JP2785952B2 - Method for producing deodorant - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a deodorant for deodorizing malodorous substances.

[Conventional technology]

Known deodorizing treatment methods for malodor include, for example, an adsorption method using a porous substance such as activated carbon, zeolite, and bentonite, a catalytic combustion method, an oxidation method using ozone or a chemical, a neutralization method, a bacterial decomposition method, and an enzyme method. However, all have high running costs, management difficulties,
It has many disadvantages, such as poor persistence and relatively low deodorant efficiency.

A deodorant using a redox catalyst as a deodorant that has long-lasting deodorizing performance and is easy to handle
55 publication. The deodorant disclosed in this publication utilizes the redox ability of metalloporphyrin and metalloporphyrazine.

[Problems to be solved by the invention]

The present invention has been made to further improve the deodorant disclosed in the publication, and provides a method for producing a deodorant excellent in deodorizing performance, which can decompose malodorous substances in a short time. .

[Means for solving the problem]

The present inventors have continued research on metal porphyrin, a deodorant applying the redox ability of metal porphyrazine, and as a result, among metal porphyrazines, metal phthalocyanine derivatives represented by the following formula have excellent deodorizing function. I found that.

M in the formula is a metal atom, for example, iron, cobalt, copper, nickel, manganese, osmium, titanium, molybdenum,
There are tungsten and the like, and among them, iron and cobalt are preferable. Y is preferably a compound in which two or more are carboxyl groups, and the residue other than the carboxyl group is -H or another substituent such as an alkyl group, a substituted alkyl group, a halogen group, a nitro group, an amino group, an azo group. Group, thiocyanate group, carbonyl chloride group, aldehyde group, carboxamide group, nitrile group, hydroxyl group, alkoxyl group, phenoxyl group, sulfonic acid group, sulfonyl chloride group,
In addition to a sulfonamide group, a thiol group, a chloromethyl group, an alkylsilicon group, a vinyl group, and the like, there are alkali salts of a sulfonic acid group. These metal phthalocyanine derivatives are hereinafter referred to as metal phthalocyanine polycarboxylic acids.

Furthermore, they found that when the metal phthalocyanine polycarboxylic acid was supported on alumina, the deodorizing function was further enhanced, and the present invention was completed.

That is, the deodorant produced by the production method of the present invention has a total amount of metal phthalocyanine polycarboxylic acid of 0.01%.
-5% by weight is supported on alumina.

It seems that the larger the amount of the metal phthalocyanine polycarboxylic acid, the higher the deodorizing performance. However, if it exceeds 5% by weight, the deodorizing performance is not improved. The reason for this is not always clear,
Probably, it is presumed that if too much, the surface pores of alumina are blocked with the metal phthalocyanine polycarboxylic acid, and the surface area of the alumina, that is, the contact area between the metal phthalocyanine polycarboxylic acid and the malodorous substance becomes small. In addition, loading exceeding 5% by weight may be difficult.
When the amount of the metal phthalocyanine polycarboxylic acid is 0.01% by weight or less, the deodorizing performance is low.

The present inventor has also studied a method for producing the above deodorant and found an optimal method.

That is, the method for producing a deodorant of the present invention comprises the steps of: immersing alumina in a bath in which metal phthalocyanine polycarboxylic acid is dissolved in an alkaline solution to attach metal phthalocyanine polycarboxylic acid to alumina; After treating the treated alumina in an acid bath,
It is characterized by washing and drying.

As the alkali solution for dissolving the metal phthalocyanine polycarboxylic acid, for example, an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, an aqueous solution of sodium carbonate and an aqueous solution of potassium carbonate can be used, and the pH is appropriately adjusted with an acid. The dissolution concentration of the metal phthalocyanine polycarboxylic acid is 0.5 × 10 ^{-3 to} 0.5
mol / l is preferred. When the alumina is immersed in the dissolving bath for about 20 to 120 minutes, the metal phthalocyanine polycarboxylic acid adheres. This is immersed in an acid bath to prevent the metal phthalocyanine polycarboxylic acid from being redissolved during washing with water. The acid bath is, for example, an aqueous solution of a lower organic acid such as formic acid or acetic acid, and is adjusted to pH 1.25 to 5 when alumina is added.

The type of alumina is not particularly limited, and known alumina can be used.

[Action]

Alumina, which is the base material of the deodorant, is porous and takes up when it comes into contact with malodorous substances. It is carried and catalyzed by metal phthalocyanine polycarboxylic acid, which causes a redox reaction to decompose malodorous substances and deodorize them. I do. In the metal phthalocyanine polycarboxylic acid, the central metal coordinates an electron to promote a redox reaction by a catalytic action similar to that of a biological enzyme.

〔Example〕

Hereinafter, a deodorant is produced according to the production method of the present invention, and its performance is evaluated.

<< Sample >> As the metal phthalocyanine polycarboxylic acid, iron phthalocyanine octacarboxylic acid manufactured by Nisshin Seifun KK is used.

As the carrier, two types of spherical alumina (hereinafter, referred to as alumina A and alumina B) manufactured by Toyo CCI are used. Table 1 shows the particle size and chemical composition.

Example 1 0.1 g of iron phthalocyanine octacarboxylic acid was added to 0.1 mol of
Stir and dissolve in 10 ml of NaOH aqueous solution, concentration 1.1 × 10 ^-2 mol / l, PH
= Prepare an immersion bath (hereinafter abbreviated as "Pc bath") of iron phthalocyanine octacarboxylic acid of 12.6-12.8. 0.9 g of alumina A (or alumina B) is immersed in the Pc bath for 30 minutes and taken out (bath ratio of alumina to Pc bath is 0.9 g / 10 g). this
Neutralization treatment is performed by immersion in a fixing bath of an acetic acid aqueous solution having a pH of 3.3 to 3.6 for 5 minutes to fix iron phthalocyanine octacarboxylic acid adhering to alumina. The temperature of the Pc bath is
Set to 21 ° C. It is washed with water until neutral, and then dried to obtain a deodorant.

0.16 g of the deodorant produced as described above is precisely weighed in a 100 ml beaker, 5 ml of nitric acid and 2 ml of perchloric acid are put, and the plate is covered with a watch glass and heated on a hot plate. When the form of alumina decomposes and nitric acid disappears, cool it down on a hot plate and cool. After natural filtration while washing the watch glass, beaker, etc., the volume is raised in a 100 ml volumetric flask.

The concentration is determined from a calibration curve using an acetylene combustion atomic absorption spectrophotometer. By quantifying the iron content,
The loading ratio of iron phthalocyanine octacarboxylic acid is calculated. The loading ratio of iron phthalocyanine octacarboxylic acid in the obtained deodorant was 0.18% by weight. Alumina B
As for the deodorant produced using the above method, 0.11 g of the deodorant was precisely weighed and subjected to the same quantitative analysis to find that the supporting rate was 0.53% by weight.

Example 2 << Change in loading ratio of iron phthalocyanine octacarboxylic acid due to change in bath ratio between alumina and Pc bath >> In Example 1, the bath ratio between alumina and Pc bath was 0.9 g / 10 g. Was changed to 0.23 g and 5.0 g, and the bath ratio was set to 0.23 g / 10 g and 5 g / 10 g, respectively. Others are Example 1.
A deodorant was produced in the same manner as described above, and the loading ratio of iron phthalocyanine octacarboxylic acid was determined. Bath ratio is 0.
Loading rate 0.16 wt% at 23 g / 10 g, loading rate 0.13 at bath ratio 5 g / 10 g
% By weight. Alumina B loading rate at bath ratio 0.23g / 10g
The loading ratio is 0.41% by weight at a bath ratio of 5g / 10g at 0.62% by weight.

Figure 1 shows alumina and Pc for alumina A and alumina B.
The change of the loading rate of iron phthalocyanine octacarboxylic acid according to the change of the bath ratio of the bath is illustrated.

Example 3 << Change in loading rate of iron phthalocyanine octacarboxylic acid due to change in Pc bath concentration >> In Example 1, the Pc bath concentration was 1.1 × 10 ^-2 mol / l (= 0.1 g / 10m).
l) is 1.1 × 10 ^-1 mol / l, 1.1 × 10 ^-3 mol / l, 5.5
× 10 ^-2 mol / l. Otherwise, a deodorant was produced in the same manner as in Example 1, and the loading ratio of iron phthalocyanine octacarboxylic acid was quantified. Alumina A has a Pc bath concentration of 1.1 × 10 ^-1 m
loading rate of iron phthalocyanine octacarboxylic acid at ol / l
1.08% by weight, 0.01% by weight at 1.1 × 10 ^-3 mol / l, 5.5 × 1
When it is 0 ^-2 mol / l, it is 0.95% by weight. In the case of alumina B, the loading rate of iron phthalocyanine octacarboxylic acid was 4.18% by weight when the Pc bath concentration was 1.1 × 10 ⁻¹ mol / l, and 0.1% when the concentration was 1.1 × 10 ⁻³ mol / l.
08% by weight and 3.83% by weight at 5.5 × 10 ^-2 mol / l.

FIG. 2 shows the change in the loading rate of iron phthalocyanine octacarboxylic acid with respect to the alumina A and alumina B depending on the concentration of the Pc bath.

Example 4 << Change in loading rate of iron phthalocyanine octacarboxylic acid depending on time for immersing alumina in Pc bath >> In Example 1, the time for immersing alumina in 30 minutes is 180 minutes and 10 minutes, respectively. Otherwise, a deodorant was produced in the same manner as in Example 1, and the amount of iron phthalocyanine octacarboxylic acid carried was determined. The immersion time for alumina A is 18
Loading rate of iron phthalocyanine octacarboxylic acid at 0 minutes
0.26% by weight, 0.13% by weight for 10 minutes. Alumina B
In this case, the loading rate is 0.63% by weight at 180 minutes and 0.21% by weight at 10 minutes.

FIG. 3 illustrates the change in the loading ratio of iron phthalocyanine octacarboxylic acid with respect to alumina A and alumina B due to the change in the time for immersing alumina in the Pc bath.

Example 5 << Change in loading rate of iron phthalocyanine octacarboxylic acid due to change in pH of Pc bath >> 12N hydrochloric acid was dropped into a Pc bath prepared in the same manner as in Example 1 using a dropper, and the PH of the Pc bath was adjusted as shown in Table 2 below. The deodorant was obtained in the same manner as in Example 1 except for the following.

Table 2 shows the loading ratio of iron phthalocyanine octacarboxylic acid for alumina A and alumina B when the pH of the Pc bath was changed.

Fig. 4 shows the pH of Pc bath for alumina A and alumina B.
3 shows the change in the loading ratio of iron phthalocyanine octacarboxylate due to the change in the amount of iron.

Example 6 << Change in loading rate of iron phthalocyanine octacarboxylic acid due to change in fixing bath PH >> In Example 1, the pH of the fixing bath was 3.3 to 3.6. ~ 1.3, 4.3 ~ 4.5. Otherwise, a deodorant was produced in the same manner as in Example 1, and the amount of iron phthalocyanine octacarboxylic acid carried was determined.
In the case of alumina A, the loading ratio of iron phthalocyanine octacarboxylic acid is 0.18% by weight when the pH is 1.2 to 1.3, and 0.1% by weight when the pH is 4.3 to 4.5.
20% by weight. In the case of alumina B, the loading is 0.30% by weight when the pH is 1.2 to 1.3, and 0.19% by weight when the pH is 4.3 to 4.5.

FIG. 5 shows the change in the loading rate of iron phthalocyanine octacarboxylic acid with respect to alumina A and alumina B due to the change in the fixing bath PH.

Example 7 << Change in loading rate of iron phthalocyanine octacarboxylic acid due to temperature change in Pc bath >> In Example 1, the temperature of the Pc bath was set at 21 ° C., but 0 ° C.
And 50 ° C. Otherwise, a deodorant was produced in the same manner as in Example 1, and the amount of iron phthalocyanine octacarboxylic acid carried was determined. In the case of alumina A, the loading rate of iron phthalocyanine octacarboxylic acid is 0.2% by weight when the temperature of the Pc bath is 0 ° C., and 0.17% by weight when the temperature is 50 ° C. 0 ° C for alumina B
Is 0.28% by weight at 50 ° C. and 0.33% by weight at 50 ° C.

FIG. 6 shows the Pc for alumina A and alumina B.
The graph shows the relationship between the loading rate of iron phthalocyanine octacarboxylic acid and the change in the temperature of the bath.

Example of use From among the deodorants experimentally produced in the above example, the pH of the Pc bath was changed from 11.9 to 12.0 with respect to Example 1 (PH = 12.6 to 12.8), and the others were manufactured in the same manner as in Example 1. The obtained deodorant can carry iron phthalocyanine octacarboxylic acid efficiently. Among these, the deodorant in which iron phthalocyanine octacarboxylic acid is supported on alumina A is referred to as deodorant A (loading rate: 0.18% by weight), and the deodorant in which iron phthalocyanine octacarboxylic acid is supported on alumina B is deodorized. Agent B (loading rate
0.87% by weight) as a sample for performance evaluation.

In addition to the above, for comparison, blank alumina A (alumina A without any support), blank alumina B (alumina B without any support), and deodorant A and deodorant using bentonite instead of alumina were used. A bentonite deodorant loaded with iron phthalocyanine octacarboxylic acid under the same conditions as the odorant B, and a zeolite deodorant loaded with iron phthalocyanine octacarboxylic acid using zeolite instead of alumina were also used for performance evaluation. Deodorant sample.

In addition, in order to know the tendency of the deodorizing performance due to the loading ratio of iron phthalocyanine octacarboxylic acid supported on alumina, among the deodorants experimentally manufactured as described above, the loading ratio of iron phthalocyanine octacarboxylic acid to alumina B was 4.18 wt. %, 3.83% by weight, 1.09% by weight, 0.53% by weight, 0.36% by weight, 0.08% by weight deodorant B (4.18), deodorant B (3.83), deodorant B (1.09), deodorant The performance of the deodorant B (0.53), deodorant B (0.36), and deodorant B (0.08) is evaluated as a deodorant sample.

<< Evaluation of Deodorizing Performance by Gas Detector Tube >> FIG. 7 schematically shows a process of evaluating the deodorant performance by the gas detector tube. 1 g of the deodorant sample 1 is put into a 1.5-liter fastener pack 3, and the air inside is discharged.
After 1.5 liters, hydrogen sulfide (H ₂ S), which is an odorous gas, is filled to a concentration of 130 ppm. The internal odor gas is sampled at regular intervals, the concentration of hydrogen sulfide is measured using the gas detection tube 7, and the residual ratio is determined. As the gas detection tube 7, a detection tube for high concentration and a detection tube for low concentration were used together.

Among the deodorant samples, the results of individually evaluating the performance of the deodorant A, the deodorant B, the blank alumina A, the blank alumina B, the bentonite deodorant, and the zeolite deodorant using a gas detector tube are as follows. This is shown in FIG. The horizontal axis of the figure indicates the elapsed time from the filling of the offensive odor gas to its collection, and the vertical axis indicates the residual rate of hydrogen sulfide (H ₂ S).

Among the deodorant samples, deodorant B (4.18), deodorant B (3.83), deodorant B (0.53), deodorant B (0.36),
FIG. 9 shows the results of performance evaluation of the deodorant B (0.08) and the blank alumina B.

<< Evaluation of Deodorizing Performance by Gas Chromatograph >> FIG. 10 shows an outline of a process of evaluating the deodorizing performance by gas chromatography.

1 g of the above deodorant sample 1 in a 1.5 l desiccator 10
After degassing the gas inside, the initial concentration of each was 13
0 ppm hydrogen sulfide (H ₂ S), methyl mercaptan (MM),
1.5 liter of mixed odor gas consisting of methyl sulfide (DMS) and methyl disulfide (DMDS) is enclosed. While stirring the mixed odorous gas with the magnetic stirrer 11, the internal gas is sampled at regular intervals using a gas tight syringe. The collected gas was introduced into a gas chromatograph 15 for concentration analysis.

FIG. 11 shows the results of gas chromatographic evaluation of deodorant performance of deodorant A for (a) and blank alumina A for (b) among the deodorant samples. In the figure, the horizontal axis indicates the elapsed time when the mixed malodorous gas was collected, and the vertical axis indicates the residual rate of each malodorous gas (H ₂ S, MM, DMS, DMDS).

FIG. 12 shows the results of evaluation of deodorant performance of mixed deodorant gas by gas chromatography on deodorant B (a) and blank alumina B on (b) among deodorant samples.

Select deodorant B (4.18), deodorant B (1.09), deodorant B (0.53) and blank alumina B from deodorant samples, and reduce the amount of deodorant 1 to 0.1 g. The results of evaluating the deodorizing performance of the mixed malodorous gas by gas chromatography are shown in (a) to (d) of FIG. 13 in order.
Ethyl mercaptan (EM) is mixed with the mixed malodorous gas for evaluating the deodorizing performance in addition to the above-mentioned gases (H ₂ S, MM, DMS, DMDS).

〔The invention's effect〕

As described above, since the deodorant produced by the production method of the present invention decomposes a malodorous substance by a catalytic action, it does not consume itself or contain a malodorous substance. Therefore, the service life is long, and there is no fear of secondary contamination by chemicals. According to the production method of the present invention, metal phthalocyanine polycarboxylic acid can be reliably and efficiently supported on alumina.

[Brief description of the drawings]

1 to 6 show the relationship between the change in the production conditions of the deodorant produced by the production method of the present invention and the loading of the deodorant component, and FIG. 7 shows an example of the evaluation of deodorant performance. Process schematic, eighth
Fig. 9 is a diagram showing the test results of the deodorant performance evaluated in the process, Fig. 10 is a schematic diagram of the process of another example of the evaluation of deodorant performance, Figs. It is a figure which shows the test result of the deodorant which evaluated performance. 1 deodorant 3 fastener pack 7 detection tube 10 desiccator 15 gas chromatograph

Continued on the front page (51) Int.Cl. ⁶ Identification code FI B01J 20/32

Claims (3)

(57) [Claims] 1. A method in which alumina is immersed in an alkaline bath in which a metal phthalocyanine polycarboxylic acid is dissolved to adhere the metal phthalocyanine polycarboxylic acid to the alumina. A method for producing a deodorant in which 0.01 to 5% by weight of metal phthalocyanine polycarboxylic acid is supported on alumina by washing with water and drying. 2. The alkaline bath is a solution selected from an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, an aqueous solution of sodium carbonate, and an aqueous solution of potassium carbonate, wherein the concentration of the metal phthalocyanine polycarboxylic acid is 0.5 × 10 ⁻³ to 0.5 mol. / L
The method for producing a deodorant according to claim 1, wherein: 3. The acid bath contains PH1.
The method for producing a deodorant according to claim 1 or 2, wherein the method is adjusted to be 25 to 5.