthalocyanine at a predetermined concentration adjusted to pH 9-13 on the activated carbon to sufficiently adsorb the metal phthalocyanine compound on the activated carbon, washing it with distilled water or an aqueous acid solution and then drying it. have.

After supporting the metal phthalocyanine compound on the activated carbon, drying is preferably performed at 150 ° C. or lower.

The amount of the metal phthalocyanine compound supported is in the range of 0.01 to 2.0% by weight, more preferably 0.1 to 1.0% by weight.

If the supported amount of the metal phthalocyanine compound is 0.01% by weight or less, the catalytic activity is insufficient. If the supported amount of the metal phthalocyanine compound is 2.0% by weight or more, the catalytic activity is not improved and the adsorption performance of the activated carbon itself is reduced.

The supported amount of the metal phthalocyanine compound can be adjusted by changing the ratio of the metal phthalocyanine compound and the activated carbon in the aqueous solution. Usually, the metal phthalocyanine compound in solution is almost completely adsorbed to activated carbon.

Two or more kinds of these metal phthalocyanine compounds may be mixed and used, and when two or more kinds are used together, catalytic performance may be improved.

The metal phthalocyanine compound is represented by following formula (1).

Wherein M is a metal atom, Y is at least 4 carboxyl or sulfonic acid groups and the rest are hydrogen atoms.

The metal atom M is iron, cobalt, copper, nickel, manganese, ossium, titanium, molybdenum or tungsten, with iron and cobalt being particularly preferred.

At least 4 substituent Y is a carboxyl group or a sulfonic acid group, and the remainder is a hydrogen atom, but metal phthalocyanine tetrasulfonic acid or metal phthalocyanine octacarboxylic acid is especially preferable.

If necessary, the activated carbon on which the metal phthalocyanine compound according to the present invention can be supported can be supported on the metal compound by the method described above.

The prepared activated carbon deodorant may be used as a deodorant by itself, and may be molded and used in a honeycomb form or a plate form as necessary. In the case of molding, a higher function may be exhibited as a catalyst. That is, in order to reduce a pressure loss and to increase the contact surface with gas, the shape which can superpose | polymerize a honeycomb shape or a plate-shaped molded object, and can pass gas at high speed between them is more preferable. Highly catalyzed products also have a shaped body such as a lashing ring type or a versadol type.

When shaping activated carbon, it is preferable to grind and use activated carbon at a particle diameter of about 0.1 μm to 4 mm, and the activated carbon particle diameter can be selected according to the purpose of use.

As a binder for molding, a commonly used plastic powder may be used, and in addition, it may be widely used as long as it can form a molding when mixed with activated carbon powder and pressurized at a high temperature. For example, a thermoplastic resin, a thermosetting resin, a hydrophilic resin, an electroconductive resin, etc. is suitable for heat fusion without using water or an organic solvent.

Thermoplastic resins include polyethylene, polypropylene, ABS (acrylonitrile butadiene, styrene resin), PET (polyethylene terephthalate), nylon, PBT (polybutylene terephthalate), PMMA (polymethyl methacrylate) resin, etc. Acrylic resin, mesoface pitch, etc. can be used.

Phenol resin, furan resin, etc. can be used as a thermosetting resin.

As the hydrophilic resin, polyvinyl alcohol resin, eval resin and the like can be used.

1-50 micrometers is suitable and, as for the plastic particle diameter used as a binder, 5-30 micrometers is more preferable. When the particle diameter of the plastic tack powder is 1 µm or less, the specific gravity of the molded product increases, and thus it is difficult to form a molded product having high strength and high density. If the particle diameter exceeds 50 mu m, the adhesive strength drops, and a molded article having a high strength cannot be obtained.

The use amount of the binder is suitably 1 to 50 parts with respect to 100 parts of activated carbon, and more preferably 2 to 25 parts. If the amount of the binder is 1 part or less, the molded body is insufficient. If the amount of the binder is 50 parts or more, the surface of the activated carbon is coated with the binder, so that the adsorption of activated carbon is lowered and the catalytic activity of the deodorant is lowered.

If necessary, reinforcing materials may be mixed in order to increase the mechanical strength of molded articles such as honeycomb or plate.

Reinforcing materials include titanium, aluminum, iron, copper and crude oil (brass). Inorganic fibers such as metal fibers such as styrene, silicon carbide, boron nitrite, barium titanate and glass fibers, polypropylene, vinylon, polyester, nylon, etc., fused fibers such as polyester-polyethylene and polypropylene-polyethylene, and carbon fibers Organic fibers, such as these, can be used, and the fiber of monofilament or multifilament about 0.2-20 mm in length and 3-100 micrometers in diameter is especially preferable.

In the case of forming a honeycomb or a plate, activated carbon and a binder may be mixed by a conventional industrial mixing method such as a mixer, a ribbon mixer, a star mixer, a ball mill, a sample mill, a kneader or the like. Although the binder can be attached to the surface of the activated carbon only by mixing, it is preferable to slightly heat the mixing process in order to uniformly mix the binder and the activated carbon and to bind more strongly. Microwave, infrared ray, ultraviolet ray, high frequency, etc. can be used as a heat source of heating. The effects of static electricity and heating that occur during mixing can be combined with each other to more strongly adhere the binder particles to the surface of the activated carbon.

A molded activated carbon filter is obtained by filling a molding case with a mixture of activated carbon, a binder, or a reinforcing material, heating it above the curing point of the binder, and compression molding and cooling by applying a pressure of 0.1 to 10 kg / cm ² .

Since the activated carbon catalyst of the present invention has extremely low pressure loss and excellent oxidation catalyst activity at low temperature as well as at room temperature, the activated carbon catalyst can effectively remove odor gas even in a low temperature environment such as a refrigerator.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited by these Examples.

Example 1. Catalyst Preparation

(A) The specific surface area of activated carbon using coal propagated at 10 to 30 mesh is dried at 800 ° C and then propane combustion gas (gas composition; 80% nitrogen, 0.2% oxygen, 9.8% carbon dioxide, 10% water vapor) is used. It was activated at 900 ° C until it became 1300 m 2 / g, and cooled to 300 ° C or less in a vessel substituted with nitrogen to obtain activated carbon.

(A) The obtained activated carbon was molded into a honeycomb phase of 300 cells.

(B) The obtained activated carbon was pulverized to 0.1 to 1 mm, and then 25 parts of polyethylene powder having an average particle diameter of 20 µm was added to 100 parts of activated carbon, and then formed into a honeycomb of 10 cells / in ² in a heat-forming press.

Each activated carbon thus obtained was supported with cobalt phthalocyanine as follows.

100 g of activated carbon was added to 200 m 1 of 0.1 N sodium hydroxide aqueous solution containing 0.1 g of cobalt phthalocyanine and left to stir for 3 hours, and then adjusted to pH 2 by adding 0.1 N hydrochloric acid, and left for 3 hours. The resultant was filtered, washed with 100 ml of distilled water, and dried at 130 ° C. to obtain activated carbon having 0.1 wt% of cobalt phthalocyanine.

Next, 100 g of the activated carbon loaded with cobalt phthalocyanine was added to 200 ml of an aqueous nitric acid solution containing 2.0 wt% of magnesium and 3.0 wt% of copper, followed by stirring for 3 hours. After filtration, washed with distilled water 100ml and dried at 130 ℃.

Example 2 Deodorization Performance Test

First, the concentrations of metallethane and trimethylamine generally generated in the refrigerator were measured, and the amount of gas emitted in seven years, which is the average shelf life of general household appliances such as refrigerators, was calculated. The amount is about 572 mg of methylmultan and about 34 mg of trimethylamine.

After treating the catalyst with 572mg of methylmultantan and 34mg of trimethylamine in advance, check if the removal performance is impaired by circulating the malodorous gas to the catalyst at a constant concentration. I found out.

One deodorizing catalyst was put into a desiccator with an internal volume of 4 L and vacuum degassed. After injecting 572 mg of methylmultanite, introducing the outside air to normal pressure, and leaving it at 5 ° C for 24 hours, the initial load of the catalyst for 7 years was applied. Given. This catalyst was mounted in an acrylic reactor having a diameter of 10 cm and a length of 30 cm, and air containing 3 ppm of methyl anthractan was flowed at 5 ° C.

The flow rate of SV was 31,200 hours and the relative humidity was 50 ± 10%.

The outlet gas was collected with a syringe and the gas concentration was analyzed by gas chromatography.

Also about trimethylamine, the initial load amount was 34 mg, and the gas removal test was done by the method similar to methylmultan. Table 1 shows the results of the methylmethane charcoal removal rate and Table 2 shows the results of the trimethylamine removal rate.

Comparative Example 1.

The coal pulverized into 10-30 mesh was carbonized at 800 ° C., activated using a conventional activating gas having a water vapor content of 40% by volume, and then activated carbon was discharged and cooled in air. Thereafter, an activated carbon catalyst was prepared by supporting a metal phthalocyanine compound and a metal compound in the same manner as in Example 1. For the catalyst prepared, the deodorization performance was tested according to the method of Example 2. Table 1 shows the results of the methylmultanane removal rate measurement and Table 2 shows the results of the trimethylamine removal rate.

Comparative Example 2.

Deodorization performance was tested according to the method of Example 2 using only the activated carbon carrier prepared in Comparative Example 1. Table 1 shows the results of the methylmultanane removal rate measurement and Table 2 shows the results of the trimethylamine removal rate.

Comparative Example 3.

Deodorizing performance was tested in accordance with the method of Example 2 using a commercially available ceramic manganese catalyst (manufactured by Kobe Steel Co., Ltd., trade name: Manganese Citrate). Table 1 shows the results of the methylmultanane removal rate measurement and Table 2 shows the results of the trimethylamine removal rate.

Deodorization Performance for Methyl Melcaptan

TABLE 1

Co-PCTS: Cobalt Phthalocyanine Tetrasulfonic Acid

Reaction conditions: 5 ° C, SV = 31,200 hr, relative humidity: 50 ± 10%, initial load 572 mg, inlet concentration of merylmultantan: 3 ppm

Deodorization Performance for Trimethylamine

TABLE 2

Co-PCTS: Cobalt Phthalocyanine Tetrasulfonic Acid

Reaction condition: 5 ℃, SV = 31,200 hr, relative humidity: 50 ± 10%, initial load 34mg,

Inlet concentration of trimethylamine: 3 ppm

The activated carbon catalyst of the present invention removed methylmultan and trimethylamine in a short time at a low temperature of 5 ° C. Conventional oxidized activated carbon has a significant decrease in oxidation catalyst activity (Comparative Examples 1 and 2), and commercially available ceramic catalysts have not eliminated the initial load for 7 years, and further gas distribution tests result in deodorization of the odor gas. The outlet concentration of was higher than the inlet concentration (Comparative Example 3).

Example 3.

The activated carbon carrier of Comparative Example 1 was treated at 900 ° C. for 5 minutes in nitrogen, and then cooled to room temperature in nitrogen to obtain an activated carbon carrier. Cobalt phthalocyanine, magnesium oxide, and copper oxide were supported on the obtained activated carbon carrier in the same manner as in Example 1. According to the method of Example 2, the deodorizing performance for methylmultantan was tested and the results are shown in Table 3.

Example 4.

When the activated activated carbon was cooled in nitrogen, a catalyst was prepared in the same manner as in Example 1 except that the activated activated carbon was discharged to air after cooling to 400 ° C. According to the method of Example 2, the deodorizing performance for methylmultantan was tested and the results are shown in Table 3.

Comparative Example 4.

Using a commercially available ozone deodorizing agent (supporting Fe ₂ O ₃ and Mn ₂ O ₃ ) in accordance with the method of Example 2 to test the deodorizing performance for methyl multantan and the results are shown in Table 3.

Deodorization Performance for Methyl Melcaptan

TABLE 3

Co-PCTS: Cobalt Phthalocyanine Tetrasulfonic Acid

Fe-PCTS: iron phthalocyanine tetrasulfonic acid

Reaction conditions: 5 ° C, SV = 31,200 hr, relative humidity: 50 ± 10%, initial load 572 mg, inlet concentration of methylmultantan: 3 ppm

As can be seen from Table 3, the performance of the activated carbon deodorant of the present invention is dependent on the temperature of the first contact with air after cooling, and the ability to remove odor is reduced when the cooling temperature exceeds 300 ℃.

Example 5 Deodorization Performance Test According to Activation Gas Composition

When activating granular palm charcoal, the activated carbon was cooled to 300 ° C. or lower in a nitrogen-substituted container after activating at 900 ° C. until the specific surface area was 1000 m ² / g while varying the vapor partial pressure of the activated gas. . In the same manner as in Example 1, cobalt phthalocyanine, magnesium oxide, and copper oxide were supported, and trimethylamine initial load was applied as in Example 2 using the obtained activated carbon catalyst. Table 4 shows the properties and deodorization performance test results of the activated carbon used.

Deodorization Performance for Trimethylamine According to Activation Conditions

TABLE 4

Co-PCOC: cobalt phthalocyanine octacarboxylic acid

Reaction condition: 5 ℃, SV = 31,200 hr, relative humidity: 50 ± 10%, initial load 32 mg,

Inlet concentration of methylmelcuptane: 3 ppm

As can be seen from Table 4, the deodorizing performance of the activated carbon catalyst of the present invention depends on the water vapor concentration at the time of activation of the activated carbon, it shows a high catalytic activity when the water vapor concentration is 15% or less.

Example 6 Methyl Multantan Deodorization Performance Test in a Refrigerator

Example 1 (a) 300 cell / in ² , 50mm × 50mm × 20mm honeycomb activated carbon, 0.1% by weight of cobalt phthalocyanine tetrasulfonic acid, 2% by weight of manganese oxide, 3% by weight of copper oxide Catalyst was used.

The catalyst was attached to the cold air circulation port (cold suction port) of the 499L refrigerator's refrigerating chamber (the size of the refrigerating chamber is about 364L), and methylmultan was removed at a concentration of 20 ppm in the refrigerating chamber. Is shown in Table 5. A commercially available ceramics-Mn catalyst (manufactured by Kobe Steel Co., Ltd., trade name: Manganese Cit) was used as a control.

Example 7 Trimethylamine Deodorization Performance Test in Refrigerator

Trimethylamine deodorization performance in the refrigerator was tested in the same manner as in Example 6. Trimethylamine was introduced at an initial concentration of 20 ppm in the refrigerating chamber, and the trimethylamine removal rate was measured over time, and the results are shown in Table 6. A commercially available ceramics-Mn catalyst (manufactured by Kobe Steel Co., Ltd., trade name: Manganese Cit) was used as a control.

Methyl Multantan Deodorization Effect in Refrigerator

TABLE 5

Co-PCTS: Cobalt Phthalocyanine Tetrasulfonic Acid

Deodorizing Effect of Trimethylamine in Refrigerator

TABLE 6

Co-PCTS: cobalt phthalocyanine tetrasulfonic acid

Example 8. Antibacterial Experiment

The activated carbon catalyst prepared in Example 1 was heated and sterilized at 100 ° C. for 1 hour, and then, the sample was placed in 100 m 1 of the bacterial solution and stirred for 1 minute. After preservation at 25 ± 2 ° C. for 24 hours, 100 μl was collected and incubated at 35 ° C. for 24 hours and 48 hours in agar plate medium, respectively.

Antimicrobial experiments were carried out in the same manner using the catalyst prepared in Comparative Example 1 and the microbial solution itself. The results of the antimicrobial experiments are shown in Table 7.

Antibacterial Test Results

TABLE 7

Sample amount of 0.5g / 100ml bacteria solution

Claims (9)

Activated carbon prepared by carbonizing a carbonaceous raw material, activating in an atmosphere having a water content of 15% by volume or less, and then cooling it to 300 ° C. or less while maintaining the water vapor content in a gas composition, at least one metal phthalocyanine compound supported on the activated carbon, and , Iron, chromium, nickel, cobalt, manganese, zinc, copper, magnesium and calcium, and at least one metal oxide selected from the group consisting of 0.1 to 10% by weight of the total amount of deodorant, The metal phthalocyanine compound contains 0.01 to 2.0% by weight based on the total amount of deodorant, and the metal phthalocyanine compound is represented by the following general formula (I): Wherein M is a metal atom selected from the group consisting of iron, cobalt, copper, nickel, manganese, osmium, titanium, molybdenum and tungsten, Y is at least 4 carboxyl or sulfonic acid groups and the rest are hydrogen atoms. The deodorant according to claim 1, wherein the deodorant is capable of removing up to 100 ppm of methylmultantan or trimethylamine at 0 to 40 ° C. Activated carbon produced by heat-treating the oxidized activated carbon to 500 ° C. or higher in an atmosphere substantially free of oxygen and water, and then cooling it to 300 ° C. or lower in an atmosphere substantially free of oxygen and water vapor in the gas composition; At least one metal phthalocyanine compound supported thereon and at least one metal oxide selected from the group consisting of iron, chromium, nickel, cobalt, manganese, zinc, copper, magnesium and calcium, the metal oxide being added to the total deodorant amount. 0.1 to 10% by weight, and the metal phthalocyanine compound is present in an amount of 0.01 to 2.0% by weight based on the total amount of deodorant, and the metal phthalocyanine compound is represented by the following general formula (I): Wherein M is a metal atom selected from the group consisting of iron, cobalt, copper, nickel, manganese, osmium, titanium, molybdenum and tungsten, Y is at least 4 carboxyl or sulfonic acid groups and the rest are hydrogen atoms. Activated carbon prepared by carbonizing a carbonaceous raw material, activating in an atmosphere having a water content of 15% by volume or less, and then cooling it to 300 ° C. or less while maintaining the water vapor content in a gas composition as follows, is a metal phthalocyanine represented by the following general formula (I): After treating with a basic aqueous solution of pH 9-13 containing a predetermined amount of the compound, and then treated with acid or distilled water, 0.01 to 2.0% by weight of the metal phthalocyanine compound is supported on the activated carbon relative to the total amount of deodorant, iron, chromium, nickel Method for preparing an oxidation catalyst deodorant comprising 0.1 to 10% by weight of one or more metal oxides selected from the group consisting of cobalt, manganese, zinc, copper, magnesium and calcium, based on the total amount of deodorant: Wherein M is a metal atom selected from the group consisting of iron, cobalt, copper, nickel, manganese, osmium, titanium, molybdenum and tungsten, Y is at least 4 carboxyl or sulfonic acid groups and the rest are hydrogen atoms. The activated metal is stirred in a basic aqueous solution having a pH of 9 to 13 containing a predetermined amount of metal phthalocyanine compound, and the activated carbon adsorbs the metal phthalocyanine compound to the activated carbon, and an acid is added thereto. To form the aqueous solution at a pH of 6 to 8, followed by drying the activated carbon on which the metal phthalocyanine compound is loaded. (Correction) The method according to claim 4, wherein the supporting of the metal phthalocyanine compound is a basic aqueous solution having a pH of 9 to 13 containing a predetermined amount of the metal phthalocyanine compound in the activated carbon, washed with distilled water, and then dried the activated carbon. Manufacturing method. Activated carbon produced by heat-treating the oxidized activated carbon to 500 ° C. or higher in an atmosphere substantially free of oxygen and water, and then cooling it to 300 ° C. or lower in an atmosphere substantially free of oxygen and water vapor in the gas composition. Treatment with a basic aqueous solution of pH 9-13 containing a predetermined amount of the metal phthalocyanine compound represented by formula (I), followed by treatment with acid or distilled water, and the metal phthalocyanine compound in the activated carbon is 0.01-2.0 with respect to the total amount of deodorant. Oxidation catalyst comprising carrying by weight% and carrying at least 0.1 to 10% by weight of one or more metal oxides selected from the group consisting of iron, chromium, nickel, cobalt, manganese, zinc, copper, magnesium and calcium with respect to the total amount of deodorant. Method of Making Deodorant: Wherein M is a metal atom selected from the group consisting of iron, cobalt, copper, nickel, manganese, osmium, titanium, molybdenum and tungsten, Y is at least 4 carboxyl or sulfonic acid groups and the rest are hydrogen atoms. 8. The metal phthalocyanine compound according to claim 7, wherein the supported metal phthalocyanine compound is added to an activated carbon in a basic aqueous solution containing a predetermined amount of a metal phthalocyanine compound at a pH of 9 to 13 and stirred to adsorb the metal phthalocyanine compound to the activated carbon, and an acid is added thereto. To form the aqueous solution at a pH of 6 to 8, followed by drying the activated carbon on which the metal phthalocyanine compound is loaded. 8. The production method according to claim 7, wherein the supporting of the metal phthalocyanine compound comprises a basic aqueous solution having a pH of 9 to 13 containing a predetermined amount of the metal phthalocyanine compound on the activated carbon, washed with distilled water, and drying the activated carbon. .