JPS62114647A - Deodorizing base material - Google Patents

Abstract

PURPOSE:To enhance the adsorbing capacity of an acidic malodorous gaseous component, by mixing specific granulated slag with a composition containing an iron (II) compound as a main component and having an org. acid component bonded to solid iron compound to adjust water content of the resulting mixture to 10wt% or more. CONSTITUTION:Fine powdery granulated slag is treated in an alkali solution having concn. of at least 0.5N for at least 30min and the treated granulated slag is separated by filtering, washed and dried to obtain granulated slag lowered in specific gravity, increased in a specific area and improved in surface characteristics. This granulated slag is neutralized with an org. acid to be mixed with a composition containing an iron (II) compound as a main component and having the org. acid component bonded to said iron compound to obtain a deodorizing base material with water content of 10wt% or more. The pref. mixing ratio of the iron (II) composition to granulated slag is 5-60wt%.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel deodorizing base comprising a combination of alkali-treated granulated slag and an iron(II) compound.

(Prior art) M1 composition (hereinafter referred to as iron (II)
II) The present inventors have previously discovered and proposed that M (referred to as acid) has extremely high activity and exhibits various functions (Japanese Patent Application Laid-Open No. 11/159-132937, No. 60-66753).
(Republication).

Especially this iron (II)! Lit products are impaired in their ability to adsorb and remove acidic gases such as ammonia and acid-containing 7I compounds.

(Problems to be Solved by the Invention) However, although the iron(II) composition described in -1- exhibits a deodorizing function that is significantly superior to conventional compositions, the adsorption performance is affected by the pH of the adsorbed gas. There is a drawback that the adsorption of acidic gas is inferior to that of ammonia gas, and it is necessary to overcome this point.
In terms of control, it was not yet satisfactory.

Furthermore, since iron (II) compositions alone are expensive, development of suitable carriers has been required from a practical standpoint.

(Means for Solving the Problems) As a result of extensive research in order to overcome the problems of the iron (II) composition described in F, the present inventors have discovered that the alkali treatment proposed by the present inventors earlier. Granulated slag (Patent No. 1115603
It was discovered that the cost could be lowered and the pH dependence could be overcome by mixing the water in a predetermined ratio and containing a predetermined amount of water, and based on this knowledge, the present invention was completed.

That is, the present invention provides finely powdered granulated slag at least 0.0%.
After treatment with a 5N alkaline solution for at least 30 minutes, the treated granulated slag was separated by filtration, washed with water, and then heated and dried to obtain a granulated slag with improved surface characteristics, with a lower bulk specific gravity and an increased specific surface area. For slag (hereinafter referred to as BS),
A deodorizing base (hereinafter referred to as the first
The invention is characterized in that, after neutralizing BS and BS with an organic acid, the granulated slag is mixed with a composition consisting mainly of an iron compound and an organic acid component bonded thereto. This invention provides a deodorizing base (hereinafter referred to as the second invention).

In the present invention (referring to the first invention and the second invention), the mixing ratio of the iron (n) composition to BS is preferably 5 to 60% by weight, more preferably 10 to 50% by weight, and 20 to 30% by weight.
% by weight is particularly preferred. 5% iron(II) composition by weight
If the iron(II) composition is less than
The amount is insufficient.

If the amount exceeds 60% by weight, the performance will not improve compared to the addition ratio of the iron(II) composition.

The BS used in the present invention is an inexpensive solid base with a large specific surface area, and can be prepared by the method described in Patent No. 1,115,603. This BS significantly improves the absorption of acidic gases (hydrogen sulfide, methyl mercaptan, methyl disulfide, and malodorous organic acids) as malodors due to its coexistence with the iron composition. Although it has a deodorizing effect, even a simple mixture of an iron (II) composition and BS exhibits its effect synergistically.

Examples of iron(II) compounds that are the main components of the iron(II) composition used in the present invention include ferrous sulfate, ferrous chloride, ferrous nitrate, ferrous bromide, and iodide. No.-
Iron, ferrous ammonium sulfate (such as iron)
II) In addition to inorganic salts, organic iron (II) salts such as ferrous gallate, ferrous malate, and ferrous fumarate can be mentioned. The iron(II) compound is not limited to those exemplified above, and any compound can be used as long as it dissolves in water and forms divalent iron ions.

In the present invention, organic acid is used in a broad sense. The organic acid component has the effect of stabilizing active divalent iron ions by coordinating with the divalent iron ions of the iron(II) compound. Examples of such organic acids include ascorbic acids, gluconic acids, and carboxylic acids. Here, the 7-scorbic acids refer to ascorbic acid, isoascorbic acid, alkali metal salts thereof, and include all of D-unit, L-unit, and DL-unit. Particularly preferred is L-ascorbic acid.

The carboxylic acids are not particularly limited, but oxyacids such as citric acid, ink citric acid, tartaric acid, malic acid, and the like can be used. Also, amino acid,
For example, ethylenediaminetetraacetic acids, 4,5-diaminopyrimidines, etc. are preferably used.

This iron (II) composition contains an iron (II) compound as a main component. The ratio of iron (II) in the iron (II) compound to the organic acid component is usually 1:0.02 to 0.30 (1'1Ht) when the organic acid component is ascorbic acid.
(7) lfi range is preferable, more preferably 1:0.
02-0.13, particularly preferably 1:0.03-0. lO
is within the range of Furthermore, when the organic acid component is a carboxylic acid such as citric acids, the ratio of iron(II) to the organic acid component is 1.
:O, 0f-o, ao is preferable. Even if organic acids are used in amounts exceeding the upper limit of the above-mentioned range, no improvement in effectiveness can be expected and it becomes uneconomical, while below the lower limit, freshness preservation and deodorizing functions become insufficient.

In the present invention, the organic acid component may be used alone or in combination of two or more. When used in combination, a combination of ascorbic acid and citric acid is preferred, and in this case, citric acid acts as an auxiliary stabilizer for ascorbic acid. Therefore, the amount should be small.

In addition, sodium chloride in this iron (■) composition is 0.5~
A content of 15% by weight is preferable in terms of promoting the deodorizing effect.

In order for the iron (II) composition of the present invention to exhibit activity, it is necessary that an iron (II) compound as a main component is bound to an m-acid component such as 7-scorbic acid, gluconic acid, or citric acid. is necessary. Such a composition is made by mixing both components once,
It can be prepared by drying and powdering the dissolved aqueous solution by spray drying, freeze drying, or the like.

It is also preferable to add alum to the iron(II) composition to stabilize the deodorizing unit.The amount of such alum added depends on the purpose and type of use of the deodorizing base! Although it varies depending on the island, 1% of the total amount of iron (■) compounds and organic acid components
The amount of alum used is up to 0.00% by weight, but preferably from 2 to 20% by weight.Although there are no particular restrictions on the alum, potassium alum, ammonia alum, sodium alum, etc. are preferred, with burnt alum being particularly preferred.

There is no particular restriction on the method for preparing the composition comprising BS and iron (H) composition of the present invention, but it is preferable to prepare the composition by mixing the powders of both in a predetermined ratio.
The specific surface area of the powder is preferably 50 to 70 rn'/g. This mixture is molded by a conventional method and used as a plate side or one tablet.

In the composition of the first invention, when a small amount of water is retained, the effect is further improved. Its water content is usually 10% by weight or more, preferably 10 to 50% by weight, and 20 to 50% by weight.
More preferably 30% by weight. Since BS has a water absorption rate of 60% or more of its own weight at saturated water vapor pressure, moisture adjustment can be achieved by leaving it in the place where it will be used.

In the composition of the second invention, a basic gas (ammonia,
In order to further increase the absorption of BS such as trimethylamine, BS may be neutralized with an organic acid and dried. Examples of such organic acids include monobasic acids such as acetic acid and propionic acid.

Dibasic acids such as maleic acid, malonic acid, succinic acid, oxalic acid, and other oxy-acids such as sungoic acid, tartaric acid, and citric acid! If BS treated with a base acid is mixed with an iron (II) composition and used in the form of powder or granules, it will not only be excellent in deodorizing basic gases such as ammonia, but also have the high specific surface area of BS. (60-100rn'/g
) becomes a modified surface layer, and gas components such as organic solvents (e.g. styrene, cresol, acetaldehyde, etc.)
It also shows affinity for, and can be applied to a wide range of applications. In this case as well, acid-treated BS and iron (mixture of acid-treated composition-11
The water content may be the same as above, and in this case, it is preferable to contain 5% or more of water, and more preferably a water content of about 5 to 10%.

A composition using such organic acid-treated BS can be prepared, for example, as follows. 510 g of B was added to 50 g of a 1-5% organic acid solution, and after stirring for 30 minutes, -
The iron(II) composition was added to the solution which was filtered and dried overnight at 110°C.

-50 tons Id 1%, preferably 25 to 30% by weight is supported to obtain an adsorbent having excellent adsorption properties for ammonia gas.

Furthermore, as a surface modification method for BS, an aqueous solution of an iron (II) composition was directly added to change the liquid from neutral to acidic, and from this a powder of the composition of the present invention having excellent ammonia odor removal performance was prepared. It's okay.

(Effects of the Invention) The present invention is composed of an iron (II) composition in which BS and M1 are combined, and exhibits significantly higher adsorption power for acidic malodorous gas components than when each is used alone.
Since the iron (II) composition originally exhibits high adsorption performance for ammonia gas, the adsorption performance is rarely affected by the pH of the malodorous gas, and it has the excellent effect of maintaining high activity for a long period of time. play. In particular, the 7iS2 invention's certain adsorbent base also exhibits adsorption properties for organic solvent-based gases.
II) The adsorption activity can be increased while reducing the content of the composition, and the cost advantage is also extremely large.

Such a composition of the present invention can be obtained by molding the mixture into a plate shape (60 to 150 kg/cm') or by simply compression molding.
Not only can it be used in the R& shape as housing, furniture, and packaging materials with deodorizing functions, but it can also be mixed as a feeler in plastics and used as molding materials and films with similar functions.

(Example) Next, Unreleased II will be explained in more detail based on an example. Note that the iron-7 scorbic acid used in the examples was equivalent to 190.0 L-amecorhif per 1 mole of iron in ferrous sulfate.
It is an agent that combines 3 moles. Moreover, BS was adjusted as follows.

[Preparation method] Decompose the sample according to method 8 of the following reference example.

Bulk specific gravity 0.584 Specific surface area 5? , 1.
m'/g [Reference Example 1] An example of preparing BS used for unreleased 1 is shown.

Table 1 100g of granulated slag with the particle size distribution shown in Table 1 was 3N
- Added to 1000 m of NaOH solution, treated at 90°C for 3 hours with stirring, then filtered and separated the treated granulated slag,
After hydration, the samples were dried at 110° C. (1) and the bulk specific gravity and specific surface area of each sample were determined. The result is second
As shown in the table.

Table 2 From the results in Table 2, it can be seen that in the particle size 41, 5-j with a particle size of 325 mesh or less was particularly abundant due to alkali treatment [this resulted in a significant decrease in bulk specific gravity and increase in specific surface area. Recognize.

[Example 1] 2.42 pieces of waste adjusted to an initial hydrogen sulfide concentration of 4,000 to 5,000 mfl/m' were placed in a tetrapar, and as a 7' scraper, BS and (ES) + (iron-ascorbic acid) (
Hereinafter, 1 g of powder (hereinafter referred to as iron (II) composition) is
It was pressurized to kg/crn' and molded to form a disc with a diameter of 13 mm. This is crushed into approximately 8 fractions, this deodorizing base is packed into a column of a deodorant analyzer, and a fixed concentration of dregs is passed through at a rate of 60 ffiin at a rate of 1 sentence/++in to adsorb it. The initial concentration and the gas concentration after 601n are measured and considered as the first time (one time). Next, the gas in Tetravac was replaced with the initial concentration, and adsorption was performed on the same adsorbent under the same conditions.The concentration of the treated gas after 60 fflin was measured, and the process was repeated approximately 8 times. The results are shown in Figure 1. Next, add 23.1% water to the above deodorizing base.
A similar test was conducted with the addition of % heavy machinery.

The graph in FIG. 1 is as follows.

N2
0 23.1G
30 23.1 As is clear from the drawing, in dry conditions, the adsorption amount of hydrogen sulfide is small with BS, a mixture of iron-ascorbic acid and BS, and iron-ascorbic acid alone. However, when BS is mixed with iron-ascorbic acid ( If you mix and mold BS with iron-ascorbic acid powder (approximately 30% solvent) or mix BS and iron-ascorbic acid powder (freeze-dried or spray-dried) and mold it, the adsorbent retains moisture, the properties of which are significantly improved. It can be seen that the results are improved.

This is due to the solid base properties of BS; hydrogen sulfide dissociates in the basic region and becomes ionic, and this sulfide ion (S'-) becomes a hydrosulfide ion (HS-). is converted into an iron (if) composition [Example 2] BSL:, Adsorption of H, S using a composition in which the addition of iron (II)-ascorbic acid and tz is changed. The test was conducted. When 200g of water is added to 1g of desiccant, the water content is 16.7%.

The results are shown in FIG. From the results shown in Fig. 2, this is the addition of iron (H)-ascorbic acid to BS.
It can be seen that even when P is changed from 20 to 40%, there is no significant difference in adsorption performance between these values.

[Example 3] Addition rate of iron-ascorbic acid to BS: 40+
In the case of IE%, a hydrogen sulfide adsorption test was conducted in the same manner as in Example 1 while changing the water content from 9.1 to 23.1%. The results are shown in Figure 3.

From the results shown in the figure, it can be seen that when the water content is about 10%, sufficient adsorption performance is not exhibited, but when the water content increases from about 15% to about 25%, the effect increases.

[Example 41 BS was treated with a 5% citric acid solution, and a composition in which this acid-treated BS was mixed with iron-ascorbic acid (iron (II) composition) at a predetermined ratio was used, and ammonia gas at a predetermined concentration was used. The adsorption test was conducted in the same manner as in Example 1 except for this.

The results are shown in Figure 4.

From the results in the same figure, it can be seen that BS treated with 5% citric acid and containing iron-ascorbic acid at a weight ratio of 1:1 are iron-
It can be seen that the adsorption performance is lower than that of 7 Scorbine m1OO% when the number of suctions is small, but when adsorption is repeated, the adsorption performance reverses.

[Brief explanation of drawings]

Figure 1 is a graph showing the relationship between the number of adsorption treatments and the residual concentration of hydrogen sulfide gas, and Figure 2 is a graph showing the relationship between the number of adsorption treatments and the residual concentration of hydrogen sulfide gas.
Graph showing the relationship between and the residual concentration of hydrogen sulfide gas, 3rd
The figure is a graph showing the relationship between the water content in the deodorizing base and the residual concentration of sulfide water and gas.
It is a graph showing the residual concentration of ammonia gas in Shiguro An using nS. Patent applicant Tatsudo Todoroki, Director of the Agency of Industrial Science and Technology Minato Sangyo Co., Ltd. Figure 1 Number of suctions (times) Figure 2 Number of suctions (times) Figure 3 Number of +oooo suctions (times)

Claims (4)

[Claims] (1) After treating finely powdered granulated slag with an alkaline solution of at least 0.5N for at least 30 minutes, the treated granulated slag is separated by filtration, washed with water, and then heated and dried.The bulk specific gravity is reduced and the specific surface area is reduced. It is made by mixing granulated slag with improved surface properties with increased water content and a composition containing an iron (II) compound as the main component and bonding an organic acid component thereto.
A deodorizing base characterized by having a content of 0% by weight or more. (2) The deodorizing base according to claim 1, which contains 5 to 60% by weight of a composition comprising an iron (II) compound as a main component and combined with an organic acid component. (3) After treating finely powdered granulated slag with an alkaline solution of at least 0.5N for at least 30 minutes, the treated granulated slag is separated by filtration, washed with water, and then heated and dried to obtain a product with a reduced bulk specific gravity and a specific surface area. After neutralizing the granulated slag with improved surface properties with increased iron (I)
I) A deodorizing base comprising a compound as a main component and a composition formed by bonding an organic acid component thereto. (4) Claim 3 in which the water content is 5% by weight or more
Deodorizing base as described in section.