JP2008104845A - Deodorizer, its manufacture method, and deodorizing filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a deodorizer and its manufacture process, and a deodorizing filter, highly efficiently removing a lower aldehyde including acetaldehyde and formaldehyde at room temperature without using any expensive catalyst such as platinum, palladium. <P>SOLUTION: The deodorizer includes a catalyst having a base material of a manganese oxide which carries a ruthenium or phosphate compound. When the ruthenium compound is carried, the amount of the ruthenium element carried in the ruthenium compound to the amount of the deodorizer is preferably between 0.1% and 0.6% by mass, and when the phosphate compound is carried, the amount of the phosphate element carried to the amount of the deodorizer is preferably between 0.1% and 20% by mass. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a deodorizing material capable of efficiently removing aldehydes such as acetaldehyde and formaldehyde, a method for producing the same, and a deodorizing filter.

  In recent years, there has been a strong demand for removing unpleasant odors generated in living spaces, etc., for the purpose of improving the comfort of indoors and cars, and in particular, there is a demand for efficient removal of aldehydes contained in tobacco odors. Is growing. On the other hand, lower aliphatic aldehydes such as acetaldehyde and formaldehyde have low vapor adsorption due to their high vapor pressure, and adsorbed with acids and alkalis because they are neutral components. Since it is difficult to chemisorb with chemicals, the development of effective removal methods for aldehydes has become a major technical issue.

  Conventionally, various deodorizing agents or air purifying agents having improved removal performance of lower aliphatic aldehydes have been proposed. For example, Patent Document 1 proposes an activated carbon impregnated with aniline, and Patent Document 2 and Patent Document 3 propose an activated carbon impregnated with an amino acid or aminobenzoic acid. In addition to activated carbon, Patent Document 4 proposes an aluminosilicate such as zeolite, and Patent Document 5 proposes an activated carbon fiber impregnated with aminobenzenesulfonic acid. These deodorizers are deodorizers utilizing a chemical reaction between a drug and an aldehyde and have high aldehyde removal performance. However, there is a problem in that the deodorization performance is reduced when the attached drug is consumed by a chemical reaction with an aldehyde.

  On the other hand, a technique for removing an aldehyde using a catalytic action instead of using a chemical reaction between a drug and an aldehyde has been studied. For example, Patent Document 6 proposes a catalyst in which platinum is supported on a support mainly composed of zirconia. Although it is said that aldehyde can be removed at a relatively low temperature of 60 ° C. or higher, it is difficult to remove acetaldehyde at room temperature, and there is a problem that the price of a deodorant is high because an expensive noble metal such as platinum is used. Patent Document 7 discloses a method of removing formaldehyde at room temperature by using a catalyst in which palladium is supported on activated carbon, but the effect on acetaldehyde is not sufficient, and expensive palladium is used in the same manner as platinum. Since it used, there existed a subject that the price of a deodorizing agent became high.

  Patent Document 8 proposes a deodorization catalyst in which ruthenium is supported on a copper manganese composite oxide or an iron manganese composite oxide. However, when these composite oxides are used, the removal performance of acetaldehyde is improved, but the removal performance of formaldehyde is not always sufficient.

  Patent Document 9 proposes a deodorizing catalyst in which a catalyst made of manganese oxide is arranged upstream of the gas to be treated and a catalyst made of ruthenium is arranged in series downstream. However, since ruthenium is not directly supported on the manganese oxide, an improvement effect of the catalytic action based on the interaction by two kinds of substances such as the deodorizing material according to the present invention cannot be obtained, and the performance of removing aldehydes is not improved. There is not enough problem.

Patent Document 10 proposes a deodorization catalyst (see claim 1) in which a photocatalyst and a metal oxide-based room temperature catalyst are supported on a base material. And although a ruthenium complex is exemplified as a photocatalyst and a manganese oxide is exemplified as a normal temperature catalyst as one of many alternative substances, a deodorizing catalyst that specifically combines a ruthenium complex and manganese oxide is disclosed. Absent. Moreover, in order to ensure the photoactive performance of the photocatalyst, the weight ratio of the room temperature catalyst is limited to 22% or less with respect to the total weight of the photocatalyst and the room temperature catalyst (see claim 3, paragraph [0024]). ), Even if a ruthenium complex is selected as the photocatalyst and manganese oxide is selected as the room temperature catalyst, and these can be combined, less manganese oxide is added than the ruthenium complex, and a small amount of ruthenium compound is added to the manganese oxide. The technical idea is completely different from the deodorizing material of the invention according to claims 1 to 3 which improves the catalytic action by being supported.
Japanese Patent Publication No. 60-54095 JP-A-4-2350 JP-A-5-23588 Japanese Patent Publication No. 5-16299 JP-A-7-136502 JP 2001-239162 A JP 52-30283 A Japanese Patent Laid-Open No. 2003-159315 JP-A-10-249197 JP-A-11-137656

  The present invention has been made for such a current situation, and without using an expensive catalyst such as platinum or palladium, a deodorizing material capable of removing acetaldehyde and lower aldehydes including formaldehyde with high performance at room temperature, a method for producing the same, and An object is to provide a deodorizing filter.

  Invention of Claim 1 is a deodorizing material characterized by including the catalyst formed by carrying | supporting a ruthenium compound in the manganese oxide as a base material.

  The invention according to claim 2 is the deodorization according to claim 1, wherein the base material further contains at least one selected from the group consisting of a copper manganese composite oxide, an iron manganese composite oxide, activated carbon, and zeolite. It is a material.

  Invention of Claim 3 is a deodorizing material of Claim 1 or 2 with which the load of the ruthenium element in the said ruthenium compound with respect to a deodorizing material is 0.1 mass% or more and less than 0.6 mass.

  The invention according to claim 4 is characterized in that the ruthenium compound is supported on the manganese oxide by spraying an aqueous solution of the ruthenium compound onto the base material. It is a manufacturing method of a deodorizing material.

  The invention according to claim 5 is a deodorizing material characterized by including a catalyst obtained by supporting a phosphate compound on manganese oxide as a base material.

  The invention according to claim 6 is the deodorizing material according to claim 5, wherein the phosphate compound is iron phosphate.

The invention according to claim 7 is the deodorizing material according to claim 5 or 6, wherein the supported amount of the phosphate compound with respect to the deodorizing material is 0.1 mass% or more and 20 mass% or less.
It is.

  The invention according to claim 8 is any one of claims 5 to 7, wherein the base material further contains at least one selected from the group consisting of a copper manganese composite oxide, an iron manganese composite oxide, activated carbon and zeolite. 2. The deodorizing material according to item 1.

  Invention of Claim 8 is a deodorizing filter using the deodorizing material of any one of Claims 1-3, 5-8 formed in the honeycomb form.

  According to the present invention, by using a catalyst in which a ruthenium compound or a phosphate compound is supported on a manganese oxide, not only acetaldehyde but also lower formaldehyde is used without using an expensive catalyst such as platinum or palladium. It has become possible to remove low-grade aldehydes with high performance, and to provide a deodorizing material excellent in deodorizing performance at a low cost and a deodorizing filter using the same.

  Hereinafter, the present invention will be described in detail.

[Embodiment 1]
For the deodorizing material according to Embodiment 1 of the present invention, a catalyst in which a ruthenium compound is supported on a manganese oxide as a base material is used. The specific surface area of the manganese oxide used as the substrate is preferably high in terms of adsorption performance, and a BET specific surface area of 200 m ² / g or more can be suitably used. As the ruthenium compound to be supported, potassium ruthenate, ruthenium chloride or the like can be used. The method for supporting the ruthenium compound on the manganese oxide is not particularly limited. For example, a spray method in which an aqueous solution of a ruthenium compound is supported on manganese oxide by spraying can be used. And after spraying the sample, it is desirable to dry at about 80-120 degreeC with a dryer, after drying at room temperature for about 1 day in a desiccator. As a method for supporting the ruthenium compound on the manganese oxide, a method of extruding into a pellet shape or a honeycomb shape after adding a ruthenium compound and a binder to the manganese oxide and kneading may be used. The use is more recommended because it provides a closer contact between the manganese oxide and the ruthenium compound.

  When the copper manganese complex oxide or the iron manganese complex oxide is used instead of the manganese oxide as in the deodorizing material described in Patent Document 8, the acetaldehyde removal performance is improved, but the formaldehyde removal performance is not necessarily limited. Not high (see comparative examples in Examples below). In order to efficiently remove lower aldehydes including lower formaldehyde, it is effective to use manganese oxide instead of complex oxide of manganese and other metal elements.

  Here, it is considered that the difference in formaldehyde removal performance between the manganese oxide and the composite oxide of manganese and other metal elements such as copper and iron is due to the following reason.

  That is, the aldehyde is removed by oxidation of the aldehyde through a process of aldehyde → acid → carbon dioxide + water, and finally decomposition into carbon dioxide and water. Here, acetaldehyde is difficult to oxidize to acid as compared to formaldehyde, and complex oxides of manganese and other metal elements are effective catalysts in the oxidation reaction process to acid. On the other hand, since formaldehyde is relatively easily oxidized to acid (formic acid), the oxidative decomposition process from formic acid to carbon dioxide + water controls the overall reaction. Manganese oxide is an effective catalyst for this oxidative decomposition reaction of formic acid.

  However, the use of complex oxides of manganese and other metal elements (such as copper and iron) is effective in improving the deodorization performance against mercaptans, which are odor components other than aldehydes. By using a deodorizing agent carrying a ruthenium compound on a base material to which a complex oxide of manganese and other metal elements is added, it is possible to deodorize many kinds of odors simultaneously.

  The supported amount of ruthenium element in the ruthenium compound with respect to the deodorizing material is preferably 0.1% by mass or more and less than 0.6% by mass. When the supported amount is less than 0.1% by mass, the effect of improving the catalytic action is not sufficiently exhibited. On the other hand, when the supported amount is 0.6% by weight or more, the cost of the deodorizing material is increased, and the manganese oxide is inherently used. This is because the deodorizing performance with respect to the aldehyde possessed by is hindered by the supported ruthenium compound, and the aldehyde deodorizing performance of the deodorizing material as a whole deteriorates.

  The deodorizing material carrying the ruthenium compound as described above can be used after being molded into a pellet using a binder, but it can be extruded into a honeycomb using a binder, or the deodorizing material can be corrugated with a binder. It is also possible to use it as a corrugated honeycomb by attaching it to the above. By using a honeycomb shape, the pressure loss during use can be kept low, and the filter can be used as a high-performance deodorizing filter. When used as a deodorizing filter for air purifiers, in addition to manganese oxide, activated carbon, zeolite, copper manganese composite oxide, ferromanganese composite oxidation, in addition to manganese oxide, can be widely deodorized for malodorous components other than aldehydes. It is also possible to use a deodorizing material in which a ruthenium compound is supported on a base material to which an adsorbent such as a product or a deodorizing catalyst is added. Alternatively, after a ruthenium compound is supported on manganese oxide, an adsorbent or a deodorizing catalyst such as activated carbon, zeolite, copper manganese composite oxide, or iron manganese composite oxide may be used as a deodorizing material.

[Embodiment 2]
For the deodorizing material according to Embodiment 2 of the present invention, a catalyst in which a phosphate compound is supported on manganese oxide as a base material is used. By supporting the phosphate compound instead of the ruthenium compound of the first embodiment, the cost can be further reduced. The specific surface area of the manganese oxide used as the substrate is preferably high in terms of adsorption performance, as in Embodiment 1, and a BET specific surface area of 200 m ² / g or more can be suitably used. As the phosphate compound to be supported, phosphates such as lithium, magnesium, calcium, and iron can be used. Particularly, the deodorizing material having iron phosphate supported on manganese oxide has high aldehyde removal performance. The method for supporting the phosphate compound on the manganese oxide is not particularly limited. For example, a method in which a phosphate compound and a binder are added to the manganese oxide and kneaded and then extruded into a pellet shape or a honeycomb shape can be employed. . It is also possible to drip the corrugated honeycomb into a slurry in which a manganese oxide, a phosphate compound and a binder are mixed to attach a deodorizing material component to the honeycomb surface and then dry the honeycomb to form a deodorizing filter.

  The amount of the phosphate compound supported on the deodorizing material is preferably 0.1% by mass or more and 20% by mass or less. When the supported amount is less than 0.1% by mass, the effect of improving the catalytic action is not sufficiently exhibited. On the other hand, when the supported amount exceeds 20% by weight, the deodorizing performance with respect to the aldehyde originally possessed by manganese oxide is not supported. This is because the aldehyde deodorizing performance of the deodorizing material as a whole is deteriorated by being inhibited by the phosphate compound. The lower limit of the amount of the phosphate compound supported is more preferably 0.5% by mass, as will be described in Examples below.

  The deodorizing material carrying the phosphate compound as described above can be used after being molded into a pellet shape using a binder, as in the first embodiment, but is extruded into a honeycomb shape using a binder. It is also possible to use it by molding or attaching a deodorizing material to a corrugate with a binder to form a corrugated honeycomb. By using a honeycomb shape, the pressure loss during use can be kept low, and the filter can be used as a high-performance deodorizing filter. When used as a deodorizing filter for an air purifier, in addition to manganese oxide, in addition to manganese oxide, activated carbon, zeolite, copper manganese composite oxide, ferromanganese are used in addition to manganese oxide so that malodorous components other than aldehydes can be widely deodorized. It is also possible to use a deodorizing material in which a phosphate compound is supported on a base material to which an adsorbent such as a composite oxide or a deodorizing catalyst is added. Or after carrying | supporting a phosphate compound to manganese oxide, you may use what added adsorbents and deodorizing catalysts, such as activated carbon, a zeolite, copper manganese complex oxide, and iron manganese complex oxide.

[Confirmation test regarding Embodiment 1]
In order to confirm the effect of the deodorizing material according to Embodiment 1 of the present invention, the following test was performed. As the manganese oxide, two types of manganese oxides having different BET specific surface areas (manganese oxide (1): BET specific surface area 280 m ² / g, manganese oxide (2): BET specific surface area 225 m ² / g) were used. In addition, copper-manganese composite oxide powder, iron-manganese composite oxide powder, and powdered activated carbon of coconut shell material were used as comparative materials.

  To each of the above powders, a silica sol (Nissan Chemical Snowtex) as a binder is added with 30% by mass and an appropriate amount of water. ").

  The ruthenium compound was supported by spraying a diluted potassium ruthenate aqueous solution onto a dried pellet substrate, and the ruthenium loading was adjusted by changing the dilution rate of the potassium ruthenate aqueous solution. The pellet after supporting ruthenium was dried at room temperature in a desiccator for 1 day, and then dried overnight at 80 ° C. to obtain an evaluation material.

The aldehyde removal performance was measured by the following odor gas flow test. As the odor gas, a sample holder (inner diameter 8 mm × length) filled with each evaluation material under the condition of space velocity (GHSV) 180,000 h ⁻¹ using a simulated gas having an acetaldehyde concentration of 2 ppm or a formaldehyde concentration of 10 ppm and a relative humidity of 60%. The aldehyde concentration at the outlet of the sample holder was measured. The removal performance was determined by the following formula, the aldehyde removal rate was calculated, and the evaluation materials were compared.

Aldehyde removal rate (%) = [(Ci-Co) / Ci] × 100
[Ci: aldehyde concentration at sample holder inlet, Co: aldehyde concentration at sample holder outlet]

  Table 1 shows the acetaldehyde removal rate and the formaldehyde removal rate after 30 minutes and 60 minutes from the start of the test of each evaluation material tested.

[Influence of catalyst type and combination]
Compared to the samples (Comparative Example 1 and Comparative Example 2) in which manganese oxide is simply molded with a binder, ruthenium is supported on the molded product of manganese oxide, so that not only acetaldehyde but also formaldehyde is significantly improved in deodorizing performance. Is observed (Example 1, Example 2).

  In addition, as shown in Comparative Example 3, the aldehyde removal performance of the sample in which the ruthenium compound is supported on the activated carbon is acetaldehyde even when compared with the sample (Comparative Example 1 and Comparative Example 2) in which manganese oxide is simply formed with a binder. It can be seen that the removal rate is only comparable and the formaldehyde removal rate is significantly lower.

  In the sample in which the ruthenium compound was supported on the copper manganese composite oxide (Comparative Example 4) and the iron manganese composite oxide (Comparative Example 5), the acetaldehyde removal performance was improved to the same extent as when the ruthenium compound was supported on manganese oxide. However, it can be seen that the formaldehyde removal performance can be obtained only to the same extent as in the case of manganese oxide alone (Comparative Examples 1 and 2).

  From the above, it was confirmed that it is effective to support a ruthenium compound on a manganese oxide in order to effectively remove lower aldehydes including formaldehyde.

[Influence of ruthenium loading]
Aldehyde removal performance is improved by increasing the amount of ruthenium supported (Examples 1 and 5 to 7). However, if a certain amount (0.6% by mass) or more is supported, the aldehyde removal performance decreases (Example 8). 9) Further, since the material cost of ruthenium increases as the loading amount increases, the loading amount of ruthenium is preferably 0.1% by mass or more and less than 0.6% by mass.

[Effect of adding other catalyst to the base material]
As a deodorizing material, ruthenium is applied to a base material comprising manganese oxide (2): 30% by mass, copper manganese composite oxide: 18% by mass, zeolite (ZSM-5 type): 27% by mass, binder (silica sol): 25% by mass. A deodorizing material supporting a compound and a deodorizing material not supporting a ruthenium compound on the same base material were attached to a corrugate of 350 cells, respectively, and a test for investigating acetaldehyde removal performance was performed. The ruthenium compound was supported by the same spraying method as described above, and 0.2% by mass of the deodorizing material amount was supported. The amount of deodorizing material attached to the corrugate was 0.23 g / cm ³ . The test results are shown in Table 2 below.

As is apparent from Table 2, even in the base material in which copper manganese composite oxide and zeolite are added to manganese oxide, acetaldehyde deodorization performance is remarkably improved in addition to formaldehyde deodorization performance by supporting a ruthenium compound. Was confirmed.

[Confirmation test concerning Embodiment 2]
Next, the following tests were conducted to confirm the effect of the deodorizing material according to Embodiment 2 of the present invention.

[Influence of catalyst type and combination]
As the manganese oxide, manganese oxide (2) having a BET specific surface area of 225 m ² / g among the two types of powders used in the above [Verification Test Regarding Embodiment 1] was used.

  To the above-mentioned manganese oxide powder, various phosphate compounds are 7% by mass with respect to the entire evaluation material (deodorizing material), silica sol (Snowtex manufactured by Nissan Chemical Co., Ltd.) as a binder is 30% by mass, and appropriate amounts of water After adding, kneading and extruding, a pellet-shaped deodorizing performance evaluation material was produced. For iron phosphate, the amount of iron phosphate supported is 0.1 to 7% by mass (the amount of binder is fixed and the amount of manganese oxide is adjusted according to the amount of iron phosphate supported in order to evaluate the effect of the amount supported. ) Was also performed in the range of

  The acetaldehyde removal performance measurement was performed under the same conditions as the above [Verification Test for Embodiment 1].

  Table 3 shows the acetaldehyde removal rate after 30 minutes and 60 minutes from the start of the test for each of the evaluated evaluation materials.

  Compared with the sample (Comparative Example 11) in which manganese oxide is simply molded with a binder, the deodorizing performance of acetaldehyde is improved by using a deodorizing material in which a phosphate compound is supported on manganese oxide, especially iron phosphate. When it does, the remarkable improvement in deodorizing performance is recognized (Examples 11-14).

Moreover, although the load of iron phosphate (phosphate compound) is 0.1% by mass or more, the effect of improving the deodorizing performance is recognized, but the effect is particularly large at 0.5% by mass or more (Examples 14 to 17).

[Effect of adding other catalyst to the base material]
As a deodorizing material, the same as the deodorizing material in which iron phosphate is supported on a base material consisting of manganese oxide (2): 69% by mass, zeolite (ZSM-5 type): 16% by mass, binder (silica sol): 15% by mass. The deodorizing material which does not carry | support iron phosphate on a base material was each attached to the corrugate of 350 cells, and the test which investigates the removal performance of acetaldehyde and formaldehyde was implemented. The amount of iron phosphate supported was 7% by mass of the amount of deodorizing material. The amount of deodorizing material attached to the corrugate was 0.22 g / cm ³ . The test results are shown in Table 4 below. The conditions for the formaldehyde removal performance evaluation test were set to a formaldehyde concentration of 10 ppm, and the other conditions were the same as the conditions for the acetaldehyde removal evaluation test.

As is apparent from Table 4, it was confirmed that even in the base material in which zeolite was added to manganese oxide, acetaldehyde deodorization performance was significantly improved by supporting iron phosphate in addition to formaldehyde deodorization performance.

Claims (9)

  A deodorizing material comprising a catalyst in which a ruthenium compound is supported on a manganese oxide as a base material.   The deodorizing material according to claim 1, wherein the base material further contains at least one selected from the group consisting of a copper manganese composite oxide, an iron manganese composite oxide, activated carbon, and zeolite.   3. The deodorizing material according to claim 1, wherein a loading of the ruthenium element in the ruthenium compound with respect to the deodorizing material is 0.1 mass% or more and less than 0.6 mass.   The method for producing a deodorizing material according to any one of claims 1 to 3, wherein the ruthenium compound is supported on the manganese oxide by spraying an aqueous solution of a ruthenium compound onto the substrate.   A deodorizing material comprising a catalyst in which a phosphate compound is supported on a manganese oxide as a base material.   The deodorizing material according to claim 5, wherein the phosphate compound is iron phosphate.   The deodorizing material according to claim 5 or 6, wherein the supported amount of the phosphate compound with respect to the deodorizing material is 0.1 mass% or more and 20 mass% or less.   The deodorizing material according to any one of claims 5 to 7, wherein the base material further includes at least one selected from the group consisting of a copper manganese composite oxide, an iron manganese composite oxide, activated carbon, and zeolite.   The deodorizing filter using the deodorizing material of any one of Claims 1-3, 5-8 formed in the honeycomb form.