KR20190032001A - Granule-type gas filter media compositions for removing harmful gas with copper-manganese oxide - Google Patents

Abstract

The present invention relates to a granular filter media composition for removing noxious gas containing copper-manganese catalyst oxide. More particularly, the present invention relates to a granular filter media composition in which a wetting agent and a cellulose-based polymer binder are added to enable uniform mixing, and which improves pellet mechanical strength and exhibits excellent gas removal characteristics. The composition of the present invention comprises: a copper-manganese catalyst oxide; a cellulose-based polymer binder; an inorganic binder; a wetting agent; silica; and activated carbon.

Description

TECHNICAL FIELD [0001] The present invention relates to a granular filter media composition for removing harmful gas containing copper-manganese catalyst oxide.

The present invention relates to a granular filter media composition for removing noxious gas containing copper-manganese catalyst oxide, more specifically, a wetting agent and a cellulose-based polymer binder are added to allow uniform mixing, To a granular filter media composition exhibiting improved mechanical strength and excellent gas removal characteristics.

It is harmful or uncomfortable to humans such as carbon monoxide, nitrogen oxides, sulfur oxides and volatile organic compounds in everyday living space, market, shopping center, automobile, industrial field, chemical plant, power plant, incinerator, boiler, underpass road, It contains harmful gas components and filter media are used to physically or chemically trap or remove harmful fine particles contained in the air.

The filter medium is generally referred to as a filter media in general. The filter medium that has been provided in the past is made of a synthetic polymer, and a method of collecting fine particles by applying an electrostatic force to the ultrafine fiber layer is mainly used. However, this method not only lowers the collection efficiency when used for a long period of time, but also has a problem that fungi and bacteria grow on the surface and odor is generated.

Recently, as disclosed in Korean Patent Laid-Open Publication No. 10-2016-0047609, a method of fixing a deodorant such as a porous activated carbon powder, an activated carbon fiber or a zeolite to a filter medium by using a predetermined binder mixture has been proposed. However, The binder can not be uniformly mixed with the fibrous layer and is partially buried, thereby deteriorating the deodorizing effect.

Accordingly, the present inventors have developed a filter media composition containing a copper-manganese oxide having excellent adsorption characteristics, and adding a wetting agent and a cellulose-based polymer binder to achieve uniform mixing and thereby exhibiting excellent gas removal characteristics.

Korean Patent Laid-Open Publication No. 10-1997-0041260 (entitled " Composite Air Filter Medium in Automobile Room with Deodorizing Function ", Applicant: TEXT Co., Ltd., Publication Date: Mar. 15, 1999) Korean Patent Laid-Open No. 2001-0089865 (entitled: Multifunctional Air Filter Medium, Applicant: Bumsoo Hwang, Disclosure Date: October 12, 2001) Korean Patent Laid-Open No. 10-2016-0047609 (entitled: Porous copper-manganese filter media and method for manufacturing the same, filed by Sail F Co., Ltd., published on May 03, 2016)

It is an object of the present invention to provide a pelletized filter medium having improved gas removing performance by improving the mixing characteristics with a powdery molding composition by adding a wetting agent for improving the surface tension of water.

Another object of the present invention is to improve the moldability and molding speed in the extrusion molding process by mixing the cellulose-based polymer binder and the inorganic binder to improve the abrasion due to friction of the molding equipment parts, And to improve the gas removal rate.

The present invention relates to a granular filter media composition for removing harmful gas containing copper-manganese catalyst oxide, which comprises copper-manganese catalyst oxide, cellulose-based polymer binder, inorganic binder, wetting agent, silica and activated carbon.

It is more preferable that the copper-manganese catalyst oxide is mixed with a copper salt and a manganese salt in a molar ratio of 1: 1 to 1: 4.

The copper salt is more preferably one or more selected from the group consisting of copper acetate, copper nitrate, copper chloride, copper iodide, copper bromide, cuprous sulfate and copper acetate. The manganese salt may be at least one selected from the group consisting of manganese nitrate, More preferably at least one member selected from the group consisting of manganese chloride, manganese iodide, manganese bromide, manganese sulfate, potassium permanganate and manganese acetate.

The cellulose-based polymer binder is preferably one or more selected from the group consisting of methyl cellulose, ethyl cellulose, methyl ethyl cellulose, propyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose and hydroxypropyl cellulose Do.

The inorganic binder is preferably a liquid silicate.

The wetting agent may be selected from the group consisting of polyether-modified dimethylpolysiloxanes, polydimethylsiloxanes of polyether-modified hydroxy functional groups, polyester-modified hydroxy-functional polydimethylsiloxanes, polyester-modified polymethylalkylsiloxanes, polyether-modified polymethylalkylsiloxanes, and polyester- And at least one modified silicone series selected from the group consisting of hydroxypropylmethylsiloxane and hydroxypropylmethylsiloxane.

In the granular filter media composition for removing harmful gas containing copper-manganese catalyst oxide according to the present invention, 5 to 25 parts by weight of a cellulose-based polymer binder, 90 to 110 parts by weight of an inorganic binder, 0.5 to 5 parts by weight of silica, 650 to 700 parts by weight of silica, and 20 to 50 parts by weight of activated carbon.

The present invention also provides a method for preparing a mixed solution comprising: a first step of mixing purified water and a cellulose-based polymer binder and stirring the mixture to prepare a mixed solution;

A second step of adding a copper-manganese catalyst oxide and an inorganic binder to the mixed solution prepared in the first step and stirring, and then adding a wetting agent to prepare a liquid-state molding composition;

A third step of preparing a molding composition by mixing a powdery molding composition comprising silica and activated carbon with the liquid molding composition prepared in the second step; And

The method for producing a granular filter media composition for removing harmful gases according to any one of claims 1 to 3, wherein the granular filter media composition comprises copper-manganese catalyst oxide, and a fourth step of preparing a molding composition of the third step as pellet granules, followed by drying and heat- to provide.

Hereinafter, the present invention will be described in detail.

The present invention relates to a granular filter media composition for removing harmful gas containing copper-manganese catalyst oxide, which comprises copper-manganese catalyst oxide, cellulose-based polymer binder, inorganic binder, wetting agent, silica and activated carbon.

It is advantageous that the copper-manganese catalyst oxide is a mixture of copper salt and manganese salt in a molar ratio of 1: 1 to 1: 4.

If the molar ratio of the copper salt to the manganese salt is less than 1: 1, the noxious gas removal performance is not sufficient. If the molar ratio exceeds 1: 4, the catalytic property may be reduced in the presence of water.

The copper salt may be at least one selected from the group consisting of copper acetate, copper nitrate, copper chloride, copper iodide, copper bromide, cuprous sulfate and copper acetate. The manganese salt may be at least one selected from the group consisting of manganese nitrate, It is more advantageous to use at least one selected from the group consisting of manganese chloride, manganese iodide, manganese bromide, manganese sulfate, potassium permanganate and manganese acetate.

The cellulose-based polymeric binder is used for improving the moldability and molding speed of a molding composition in an extrusion molding process. Examples of the binder include methylcellulose, ethylcellulose, methylethylcellulose, propylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, At least one member selected from the group consisting of propylmethylcellulose and hydroxypropylcellulose.

Further, the cellulose-based polymer binder is more preferably contained in an amount of 5 to 25 parts by weight based on 100 parts by weight of the copper-manganese catalyst oxide. If the content of the cellulose-based polymeric binder is less than 5 parts by weight based on 100 parts by weight of the copper-manganese catalyst oxide, the effect of improving moldability and molding speed is insignificant. If it exceeds 25 parts by weight,

The inorganic binder is a liquid silicate and has a molecular formula of M ₂ O _n SiO ₂ .XH ₂ O (M is an alkali metal such as Na, Li, K, etc.) and contains water. And pores are generated therefrom to increase the specific surface area of the molded article. The inorganic binder is preferably contained in an amount of 90 to 110 parts by weight based on 100 parts by weight of the copper-manganese catalyst oxide. When the content of the inorganic binder is less than 90 parts by weight with respect to 100 parts by weight of the copper-manganese catalyst oxide, the effect of improving the specific surface area of the molded product is insufficient. When the content of the inorganic binder is more than 110 parts by weight,

The wetting agent is used for improving the mixing ability with the powdery molding composition by improving the surface tension of water to improve the noxious gas removing performance. The wetting agent includes polyether-modified dimethylpolysiloxane, polydimethylsiloxane of polyether-modified hydroxy functional group, polyester Denatured hydroxy functional polydimethylsiloxane, polyester denatured polymethylalkylsiloxane, polyether denatured polymethylalkylsiloxane, and polyester denatured hydroxypolymethylsiloxane, and it is preferable that at least one denatured silicone series is selected from the group consisting of But are not limited to, BYK-348 (BYK Additives & Instruments) or KP-341 (Shinetsu Silicones).

The wetting agent is more preferably contained in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the copper-manganese catalyst oxide. When the content of the wetting agent is less than 0.5 parts by weight based on 100 parts by weight of the copper-manganese catalyst oxide, the surface tension of the water can not be sufficiently improved and the mixing properties of the liquid and powdery compositions are not excellent. When the content is more than 5 parts by weight, Is undesirable.

The silica is preferably contained in an amount of 650 to 700 parts by weight based on 100 parts by weight of the copper-manganese catalyst oxide. When the amount of silica is less than 650 parts by weight based on 100 parts by weight of the copper-manganese catalyst oxide, the noxious gas can not be sufficiently removed. If the amount exceeds 700 parts by weight, excessive deodorizing effect may be deteriorated due to excess silica.

The activated carbon is preferably contained in an amount of 20 to 50 parts by weight based on 100 parts by weight of the copper-manganese catalyst oxide. If the content of activated carbon is less than 20 parts by weight based on 100 parts by weight of the copper-manganese catalyst oxide, the harmful gas can not be sufficiently removed. If the amount of activated carbon is more than 50 parts by weight, excessively active carbon may deteriorate the harmful gas removing effect. not.

The present invention relates to a process for preparing a mixed solution by mixing purified water and a cellulose-based polymer binder and stirring the mixture,

A second step of adding a copper-manganese catalyst oxide and an inorganic binder to the mixed solution prepared in the first step and stirring, and then adding a wetting agent to prepare a liquid-state molding composition;

A third step of preparing a molding composition by mixing a powdery molding composition comprising silica and activated carbon with the liquid molding composition prepared in the second step; And

The method for producing a granular filter media composition for removing harmful gases according to any one of claims 1 to 3, wherein the granular filter media composition comprises copper-manganese catalyst oxide, and a fourth step of preparing a molding composition of the third step as pellet granules, followed by drying and heat- to provide.

In this case, in the first step, the purified water is mixed with 700 to 800 parts by weight based on 100 parts by weight of the copper-manganese catalyst oxide.

In the fourth step, the heat treatment temperature is 250 to 350 ° C, and the heat treatment time is 1 to 24 hours. If the heat treatment temperature and time are less than the above ranges, the composition is difficult to synthesize and the strength of the molded product is weak. If the temperature and time are more than the above range, the liquid phase sintering by the inorganic binder proceeds to increase the density and decrease the specific surface area and pore volume of the molded product, It is undesirable because it may lower the efficiency.

The granular filter media composition for removing harmful gas containing copper-manganese catalyst oxide according to the present invention is excellent in mechanical strength and gas removal performance of pellets, and can be used in industrial fields, automobiles, boilers, underground roads, tunnels, It can be effectively applied to the purpose of removing harmful gases in the fields of underground parking lots and general household air conditioners.

1 is a photograph showing the result of a droplet comparison test according to whether a wetting agent is added or not.

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art.

≪ Example 1 >

First, 13.33 g of methyl cellulose (MC-4000 / purified water) was added to 800 g of industrial water and stirred for 30 minutes. Subsequently, 100 g of copper-manganese catalyst oxide and 100 g of liquid sodium silicate were added in this order, 1.33 g of a silicone-based wetting agent (BYK-348, BYK Additives & Instruments) was added to prepare a liquid molding composition. Since powdery silica (SiO ₂₎ 666.67g and 33.33g of activated carbon is mixed with a powdered cosmetic composition and the molding composition aeksanghyeong the mixture for 10 minutes using a high speed mixer and extrusion type pellet-type granules molding equipment to manufacture diameter 3.5mm , And pellet type granules having a length of about 10 mm were prepared. Then, it was hot-air dried at 65 ° C for 20 hours and then heat-treated at 300 ° C for 2 hours to prepare a pellet-shaped filter media.

≪ Example 2 >

A pelletized filter medium was prepared in the same manner as in Example 1 except that 20 g of methylcellulose was added.

≪ Example 3 >

A pelletized filter medium was prepared in the same manner as in Example 1 except that 20 g of hydroxypropylcellulose (HPMC, MECELLOSE) was added instead of 13.33 g of methylcellulose.

<Example 4>

A pellet filter medium was prepared in the same manner as in Example 1 except that 6.67 g of hydroxypropylcellulose (HPMC, MECELLOSE) was added instead of 13.33 g of methylcellulose.

&Lt; Example 5 >

A pelletized filter medium was prepared in the same manner as in Example 1 except that 2.67 g of a wetting agent was added.

&Lt; Comparative Example 1 &

A pelletized filter medium was prepared in the same manner as in Example 1 except that no wetting agent was added.

&Lt; Comparative Example 2 &

A pellet-type filter medium was prepared in the same manner as in Example 1, except that Triton X-100, a nonionic surfactant, was used in place of the modified silicone-based wetting agent.

< Comparative Example  3 to 5>

The pellet type filter media was prepared in the same manner as in Example 1 except that the weight of the composition was prepared by referring to the values shown in Table 1 below.

Furtherance
(Parts by weight) Copper-manganese catalyst oxide Cellulose-based polymer binder weapon
bookbinder Wetting agent Silica Activated carbon Example 1 100 13.33 100 1.33 666.67 33.33 Example 2 100 20 100 1.33 666.67 33.33 Example 3 100 20 100 1.33 666.67 33.33 Example 4 100 6.67 100 1.33 666.67 33.33 Example 5 100 13.3 100 2.67 666.67 33.33 Comparative Example 1 100 13.33 100 - 666.67 33.33 Comparative Example 2 100 13.33 100 1.33 666.67 33.33 Comparative Example 3 100 - 100 1.33 666.67 33.33 Comparative Example 4 100 13.33 100 1.33 466.67 33.33 Comparative Example 5 100 13.33 100 1.33 666.67 6.67

<Evaluation Example 1. Droplet Comparative Test>

A liquid phase molding composition prepared by adding the modified silicone wetting agent of Example 1, a liquid phase molding composition prepared by adding the wetting agent of Comparative Example 1, and a liquid phase molding produced by adding a nonionic surfactant instead of the modified silicone wetting agent of Comparative Example 2 The mixing characteristics of the liquid and powdery compositions were evaluated through improvement of the surface tension of water through comparison of liquid crystal formation of the composition. The droplet comparison experiment was carried out by forming a droplet of 100 μl on the surface of the water-repellent plastic and visually observing spreadability. The results are shown in FIG.

Referring to FIG. 1, it can be seen that the composition of Example 1 to which a modified silicone wetting agent was added had a lower surface tension than Comparative Example 1 to which no wetting agent was added and Comparative Example 2 to which a nonionic surfactant was added. It was found that the characteristics were improved.

&Lt; Evaluation Example 2. Moldability comparison >

Moldability of the molding compositions obtained through Examples 1 to 5 and Comparative Examples 1 to 5 was compared. The pellet-type granules were formed using a roller-ring dice extruder, and the moldability was measured by comparing the molding speed based on the increment of the pellets molded for 10 minutes. The results are shown in Table 2 below .

Molding speed (kg / 10 min) Example 1 9.7 Example 2 8.4 Example 3 8.8 Example 4 9.1 Example 5 9.5 Comparative Example 1 5.4 Comparative Example 2 8.8 Comparative Example 3 6.7 Comparative Example 4 8.0 Comparative Example 5 7.9

It can be seen from Table 2 that the molding speed of Comparative Example 1 in which the wetting agent was not added first and Comparative Example 3 in which the cellulose based polymer binder was not added was remarkably low, The molding speed is improved, and the flexibility of the composition is improved according to the addition of the cellulose-based polymer binder, so that the molding speed is improved.

<Evaluation Example 3> Hardness comparison of pellets>

The hardness of the pellet type filter media obtained through Examples 1 to 5 and Comparative Examples 1 to 5 was measured using a hardness tester (Campbell Tablet). The results are shown in Table 3 below.

Hardness (kg / sq.m) Example 1 4.6 Example 2 5.6 Example 3 5.4 Example 4 3.6 Example 5 4.0 Comparative Example 1 4.3 Comparative Example 2 4.2 Comparative Example 3 2.6 Comparative Example 4 4.1 Comparative Example 5 3.9

As shown in Table 3, in Comparative Example 3 in which the cellulose-based polymer binder was not added, it was confirmed that the hardness was lower than that in the case where the cellulose-based polymer binder was added. Therefore, compact molding was induced by the addition of the cellulose- It was confirmed that the hardness of the pellet was improved.

<Evaluation Example 4. Carbon monoxide (CO) removal efficiency evaluation>

The pellet type filter media obtained through Examples 1 to 5 and Comparative Examples 1 to 5 were evaluated for carbon monoxide removal efficiency.

First, 5.0 g of the pellet-shaped filter media of Examples 1 to 5 and Comparative Examples 1 to 5 was pretreated at 120 DEG C for 1 hour. Subsequently, carbon monoxide was injected at a concentration of 50 ppm after being sealed in a 5 L teddler bag, and the change in carbon monoxide concentration was measured after 60 minutes using a composite gas detector (Q-RAE Plus). The results are shown in Table 4 Respectively.

CO Removal Rate (%) Example 1 87 Example 2 83 Example 3 83 Example 4 78 Example 5 84 Comparative Example 1 54 Comparative Example 2 66 Comparative Example 3 82 Comparative Example 4 60 Comparative Example 5 57

The results are shown in Table 4. The results are shown in Table 4. The results are shown in Table 4. The results are shown in Table 4. The results are shown in Table 4, This result appears to be due to the induction of one distribution.

On the other hand, in Comparative Examples 1, 2, 4 and 5, the gas removal performance was not excellent as compared with Examples 1 to 5, and in Comparative Example 3, the gas removal performance was excellent. It is not suitable for use because it is not excellent.

Claims (9)

A granular filter media composition for removing harmful gases, comprising copper-manganese catalyst oxide, copper-manganese catalyst oxide, cellulosic polymer binder, inorganic binder, wetting agent, silica and activated carbon. The method according to claim 1,
Wherein the copper-manganese catalyst oxide is a mixture of copper salt and manganese salt in a molar ratio of 1: 1 to 1: 4. 3. The method of claim 2,
Wherein the copper salt is at least one selected from the group consisting of copper acetate, copper nitrate, copper chloride, copper iodide, copper bromide, cuprous sulfate and copper acetate. Type filter media composition. 3. The method of claim 2,
Wherein the manganese salt is at least one selected from the group consisting of manganese nitrate, manganese nitrate, manganese chloride, manganese iodide, manganese bromide, manganese sulfate, potassium permanganate and manganese acetate. Granular filter media. The method according to claim 1,
The cellulose-based polymeric binder is at least one selected from the group consisting of methyl cellulose, ethyl cellulose, methyl ethyl cellulose, propyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose and hydroxypropyl cellulose By weight of a copper-manganese catalyst oxide. The method according to claim 1,
The granular filter media composition for removing harmful gas containing copper-manganese catalyst oxide, wherein the inorganic binder is a liquid silicate. The method according to claim 1,
The wetting agent may be selected from the group consisting of polyether-modified dimethylpolysiloxanes, polydimethylsiloxanes of polyether-modified hydroxy functional groups, polyester-modified hydroxy-functional polydimethylsiloxanes, polyester-modified polymethylalkylsiloxanes, polyether-modified polymethylalkylsiloxanes, and polyester- And at least one modified silicon series selected from the group consisting of ruthenium, manganese, zirconium, and ricifolimethylsiloxane. The method according to claim 1,
The granular filter media composition for removing harmful gases containing copper-manganese catalyst oxide comprises 5 to 25 parts by weight of a cellulose-based polymer binder, 90 to 110 parts by weight of an inorganic binder, 0.5 to 5 parts by weight of a wetting agent based on 100 parts by weight of copper- By weight of silica, from 650 to 700 parts by weight of silica, and from 20 to 50 parts by weight of activated carbon, based on the total weight of the granular filter media. A first step of mixing a purified water and a cellulose-based polymer binder and stirring to prepare a mixed solution;
A second step of adding a copper-manganese catalyst oxide and an inorganic binder to the mixed solution prepared in the first step, stirring the mixed solution, and then adding a wetting agent to prepare a liquid molding composition;
A third step of mixing the liquid molding composition prepared in the second step with a powdery molding composition containing silica and activated carbon to prepare a molding composition;
The method for producing a granular filter media composition for removing harmful gas according to any one of claims 1 to 3, wherein the granular filter media composition comprises copper-manganese catalyst oxide.

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