WO2005032605A1

WO2005032605A1 - Deodorant and process for producing the same

Info

Publication number: WO2005032605A1
Application number: PCT/JP2004/012551
Authority: WO
Inventors: Toshihiko Tsuda
Original assignee: Kobayashi Pharmaceutical Co., Ltd.
Priority date: 2003-09-30
Filing date: 2004-08-31
Publication date: 2005-04-14
Also published as: JP2005103110A

Abstract

[PROBLEMS] A deodorant which has a high deodorizing effect on odorous ingredients regardless of whether they are acid, alkaline, or neutral and which has sufficient strength. [MEANS FOR SOLVING PROBLEMS] The deodorant is obtained by mixing an inorganic raw material with an organic material for carbonization/burning so that the amount of the organic material on a dry basis is less than 30 wt.% based on the whole mixture, kneading the mixture, and carbonizing/burning the resultant mixture into an unglazed-pottery-like product.

Description

Specification

Deodorant and method for producing the same

Technical field

The present invention relates to a deodorant having a high deodorizing effect on acidic, alkaline and neutral odor components.

Background art

[0002] Conventionally, as a deodorant for removing odor components in the air, one that adsorbs and removes odor components using an adsorbent having a porous structure such as activated carbon is known. The activated carbon has excellent adsorption performance and is widely used as a deodorant.However, it has low strength and is difficult to be formed into an arbitrary shape.At present, it is used as a granular material in a container. And there were restrictions on the design.

[0003] As a solution to the above problem, Patent Document 1 discloses a papermaking sludge containing 30 to 60% by weight, 5 to 30% by weight of aluminums, and 10 to 60% by weight of clays, which is calcined. The adsorbent obtained is described. This adsorbent can be formed into an arbitrary shape by using clays.

Patent Document 1: JP-A-63-256132

Disclosure of the invention

Problems to be solved by the invention

[0004] However, in the above adsorbent, a large amount of papermaking sludge of 30 to 60% by weight is blended in order to enhance the deodorizing ability. Therefore, when the strength of the adsorbent decreases, the following problem occurs. I was In addition, the adsorbent is effective for either acidic odor components or alkaline odor components depending on the surface properties thereof, but generally has little effect on the other. However, in the case of activated carbon, there is a problem that the ability to adsorb odorous components such as ammonia is relatively weak.

[0005] Therefore, the present invention provides a deodorizing agent that can be molded into an arbitrary shape that has a high deodorizing effect against any of acidic, alkaline, and neutral odor components, and that has sufficient strength after molding. The purpose is to: Means for solving the problem

[0006] In order to solve the above-mentioned problems, the present inventor has conducted various studies. As a result, an inorganic raw material such as clay, which has been conventionally used for forming an adsorbent into an arbitrary shape, and an organic material for carbonizing and firing. And carbonizing and firing in a calcined state, it is possible to deodorize acidic odor components such as sulfuric acid hydrogen and methyl mercaptan at the same level as activated carbon, even if the amount of organic materials to be blended is small. As a result, it was found that both the power and ammonia can be effectively deodorized, and the present invention was completed.

[0007] That is, in the present invention, when mixing the inorganic raw material and the organic material for carbonizing and firing, the inorganic material and the organic material are mixed so that the dry weight of the organic material is less than 30% by weight based on the total dry weight. After kneading and shaping the mixture, the kneaded product is carbonized and fired in an unfired state.

[0008] According to the above configuration, it is possible to obtain a deodorant exhibiting a deodorizing effect even for acidic, alkaline, and neutral! /, Offset odor components, and to reduce the amount of the organic raw material relative to the inorganic raw material. Since there is not much, a mixture obtained by mixing both can be easily formed into an arbitrary shape, and a fired body having sufficient strength can be obtained even in a state of being fired in an unfired state.

[0009] Here, the dry weight refers to the weight of an inorganic raw material and an organic material each dried at 105 ° C for 24 hours. Further, firing in the unfired state means firing at a temperature lower than the sintering temperature of the inorganic raw material to form a porous inorganic structure having air permeability. In addition, carbonization firing is generated when an organic material is carbonized by firing an organic material together with an inorganic material in a state where air is shut off as in a closed space or a nitrogen atmosphere, and when the organic material is carbonized. This means fixing soot to the fired body.

[0010] In the present invention, since the organic material is mixed with the inorganic raw material, the state of the fired body after carbonization firing is such that the carbide generated by carbonizing the organic material is dispersed in the inorganic porous structure. And a state in which soot is adhered and held on the surface of the porous structure. Therefore, as the deodorant, a fired body whose surface and cross section are colored black can be obtained. [0011] It should be noted that the deodorant obtained in the present invention has the ability to deodorize acidic odor components even when the amount of the organic material used as a raw material for carbide is as small as less than 30% by weight. This is a high point. Normally, the calcined inorganic structure has almost no ability to deodorize acidic odor components such as sulfuric acid hydrogen and methyl mercaptan, so that the ability to deodorize acidic odor components depends exclusively on the deodorizing capability of activated carbon. become. Therefore, conventionally, it has been considered that it is necessary to increase the amount of activated carbon (carbide) in order to deodorize an acidic odor component. Therefore, there has been a problem that the strength of the fired body is reduced as a result.

[0012] However, the deodorant according to the present invention can sufficiently deodorize acidic odor components even when the amount of the organic material is small, so that the amount of carbide finally remaining in the fired body is reduced. By suppressing it, the strength of the deodorant can be increased.

[0013] In the embodiment described below, the amount of the paper sludge (hereinafter referred to as "PS") is changed from 74 to 6% by weight based on the dry weight of the entire mixture to obtain six types of fired bodies. Samples were prepared and their deodorizing performance was evaluated.Each sample was confirmed to deodorize acidic and alkaline odor components at the same level in a well-balanced manner!

[0014] As described above, it is not known at all that a deodorant having a PS content of less than 30% by weight has a deodorizing performance equivalent to that of a deodorant containing PS of 30% by weight or more. Thus, a deodorant having sufficient strength can be obtained.

[0015] Specifically, when the strength of a fired body (hereinafter, referred to as unglazed product) obtained by firing a 100% inorganic raw material containing no organic material under the same conditions as the above-described sample is assumed to be 100, When the PS content in the mixture is less than 30% by weight, the strength exceeds 60% of that of the unbaked product, and when the PS content is 23% by weight, the strength of 69% of the unbaked product is increased. When the amount is 12% by weight, the strength is 74% that of the unglazed product, and when the PS content is 6% by weight, the strength is 81% that of the unglazed product.

[0016] As for the strength of the fired body, it has been confirmed that if the strength of the unbaked product is 50%, it can be used without any practical problem, and the PS content in the mixture of the deodorant according to the present invention is determined. Is less than 30% by weight, PS content is 23% by weight, 12% by weight, 6% by weight % Is preferable because the strength of the fired body increases.

[0017] Although the reason why the acidic odor component can be deodorized even when the content of the carbide is small is not clear, the deodorizing performance as a deodorant is equivalent even when the amount of the organic material is changed. However, taking into account the fact that non-carbon-fired products that are not carbonized and fired cannot deodorize acidic odor components such as hydrogen sulfide and methyl mercaptan, etc.

It is presumed that the soot attached to the surface of the inorganic porous structure by carbonization and firing acts synergistically.

[0018] In the present embodiment, although the evaluation was performed only when the PS content was in the range of 6% by weight or more, the evaluation results show that even if the amount of the organic material is less than 6% by weight, sufficient deodorizing performance was obtained. It is presumed to exhibit As the minimum amount of organic material required to exhibit sufficient deodorizing performance, an organic material that can generate soot enough to cover the entire surface of the porous structure should be used. It is presumed that.

[0019] In the present invention, the inorganic raw material is a raw material for firing, and generally, clay which is a raw material for ceramics or the like can be used. The firing temperature for firing this inorganic raw material in an unglazed state varies depending on the sintering temperature of the inorganic raw material, but is about 770 ° C to 930 ° C for general clay for ceramics. If the temperature is lower than 770 ° C, the strength of the fired body may decrease. If the temperature is higher than 930 ° C, the porous structure may be densified and the surface area of the fired body may decrease.

[0020] As the organic material, any material that carbonizes while generating soot by carbonization and firing, such as rice hulls, paper, wood chips, rice straw, and paper sludge, can be used. However, in order to reduce the variation in the strength of the fired body after carbonization firing, it is necessary to make the structure of the fired body uniform, and for that purpose, it is desirable to use the organic material as finely as possible and pulverize it. . In terms of this perspective, paper sludge is discharged in large quantities from paper mills, is easily available, and has short fibers of paper and inorganic substances derived from fillers (kaolin, talc, calcium carbonate, etc.) It is also preferable because it can be easily mixed with inorganic raw materials and a fired body having a uniform structure can be obtained.

[0021] The deodorant obtained as described above can be formed into an arbitrary shape having a high deodorizing effect on any of acidic, alkaline, and neutral odor components, and has sufficient strength even after firing. Is very high added value.

The invention's effect

[0022] The deodorant according to the present invention can be formed into an arbitrary shape because the inorganic raw material and the organic material are mixed at a predetermined weight ratio, and this is obtained by carbonizing and firing the raw material. Therefore, although the amount of carbon in the deodorant is small, it is possible to efficiently deodorize acidic odor components, and it is possible to suppress a decrease in the strength of the fired body.

BEST MODE FOR CARRYING OUT THE INVENTION

[Preparation of deodorant]

Next, a method for producing the deodorant according to the present invention will be described. In the present embodiment, unless otherwise specified, “%” indicates “% by weight”.

As an inorganic raw material, clay which is a raw material for ceramics (water content: 20%, SiO: 54.3%, Al 2 O 3

2 2 3

: 16.4%, Fe O: 0.4%, TiO: 0.2%, CaO: 0.2%, MgO: 0.2%, Κ Ο: 2.4

2 3 2 2

%, Na 0: 1.2%, Others: 4.7%), and PS (including

2

Water content: 3.5%, loss on ignition: 59.8%, residue: 36.7%). The moisture content of the clay and PS was sampled in advance, the initial weight was measured, the dry weight after drying at 105 ° C for 24 hours was measured, and calculated by the following equation (1).

[0025] Moisture content (% by weight) = (initial weight-weight after drying) X 100Z initial weight · · · · (1)

Next, as shown in Table 1, seven types of mixtures in which the actual weight ratio of clay to PS was changed were prepared and uniformly kneaded. Table 1 also shows the dry weight ratio of clay and PS and the content of dry weight of PS relative to the total dry weight of the mixture. The dry weight of the clay and PS was calculated as follows based on the water content calculated by the above equation (1).

[0026] Clay dry weight = actual clay use weight X (l—0.20)

PS dry weight = actual PS weight X (1-0. 035)

Next, the above mixture was molded, and the obtained molded body was placed in a sealed container (sheath) and carbonized and fired in a kiln (800 ° C, 7.5 to 8.5 hours). The shape of the fired body thus obtained was a bowl shape having a bottom area of 9.4 cm ² , a height of 6. Ocm, an opening circumference of 21.6 cm, and a wall thickness of 4.7 mm.

[0027] The fired body has an inorganic porous structure, and carbide is dispersed and maintained in the inorganic porous structure. At the same time, the soot adhered to the porous surface and was in a black state as a whole. Table 1 also shows the weight of the fired body obtained for each sample.

[Table 1]

1: Weight of organic material (dry weight) in mixture (dry weight) <%

[Performance evaluation of deodorant]

The deodorizing performance was evaluated using the seven types of deodorizing agents prepared as described above. As an evaluation method, first, each sample was grouped in groups of four, and each of the samples was stored in a 10 liter tedranock. Four types of odor components, ammonia, trimethylamine, hydrogen sulfide, and methylmercaptan were used.Eight liters of the reference gas, each prepared to a concentration of 100 ppm, was sealed in the four tedrapacks above, and at predetermined intervals The gas concentration was measured (detector tube method), and based on the measured gas concentration, the deodorization rate was calculated by the following equation (2).

[0029] Deodorization rate (%) = (initial gas concentration measured gas concentration) x 100Z initial gas concentration · · · · (2)

As a comparison, the same evaluation was performed using a fired body (unfired product) fired using clay alone without mixing PS and a commercially available deodorant containing 44 g of activated carbon (hereinafter referred to as activated carbon). The results of the deodorization rate are shown in Figure 14 and Table 2-5.

[Table 2] ammonia

[0031] [Table 3]

Trimethylamine

[0032] [Table 4]

Hydrogen sulfide

[0033] [Table 5]

[Measurement of carbon content and carbon content of deodorant]

In the deodorizer according to the present invention, it is considered that carbon derived from carbide and soot present in the sample contributes to the deodorizing performance of acidic odor components. Therefore, the carbon content (% by weight) in the deodorant was measured using the above seven types of deodorants. The measurement conditions are described below.

[0034] As an analysis method, an elemental CHN automatic analyzer (varioEL) equipped with a thermal conductivity detector was used, and helium gas (gas flow rate: 200 ± 5 ml Zmin) was used as a carrier gas. The temperature was set at 950 ° C for the combustion tube and 500 ° C for the reduction tube. Acetairide was used as a reagent, and analysis was performed with a sample amount of 3 mg. The obtained carbon content was multiplied by the weight of each sample to calculate the carbon content (g) present in the sample (fired body). Table 1 shows the results of these analyses.

[Strength Evaluation of Deodorant]

A strength test was performed using the above seven types of deodorants. The test contents are as follows. The strength was evaluated using a rheometer (manufactured by Sun Kagaku) under the following conditions.

[0036] The sample was placed on a test table, a probe having a tip diameter of 0.45mm was pressed in, and the maximum strength was measured at an approach speed of 60mmZmin. Table 1 shows the test results.

[0037] [Evaluation results]

From Fig. 14 and Table 2-5, the unbaked product has an acidic odor component, hydrogen sulfide and methyl mercaptan, which have poor deodorizing performance. It can be seen that the deodorization rate is lower than other baked samples (samples 16 and unbaked products) even after the elapse.

[0038] On the other hand, it was confirmed that the samples 116 produced in the present embodiment efficiently deodorized any of the odor components of ammonia, trimethylamine, hydrogen sulfide and methyl mercaptan. In particular, in the deodorizing test for methyl mercaptan, which is an acidic odor component (FIG. 4, Table 5), it can be seen that the deodorizing rate is higher and the deodorizing rate is reached earlier than activated carbon.

[0039] This is because the sample 116 has a bowl shape and has a large contact area in direct contact with the odor component, whereas the activated carbon is contained in a container as a set of granular materials, and therefore exists inside. This was presumed to be due to the fact that the granular material was unlikely to come into contact with the odor component. Thus, the performance of the deodorant It is considered that the shape is greatly affected by the shape of the material as well as the adsorption performance of the material itself.

[0040] Comparing Sample 116 with activated carbon, the carbon content of Sample 116 is 3.1-0.8 g, which is significantly smaller than that of activated carbon 44 g. In particular, it was confirmed that Sample 6 exhibited the same level of deodorizing performance as the other samples, despite having the smallest carbon content of 0.8 g.

[0041] Samples 1 and 2, however, have excellent deodorizing performance, but their strength is only about 23-29% of the strength of the unfired product and is brittle (Table 1). Assuming that the strength is Y and the PS dry weight% is X, there is a correlation between the two, Y = −960.7. + 8695 (R ² = 0.9531).

[0042] Therefore, when the dry weight% of the PS is less than 30% with respect to the dry weight of the whole mixture, the strength of the deodorant exceeds 5815, and the strength of the deodorant is higher than about 60% of the strength of the unglazed product. Will be. It has been confirmed that if it has a strength that is 50% of the strength of the unglazed product, it can be used practically without any problems, and as a result, a deodorant with unprecedented superior strength Can be obtained.

[0043] Further, when the PS content is 23% by weight, the strength of the unbaked product is 69%, when the PS content is 12% by weight, the strength of the unbaked product is 74%, and the PS content is 6% by weight. In case (1), the strength of each of the unbaked products is 81%, and it can be seen that the strength of the fired body increases as the PS content decreases. Therefore, the lower the PS content, the more preferable the strength of the fired body.

[0044] The relationship between the PS content and the strength of the fired body with respect to the entire mixture has been described above, but the same relationship can be found with respect to the carbon content and the strength of the fired body. That is, the smaller the carbon content in the sintered body, the greater the strength of the sintered body. Specifically, when the carbon content is less than 2.1%, the strength of the unfired product is maintained at a strength greater than 56%. When the carbon content is 1.8%, the strength is 69% that of the unbaked product, when the carbon content is 1.2%, the strength is 74% of the unbaked product, and when the carbon content is 1.0%. Has a strength of 81% that of unglazed products, and the lower the carbon content, the greater the strength of the fired product. [0045] In this embodiment, the PS content in the entire mixture was evaluated as the lowest level of 6%, and the carbon content was evaluated as the lowest level of 1.0% (Sample 6). The result was the same as 5).

[0046] On the other hand, carbonized and calcined! /, The unbaked product has almost no deodorizing ability with respect to sulfuric acid hydrogen / methyl mercaptan and! /, Ivy odor components. Taking these into account, it is speculated that the deodorizing ability of acidic odor components is exhibited mainly by the synergistic action of the inorganic porous structure and the soot attached to the surface of the inorganic porous structure. Was.

[0047] From the above evaluation results, the amount of the organic material was less than 6% by weight, or the carbon content was 1.

It is estimated that even below 0%, sufficient deodorizing performance is still exhibited. The minimum amount of organic material required to exhibit sufficient deodorizing performance should be an amount of organic material capable of generating soot enough to cover the entire surface of the porous structure. Brief description of the presumed drawing

FIG. 1 is a graph showing the ammonia deodorizing performance of each deodorizing agent.

FIG. 2 is a graph showing the deodorizing performance of trimethylamine in each deodorant.

FIG. 3 is a graph showing the deodorizing performance of sulfur dioxide on each deodorant.

FIG. 4 is a graph showing the deodorizing performance of methyl mercaptan for each deodorant.

Claims

The scope of the claims

[1] When mixing the inorganic raw material and the organic material for carbonization and firing, the inorganic material is blended so that the dry weight of the organic material is less than 30% by weight based on the total dry weight, and the mixture is kneaded. And carbonizing and firing the kneaded product in an unfired state.

2. The method for producing a deodorant according to claim 1, wherein the organic material is paper sludge.

[3] A deodorant obtained by molding a mixture of an inorganic raw material and an organic material and carbonizing and firing the mixture in an unfired state, wherein the blending ratio of the organic material in the mixture is less than 30% by dry weight%. A deodorant characterized by the following.

[4] A porous structure obtained by carbonizing and firing a mixture of an inorganic raw material and an organic material in an unfired state, wherein the carbon content in the structure is less than 2.1% by weight. Deodorant.

5. The deodorant according to claim 3, wherein the organic material is paper sludge.