JP5221872B2 - Deodorizing material - Google Patents

Description

  The present invention relates to a deodorizing material excellent in removal performance of odorous components of aldehydes such as formaldehyde and acetaldehyde.

  In general, in a commercial ventilation apparatus used in commercial facilities, factories, restaurants, etc., deodorizing material is disposed in an exhaust passage to deodorize it.

2. Description of the Related Art Conventionally, as a deodorizing material used for this deodorization, a honeycomb porous continuous porous structure having a hydrous magnesium silicate clay mineral as a main component is known. (For example, refer to Patent Document 1).
JP-A-2005-305268

  However, the above-mentioned conventional deodorizing materials have deodorizing performance against gaseous organic compounds, but deodorizing performance of formaldehyde, acetaldehyde and other aldehydes that cause the irritating odor of sick house syndrome and tobacco. Caused the inconvenience that it could not be fully demonstrated.

The present invention was made in view of the circumstances of, aims at a high removal efficiency to aldehydes and outgoing current, and provides a deodorizing material can be used for a long time.

  As a result of intensive studies on the removal of odorous components from aldehydes, the present inventors have found that a hydrated magnesium silicate composition with carbodihydrazide exerts an excellent deodorizing effect, leading to the present invention. It is a thing.

  That is, the present invention is a deodorizing material characterized in that carbodihydrazide is attached to pellets obtained from a hydrous magnesium silicate composition.

  The hydrous magnesium silicate composition is, for example, wet kneaded together with a binder with a powder material mainly composed of hydrous magnesium silicate clay mineral, then extruded into any shape such as rod, pellet, macaroni, etc., and after drying It can be fired to form hydrous magnesium silicate pellets. Examples of the hydrous magnesium silicate clay mineral used here include holmite, zeolite, sepiolite, sirotile, rafrinite, and attapulgite. The binder is a polymer such as PVA resin, PTFE (polytetrafluoroethylene), PVDF (polyvinylidene fluoride), PVC (polyvinyl chloride), polyacrylate, epoxy resin, phenol resin, polyethylene, polypropylene, ABS resin, polyester, etc. And clay minerals such as silica sol, alumina sol, bentonite and kaolinite.

The hydrous magnesium silicate pellet is particularly suitable if it has a continuous porous structure so that a large number of voids formed by filling a large number of the pellets can be continuously vented. It is not limited, and for example, granular hydrous magnesium silicate pellets may be stacked and aerated from the gap between adjacent pellets, or may be hollow rod or macaroni It may be formed as a hydrous magnesium silicate pellet having the above and filled with a breathable container. If the particles are made finer or the packing density is increased in order to increase the contact between the hydrous magnesium silicate pellets and the aeration gas during ventilation, the ventilation resistance will increase, and if the ventilation resistance is lowered, the hydrous magnesium silicate will increase. It becomes impossible to sufficiently contact the pellet and the aeration gas. Accordingly, the size, ventilation resistance, etc. of these hydrous magnesium silicate pellets can be appropriately selected according to the place of use and the allowable ventilation pressure loss.

Carbodihydrazide is represented by the chemical formula NH ₂ NH—CO—NHNH ₂ . The carbodihydrazide is attached to the hydrous magnesium silicate pellet so that it is 1 to 15 parts by weight, preferably 5 to 10 parts by weight, per 100 parts by weight of the hydrous magnesium silicate pellets. Is done.

  This attachment can be carried out by impregnating the hydrated magnesium silicate pellets in a carbodihydrazide agent and attaching carbodihydrazide to the hydrated magnesium silicate pellets. When this carbodihydrazide is less than 1 part by weight relative to 100 parts by weight of the hydrous magnesium silicate pellets, sufficient deodorizing ability cannot be obtained with respect to aldehydes. The deodorizing ability with respect to the odor is saturated, and the amine group contained in the carbodihydrazide itself increases the amine odor emitted from the deodorizing material itself.

  Note that this attachment is not limited to impregnation attachment, and the hydrated magnesium silicate pellets may be attached by spraying a carbodihydrazide drug by spraying, or applied with a brush or the like. It may be attached by doing.

  In the deodorizing material thus configured, the odor of the deodorizing material itself is generated because the carbodihydrazide added to the hydrous magnesium silicate pellets has an amino group. Therefore, phosphoric acid may be added so as to be 5 parts by weight or more with respect to 100 parts by weight of the hydrous magnesium silicate pellets for the purpose of reducing the amine odor of the deodorizing material itself. In this case, phosphoric acid may be added by adding carbodihydrazide to the hydrous magnesium silicate pellet and then adding phosphoric acid in the same manner, or adding phosphoric acid to the hydrous magnesium silicate pellet. Then, carbodihydrazide may be attached in the same manner, or carbodihydrazide and phosphoric acid may be attached simultaneously to the hydrous magnesium silicate pellet. When the amount of phosphoric acid added is less than 5 parts by weight with respect to 100 parts by weight of the hydrous magnesium silicate pellets, the amine odor reducing effect is low and the odor of the deodorizing material itself cannot be sufficiently removed. Moreover, the removal effect of an amine odor is recognized by 5 weight part or more. However, as the amount of phosphoric acid added increases, there is a phenomenon that the removal rate of acetaldehyde decreases. Therefore, the amount of phosphoric acid added to the hydrous magnesium silicate pellets is 100 parts by weight of hydrous magnesium silicate pellets. On the other hand, in the range of 5 parts by weight or more and 10 parts by weight or less, it can be appropriately adjusted according to the deodorizing ability required for the deodorizing material. The addition of phosphoric acid is not limited to impregnation as in the case of carbodihydrazide, but may be applied by spraying with a spray, or by application with a brush or the like. May be.

  The deodorizing material constituted in this way not only removes the odor of aldehydes with high removal efficiency and maintains the deodorizing effect over a long period of time, but also the conventional hydrous magnesium silicate pellets have The removal performance of other odorous components that have been present can also be maintained. Therefore, it is possible to remove even a complex odor containing aldehydes in other odor components with this single deodorizing material.

  As described above, according to the deodorizing material of the present invention, the odor of aldehydes can be removed with high removal efficiency, and the deodorizing effect can be maintained over a long period of time.

Further, by impregnating the-phosphate, it can be suppressed even odor deodorizing material itself, and can be applied in a wide range of applications.

Examples of the present invention will be specifically described below.
Acetaldehyde 1-pass removal characteristic test 1
About 12-14 g (volume 20-24 cc) of the pellet-shaped material which adjusted the pellet-form thing of the hydrous magnesium silicate molded object through the sieve of 6-8 mesh, and prepared the particle size.

This pelletized product, carbodihydrazide, adipic acid dihydrazide, and each impregnating and adding succinic acid dihydrazide, as shown in Table 1, Reference Example 1 to Reference Example 3, were prepared each test deodorizing material of Comparative Example 1-3 .

  Each test deodorizing material is filled in a cylindrical container of 25 mmφ, acetaldehyde gas adjusted to 10 ppm is supplied from the inlet side at a linear velocity of 1.0 m / s, and acetaldehyde gas is passed on the outlet side after passing through each test deodorizing material. The concentration was measured. The measurement was performed using a gas detection tube manufactured by Gastec Co., Ltd., after 1 minute, 60 minutes, and 120 minutes after gas passage. The removal rate of the acetaldehyde gas removed by each test deodorizing material was determined from the outlet concentration. The results are shown in Table 1.

表１の結果から、含水珪酸マグネシウムのペレット状物１００重量部に対して１０重量部となるようにカルボジヒドラジドを含浸添着した参考例３の試験脱臭材は、１分後から１２０分後の長時間にわたって高い除去率を維持することが確認できた。また、含水珪酸マグネシウムのペレット状物１００重量部に対して１重量部となるようにカルボジヒドラジドを含浸添着した参考例１の試験脱臭材でも、１分後から１２０分後の長時間にわたって、他の比較例と比べて良好な除去率を維持することが確認できた。
アセトアルデヒド１パス除去特性試験２
含水珪酸マグネシウム成形体のペレット状物を、６〜８メッシュの篩にかけ、整粒したペレット状物服１２〜１４ｇ（容積２０〜２４ｃｃ）と、同じく６〜８メッシュの篩にかけて整粒した活性炭のペレット状物とを用意した。

From the results of Table 1, the test deodorizing material of Reference Example 3 impregnated with carbodihydrazide so as to be 10 parts by weight with respect to 100 parts by weight of the hydrous magnesium silicate pellets was long after 1 minute to 120 minutes. It was confirmed that a high removal rate was maintained over time. Further, the test deodorizing material of Reference Example 1 impregnated and impregnated with carbodihydrazide so as to be 1 part by weight with respect to 100 parts by weight of the hydrous magnesium silicate pellets also has a long period of time after 1 minute to 120 minutes. It was confirmed that a good removal rate was maintained as compared with the comparative example.
Acetaldehyde 1-pass removal characteristic test 2
The pellets of the hydrous magnesium silicate compact were passed through a 6-8 mesh sieve, and the size of the pelletized clothes 12-14 g (volume 20-24 cc), and the activated carbon which was also granulated through a 6-8 mesh sieve. A pellet was prepared.

These pellets was carbodihydrazide were respectively impregnated impregnation, consisting of pellets of hydrous magnesium silicate impregnated impregnated with carbodihydrazide so as to be 10 parts by weight relative to pellets was 100 parts by weight of Referential Example 4 The test deodorizing material, the test deodorizing material of Comparative Example 4 consisting of activated carbon pellets impregnated with carbodihydrazide so as to be 5 parts by weight with respect to 100 parts by weight of the pellets, and 100 parts by weight of the pellets On the other hand, the test deodorizing material of Comparative Example 5 made of activated carbon pellets impregnated with carbodihydrazide so as to be 10 parts by weight was prepared.

  Each test deodorizing material is filled in a cylindrical container of 25 mmφ, and acetaldehyde gas adjusted to 10 ppm is supplied from the inlet side of each test deodorizing material at a linear velocity of 1.0 m / s, and after passing through each test deodorizing material. The concentration of acetaldehyde gas was measured on the outlet side. The measurement was performed every 2 hours through the gas passage using a gas detector manufactured by Gastec. The removal rate of the acetaldehyde gas removed by each test deodorizing material was determined from the outlet concentration. The results are shown in the graph of FIG.

From the results of FIG. 1, it is not possible to obtain a sufficient removal rate even if carbodihydrazide is impregnated and impregnated into the honeycomb structure of activated carbon. However, when carbodihydrazide is impregnated and impregnated into a pellet of hydrous magnesium silicate, it is removed. It was confirmed that the rate improved dramatically.
Aldehyde equilibrium adsorption amount evaluation test
The test deodorant of Example 3, a carbodihydrazide of Reference Example 3 was changed to adipic acid dihydrazide, otherwise the test deodorizing material of Comparative Example 6 were constituted in the same manner as in Reference Example 3, a carbodihydrazide of Reference Example 3 The test deodorizing material of Comparative Example 7 was prepared in the same manner as Reference Example 3 except that the succinic acid dihydrazide was used. Further, as other company's products, the test deodorizing material of the aniline-based additive according to Comparative Example 8, the test deodorizing material of the potassium permanganate-based additive according to Comparative Example 9, and the test deodorizing of the morpholine-based additive according to Comparative Example 10 Each material was prepared.

  1.0 g of each test deodorizing material was put into a 22 liter capacity closed circulation type equilibrium adsorption amount evaluation apparatus, and a mixed gas of 50 ppm acetaldehyde and 50 ppm formaldehyde was circulated at a circulation air volume of 5 liters / minute. The concentration of the mixed gas was measured using a gas detection tube manufactured by Gastec Co., Ltd., and the mixture was circulated until equilibration without any change in concentration. Then, the equilibrium adsorption amount of each test deodorizing material was evaluated from the final measured concentration. The results are shown in Table 2, FIG. 2 and FIG.

これらの結果から、カルボジヒドラジドを含水珪酸マグネシウムのペレット状物に含浸添着した本願発明に係る脱臭材の場合には、他の脱臭材と比べても、アセトアルデヒド、ホルムアルデヒドの双方に対して優れた平衡吸着量を有することが確認できた。

From these results, in the case of the deodorizing material according to the present invention in which carbodihydrazide is impregnated and impregnated into a pellet of hydrous magnesium silicate, an excellent equilibrium with respect to both acetaldehyde and formaldehyde as compared with other deodorizing materials. It was confirmed that it had an adsorption amount.

  In addition, 5 g of each additive of carbodihydrazide, adipic acid dihydrazide, succinic acid dihydrazide, and morpholine used in this test was sealed in a 3-liter sealed bag, and the odor intensity of each additive was controlled by three panelists. Sensory evaluation was performed.

As a result, it was confirmed that the amine odor decreased in the order of morpholine> adipic acid dihydrazide> succinic acid dihydrazide> carbodihydrazide.
Acetaldehyde 1-pass removal characteristic test 3
The test deodorizing material of Reference Example 3 was impregnated with phosphoric acid, and the test deodorizing materials of Reference Example 3, Reference Example 5, and Examples 1 and 2 were prepared as shown in Table 3 and FIG.

  The presence or absence of amine odor of 12 to 14 g of each test deodorizing material was sensory-evaluated by three panelists. As a result, when the phosphoric acid was impregnated and impregnated so as to be 5 parts by weight or more with respect to 100 parts by weight of the pellet-like material, a result that the amine odor was not a concern was obtained.

  Next, 12 to 14 g of each test deodorizing material impregnated and impregnated with phosphoric acid in this manner was filled into a cylindrical container of 25 mmφ, and acetaldehyde gas adjusted to 10 ppm from the inlet side of each test deodorizing material was 1.0 m / The concentration of acetaldehyde gas was measured at the outlet side after feeding at the linear velocity of s and passing through each test deodorizing material. The measurement was performed for each gas passage 120 minutes after using a gas detection tube manufactured by Gastec. The removal rate of the acetaldehyde gas removed by each test deodorizing material was determined from the outlet concentration. The results are shown in FIG.

From the results shown in FIG. 4, it was found that the amine odor can be reduced although the removal rate decreases as the amount of impregnated and impregnated phosphoric acid increases. Even when phosphoric acid was impregnated and impregnated so as to be 15 parts by weight or more with respect to 100 parts by weight of the pellets, it was confirmed that a good removal rate of 30% was maintained as the acetaldehyde removal performance.
Compound odor (kitchen odor) 1-pass removal characteristics test
The test deodorizing material of Reference Example 3 and the test deodorizing material of Comparative Example 1 were prepared.

  In addition to ammonia, trimethylamine, methyl mercaptan, and hydrogen sulfide, which are the so-called four major malodors, kitchen odors containing aldehydes, volatile organic compounds (VOC), and lower fatty acids were collected in gas bags at actual stores.

  Next, 12 to 14 g of each test deodorizing material prepared in Example 3 and Comparative Example 1 was filled in a cylindrical container of 25 mmφ, and the kitchen odor from the entrance side of each test deodorizing material was a linear velocity of 1.0 m / s. The odor intensity (concentration) was measured on the outlet side after passing through each test deodorizing material. For the measurement, “Odor sensor XP329” (trade name) manufactured by Shin Cosmos Electric Co., Ltd. was used, and the determination was made based on the display value of the measuring instrument. The results are shown in Table 3.

表３の結果から、カルボジヒドラジドを含水珪酸マグネシウムのペレット状物に含浸添着した本願発明に係る脱臭材の場合には、複合臭気に対しても優れた脱臭性能を有することが確認できた。
清浄空気１パス除去特性試験
参考例３の試験脱臭材を用意した。また、この参考例３の試験脱臭材にリン酸を５％含浸添着し、それ以外は参考例３と同様に構成した実施例１の試験脱臭材と、参考例３の試験脱臭材におけるカルボジヒドラジドの添加量を１５重量部に変更し、それ以外は参考例３と同様に構成した参考例５の試験脱臭材と、参考例５の試験脱臭材にリン酸を５％含浸添着し、それ以外は参考例５と同様に構成した実施例３の試験脱臭材と、参考例３の試験脱臭材におけるカルボジヒドラジドの添加量を２０重量部に変更し、それ以外は参考例３と同様に構成した比較例１１の試験脱臭材と、この比較例１１の試験脱臭材にリン酸を５％含浸添着し、それ以外は比較例１１と同様に構成した比較例１２の試験脱臭材とを用意した。

From the results shown in Table 3, it was confirmed that the deodorizing material according to the present invention in which carbodihydrazide was impregnated and impregnated into a pellet of hydrous magnesium silicate had excellent deodorizing performance even for complex odors.
Clean air 1-pass removal characteristic test
The test deodorizing material of Reference Example 3 was prepared. Also, the phosphoric acid to the test deodorant of Reference Example 3 and 5% impregnation impregnation, otherwise the test deodorant of Example 1 configured in the same manner as in Reference Example 3, carbodihydrazide in the test deodorant of Example 3 change amount of the additive to 15 parts by weight, otherwise the test deodorant of example 5 was constituted in the same manner as in reference example 3, the phosphoric acid to the test deodorant of example 5 was 5% impregnating and adding, otherwise The test deodorizing material of Example 3 configured in the same manner as in Reference Example 5 and the amount of carbodihydrazide added in the test deodorizing material of Reference Example 3 were changed to 20 parts by weight, and the other configurations were the same as in Reference Example 3. A test deodorizing material of Comparative Example 11 and a test deodorizing material of Comparative Example 12 configured in the same manner as Comparative Example 11 except that 5% phosphoric acid was impregnated and impregnated into the test deodorizing material of Comparative Example 11 were prepared.

Next, 12 to 14 g of each test deodorizing material prepared in Example 1, Example 3, Reference Example 3, Reference Example 5 , Comparative Example 11 and Comparative Example 12 was filled in a cylindrical container of 25 mmφ, and each test deodorization was performed. Clean air was supplied at a linear velocity of 1.0 m / s from the inlet side of the material, and the odor intensity (concentration) was measured on the outlet side after passing through each test deodorizing material. For the measurement, “Odor sensor XP329” (trade name) manufactured by Shin Cosmos Electric Co., Ltd. was used, and the determination was made based on the display value of the measuring instrument. The results are shown in Table 4.

表４の結果から、含水珪酸マグネシウムのペレット状物１００重量部に対してカルボジヒドラジドを１０重量部および１５重量部とした脱臭材の場合には、リン酸を５％含浸添着させたか否かに関係無く、脱臭性能を有することが確認できるが、カルボジヒドラジドの含浸添着量が２０重量部までになると、測定値が上昇してしまう。恐らくカルボジヒドラジドのアミン臭が脱離発生している可能性が考えられる。

From the results of Table 4, in the case of a deodorizing material in which carbodihydrazide was 10 parts by weight and 15 parts by weight with respect to 100 parts by weight of hydrous magnesium silicate pellets, whether or not 5% phosphoric acid was impregnated and impregnated. Regardless, it can be confirmed that it has deodorizing performance. However, when the amount of impregnated carbodihydrazide is up to 20 parts by weight, the measured value increases. Probably the amine odor of carbodihydrazide may be eliminated.

  It can be used as a deodorizing material to be installed in various ventilation devices.

It is a graph which shows the time-dependent change of the acetaldehyde removal rate by the difference in a pellet-like thing. It is a graph which shows the difference in the amount of equilibrium adsorption of acetaldehyde by the difference in an impregnating agent. It is a graph which shows the difference in the amount of equilibrium adsorption of formaldehyde by the difference in an impregnating agent. It is a graph which shows the difference in the removal rate of acetaldehyde by the difference in the amount of phosphoric acid addition.

Claims (1)

A pellet obtained from a hydrous magnesium silicate clay mineral which is at least one selected from holmite, zeolite, sepiolite, sirotile, rafrinite and attapulgite and a binder, and carbodihydrazide with respect to 100 parts by weight of the pellet deodorized but which is affixed so as to be 15 parts by weight or less 1 0 part by weight or more, the phosphate to be 5 parts by weight or more than 10 parts by weight relative to pellets was 100 parts by weight, characterized in that it is affixed Wood.

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