WO2021229799A1 - Deodorizing catalyst for refrigerator and deodorizing material for refrigerator using this - Google Patents
Deodorizing catalyst for refrigerator and deodorizing material for refrigerator using this Download PDFInfo
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- WO2021229799A1 WO2021229799A1 PCT/JP2020/019454 JP2020019454W WO2021229799A1 WO 2021229799 A1 WO2021229799 A1 WO 2021229799A1 JP 2020019454 W JP2020019454 W JP 2020019454W WO 2021229799 A1 WO2021229799 A1 WO 2021229799A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
Definitions
- This disclosure relates to a refrigerator deodorizing catalyst and a refrigerator deodorizing material using the same.
- the odor derived from food is generated in the refrigerator.
- the odor-causing substances are sulfur oxides such as hydrogen sulfide and mercaptan, nitrogen compounds such as ammonia and amines, organic acids and alcohols.
- sulfur oxides such as hydrogen sulfide and mercaptan
- nitrogen compounds such as ammonia and amines
- organic acids and alcohols Various means and methods for adsorbing and removing these substances have been developed so far (see Patent Documents 1 to 3).
- Japanese Unexamined Patent Publication No. 11-188263 Japanese Unexamined Patent Publication No. 10-137591 Japanese Unexamined Patent Publication No. 8-266866
- the conventional deodorizing catalyst can reduce the odor by adsorbing the odor-causing substance, there is still room for improvement in reducing the odor caused by the by-products generated by the decomposition of the adsorbed causative substance.
- dimethyldisulfide is known as a decomposition by-product of methyl mercaptan.
- Dimethyldisulfide is also a causative agent of odor.
- the present disclosure provides a deodorizing catalyst for a refrigerator and a deodorizing material for a refrigerator using the deodorizing catalyst for a refrigerator, which has excellent removal performance for methyl mercaptan and can sufficiently suppress the release of dimethyldisulfide which is a decomposition by-product of methyl mercaptan. ..
- the deodorizing catalyst for a refrigerator contains a Cu—Mn composite oxide and a zeolite having a silica / alumina molar ratio of 100 or more, and the ratio of the mass A of the Cu—Mn composite oxide to the mass B of the zeolite (A). / B) is 0.1 or more and 1.25 or less.
- the silica / alumina molar ratio of zeolite means a value measured by a fluorescent X-ray analyzer (XRF).
- the deodorizing catalyst for a refrigerator uses a specific composite oxide and a zeolite satisfying a specific condition in combination, and the mass ratio (A / B) of these is in the range of 0.1 to 1.25. According to such a deodorizing catalyst for a refrigerator, not only a high removal rate of methyl mercaptan can be achieved, but also the release of dimethyl disulfide, which is a decomposition by-product of methyl mercaptan, can be sufficiently suppressed.
- the zeolite is, for example, powdery. From the viewpoint of catalytic activity, the zeolite preferably has a specific surface area of 300 m 2 / g or more as measured by the BET method.
- the zeolite preferably has a maximum value in the range of the pore diameter of 0.8 nm or more and 1.2 nm or less in the pore distribution by the MP method obtained from the nitrogen adsorption / desorption isotherm measurement. It can be said that a zeolite having a maximum pore diameter in the above range has a relatively large number of pores having an opening diameter of about 1 nm.
- the mass ratio (A / B) of both is within the above range, the effect of the present invention can be achieved even more highly.
- the total acid amount of the above zeolite calculated by the ammonia heated desorption method is 0.3 mmol / g or less.
- This total acid amount is a value that reflects the acid amount of zeolite.
- a zeolite having a large silica / alumina molar ratio has a high acid strength and a small total acid amount measured by the above method.
- a zeolite having a silica / alumina molar ratio of 100 or more and a total acid amount of 0.3 mmol / g or less measured by the above method is used in combination with a Cu—Mn composite oxide, and the mass ratio of both ( When A / B) is within the above range, the effect of the present invention can be achieved even more highly.
- the Cu—Mn composite oxide is, for example, powdery. From the viewpoint of catalytic activity, the Cu—Mn composite oxide preferably has a specific surface area of 150 m 2 / g or more as measured by the BET method.
- the Cu—Mn composite oxide has, for example, a Cu content of 10 to 40% by mass in terms of CuO and a Mn content of 60 to 90% by mass in terms of MnO 2.
- the refrigerator deodorizing material according to the present disclosure includes the above-mentioned refrigerator deodorizing catalyst and a base material having a surface coated with the refrigerator deodorizing catalyst.
- a refrigerator deodorizing material can be manufactured by forming a refrigerator deodorizing catalyst in a layer on the surface of a base material by a coating technique such as a wash coat.
- An example of the base material is a honeycomb base material.
- the deodorizing material for a refrigerator can be used as a deodorizing filter, for example, and is mounted in a refrigerator where cold air flows.
- a deodorizing catalyst for a refrigerator and a deodorizing material for a refrigerator using the deodorizing catalyst for a refrigerator which has excellent removal performance for methyl mercaptan and can sufficiently suppress the release of dimethyldisulfide which is a decomposition by-product of methyl mercaptan, are described. Provided.
- FIG. 1 is a graph showing the pore distribution of zeolite used in Examples and Comparative Examples.
- FIG. 2 is a graph showing a temperature-increasing desorption curve of adsorbed ammonia of zeolite used in Examples and Comparative Examples.
- FIG. 3 is a graph showing the XRD analysis results of the zeolites used in Examples and Comparative Examples.
- the deodorizing catalyst according to the present embodiment is mounted on a refrigerator or installed in a refrigerator in a state of being applied to a base material such as a honeycomb base material, for example.
- This deodorizing catalyst contains a Cu—Mn composite oxide and a zeolite having a silica / alumina molar ratio of 100 or more.
- the ratio (A / B) of the mass A of the Cu—Mn composite oxide to the mass B of the zeolite is 0.1 or more and 1.25 or less.
- DMDS dimethyl disulfide
- the lower limit of the ratio (A / B) is preferably 0.15, and may be 0.2 or 0.25, from the viewpoint of improving the removal rate of methyl mercaptan.
- the upper limit of the ratio (A / B) is preferably 1.0, and may be 0.9 or 0.8 from the viewpoint of suppressing the release of dimethyldisulfide.
- the Cu—Mn composite oxide has a deodorizing effect.
- the Cu—Mn composite oxide is, for example, powdery.
- the Cu—Mn composite oxide preferably has a specific surface area of 150 m 2 / g or more, more preferably 200 to 300 m 2 / g, as measured by the BET method.
- the average particle size of the Cu—Mn composite oxide can be measured by the BET method.
- the Cu-Mn composite oxide has, for example, a Cu content of 10 to 40% by mass (more preferably 15 to 30% by mass) in terms of CuO and a Mn content of 60 to 90% by mass in terms of MnO 2. More preferably, it is 65 to 80% by mass).
- the Cu—Mn composite oxide may contain components other than Cu and Mn. The content of such a component (based on the mass of the Cu—Mn composite oxide) may be, for example, 20% by mass or less.
- Hopcalite is an example of a Cu—Mn composite oxide. Hopcalite contains about 1 to 4% by mass of potassium as a component other than Cu and Mn.
- Zeolites are substances with pores and have the effect of adsorbing odor-causing substances.
- the silica / alumina molar ratio of the zeolite is 100 or more, and may be 100 to 1000.
- a zeolite having a silica / alumina molar ratio of 100 or more in combination with a Cu—Mn composite oxide the above-mentioned effect of the present invention can be obtained.
- the zeolite is, for example, powdery.
- the specific surface area of the zeolite measured by the BET method is preferably 300 m 2 / g or more, and more preferably 350 to 800 m 2 / g.
- the zeolite preferably has a maximum value in the range of the pore diameter of 0.8 nm or more and 1.2 nm or less in the pore distribution by the MP method obtained from the nitrogen adsorption / desorption isotherm measurement.
- the zeolite may have a maximum value even in the range where the pore diameter is 0.4 nm or more and 0.7 nm or less.
- the average particle size of zeolite can be measured by the BET method.
- the total acid content of the zeolite calculated by the ammonia temperature desorption method is preferably 0.3 mmol / g or less, and more preferably 0.01 to 0.2 mmol / g.
- This total acid amount is a value that reflects the acid amount of zeolite.
- a zeolite having a large silica / alumina molar ratio has a high acid strength and a small total acid amount measured by the above method.
- a zeolite having a silica / alumina molar ratio of 100 or more and a total acid amount of 0.3 mmol / g or less measured by the above method is used in combination with a Cu—Mn composite oxide, and the mass ratio of both is used.
- (A / B) is within the above range, the above-mentioned effect of the present invention can be achieved even more highly.
- Examples of the zeolite type include MFI type, Y type, A type, L type and the like. Of these, it is preferable to use MFI-type zeolite from the viewpoint of deodorizing performance.
- Examples of the cation species contained in zeolite include sodium ion, hydrogen ion, potassium ion, calcium ion and the like. Of these, from the viewpoint of cost, it is preferable to use zeolite whose cation species is sodium ion.
- the deodorizing catalyst may contain, for example, a binder as a component other than the above. Since the deodorizing catalyst contains a binder, a catalyst layer can be formed on the surface of the base material by the slurry method.
- the binder may be an inorganic binder or an organic binder. Examples of the inorganic binder include silica sol and alumina sol. Examples of the organic binder include natural resins such as starch, casein and gelatin; synthetic resins such as cellulose, water-soluble polyamide, quaternary ammonium salt, acrylic resin, urethane resin, vinyl acetate resin, SBR resin, epoxy resin and polyvinyl alcohol resin. Be done. Among these, by using an inorganic binder (for example, silica particles), the effect that the binder has a small inhibitory effect on the deodorizing performance is exhibited.
- an inorganic binder for example, silica particles
- the content of the inorganic binder in the deodorizing catalyst is, for example, 5 to 30% by mass, and may be 10 to 20% by mass, based on the total mass of the deodorizing catalyst.
- the content of the organic binder in the deodorizing catalyst is, for example, 2.5 to 20% by mass, and may be 5 to 15% by mass, based on the total mass of the deodorizing catalyst.
- the refrigerator deodorizing material includes the refrigerator deodorizing catalyst and a base material having a surface coated with the refrigerator deodorizing catalyst.
- a refrigerator deodorizing material can be manufactured by forming a refrigerator deodorizing catalyst in a layer on the surface of a base material by a coating technique such as a wash coat.
- the base material include a honeycomb base material, a pellet-shaped base material, a woven fabric or a non-woven fabric-like base material, and a plate-shaped or block-shaped bulk member.
- the material of the base material is not particularly limited, and examples thereof include metals, ceramics, glass, plastics, cellulosic materials, and materials combining these (composite materials, laminated materials, etc.).
- the metal include stainless steel, aluminum, copper, galvanized steel sheet and iron.
- the ceramics include cordylite, alumina, barium titanate, boron nitride and silicon nitride.
- the glass include ordinary soda lime glass, borosilicate glass, non-alkali glass, quartz glass and aluminosilicate glass.
- the plastic include an acrylic resin such as polymethylmethacrylate, an aromatic polycarbonate resin such as polyphenylene carbonate, and an aromatic polyester resin such as polyethylene terephthalate (PET).
- Cellulosic materials include, for example, cotton, linen, rayon, and cupra.
- the deodorizing material for a refrigerator can be used as a deodorizing filter, for example, and is mounted in a refrigerator where cold air flows.
- Example 1 A slurry for forming a deodorizing catalyst layer was prepared using the following components.
- Example 2 As the zeolite, the following NU-2080 was used instead of NU-1080, and a slurry was obtained in the same manner as in Example 1 except that the blending amount of each component was set to the amount shown in Table 1.
- Example 3 Slurries according to Examples 3 and 4 were obtained in the same manner as in Example 1 except that the blending amount of each component was set to the amount shown in Table 1.
- EX-122 Mizuka Sieves EX-122 (hereinafter referred to as "EX-122”) was used instead of NU-1080, and the blending amount of each component was set to the amount shown in Table 2.
- a slurry was obtained in the same manner as in Example 1.
- NFK-7-2SC1.0-HWOS As the zeolite, the following NFK-7-2SC1.0-HWOS was used instead of NU-1080, and the blending amount of each component was set to the amount shown in Table 2, in the same manner as in Example 1. A slurry was obtained.
- Y-420 the following Mizuka Sieves Y-420 (hereinafter referred to as "Y-420”) was used instead of NU-1080, and the blending amount of each component was set to the amount shown in Table 2.
- a slurry was obtained in the same manner as in Example 1.
- Comparative Examples 5 to 8 Slurries according to Comparative Examples 5 to 8 were obtained in the same manner as in Example 1 except that the blending amount of each component was set to the amount shown in Table 3.
- ⁇ Zeolite pore distribution> The pore distribution of the zeolite used in the examples and comparative examples was measured by the MP method obtained from the nitrogen adsorption / desorption isotherm measurement. The results are shown in FIG. It was found that the zeolites (NU-1080 and NU-2080) used in the examples had pores having a diameter of about 1 nm.
- FIG. 2 shows a temperature-increasing desorption curve of adsorbed ammonia. It was found that the zeolites (NU-1080 and NU-2080) used in the examples had a small amount of ammonia adsorbed and a small amount of acid as a whole. The total amount of acid calculated from the temperature desorption curve was as follows. NU-1080: 0.184 mmol / g NU-2080: 0.083 mmol / g EX122: 1.147 mmol / g Y-420: 2.360 mmol / g
- FIG. 3 shows the XRD analysis results of the zeolites used in Examples and Comparative Examples.
- a ceramic honeycomb (cell number 200 / inch 2 , cell opening surface diameter 21 mm, ventilation direction length 7.0 mm, manufactured by Seibu Giken Co., Ltd.) was prepared.
- a catalyst layer was formed on the surface of this honeycomb base material by a wash coat. That is, after the base material was immersed in each of the slurries according to the examples and the comparative examples, the excess slurry was blown off by an air blow. Then, a deodorizing filter was obtained by putting it in a dryer set at 150 ° C. for 1 hour to dry it. The amount of the slurry applied was adjusted so that the mass of the catalyst layer after drying was 150 g per 1 L of the honeycomb base material.
- MMP Metal mercaptan distribution test> (1) MMP removal rate Each deodorant (cell opening surface diameter: 21 mm) according to Examples and Comparative Examples was installed in a glass tube. Air at a temperature of 25 ° C. and a humidity of 80% RH was circulated through the deodorizing material at a flow rate of 9.1 L / min for 15 minutes. Methyl mercaptan was introduced into the circulating air so that the concentration of methyl mercaptan was 100 ppm. Ten minutes after the start of introduction of methyl mercaptan, the methyl mercaptan concentration in the air after passing through the deodorizing material was measured. This value was substituted into the following equation to calculate the removal rate.
- MMP removal rate (%) ⁇ 1- (MMP concentration [ppm] / 100 [ppm]) ⁇ x 100
- DMDS Dimethyl disulfide
- a deodorizing catalyst for a refrigerator and a deodorizing material for a refrigerator using the deodorizing catalyst for a refrigerator which has excellent removal performance for methyl mercaptan and can sufficiently suppress the release of dimethyldisulfide which is a decomposition by-product of methyl mercaptan, are described. Provided.
Abstract
This deodorizing catalyst for a refrigerator contains a Cu-Mn composite oxide, and zeolite with a silica/alumina molar ratio of at least 100, and the ratio (A/B) of the mass A of the Cu-Mn composite oxide and the mass B of the zeolite is 0.1-1.25. In a pore distribution based on the MP method, calculated with nitrogen adsorption/desorption isotherm measurement, this zeolite preferably has a pore diameter maximum value in the range 0.8-1.2nm. Alternatively, the zeolite preferably has a total acid content of less than or equal to 0.3 mmol/g, calculated by ammonia temperature-programmed desorption.
Description
本開示は、冷蔵庫用脱臭触媒及びこれを用いた冷蔵庫用脱臭材に関する。
This disclosure relates to a refrigerator deodorizing catalyst and a refrigerator deodorizing material using the same.
冷蔵庫内では食品に由来する臭いが発生する。臭いの原因物質は、硫化水素、メルカプタン等の硫黄酸化物、アンモニア、アミン類等の窒素化合物、有機酸、アルコール類などである。これらの物質を吸着除去するための種々の手段及び方法がこれまでに開発されている（特許文献１～３参照）。
The odor derived from food is generated in the refrigerator. The odor-causing substances are sulfur oxides such as hydrogen sulfide and mercaptan, nitrogen compounds such as ammonia and amines, organic acids and alcohols. Various means and methods for adsorbing and removing these substances have been developed so far (see Patent Documents 1 to 3).
従来の脱臭触媒は、臭いの原因物質を吸着することによって臭いを低減できるものの、吸着した原因物質が分解することによって生じる副生成物に起因する臭いを低減する点において未だ改善の余地があった。例えば、メチルメルカプタンの分解副生成物としてジメチルジサルファイドが知られている。ジメチルジサルファイドも臭いの原因物質である。
Although the conventional deodorizing catalyst can reduce the odor by adsorbing the odor-causing substance, there is still room for improvement in reducing the odor caused by the by-products generated by the decomposition of the adsorbed causative substance. .. For example, dimethyldisulfide is known as a decomposition by-product of methyl mercaptan. Dimethyldisulfide is also a causative agent of odor.
本開示は、メチルメルカプタンに対する優れた除去性能を有するとともに、メチルメルカプタンの分解副生成物であるジメチルジサルファイドの放出を十分に抑制できる冷蔵庫用脱臭触媒及びこれを用いた冷蔵庫用脱臭材を提供する。
The present disclosure provides a deodorizing catalyst for a refrigerator and a deodorizing material for a refrigerator using the deodorizing catalyst for a refrigerator, which has excellent removal performance for methyl mercaptan and can sufficiently suppress the release of dimethyldisulfide which is a decomposition by-product of methyl mercaptan. ..
本開示に係る冷蔵庫用脱臭触媒は、Ｃｕ－Ｍｎ複合酸化物と、シリカ／アルミナモル比が１００以上のゼオライトとを含み、Ｃｕ－Ｍｎ複合酸化物の質量Ａとゼオライトとの質量Ｂの比（Ａ／Ｂ）が０．１以上１．２５以下である。なお、ゼオライトのシリカ／アルミナモル比は蛍光Ｘ線分析装置（ＸＲＦ）により測定される値を意味する。
The deodorizing catalyst for a refrigerator according to the present disclosure contains a Cu—Mn composite oxide and a zeolite having a silica / alumina molar ratio of 100 or more, and the ratio of the mass A of the Cu—Mn composite oxide to the mass B of the zeolite (A). / B) is 0.1 or more and 1.25 or less. The silica / alumina molar ratio of zeolite means a value measured by a fluorescent X-ray analyzer (XRF).
上記冷蔵庫用脱臭触媒は、特定の複合酸化物と、特定の条件を満たすゼオライトを併用するとともに、これらの質量比（Ａ／Ｂ）が０．１～１．２５の範囲である。かかる冷蔵庫用脱臭触媒によれば、メチルメルカプタンの高い除去率を達成できるだけでなく、メチルメルカプタンの分解副生成物であるジメチルジサルファイドの放出も十分に抑制できる。
The deodorizing catalyst for a refrigerator uses a specific composite oxide and a zeolite satisfying a specific condition in combination, and the mass ratio (A / B) of these is in the range of 0.1 to 1.25. According to such a deodorizing catalyst for a refrigerator, not only a high removal rate of methyl mercaptan can be achieved, but also the release of dimethyl disulfide, which is a decomposition by-product of methyl mercaptan, can be sufficiently suppressed.
上記ゼオライトは、例えば、粉状である。上記ゼオライトは、触媒活性の観点から、ＢＥＴ法により測定される比表面積が３００ｍ２／ｇ以上であることが好ましい。上記ゼオライトは、窒素吸脱着等温線測定から求められるＭＰ法による細孔分布において、細孔径が０．８ｎｍ以上１．２ｎｍ以下の範囲に極大値を有することが好ましい。細孔径の極大値を上記範囲に有するゼオライトは開口径が１ｎｍ程度の細孔を比較的多く有すると言える。このようなゼオライトとＣｕ－Ｍｎ複合酸化物とを併用し且つ両者の質量比（Ａ／Ｂ）が上記範囲内であることで、より一層高度に本発明の効果が奏される。
The zeolite is, for example, powdery. From the viewpoint of catalytic activity, the zeolite preferably has a specific surface area of 300 m 2 / g or more as measured by the BET method. The zeolite preferably has a maximum value in the range of the pore diameter of 0.8 nm or more and 1.2 nm or less in the pore distribution by the MP method obtained from the nitrogen adsorption / desorption isotherm measurement. It can be said that a zeolite having a maximum pore diameter in the above range has a relatively large number of pores having an opening diameter of about 1 nm. When such a zeolite and a Cu—Mn composite oxide are used in combination and the mass ratio (A / B) of both is within the above range, the effect of the present invention can be achieved even more highly.
上記ゼオライトは、アンモニア昇温脱離法により算出される全酸量が０．３ｍｍｏｌ／ｇ以下であることが好ましい。この全酸量は、ゼオライトの酸量を反映する値である。一般に、シリカ／アルミナモル比が大きいゼオライトは、高い酸強度を有し且つ上記の方法によって測定される全酸量が小さい値であることが知られている。本発明において、シリカ／アルミナモル比が１００以上であり、上記の方法によって測定される全酸量が０．３ｍｍｏｌ／ｇ以下のゼオライトとＣｕ－Ｍｎ複合酸化物とを併用し且つ両者の質量比（Ａ／Ｂ）が上記範囲内であることで、より一層高度に本発明の効果が奏される。
It is preferable that the total acid amount of the above zeolite calculated by the ammonia heated desorption method is 0.3 mmol / g or less. This total acid amount is a value that reflects the acid amount of zeolite. In general, it is known that a zeolite having a large silica / alumina molar ratio has a high acid strength and a small total acid amount measured by the above method. In the present invention, a zeolite having a silica / alumina molar ratio of 100 or more and a total acid amount of 0.3 mmol / g or less measured by the above method is used in combination with a Cu—Mn composite oxide, and the mass ratio of both ( When A / B) is within the above range, the effect of the present invention can be achieved even more highly.
上記Ｃｕ－Ｍｎ複合酸化物は、例えば、粉状である。上記Ｃｕ－Ｍｎ複合酸化物は、触媒活性の観点から、ＢＥＴ法により測定される比表面積が１５０ｍ２／ｇ以上であることが好ましい。上記Ｃｕ－Ｍｎ複合酸化物は、例えば、Ｃｕ含有量がＣｕＯ換算で１０～４０質量％であり且つＭｎ含有量がＭｎＯ２換算で６０～９０質量％である。
The Cu—Mn composite oxide is, for example, powdery. From the viewpoint of catalytic activity, the Cu—Mn composite oxide preferably has a specific surface area of 150 m 2 / g or more as measured by the BET method. The Cu—Mn composite oxide has, for example, a Cu content of 10 to 40% by mass in terms of CuO and a Mn content of 60 to 90% by mass in terms of MnO 2.
本開示に係る冷蔵庫用脱臭材は、上記冷蔵庫用脱臭触媒と、冷蔵庫用脱臭触媒が塗布された表面を有する基材とを備える。例えば、ウォッシュコート等の塗工技術によって基材の表面に冷蔵庫用脱臭触媒を層状に形成することによって冷蔵庫用脱臭材を製造することができる。基材の例として、ハニカム基材が挙げられる。冷蔵庫用脱臭材は、例えば、脱臭フィルターとして使用することができ、冷蔵庫内であって、冷えた空気が流れる箇所に搭載される。
The refrigerator deodorizing material according to the present disclosure includes the above-mentioned refrigerator deodorizing catalyst and a base material having a surface coated with the refrigerator deodorizing catalyst. For example, a refrigerator deodorizing material can be manufactured by forming a refrigerator deodorizing catalyst in a layer on the surface of a base material by a coating technique such as a wash coat. An example of the base material is a honeycomb base material. The deodorizing material for a refrigerator can be used as a deodorizing filter, for example, and is mounted in a refrigerator where cold air flows.
本開示によれば、メチルメルカプタンに対する優れた除去性能を有するとともに、メチルメルカプタンの分解副生成物であるジメチルジサルファイドの放出を十分に抑制できる冷蔵庫用脱臭触媒及びこれを用いた冷蔵庫用脱臭材が提供される。
According to the present disclosure, a deodorizing catalyst for a refrigerator and a deodorizing material for a refrigerator using the deodorizing catalyst for a refrigerator, which has excellent removal performance for methyl mercaptan and can sufficiently suppress the release of dimethyldisulfide which is a decomposition by-product of methyl mercaptan, are described. Provided.
以下、本開示の実施形態について説明する。なお、本発明は以下の実施形態に限定されるものではない。
Hereinafter, embodiments of the present disclosure will be described. The present invention is not limited to the following embodiments.
＜脱臭触媒＞
本実施形態に係る脱臭触媒は、例えば、ハニカム基材などの基材に塗布された状態で冷蔵庫に搭載又は冷蔵庫内に設置されるものである。この脱臭触媒は、Ｃｕ－Ｍｎ複合酸化物と、シリカ／アルミナモル比が１００以上のゼオライトとを含む。上記Ｃｕ－Ｍｎ複合酸化物の質量Ａと上記ゼオライトとの質量Ｂの比（Ａ／Ｂ）が０．１以上１．２５以下である。この脱臭触媒によれば、メチルメルカプタン（ＭＭＰ）の高い除去率を達成できるだけでなく、メチルメルカプタンの分解副生成物であるジメチルジサルファイド（ＤＭＤＳ）の放出も十分に抑制できる。比（Ａ／Ｂ）の下限値は、メチルメルカプタンの除去率向上の観点から、好ましくは０．１５であり、０．２又は０．２５であってもよい。比（Ａ／Ｂ）の上限値は、ジメチルジサルファイドの放出抑制の観点から、好ましくは１．０であり、０．９又は０．８であってもよい。 <Deodorizing catalyst>
The deodorizing catalyst according to the present embodiment is mounted on a refrigerator or installed in a refrigerator in a state of being applied to a base material such as a honeycomb base material, for example. This deodorizing catalyst contains a Cu—Mn composite oxide and a zeolite having a silica / alumina molar ratio of 100 or more. The ratio (A / B) of the mass A of the Cu—Mn composite oxide to the mass B of the zeolite is 0.1 or more and 1.25 or less. According to this deodorizing catalyst, not only a high removal rate of methyl mercaptan (MMP) can be achieved, but also the release of dimethyl disulfide (DMDS), which is a decomposition by-product of methyl mercaptan, can be sufficiently suppressed. The lower limit of the ratio (A / B) is preferably 0.15, and may be 0.2 or 0.25, from the viewpoint of improving the removal rate of methyl mercaptan. The upper limit of the ratio (A / B) is preferably 1.0, and may be 0.9 or 0.8 from the viewpoint of suppressing the release of dimethyldisulfide.
本実施形態に係る脱臭触媒は、例えば、ハニカム基材などの基材に塗布された状態で冷蔵庫に搭載又は冷蔵庫内に設置されるものである。この脱臭触媒は、Ｃｕ－Ｍｎ複合酸化物と、シリカ／アルミナモル比が１００以上のゼオライトとを含む。上記Ｃｕ－Ｍｎ複合酸化物の質量Ａと上記ゼオライトとの質量Ｂの比（Ａ／Ｂ）が０．１以上１．２５以下である。この脱臭触媒によれば、メチルメルカプタン（ＭＭＰ）の高い除去率を達成できるだけでなく、メチルメルカプタンの分解副生成物であるジメチルジサルファイド（ＤＭＤＳ）の放出も十分に抑制できる。比（Ａ／Ｂ）の下限値は、メチルメルカプタンの除去率向上の観点から、好ましくは０．１５であり、０．２又は０．２５であってもよい。比（Ａ／Ｂ）の上限値は、ジメチルジサルファイドの放出抑制の観点から、好ましくは１．０であり、０．９又は０．８であってもよい。 <Deodorizing catalyst>
The deodorizing catalyst according to the present embodiment is mounted on a refrigerator or installed in a refrigerator in a state of being applied to a base material such as a honeycomb base material, for example. This deodorizing catalyst contains a Cu—Mn composite oxide and a zeolite having a silica / alumina molar ratio of 100 or more. The ratio (A / B) of the mass A of the Cu—Mn composite oxide to the mass B of the zeolite is 0.1 or more and 1.25 or less. According to this deodorizing catalyst, not only a high removal rate of methyl mercaptan (MMP) can be achieved, but also the release of dimethyl disulfide (DMDS), which is a decomposition by-product of methyl mercaptan, can be sufficiently suppressed. The lower limit of the ratio (A / B) is preferably 0.15, and may be 0.2 or 0.25, from the viewpoint of improving the removal rate of methyl mercaptan. The upper limit of the ratio (A / B) is preferably 1.0, and may be 0.9 or 0.8 from the viewpoint of suppressing the release of dimethyldisulfide.
（Ｃｕ－Ｍｎ複合酸化物）
Ｃｕ－Ｍｎ複合酸化物は脱臭の作用を有する。Ｃｕ－Ｍｎ複合酸化物は、例えば、粉状である。Ｃｕ－Ｍｎ複合酸化物は、触媒活性の観点から、ＢＥＴ法により測定される比表面積が１５０ｍ２／ｇ以上であることが好ましく、２００～３００ｍ２／ｇであることがより好ましい。Ｃｕ－Ｍｎ複合酸化物の平均粒径は、ＢＥＴ法によって測定することができる。 (Cu-Mn composite oxide)
The Cu—Mn composite oxide has a deodorizing effect. The Cu—Mn composite oxide is, for example, powdery. From the viewpoint of catalytic activity, the Cu—Mn composite oxide preferably has a specific surface area of 150 m 2 / g or more, more preferably 200 to 300 m 2 / g, as measured by the BET method. The average particle size of the Cu—Mn composite oxide can be measured by the BET method.
Ｃｕ－Ｍｎ複合酸化物は脱臭の作用を有する。Ｃｕ－Ｍｎ複合酸化物は、例えば、粉状である。Ｃｕ－Ｍｎ複合酸化物は、触媒活性の観点から、ＢＥＴ法により測定される比表面積が１５０ｍ２／ｇ以上であることが好ましく、２００～３００ｍ２／ｇであることがより好ましい。Ｃｕ－Ｍｎ複合酸化物の平均粒径は、ＢＥＴ法によって測定することができる。 (Cu-Mn composite oxide)
The Cu—Mn composite oxide has a deodorizing effect. The Cu—Mn composite oxide is, for example, powdery. From the viewpoint of catalytic activity, the Cu—Mn composite oxide preferably has a specific surface area of 150 m 2 / g or more, more preferably 200 to 300 m 2 / g, as measured by the BET method. The average particle size of the Cu—Mn composite oxide can be measured by the BET method.
上記Ｃｕ－Ｍｎ複合酸化物は、例えば、Ｃｕ含有量がＣｕＯ換算で１０～４０質量％（より好ましくは１５～３０質量％）であり且つＭｎ含有量がＭｎＯ２換算で６０～９０質量％（より好ましくは６５～８０質量％）である。Ｃｕ－Ｍｎ複合酸化物はＣｕ及びＭｎ以外の成分を含んでいてもよい。かかる成分の含有量（Ｃｕ－Ｍｎ複合酸化物の質量基準）は、例えば、２０質量％以下であればよい。Ｃｕ－Ｍｎ複合酸化物の例としてホプカライトが挙げられる。ホプカライトは、Ｃｕ及びＭｎ以外の成分として、１～４質量％程度のカリウムを含んでいる。
The Cu-Mn composite oxide has, for example, a Cu content of 10 to 40% by mass (more preferably 15 to 30% by mass) in terms of CuO and a Mn content of 60 to 90% by mass in terms of MnO 2. More preferably, it is 65 to 80% by mass). The Cu—Mn composite oxide may contain components other than Cu and Mn. The content of such a component (based on the mass of the Cu—Mn composite oxide) may be, for example, 20% by mass or less. Hopcalite is an example of a Cu—Mn composite oxide. Hopcalite contains about 1 to 4% by mass of potassium as a component other than Cu and Mn.
（ゼオライト）
ゼオライトは、細孔を有する物質であり、臭いの原因物質を吸着する作用を有する。上記ゼオライトのシリカ／アルミナモル比は１００以上であり、１００～１０００であってもよい。シリカ／アルミナモル比が１００以上のゼオライトとＣｕ－Ｍｎ複合酸化物とを併用することで、本発明の上記効果が奏される。上記ゼオライトは、例えば、粉状である。上記ゼオライトは、脱臭性能の観点から、ＢＥＴ法により測定される比表面積が３００ｍ２／ｇ以上であることが好ましく、３５０～８００ｍ２／ｇであることがより好ましい。上記ゼオライトは、窒素吸脱着等温線測定から求められるＭＰ法による細孔分布において、細孔径が０．８ｎｍ以上１．２ｎｍ以下の範囲に極大値を有することが好ましい。なお、上記ゼオライトは、細孔径が０．４ｎｍ以上０．７ｎｍ以下の範囲にも極大値を有していてもよい。ゼオライトの平均粒径は、ＢＥＴ法によって測定することができる。 (Zeolite)
Zeolites are substances with pores and have the effect of adsorbing odor-causing substances. The silica / alumina molar ratio of the zeolite is 100 or more, and may be 100 to 1000. By using a zeolite having a silica / alumina molar ratio of 100 or more in combination with a Cu—Mn composite oxide, the above-mentioned effect of the present invention can be obtained. The zeolite is, for example, powdery. From the viewpoint of deodorizing performance, the specific surface area of the zeolite measured by the BET method is preferably 300 m 2 / g or more, and more preferably 350 to 800 m 2 / g. The zeolite preferably has a maximum value in the range of the pore diameter of 0.8 nm or more and 1.2 nm or less in the pore distribution by the MP method obtained from the nitrogen adsorption / desorption isotherm measurement. The zeolite may have a maximum value even in the range where the pore diameter is 0.4 nm or more and 0.7 nm or less. The average particle size of zeolite can be measured by the BET method.
ゼオライトは、細孔を有する物質であり、臭いの原因物質を吸着する作用を有する。上記ゼオライトのシリカ／アルミナモル比は１００以上であり、１００～１０００であってもよい。シリカ／アルミナモル比が１００以上のゼオライトとＣｕ－Ｍｎ複合酸化物とを併用することで、本発明の上記効果が奏される。上記ゼオライトは、例えば、粉状である。上記ゼオライトは、脱臭性能の観点から、ＢＥＴ法により測定される比表面積が３００ｍ２／ｇ以上であることが好ましく、３５０～８００ｍ２／ｇであることがより好ましい。上記ゼオライトは、窒素吸脱着等温線測定から求められるＭＰ法による細孔分布において、細孔径が０．８ｎｍ以上１．２ｎｍ以下の範囲に極大値を有することが好ましい。なお、上記ゼオライトは、細孔径が０．４ｎｍ以上０．７ｎｍ以下の範囲にも極大値を有していてもよい。ゼオライトの平均粒径は、ＢＥＴ法によって測定することができる。 (Zeolite)
Zeolites are substances with pores and have the effect of adsorbing odor-causing substances. The silica / alumina molar ratio of the zeolite is 100 or more, and may be 100 to 1000. By using a zeolite having a silica / alumina molar ratio of 100 or more in combination with a Cu—Mn composite oxide, the above-mentioned effect of the present invention can be obtained. The zeolite is, for example, powdery. From the viewpoint of deodorizing performance, the specific surface area of the zeolite measured by the BET method is preferably 300 m 2 / g or more, and more preferably 350 to 800 m 2 / g. The zeolite preferably has a maximum value in the range of the pore diameter of 0.8 nm or more and 1.2 nm or less in the pore distribution by the MP method obtained from the nitrogen adsorption / desorption isotherm measurement. The zeolite may have a maximum value even in the range where the pore diameter is 0.4 nm or more and 0.7 nm or less. The average particle size of zeolite can be measured by the BET method.
上記ゼオライトは、アンモニア昇温脱離法により算出される全酸量が０．３ｍｍｏｌ／ｇ以下であることが好ましく、０．０１～０．２ｍｍｏｌ／ｇであることがより好ましい。この全酸量は、ゼオライトの酸量を反映する値である。一般に、シリカ／アルミナモル比が大きいゼオライトは、高い酸強度を有し且つ上記の方法によって測定される全酸量が小さい値であることが知られている。本実施形態において、シリカ／アルミナモル比が１００以上であり、上記の方法によって測定される全酸量が０．３ｍｍｏｌ／ｇ以下のゼオライトとＣｕ－Ｍｎ複合酸化物とを併用し且つ両者の質量比（Ａ／Ｂ）が上記範囲内であることで、より一層高度に本発明の上記効果が奏される。
The total acid content of the zeolite calculated by the ammonia temperature desorption method is preferably 0.3 mmol / g or less, and more preferably 0.01 to 0.2 mmol / g. This total acid amount is a value that reflects the acid amount of zeolite. In general, it is known that a zeolite having a large silica / alumina molar ratio has a high acid strength and a small total acid amount measured by the above method. In the present embodiment, a zeolite having a silica / alumina molar ratio of 100 or more and a total acid amount of 0.3 mmol / g or less measured by the above method is used in combination with a Cu—Mn composite oxide, and the mass ratio of both is used. When (A / B) is within the above range, the above-mentioned effect of the present invention can be achieved even more highly.
ゼオライトのタイプとして、ＭＦＩ型、Ｙ型、Ａ型、Ｌ型等が挙げられる。これらのうち、脱臭性能の観点から、ＭＦＩ型ゼオライトを使用することが好ましい。ゼオライトが有するカチオン種は、例えば、ナトリウムイオン、水素イオン、カリウムイオン、カルシウムイオン等が挙げられる。これらのうち、コストの観点から、カチオン種がナトリウムイオンであるゼオライトを使用することが好ましい。
Examples of the zeolite type include MFI type, Y type, A type, L type and the like. Of these, it is preferable to use MFI-type zeolite from the viewpoint of deodorizing performance. Examples of the cation species contained in zeolite include sodium ion, hydrogen ion, potassium ion, calcium ion and the like. Of these, from the viewpoint of cost, it is preferable to use zeolite whose cation species is sodium ion.
（その他の成分）
脱臭触媒は、上記以外の成分として、例えば、バインダーを含んでもよい。脱臭触媒がバインダーを含むことで、スラリー法によって基材の表面に触媒層を形成することができる。バインダーは、無機バインダーであっても有機バインダーであってもよい。無機バインダーとして、シリカゾル、アルミナゾルが挙げられる。有機バインダーとして、でんぷん、カゼイン、ゼラチン等の天然樹脂；セルロース、水溶性ポリアミド、四級アンモニウム塩、アクリル樹脂、ウレタン樹脂、酢酸ビニル樹脂、ＳＢＲ樹脂、エポキシ樹脂、ポリビニルアルコール樹脂等の合成樹脂が挙げられる。これらのうち、無機バインダー（例えば、シリカ粒子）を使用することで、バインダーによる脱臭性能の阻害効果が小さいという効果が奏される。 (Other ingredients)
The deodorizing catalyst may contain, for example, a binder as a component other than the above. Since the deodorizing catalyst contains a binder, a catalyst layer can be formed on the surface of the base material by the slurry method. The binder may be an inorganic binder or an organic binder. Examples of the inorganic binder include silica sol and alumina sol. Examples of the organic binder include natural resins such as starch, casein and gelatin; synthetic resins such as cellulose, water-soluble polyamide, quaternary ammonium salt, acrylic resin, urethane resin, vinyl acetate resin, SBR resin, epoxy resin and polyvinyl alcohol resin. Be done. Among these, by using an inorganic binder (for example, silica particles), the effect that the binder has a small inhibitory effect on the deodorizing performance is exhibited.
脱臭触媒は、上記以外の成分として、例えば、バインダーを含んでもよい。脱臭触媒がバインダーを含むことで、スラリー法によって基材の表面に触媒層を形成することができる。バインダーは、無機バインダーであっても有機バインダーであってもよい。無機バインダーとして、シリカゾル、アルミナゾルが挙げられる。有機バインダーとして、でんぷん、カゼイン、ゼラチン等の天然樹脂；セルロース、水溶性ポリアミド、四級アンモニウム塩、アクリル樹脂、ウレタン樹脂、酢酸ビニル樹脂、ＳＢＲ樹脂、エポキシ樹脂、ポリビニルアルコール樹脂等の合成樹脂が挙げられる。これらのうち、無機バインダー（例えば、シリカ粒子）を使用することで、バインダーによる脱臭性能の阻害効果が小さいという効果が奏される。 (Other ingredients)
The deodorizing catalyst may contain, for example, a binder as a component other than the above. Since the deodorizing catalyst contains a binder, a catalyst layer can be formed on the surface of the base material by the slurry method. The binder may be an inorganic binder or an organic binder. Examples of the inorganic binder include silica sol and alumina sol. Examples of the organic binder include natural resins such as starch, casein and gelatin; synthetic resins such as cellulose, water-soluble polyamide, quaternary ammonium salt, acrylic resin, urethane resin, vinyl acetate resin, SBR resin, epoxy resin and polyvinyl alcohol resin. Be done. Among these, by using an inorganic binder (for example, silica particles), the effect that the binder has a small inhibitory effect on the deodorizing performance is exhibited.
脱臭触媒における無機バインダーの含有量は、脱臭触媒の全質量を基準として、例えば、５～３０質量％であり、１０～２０質量％であってもよい。脱臭触媒における有機バインダーの含有量は、脱臭触媒の全質量を基準として、例えば、２．５～２０質量％であり、５～１５質量％であってもよい。脱臭触媒が適度な量のバインダーを含んでいることで、基材表面に対する優れた密着性と高い触媒活性を両立し得る。
The content of the inorganic binder in the deodorizing catalyst is, for example, 5 to 30% by mass, and may be 10 to 20% by mass, based on the total mass of the deodorizing catalyst. The content of the organic binder in the deodorizing catalyst is, for example, 2.5 to 20% by mass, and may be 5 to 15% by mass, based on the total mass of the deodorizing catalyst. When the deodorizing catalyst contains an appropriate amount of binder, both excellent adhesion to the surface of the substrate and high catalytic activity can be achieved.
＜冷蔵庫用脱臭材＞
本実施形態に係る冷蔵庫用脱臭材は、上記冷蔵庫用脱臭触媒と、冷蔵庫用脱臭触媒が塗布された表面を有する基材とを備える。例えば、ウォッシュコート等の塗工技術によって基材の表面に冷蔵庫用脱臭触媒を層状に形成することによって冷蔵庫用脱臭材を製造することができる。基材の例として、ハニカム基材、ペレット状の基材、織布や不織布状の基材、板状やブロック状のバルク部材が挙げられる。基材の材質としては、特に限定されるものではないが、例えば、金属、セラミックス、ガラス、プラスチック、セルロース系材料、及びこれらを組合せた材料（複合材料、積層材料等）が挙げられる。金属としては、例えば、ステンレス、アルミ、銅、亜鉛めっき鋼板及び鉄が挙げられる。セラミックスとしては、例えば、コージライト、アルミナ、チタン酸バリウム、窒化ホウ素及び窒化珪素が挙げられる。ガラスとしては、例えば、通常のソーダライムガラス、ホウ珪酸ガラス、無アルカリガラス、石英ガラス及びアルミノシリケートガラスが挙げられる。プラスチックとしては、例えば、ポリメチルメタクリレート等のアクリル系樹脂、ポリフェニレンカーボネート等の芳香族ポリカーボネート系樹脂、及び、ポリエチレンテレフタレート（ＰＥＴ）等の芳香族ポリエステル系樹脂が挙げられる。セルロース系材料としては、例えば綿、麻、レーヨン、及びキュプラが挙げられる。冷蔵庫用脱臭材は、例えば、脱臭フィルターとして使用することができ、冷蔵庫内であって、冷えた空気が流れる箇所に搭載される。 <Deodorant for refrigerator>
The refrigerator deodorizing material according to the present embodiment includes the refrigerator deodorizing catalyst and a base material having a surface coated with the refrigerator deodorizing catalyst. For example, a refrigerator deodorizing material can be manufactured by forming a refrigerator deodorizing catalyst in a layer on the surface of a base material by a coating technique such as a wash coat. Examples of the base material include a honeycomb base material, a pellet-shaped base material, a woven fabric or a non-woven fabric-like base material, and a plate-shaped or block-shaped bulk member. The material of the base material is not particularly limited, and examples thereof include metals, ceramics, glass, plastics, cellulosic materials, and materials combining these (composite materials, laminated materials, etc.). Examples of the metal include stainless steel, aluminum, copper, galvanized steel sheet and iron. Examples of the ceramics include cordylite, alumina, barium titanate, boron nitride and silicon nitride. Examples of the glass include ordinary soda lime glass, borosilicate glass, non-alkali glass, quartz glass and aluminosilicate glass. Examples of the plastic include an acrylic resin such as polymethylmethacrylate, an aromatic polycarbonate resin such as polyphenylene carbonate, and an aromatic polyester resin such as polyethylene terephthalate (PET). Cellulosic materials include, for example, cotton, linen, rayon, and cupra. The deodorizing material for a refrigerator can be used as a deodorizing filter, for example, and is mounted in a refrigerator where cold air flows.
本実施形態に係る冷蔵庫用脱臭材は、上記冷蔵庫用脱臭触媒と、冷蔵庫用脱臭触媒が塗布された表面を有する基材とを備える。例えば、ウォッシュコート等の塗工技術によって基材の表面に冷蔵庫用脱臭触媒を層状に形成することによって冷蔵庫用脱臭材を製造することができる。基材の例として、ハニカム基材、ペレット状の基材、織布や不織布状の基材、板状やブロック状のバルク部材が挙げられる。基材の材質としては、特に限定されるものではないが、例えば、金属、セラミックス、ガラス、プラスチック、セルロース系材料、及びこれらを組合せた材料（複合材料、積層材料等）が挙げられる。金属としては、例えば、ステンレス、アルミ、銅、亜鉛めっき鋼板及び鉄が挙げられる。セラミックスとしては、例えば、コージライト、アルミナ、チタン酸バリウム、窒化ホウ素及び窒化珪素が挙げられる。ガラスとしては、例えば、通常のソーダライムガラス、ホウ珪酸ガラス、無アルカリガラス、石英ガラス及びアルミノシリケートガラスが挙げられる。プラスチックとしては、例えば、ポリメチルメタクリレート等のアクリル系樹脂、ポリフェニレンカーボネート等の芳香族ポリカーボネート系樹脂、及び、ポリエチレンテレフタレート（ＰＥＴ）等の芳香族ポリエステル系樹脂が挙げられる。セルロース系材料としては、例えば綿、麻、レーヨン、及びキュプラが挙げられる。冷蔵庫用脱臭材は、例えば、脱臭フィルターとして使用することができ、冷蔵庫内であって、冷えた空気が流れる箇所に搭載される。 <Deodorant for refrigerator>
The refrigerator deodorizing material according to the present embodiment includes the refrigerator deodorizing catalyst and a base material having a surface coated with the refrigerator deodorizing catalyst. For example, a refrigerator deodorizing material can be manufactured by forming a refrigerator deodorizing catalyst in a layer on the surface of a base material by a coating technique such as a wash coat. Examples of the base material include a honeycomb base material, a pellet-shaped base material, a woven fabric or a non-woven fabric-like base material, and a plate-shaped or block-shaped bulk member. The material of the base material is not particularly limited, and examples thereof include metals, ceramics, glass, plastics, cellulosic materials, and materials combining these (composite materials, laminated materials, etc.). Examples of the metal include stainless steel, aluminum, copper, galvanized steel sheet and iron. Examples of the ceramics include cordylite, alumina, barium titanate, boron nitride and silicon nitride. Examples of the glass include ordinary soda lime glass, borosilicate glass, non-alkali glass, quartz glass and aluminosilicate glass. Examples of the plastic include an acrylic resin such as polymethylmethacrylate, an aromatic polycarbonate resin such as polyphenylene carbonate, and an aromatic polyester resin such as polyethylene terephthalate (PET). Cellulosic materials include, for example, cotton, linen, rayon, and cupra. The deodorizing material for a refrigerator can be used as a deodorizing filter, for example, and is mounted in a refrigerator where cold air flows.
以下、本開示の実施例及び比較例について説明する。なお、本発明は以下の実施例に限定されるものではない。
Hereinafter, examples and comparative examples of the present disclosure will be described. The present invention is not limited to the following examples.
＜スラリーの調製＞
（実施例１）
以下の成分を使用して脱臭触媒層を形成するためのスラリーを調製した。
・Ｎ－８４０Ｐ（Ｃｕ－Ｍｎ複合酸化物、比表面積：２４０ｍ２／ｇ、平均粒子径＝６．６μｍ、固形分濃度８８．０％、クラリアント触媒株式会社製）：３３．０ｇ
・ＮＵ－１０８０（ＭＦＩ型ゼオライト、シリカ／アルミナモル比＝４００、カチオン種＝ナトリウムイオン、比表面積：３７０ｍ２／ｇ、平均粒子径＝７．３μｍ、固形分濃度９８．５％、ＵＯＰ製）：６７．０ｇ
・スノーテックスＣ（シリカバインダー、固形分濃度２０％、日産化学株式会社製）：１００．０ｇ
・イオン交換水：６７．０ｇ
プロペラ撹拌機を用いてイオン交換水を撹拌しながら、イオン交換水に上記の各成分を添加した。添加後３０分間攪拌することによってスラリーを得た。 <Preparation of slurry>
(Example 1)
A slurry for forming a deodorizing catalyst layer was prepared using the following components.
N-840P (Cu-Mn composite oxide, specific surface area: 240 m 2 / g, average particle size = 6.6 μm, solid content concentration 88.0%, manufactured by Clariant Catalyst Co., Ltd.): 33.0 g
NU-1080 (MFI type zeolite, silica / alumina molar ratio = 400, cation species = sodium ion, specific surface area: 370 m 2 / g, average particle size = 7.3 μm, solid content concentration 98.5%, manufactured by UOP): 67.0g
-Snowtex C (silica binder,solid content concentration 20%, manufactured by Nissan Chemical Industries, Ltd.): 100.0 g
-Ion-exchanged water: 67.0 g
While stirring the ion-exchanged water using a propeller stirrer, each of the above components was added to the ion-exchanged water. A slurry was obtained by stirring for 30 minutes after the addition.
（実施例１）
以下の成分を使用して脱臭触媒層を形成するためのスラリーを調製した。
・Ｎ－８４０Ｐ（Ｃｕ－Ｍｎ複合酸化物、比表面積：２４０ｍ２／ｇ、平均粒子径＝６．６μｍ、固形分濃度８８．０％、クラリアント触媒株式会社製）：３３．０ｇ
・ＮＵ－１０８０（ＭＦＩ型ゼオライト、シリカ／アルミナモル比＝４００、カチオン種＝ナトリウムイオン、比表面積：３７０ｍ２／ｇ、平均粒子径＝７．３μｍ、固形分濃度９８．５％、ＵＯＰ製）：６７．０ｇ
・スノーテックスＣ（シリカバインダー、固形分濃度２０％、日産化学株式会社製）：１００．０ｇ
・イオン交換水：６７．０ｇ
プロペラ撹拌機を用いてイオン交換水を撹拌しながら、イオン交換水に上記の各成分を添加した。添加後３０分間攪拌することによってスラリーを得た。 <Preparation of slurry>
(Example 1)
A slurry for forming a deodorizing catalyst layer was prepared using the following components.
N-840P (Cu-Mn composite oxide, specific surface area: 240 m 2 / g, average particle size = 6.6 μm, solid content concentration 88.0%, manufactured by Clariant Catalyst Co., Ltd.): 33.0 g
NU-1080 (MFI type zeolite, silica / alumina molar ratio = 400, cation species = sodium ion, specific surface area: 370 m 2 / g, average particle size = 7.3 μm, solid content concentration 98.5%, manufactured by UOP): 67.0g
-Snowtex C (silica binder,
-Ion-exchanged water: 67.0 g
While stirring the ion-exchanged water using a propeller stirrer, each of the above components was added to the ion-exchanged water. A slurry was obtained by stirring for 30 minutes after the addition.
（実施例２）
ゼオライトとして、ＮＵ－１０８０の代わりに以下のＮＵ－２０８０を使用するとともに、各成分の配合量を表１に示す量としたことの他は、実施例１と同様にしてスラリーを得た。
・ＮＵ－２０８０（ＭＦＩ型ゼオライト、シリカ／アルミナモル比＝４００、カチオン種＝水素イオン、比表面積：３９０ｍ２／ｇ、平均粒子径＝３．２μｍ、固形分濃度９６．２％、ＵＯＰ製） (Example 2)
As the zeolite, the following NU-2080 was used instead of NU-1080, and a slurry was obtained in the same manner as in Example 1 except that the blending amount of each component was set to the amount shown in Table 1.
NU-2080 (MFI type zeolite, silica / alumina molar ratio = 400, cation species = hydrogen ion, specific surface area: 390 m 2 / g, average particle size = 3.2 μm, solid content concentration 96.2%, manufactured by UOP)
ゼオライトとして、ＮＵ－１０８０の代わりに以下のＮＵ－２０８０を使用するとともに、各成分の配合量を表１に示す量としたことの他は、実施例１と同様にしてスラリーを得た。
・ＮＵ－２０８０（ＭＦＩ型ゼオライト、シリカ／アルミナモル比＝４００、カチオン種＝水素イオン、比表面積：３９０ｍ２／ｇ、平均粒子径＝３．２μｍ、固形分濃度９６．２％、ＵＯＰ製） (Example 2)
As the zeolite, the following NU-2080 was used instead of NU-1080, and a slurry was obtained in the same manner as in Example 1 except that the blending amount of each component was set to the amount shown in Table 1.
NU-2080 (MFI type zeolite, silica / alumina molar ratio = 400, cation species = hydrogen ion, specific surface area: 390 m 2 / g, average particle size = 3.2 μm, solid content concentration 96.2%, manufactured by UOP)
（実施例３，４）
各成分の配合量を表１に示す量としたことの他は、実施例１と同様にして実施例３，４に係るスラリーをそれぞれ得た。 (Examples 3 and 4)
Slurries according to Examples 3 and 4 were obtained in the same manner as in Example 1 except that the blending amount of each component was set to the amount shown in Table 1.
各成分の配合量を表１に示す量としたことの他は、実施例１と同様にして実施例３，４に係るスラリーをそれぞれ得た。 (Examples 3 and 4)
Slurries according to Examples 3 and 4 were obtained in the same manner as in Example 1 except that the blending amount of each component was set to the amount shown in Table 1.
（比較例１）
ゼオライトとして、ＮＵ－１０８０の代わりに以下のＮＦＫ－５Ｄ－２５ＨＸを使用するとともに、各成分の配合量を表２に示す量としたことの他は、実施例１と同様にしてスラリーを得た。
・ＮＦＫ－５Ｄ－２５ＨＸ（ＭＦＩ型ゼオライト、シリカ／アルミナモル比＝２８、カチオン種＝水素イオン、比表面積：３７０ｍ２／ｇ、平均粒子径＝４．４μｍ、固形分濃度９３．４％、Ｎａｎｋａｉ Ｕｎｉｖｅｒｓｉｔｙ Ｃａｔａｌｙｓｔ製） (Comparative Example 1)
As the zeolite, the following NFK-5D-25HX was used instead of NU-1080, and the slurry was obtained in the same manner as in Example 1 except that the blending amount of each component was set to the amount shown in Table 2. ..
NFK-5D-25HX (MFI type zeolite, silica / alumina molar ratio = 28, cation species = hydrogen ion, specific surface area: 370 m 2 / g, average particle size = 4.4 μm, solid content concentration 93.4%, Nankai University Made by Catalyst)
ゼオライトとして、ＮＵ－１０８０の代わりに以下のＮＦＫ－５Ｄ－２５ＨＸを使用するとともに、各成分の配合量を表２に示す量としたことの他は、実施例１と同様にしてスラリーを得た。
・ＮＦＫ－５Ｄ－２５ＨＸ（ＭＦＩ型ゼオライト、シリカ／アルミナモル比＝２８、カチオン種＝水素イオン、比表面積：３７０ｍ２／ｇ、平均粒子径＝４．４μｍ、固形分濃度９３．４％、Ｎａｎｋａｉ Ｕｎｉｖｅｒｓｉｔｙ Ｃａｔａｌｙｓｔ製） (Comparative Example 1)
As the zeolite, the following NFK-5D-25HX was used instead of NU-1080, and the slurry was obtained in the same manner as in Example 1 except that the blending amount of each component was set to the amount shown in Table 2. ..
NFK-5D-25HX (MFI type zeolite, silica / alumina molar ratio = 28, cation species = hydrogen ion, specific surface area: 370 m 2 / g, average particle size = 4.4 μm, solid content concentration 93.4%, Nankai University Made by Catalyst)
（比較例２）
ゼオライトとして、ＮＵ－１０８０の代わりに以下のミズカシーブスＥＸ－１２２（以下、「ＥＸ－１２２」と表記する。）を使用するとともに、各成分の配合量を表２に示す量としたことの他は、実施例１と同様にしてスラリーを得た。
・ＥＸ－１２２（ＭＦＩ型ゼオライト、シリカ／アルミナモル比＝２９、カチオン種＝ナトリウムイオン、比表面積：３２０ｍ２／ｇ、平均粒子径＝３．７μｍ、固形分濃度９５．２％、水澤化学工業株式会社製） (Comparative Example 2)
As the zeolite, the following Mizuka Sieves EX-122 (hereinafter referred to as "EX-122") was used instead of NU-1080, and the blending amount of each component was set to the amount shown in Table 2. , A slurry was obtained in the same manner as in Example 1.
-EX-122 (MFI type zeolite, silica / alumina molar ratio = 29, cation species = sodium ion, specific surface area: 320 m 2 / g, average particle size = 3.7 μm, solid content concentration 95.2%, Mizusawa Industrial Chemicals Co., Ltd. Made by the company)
ゼオライトとして、ＮＵ－１０８０の代わりに以下のミズカシーブスＥＸ－１２２（以下、「ＥＸ－１２２」と表記する。）を使用するとともに、各成分の配合量を表２に示す量としたことの他は、実施例１と同様にしてスラリーを得た。
・ＥＸ－１２２（ＭＦＩ型ゼオライト、シリカ／アルミナモル比＝２９、カチオン種＝ナトリウムイオン、比表面積：３２０ｍ２／ｇ、平均粒子径＝３．７μｍ、固形分濃度９５．２％、水澤化学工業株式会社製） (Comparative Example 2)
As the zeolite, the following Mizuka Sieves EX-122 (hereinafter referred to as "EX-122") was used instead of NU-1080, and the blending amount of each component was set to the amount shown in Table 2. , A slurry was obtained in the same manner as in Example 1.
-EX-122 (MFI type zeolite, silica / alumina molar ratio = 29, cation species = sodium ion, specific surface area: 320 m 2 / g, average particle size = 3.7 μm, solid content concentration 95.2%, Mizusawa Industrial Chemicals Co., Ltd. Made by the company)
（比較例３）
ゼオライトとして、ＮＵ－１０８０の代わりに以下のＮＦＫ－７－２ＳＣ１．０－ＨＷＯＳを使用するとともに、各成分の配合量を表２に示す量としたことの他は、実施例１と同様にしてスラリーを得た。
・ＮＦＫ－７－２ＳＣ１．０－ＨＷＯＳ（Ｙ型ゼオライト、シリカ／アルミナモル比＝６、カチオン種＝水素イオン、比表面積：６５０ｍ２／ｇ、平均粒子径＝３．６μｍ、固形分濃度８６．３％、Ｎａｎｋａｉ Ｕｎｉｖｅｒｓｉｔｙ Ｃａｔａｌｙｓｔ製） (Comparative Example 3)
As the zeolite, the following NFK-7-2SC1.0-HWOS was used instead of NU-1080, and the blending amount of each component was set to the amount shown in Table 2, in the same manner as in Example 1. A slurry was obtained.
NFK-7-2SC1.0-HWOS (Y-type zeolite, silica / alumina molar ratio = 6, cation species = hydrogen ion, specific surface area: 650 m 2 / g, average particle size = 3.6 μm, solid content concentration 86.3 %, Made by Nankai University Catalyst)
ゼオライトとして、ＮＵ－１０８０の代わりに以下のＮＦＫ－７－２ＳＣ１．０－ＨＷＯＳを使用するとともに、各成分の配合量を表２に示す量としたことの他は、実施例１と同様にしてスラリーを得た。
・ＮＦＫ－７－２ＳＣ１．０－ＨＷＯＳ（Ｙ型ゼオライト、シリカ／アルミナモル比＝６、カチオン種＝水素イオン、比表面積：６５０ｍ２／ｇ、平均粒子径＝３．６μｍ、固形分濃度８６．３％、Ｎａｎｋａｉ Ｕｎｉｖｅｒｓｉｔｙ Ｃａｔａｌｙｓｔ製） (Comparative Example 3)
As the zeolite, the following NFK-7-2SC1.0-HWOS was used instead of NU-1080, and the blending amount of each component was set to the amount shown in Table 2, in the same manner as in Example 1. A slurry was obtained.
NFK-7-2SC1.0-HWOS (Y-type zeolite, silica / alumina molar ratio = 6, cation species = hydrogen ion, specific surface area: 650 m 2 / g, average particle size = 3.6 μm, solid content concentration 86.3 %, Made by Nankai University Catalyst)
（比較例４）
ゼオライトとして、ＮＵ－１０８０の代わりに以下のミズカシーブスＹ－４２０（以下、「Ｙ－４２０」と表記する。）を使用するとともに、各成分の配合量を表２に示す量としたことの他は、実施例１と同様にしてスラリーを得た。
・Ｙ－４２０（Ｙ型ゼオライト、シリカ／アルミナモル比＝４、カチオン種＝水素イオン、比表面積：４３０ｍ２／ｇ、平均粒子径＝１４．２μｍ、固形分濃度９８．６％、水澤化学工業株式会社製） (Comparative Example 4)
As the zeolite, the following Mizuka Sieves Y-420 (hereinafter referred to as "Y-420") was used instead of NU-1080, and the blending amount of each component was set to the amount shown in Table 2. , A slurry was obtained in the same manner as in Example 1.
-Y-420 (Y-type zeolite, silica / alumina molar ratio = 4, cation species = hydrogen ion, specific surface area: 430 m 2 / g, average particle size = 14.2 μm, solid content concentration 98.6%, Mizusawa Industrial Chemicals Co., Ltd. Made by the company)
ゼオライトとして、ＮＵ－１０８０の代わりに以下のミズカシーブスＹ－４２０（以下、「Ｙ－４２０」と表記する。）を使用するとともに、各成分の配合量を表２に示す量としたことの他は、実施例１と同様にしてスラリーを得た。
・Ｙ－４２０（Ｙ型ゼオライト、シリカ／アルミナモル比＝４、カチオン種＝水素イオン、比表面積：４３０ｍ２／ｇ、平均粒子径＝１４．２μｍ、固形分濃度９８．６％、水澤化学工業株式会社製） (Comparative Example 4)
As the zeolite, the following Mizuka Sieves Y-420 (hereinafter referred to as "Y-420") was used instead of NU-1080, and the blending amount of each component was set to the amount shown in Table 2. , A slurry was obtained in the same manner as in Example 1.
-Y-420 (Y-type zeolite, silica / alumina molar ratio = 4, cation species = hydrogen ion, specific surface area: 430 m 2 / g, average particle size = 14.2 μm, solid content concentration 98.6%, Mizusawa Industrial Chemicals Co., Ltd. Made by the company)
（比較例５～８）
各成分の配合量を表３に示す量としたことの他は、実施例１と同様にして比較例５～８に係るスラリーをそれぞれ得た。 (Comparative Examples 5 to 8)
Slurries according to Comparative Examples 5 to 8 were obtained in the same manner as in Example 1 except that the blending amount of each component was set to the amount shown in Table 3.
各成分の配合量を表３に示す量としたことの他は、実施例１と同様にして比較例５～８に係るスラリーをそれぞれ得た。 (Comparative Examples 5 to 8)
Slurries according to Comparative Examples 5 to 8 were obtained in the same manner as in Example 1 except that the blending amount of each component was set to the amount shown in Table 3.
＜ゼオライトの細孔分布＞
実施例及び比較例で使用したゼオライトの細孔分布を、窒素吸脱着等温線測定から求められるＭＰ法によって測定した。図１に結果を示す。実施例で使用したゼオライト（ＮＵ－１０８０及びＮＵ－２０８０）は径が１ｎｍ程度の細孔を有することが分かった。 <Zeolite pore distribution>
The pore distribution of the zeolite used in the examples and comparative examples was measured by the MP method obtained from the nitrogen adsorption / desorption isotherm measurement. The results are shown in FIG. It was found that the zeolites (NU-1080 and NU-2080) used in the examples had pores having a diameter of about 1 nm.
実施例及び比較例で使用したゼオライトの細孔分布を、窒素吸脱着等温線測定から求められるＭＰ法によって測定した。図１に結果を示す。実施例で使用したゼオライト（ＮＵ－１０８０及びＮＵ－２０８０）は径が１ｎｍ程度の細孔を有することが分かった。 <Zeolite pore distribution>
The pore distribution of the zeolite used in the examples and comparative examples was measured by the MP method obtained from the nitrogen adsorption / desorption isotherm measurement. The results are shown in FIG. It was found that the zeolites (NU-1080 and NU-2080) used in the examples had pores having a diameter of about 1 nm.
＜ゼオライトの全酸量＞
実施例及び比較例で使用したゼオライトの酸性質を、アンモニア昇温脱離法によって調べた。図２に吸着アンモニアの昇温脱離曲線を示す。実施例で使用したゼオライト（ＮＵ－１０８０及びＮＵ－２０８０）は全体的にアンモニアの吸着量が少なく、酸量が少ないことが分かった。昇温脱離曲線から算出される全酸量は以下のとおりであった。
・ＮＵ－１０８０：０．１８４ｍｍｏｌ／ｇ
・ＮＵ－２０８０：０．０８３ｍｍｏｌ／ｇ
・ＥＸ１２２：１．１４７ｍｍｏｌ／ｇ
・Ｙ－４２０：２．３６０ｍｍｏｌ／ｇ <Total acid content of zeolite>
The acid properties of the zeolites used in the examples and comparative examples were investigated by the ammonia heated desorption method. FIG. 2 shows a temperature-increasing desorption curve of adsorbed ammonia. It was found that the zeolites (NU-1080 and NU-2080) used in the examples had a small amount of ammonia adsorbed and a small amount of acid as a whole. The total amount of acid calculated from the temperature desorption curve was as follows.
NU-1080: 0.184 mmol / g
NU-2080: 0.083 mmol / g
EX122: 1.147 mmol / g
Y-420: 2.360 mmol / g
実施例及び比較例で使用したゼオライトの酸性質を、アンモニア昇温脱離法によって調べた。図２に吸着アンモニアの昇温脱離曲線を示す。実施例で使用したゼオライト（ＮＵ－１０８０及びＮＵ－２０８０）は全体的にアンモニアの吸着量が少なく、酸量が少ないことが分かった。昇温脱離曲線から算出される全酸量は以下のとおりであった。
・ＮＵ－１０８０：０．１８４ｍｍｏｌ／ｇ
・ＮＵ－２０８０：０．０８３ｍｍｏｌ／ｇ
・ＥＸ１２２：１．１４７ｍｍｏｌ／ｇ
・Ｙ－４２０：２．３６０ｍｍｏｌ／ｇ <Total acid content of zeolite>
The acid properties of the zeolites used in the examples and comparative examples were investigated by the ammonia heated desorption method. FIG. 2 shows a temperature-increasing desorption curve of adsorbed ammonia. It was found that the zeolites (NU-1080 and NU-2080) used in the examples had a small amount of ammonia adsorbed and a small amount of acid as a whole. The total amount of acid calculated from the temperature desorption curve was as follows.
NU-1080: 0.184 mmol / g
NU-2080: 0.083 mmol / g
EX122: 1.147 mmol / g
Y-420: 2.360 mmol / g
＜ゼオライトのＸＲＤ分析＞
図３に実施例及び比較例で使用したゼオライトのＸＲＤ分析結果を示す。 <XRD analysis of zeolite>
FIG. 3 shows the XRD analysis results of the zeolites used in Examples and Comparative Examples.
図３に実施例及び比較例で使用したゼオライトのＸＲＤ分析結果を示す。 <XRD analysis of zeolite>
FIG. 3 shows the XRD analysis results of the zeolites used in Examples and Comparative Examples.
＜脱臭材の作製＞
脱臭材用の基材として、セラミックハニカム（セル数２００／ｉｎｃｈ２、セル開口面直径２１ｍｍ、通気方向長さ７．０ｍｍ、西部技研製）を準備した。このハニカム基材の表面にウォッシュコートによって触媒層を形成した。すなわち、実施例及び比較例に係る各スラリーに基材を浸漬した後、余剰のスラリーをエアブローにより吹き飛ばした。その後、１５０℃に設定した乾燥機に１時間入れて乾燥させる脱臭フィルターを得た。なお、乾燥後における触媒層の質量がハニカム基材１Ｌ当たり１５０ｇとなるようにスラリーの塗布量を調整した。 <Making deodorant material>
As a base material for the deodorizing material, a ceramic honeycomb (cell number 200 / inch 2 , cell opening surface diameter 21 mm, ventilation direction length 7.0 mm, manufactured by Seibu Giken Co., Ltd.) was prepared. A catalyst layer was formed on the surface of this honeycomb base material by a wash coat. That is, after the base material was immersed in each of the slurries according to the examples and the comparative examples, the excess slurry was blown off by an air blow. Then, a deodorizing filter was obtained by putting it in a dryer set at 150 ° C. for 1 hour to dry it. The amount of the slurry applied was adjusted so that the mass of the catalyst layer after drying was 150 g per 1 L of the honeycomb base material.
脱臭材用の基材として、セラミックハニカム（セル数２００／ｉｎｃｈ２、セル開口面直径２１ｍｍ、通気方向長さ７．０ｍｍ、西部技研製）を準備した。このハニカム基材の表面にウォッシュコートによって触媒層を形成した。すなわち、実施例及び比較例に係る各スラリーに基材を浸漬した後、余剰のスラリーをエアブローにより吹き飛ばした。その後、１５０℃に設定した乾燥機に１時間入れて乾燥させる脱臭フィルターを得た。なお、乾燥後における触媒層の質量がハニカム基材１Ｌ当たり１５０ｇとなるようにスラリーの塗布量を調整した。 <Making deodorant material>
As a base material for the deodorizing material, a ceramic honeycomb (
＜メチルメルカプタン（ＭＭＰ）流通試験＞
（１）ＭＭＰ除去率
実施例及び比較例に係る各脱臭材（セル開口面直径：２１ｍｍ）をガラス管に設置した。温度２５℃、湿度８０%ＲＨの空気を、９．１Ｌ／ｍｉｎの流量で脱臭材に１５分間流通させた。メチルメルカプタン濃度が１００ｐｐｍになるように、流通空気にメチルメルカプタンを導入した。メチルメルカプタンの導入開始から１０分後に、脱臭材を通過後の空気のメチルメルカプタン濃度を測定した。この値を次式に代入して除去率を算出した。
ＭＭＰ除去率（％）＝｛１－（ＭＭＰ濃度［ｐｐｍ］／１００［ｐｐｍ］）｝×１００
（２）ジメチルジサルファイド（ＤＭＤＳ）濃度
メチルメルカプタンの導入開始から１０分後に、脱臭材を通過後の空気のジメチルジサルファイド濃度を測定した。 <Methyl mercaptan (MMP) distribution test>
(1) MMP removal rate Each deodorant (cell opening surface diameter: 21 mm) according to Examples and Comparative Examples was installed in a glass tube. Air at a temperature of 25 ° C. and a humidity of 80% RH was circulated through the deodorizing material at a flow rate of 9.1 L / min for 15 minutes. Methyl mercaptan was introduced into the circulating air so that the concentration of methyl mercaptan was 100 ppm. Ten minutes after the start of introduction of methyl mercaptan, the methyl mercaptan concentration in the air after passing through the deodorizing material was measured. This value was substituted into the following equation to calculate the removal rate.
MMP removal rate (%) = {1- (MMP concentration [ppm] / 100 [ppm])} x 100
(2) Dimethyl disulfide (DMDS)concentration 10 minutes after the start of introduction of methyl mercaptan, the dimethyl disulfide concentration of the air after passing through the deodorizing material was measured.
（１）ＭＭＰ除去率
実施例及び比較例に係る各脱臭材（セル開口面直径：２１ｍｍ）をガラス管に設置した。温度２５℃、湿度８０%ＲＨの空気を、９．１Ｌ／ｍｉｎの流量で脱臭材に１５分間流通させた。メチルメルカプタン濃度が１００ｐｐｍになるように、流通空気にメチルメルカプタンを導入した。メチルメルカプタンの導入開始から１０分後に、脱臭材を通過後の空気のメチルメルカプタン濃度を測定した。この値を次式に代入して除去率を算出した。
ＭＭＰ除去率（％）＝｛１－（ＭＭＰ濃度［ｐｐｍ］／１００［ｐｐｍ］）｝×１００
（２）ジメチルジサルファイド（ＤＭＤＳ）濃度
メチルメルカプタンの導入開始から１０分後に、脱臭材を通過後の空気のジメチルジサルファイド濃度を測定した。 <Methyl mercaptan (MMP) distribution test>
(1) MMP removal rate Each deodorant (cell opening surface diameter: 21 mm) according to Examples and Comparative Examples was installed in a glass tube. Air at a temperature of 25 ° C. and a humidity of 80% RH was circulated through the deodorizing material at a flow rate of 9.1 L / min for 15 minutes. Methyl mercaptan was introduced into the circulating air so that the concentration of methyl mercaptan was 100 ppm. Ten minutes after the start of introduction of methyl mercaptan, the methyl mercaptan concentration in the air after passing through the deodorizing material was measured. This value was substituted into the following equation to calculate the removal rate.
MMP removal rate (%) = {1- (MMP concentration [ppm] / 100 [ppm])} x 100
(2) Dimethyl disulfide (DMDS)
本開示によれば、メチルメルカプタンに対する優れた除去性能を有するとともに、メチルメルカプタンの分解副生成物であるジメチルジサルファイドの放出を十分に抑制できる冷蔵庫用脱臭触媒及びこれを用いた冷蔵庫用脱臭材が提供される。
According to the present disclosure, a deodorizing catalyst for a refrigerator and a deodorizing material for a refrigerator using the deodorizing catalyst for a refrigerator, which has excellent removal performance for methyl mercaptan and can sufficiently suppress the release of dimethyldisulfide which is a decomposition by-product of methyl mercaptan, are described. Provided.
Claims (7)
- Ｃｕ－Ｍｎ複合酸化物と、
シリカ／アルミナモル比が１００以上のゼオライトと、
を含み、
前記Ｃｕ－Ｍｎ複合酸化物の質量Ａと前記ゼオライトとの質量Ｂの比（Ａ／Ｂ）が０．１以上１．２５以下である、冷蔵庫用脱臭触媒。 Cu-Mn composite oxide and
Zeolites with a silica / alumina molar ratio of 100 or more,
Including
A deodorizing catalyst for a refrigerator in which the ratio (A / B) of the mass A of the Cu—Mn composite oxide to the mass B of the zeolite is 0.1 or more and 1.25 or less. - 前記ゼオライトは、ＢＥＴ法により測定される比表面積が３００ｍ２／ｇ以上である、請求項１に記載の冷蔵庫用脱臭触媒。 The deodorizing catalyst for a refrigerator according to claim 1, wherein the zeolite has a specific surface area of 300 m 2 / g or more as measured by the BET method.
- 前記ゼオライトは、窒素吸脱着等温線測定から求められるＭＰ法による細孔分布において、細孔径が０．８ｎｍ以上１．２ｎｍ以下の範囲に極大値を有する、請求項１又は２に記載の冷蔵庫用脱臭触媒。 The refrigerator according to claim 1 or 2, wherein the zeolite has a maximum value in the range of 0.8 nm or more and 1.2 nm or less in the pore distribution by the MP method obtained from the nitrogen adsorption / desorption isotherm measurement. Deodorizing catalyst.
- 前記ゼオライトは、アンモニア昇温脱離法により算出される全酸量が０．３ｍｍｏｌ／ｇ以下である、請求項１～３のいずれか一項に記載の冷蔵庫用脱臭触媒。 The deodorizing catalyst for a refrigerator according to any one of claims 1 to 3, wherein the zeolite has a total acid amount of 0.3 mmol / g or less calculated by the ammonia temperature-heating deodorization method.
- 前記Ｃｕ－Ｍｎ複合酸化物は、ＢＥＴ法により測定される比表面積が１５０ｍ２／ｇ以上である、請求項１～４のいずれか一項に記載の冷蔵庫用脱臭触媒。 The deodorizing catalyst for a refrigerator according to any one of claims 1 to 4, wherein the Cu—Mn composite oxide has a specific surface area of 150 m 2 / g or more as measured by the BET method.
- 前記Ｃｕ－Ｍｎ複合酸化物は、Ｃｕ含有量がＣｕＯ換算で１０～４０質量％であり且つＭｎ含有量がＭｎＯ２換算で６０～９０質量％である、請求項１～５のいずれか一項に記載の冷蔵庫用脱臭触媒。 The Cu-Mn composite oxide has a Cu content of 10 to 40% by mass in terms of CuO and a Mn content of 60 to 90% by mass in terms of MnO 2, any one of claims 1 to 5. Deodorizing catalyst for refrigerators described in.
- 請求項１～６のいずれか一項に記載の冷蔵庫用脱臭触媒と、
前記冷蔵庫用脱臭触媒が塗布された表面を有する基材と、
を備える、冷蔵庫用脱臭材。 The deodorizing catalyst for a refrigerator according to any one of claims 1 to 6.
A base material having a surface coated with the deodorizing catalyst for a refrigerator,
Deodorant for refrigerators.
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| JP2022522474A JP7169515B2 (en) | 2020-05-15 | 2020-05-15 | Deodorizing catalyst for refrigerator and deodorizing material for refrigerator using the same |
| CN202080100786.8A CN115551634A (en) | 2020-05-15 | 2020-05-15 | Deodorizing catalyst for refrigerator and deodorizing material for refrigerator using the same |
| PCT/JP2020/019454 WO2021229799A1 (en) | 2020-05-15 | 2020-05-15 | Deodorizing catalyst for refrigerator and deodorizing material for refrigerator using this |
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| JP2003250872A (en) * | 2002-03-01 | 2003-09-09 | Matsushita Refrig Co Ltd | Deodorizing device and deodorizer using the same |
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| AU643908B1 (en) * | 1990-12-17 | 1993-11-25 | Uop | Modified zeolite omega and methods for preparing and for using same |
| JPH07155611A (en) * | 1993-12-09 | 1995-06-20 | Toyo C C I Kk | Catalyst and method for removing malodorous substance |
| JP3722866B2 (en) * | 1995-03-27 | 2005-11-30 | 日揮ユニバーサル株式会社 | Hydrophobic deodorizing material and method for regenerating the same |
| JP2004008515A (en) * | 2002-06-07 | 2004-01-15 | Kao Corp | Deodorant |
| KR100727549B1 (en) * | 2005-02-02 | 2007-06-14 | 임순옥 | Deodorant |
| CN104998289B (en) * | 2015-08-06 | 2017-11-17 | 苏州工业园区安泽汶环保技术有限公司 | Deodorant for refregerator material and preparation method thereof |
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- 2020-05-15 CN CN202080100786.8A patent/CN115551634A/en active Pending
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| JPH08243383A (en) * | 1995-03-10 | 1996-09-24 | Nikki Universal Co Ltd | Hydrphobic deodorant and method for regenerating same |
| JPH08266866A (en) * | 1995-03-29 | 1996-10-15 | Nichias Corp | Deodorizing filter |
| JPH0956799A (en) * | 1995-08-24 | 1997-03-04 | Kuraray Chem Corp | Self-regenerative adsorbent |
| JPH09215736A (en) * | 1996-02-14 | 1997-08-19 | Kobe Steel Ltd | Deodorant and deodorizing member |
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| CN115551634A (en) | 2022-12-30 |
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