JP2008272225A - Solid deodorizing composition to deodorize plurality of odor ingredients with single agent and manufacture process of this composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solid deodorizing composition that has excellent effects in concurrently deodorizing acid, alkaline and neutral gases with a single deodorizing agent without corroding the device for deodorization, and to provide the manufacture process of this composition. <P>SOLUTION: This solid deodorizing composition contains iron sulfate, slaked lime, active carbon and humus earth, and the solid content of the iron sulfate is 10 to 50 wt.% of the total solid deodorizing composition volume and has pH6 to 8. The manufacture process of the solid deodorizing composition is such that the slaked lime, active carbon and humus earth are prepared beforehand and then the solution of iron sulfate is added and mixed together with them, followed by the process of pelletizing and drying the mixture. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a solid deodorizing composition for deodorizing a plurality of odor components with one agent and a method for producing the composition.

  As deodorizers for various harmful gases and odorous gases, deodorizers using physical adsorption of these gas components have been widely put into practical use, and as such deodorizers, activated carbon and zeolite such as solid deodorizers are used. Mineral porous materials are known. Further, in order to obtain a higher deodorizing effect, the surface treatment of the solid deodorizer is performed according to the type of malodor, and the performance is improved.

  Generally, when deodorizing multiple odor components such as acid gas, basic gas and neutral gas, activated carbon for acidic gas, activated carbon for basic gas and activated carbon for neutral gas are known in activated carbon deodorization tower. It has been. However, in such a method, in order to deodorize a plurality of odor components, three types of activated carbon are deodorized so as to contact the gas in the order of activated carbon for acidic gas, activated carbon for basic gas, and activated carbon for neutral gas. It had to be thrown into the tower, and the work was complicated to prevent mistakes in the order.

  In such circumstances, a method of mixing two types of activated carbon in advance to make one agent has been proposed from the viewpoint of the convenience of maintenance and management of the activated carbon deodorization tower (for example, see Patent Document 1). However, for example, when alkali-added activated carbon impregnated with caustic soda and acid-added activated carbon impregnated with sulfuric acid are mixed, there is a problem that a neutralization reaction occurs at the contact surface between the two and the deodorizing effect is reduced. Especially when high-humidity gas is ventilated or when gas is ventilated while condensation occurs in winter, neutralized salt is deposited on the contact surface of the two types of activated carbon, and the activated carbon is solidified (blocking). Occurred, and the deodorizing ability was reduced.

  Furthermore, an adsorbent that can simultaneously deodorize acidic gas, basic gas, and neutral gas by adding an oxidizing agent to the porous sintered body is also known (see, for example, Patent Document 2). However, in the adsorbent, since the oxidizing agent is held or infiltrated inside, there is a problem that when the high-odor malodorous gas passes, the oxidizing agent is detached and the apparatus is corroded. The adsorbent does not contain an iron compound.

  Similarly, in the case of deodorizing acidic gases such as hydrogen sulfide and methyl mercaptan among odor components, the surface of the solid deodorizer is surface treated with a basic substance such as caustic soda and chemically neutralized and deodorized with acidic gas. It has been known. However, in such a method, there is a problem that, when a high-humidity malodorous gas passes, the basic substance adsorbed on the surface of the solid deodorant is desorbed and the apparatus is corroded.

  In addition, a desulfurization agent that uses fine particles of slaked lime containing iron ions as a desulfurization component has been proposed (see, for example, Patent Document 3). However, the desulfurization agent is an alkaline desulfurization agent mainly composed of slaked lime, and cannot solve problems such as corrosion of the apparatus.

  On the other hand, humic soils are known to absorb and adsorb various substances and have exchange and buffering effects, and are used as deodorants, water purifiers, and chelating agents. However, a deodorizer obtained by molding only humic soil using a binder has a problem that a sufficient deodorizing effect cannot be obtained.

  Therefore, it is desired to develop a deodorant that can deodorize acid gas, basic gas, and neutral gas simultaneously with one agent (one kind), which is advantageous for maintenance management, without corroding the apparatus.

JP 2005-66457 A JP 2001-137701 A Japanese Patent Laying-Open No. 2005-87893

  The present invention provides a solid deodorizing composition for deodorizing a plurality of odor components with one agent, which enables a highly convenient activated carbon deodorizing tower that is easy to maintain and maintain without corroding the apparatus, and a method for producing the composition. The purpose is to provide.

  That is, the present invention includes iron sulfate, slaked lime, activated carbon, and humic soil, the content of the iron sulfate is 10 to 50% by weight as the solid content in the total amount of the solid deodorizing composition, and the pH is 6 to 8 It is related with the solid deodorizing composition which is.

  The iron sulfate is preferably one or more compounds selected from the group consisting of ferrous sulfate, ferric sulfate and polyferric sulfate.

  The activated carbon is preferably activated carbon made of one or more raw materials selected from the group consisting of woody material, coconut husk and coal.

  It is preferable that the humic soil is a soil containing 10% by weight or more of humic substances.

  It is preferable that content of humic soil is 10 to 30 weight% in the whole quantity of a solid deodorizing composition.

  Furthermore, it is preferable that a binder is included.

  Moreover, this invention relates to the manufacturing method of the said solid deodorizing composition including the process of granulating and drying after previously mix | blending slaked lime, activated carbon, and humic soil, adding and mixing an iron sulfate solution.

  It is preferable to further include a step of adding and mixing a binder after adding and mixing the iron sulfate solution.

  The present invention includes iron sulfate, slaked lime, activated carbon, and humic soil, and the content of the iron sulfate is 10 to 50% by weight as the solid content in the total amount of the solid deodorizing composition, and the pH is 6 to 8. Thus, a solid deodorizing composition capable of simultaneously deodorizing acidic gas, basic gas and neutral gas with one agent without corroding the apparatus can be provided.

  The present invention includes iron sulfate, slaked lime, activated carbon, and humic soil, and the content of the iron sulfate is 10 to 50% by weight as a solid content in the total amount of the solid deodorizing composition, and the pH is 6 to 8. The present invention relates to a solid deodorizing composition.

  The iron sulfate used in the present invention is preferably one or more compounds selected from the group consisting of ferrous sulfate, ferric sulfate and polyferric sulfate, and polyferric sulfate is more preferable. .

Polyferric sulfate is a compound represented by [Fe ₂ (OH) _n (SO ₄ ) _{3 -n / 2} ] _m (0 <n ≦ 2, m = f (n)), and is commercially available. Can be used. Examples of commercially available products include Polytetsu (registered trademark) (trade name, manufactured by Nittetsu Mining Co., Ltd.).

  Content of iron sulfate is 10-50 weight% as solid content in the whole quantity of a solid deodorizing composition, and it is preferable that it is 20-40 weight%. If the content of iron sulfate is less than 10% by weight, a sufficient deodorizing effect tends not to be obtained, and if it exceeds 50% by weight, a sufficient deodorizing effect tends not to be obtained. Since drying requires a long time, it is not preferable economically.

  In the present invention, slaked lime is added to neutralize iron sulfate. When neutralized with slaked lime, gypsum is by-produced. The by-product gypsum is preferable because it is hardly soluble in water and thus does not elute from the pellets even when high-humidity gas is passed. On the other hand, for example, sodium sulfate is by-produced when neutralized with sodium hydroxide. Since the by-product is easily dissolved in water, it is not preferable since it may be eluted from the pellets when a high-humidity gas is passed through, and the granulated material may collapse and be pulverized. Therefore, a basic compound other than slaked lime cannot provide a sufficient deodorizing effect.

  The slaked lime content is not particularly limited as long as the amount necessary to neutralize iron sulfate is added, but is preferably 5 to 25% by weight in the total amount of the solid deodorizing composition, More preferably, it is 10 to 20% by weight. If the content of slaked lime is out of this range, iron sulfate cannot be sufficiently neutralized, and the device tends to corrode.

  Moreover, the compounding ratio of iron sulfate and slaked lime is not particularly limited, but is preferably slaked lime / iron sulfate = 0.4 to 0.6 (weight ratio), 0.5 to 0.6 ( (Weight ratio) is more preferable. If the blending ratio of slaked lime is less than 0.4, the pH of the solid deodorizing composition tends to be less than 6, and the device tends to corrode. If it exceeds 0.6, the pH of the solid deodorizing composition exceeds 8, and the device There is a tendency to corrode.

  The activated carbon used in the present invention is not particularly limited, and various activated carbons can be used. As activated carbon, graphite; coal such as lignite and bituminous coal; mineral materials such as petroleum or coal pitch; woody materials such as sawdust, thinned wood, and demolition waste; plant materials such as fruit shells (coconut husks); Animal materials such as bones and skins; activated carbons made from polymer materials such as polyacrylonitrile (PAN), phenolic resins, cellulose, and regenerated cellulose. These may be used alone or in combination of two or more. Can be used. Among these, the activated carbon which consists of 1 or more types of raw materials selected from the group which consists of a woody material, coconut husk, and coal is preferable from the point that it can obtain cheaply.

  The shape of the activated carbon is not particularly limited, but may be granular (powdered) or fibrous.

  The average particle diameter of the granular activated carbon is preferably 1-1000 μm, and the average fiber diameter of the fibrous activated carbon is preferably 10-50 μm.

The specific surface area of the activated carbon is preferably 100~1500m ² / g, more preferably 200~1000m ² / g. If the specific surface area is less than 100 m ² / g, the deodorizing effect tends to decrease, and if it exceeds 1500 m ² / g, the activated carbon price increases, which is economically undesirable.

  The content of activated carbon is preferably 5 to 80% by weight, and more preferably 5 to 60% by weight, based on the total amount of the solid deodorizing composition. If the content of the activated carbon is less than 5% by weight, it takes a long time to dry the solid deodorizing composition, which is not economically preferable. Moreover, when it exceeds 80 weight%, there exists a tendency for sufficient deodorizing effect not to be acquired.

  The humic soil used in the present invention is a volcanic ash soil that is mainly composed of allophane soil, which is an amorphous clay mineral, and contains organic components such as humic acid, nitrohumic acid, and fulvic acid. This soil is called dark soil.

  The humic soil used in the present invention preferably contains 10% by weight or more of organic components, and more preferably contains 15% by weight or more. There exists a tendency for the deodorizing effect with respect to basic gas to fall that content of an organic component is less than 10 weight%.

  The blending amount of the humic soil is preferably 5 to 60% by weight, and more preferably 10 to 30% by weight, based on the total amount of the solid deodorizing composition. When the content of humic soil is less than 5% by weight, there is a tendency that a sufficient deodorizing effect for basic gas cannot be obtained, and when it is 60% by weight or more, a sufficient deodorizing effect for neutral gas cannot be obtained. Tend.

  In addition, the solid deodorizing composition of the present invention may further contain a binder component in order to form into an appropriate shape (for example, granular shape, sheet shape, honeycomb shape, etc.).

  Examples of the binder component include urethane resin, acrylic resin, polyester-based biodegradable resin, carboxymethyl cellulose (CMC), starch, sodium alginate, xanthan gum, guar gum, carrageenan, polyvinyl alcohol, and the like. Two or more types can be used in combination. Among these, polyvinyl alcohol is preferable from the viewpoint of deodorization performance and production cost.

  As the addition amount of the binder component, the total solid content of the solid deodorizing composition is 100, and it is preferable to add 0.1 to 15% by weight as the solid content, and 1 to 5% by weight. More preferably, it is added.

  Various additives can be blended with the solid deodorizing composition of the present invention to the extent that the effects of the invention are not impaired. Specific examples of such additives include bentonite, attapulgite, sepiolite, zeolite and the like.

  Moreover, pH of the solid deodorizing composition of this invention is 6-8, and it is preferable that it is 6.5-7.5. If the pH is out of this range, the device tends to corrode, which is not preferable.

  Here, the pH of the solid deodorizing composition is indicated by a value measured by the following method.

  3 g of a solid deodorizing composition (granulated product) is weighed in a 100 cc Erlenmeyer flask, 100 cc of water is added and the total weight is measured. After it reaches room temperature, weigh the total weight and add a short amount of distilled water before boiling. The pH of the aqueous solution of the obtained solid deodorant is measured with a pH meter, and this value is defined as the pH of the solid deodorant composition of the present invention.

  Moreover, as a manufacturing method of the solid deodorizing composition of this invention, it is preferable to mix | blend slaked lime, activated carbon, and humic soil previously, and after adding and mixing an iron sulfate solution, granulating and drying and manufacturing are preferable.

  The iron sulfate solution is preferably an iron sulfate aqueous solution. Moreover, the density | concentration of an iron sulfate solution is not specifically limited, It can determine suitably.

  Preliminary blending of slaked lime, activated carbon and humic soil is preferable because it can prevent sudden generation of heat of neutralization and uniformly disperse iron hydroxide produced by neutralization.

  As the granulation method and the drying method, usual methods can be used. For example, the granulation method can be granulated by a compression granulator or an extrusion granulator, and dried by a vibration dryer, a fluidized bed dryer or the like. .

  Moreover, in the said manufacturing method, after adding and mixing an iron sulfate solution, it is preferable to further include the process of adding and mixing a binder.

  Examples of gases that can be deodorized by the solid deodorizing composition of the present invention include acidic gases such as hydrogen sulfide and methyl mercaptan, basic gases such as ammonia and trimethylamine, and neutral gases such as methyl sulfide and methyl disulfide.

  Moreover, the solid deodorizing composition of this invention can be used suitably as a filler of a dry adsorption deodorizing tower.

  Next, the present invention will be described with reference to examples, but the present invention is not limited to such examples.

<Measurement of physical properties of granulated product>
(PH)
(1) Weigh 3 g of the granulated material in a 100 cc Erlenmeyer flask, add 100 cc of water, and measure the total weight.
(2) Place on a hot plate and continue boiling gently for 5 minutes, then allow to cool at room temperature. After it reaches room temperature, weigh the total weight and add a short amount of distilled water before boiling.
(3) Measure the pH with a pH meter. The measured value is taken as the pH of the granulated product.

(hardness)
(1) Weigh the graduated cylinder in advance, then fill the pellet sample up to the 100 cc mark, measure the total weight, and then determine the sample weight.
(2) Thirty steel balls (diameter 11 mm) and 100 cc of the above sample are put into a sieve receiver, and a sieve cover is put on a sieve shaker for 30 minutes.
(3) Transfer the sample from which the steel balls of the receiver have been removed to another 10-mesh sieve weighed in advance, and put it on a sieve shaker for 3 minutes.
(4) The total weight of the sieve is measured, and the hardness is calculated by the following formula.
Hardness (%) = (sample weight on 10 mesh sieve) / (total weight of sample) × 100

(Granularity)
(1) The empty weight of a 7.5 mesh sieve is measured in advance.
(2) Set the sieve receiver in the order of 7.5 mesh and 3.5 mesh, put 100 g of the accurately weighed sample, cover the sieve lid, set on a sieve shaker, and shake for 10 minutes.
(3) Take out a 7.5 mesh screen and measure the total weight.
(4) Particle size (%) = (7.5 mesh total sieve weight−sieving weight) / sample weight × 100

<Deodorization performance evaluation method>
(Hydrogen sulfide)
(1) 5 g of the granulated sample was put into a 5 L tedra bag and filled with 3 L of odorless air.
(2) The initial hydrogen sulfide concentration was injected with a microsyringe so that the concentration was 100 ppm, and the hydrogen sulfide concentration after 30, 60, and 120 minutes from the injection point was measured with a detector tube. In addition, the blank test which does not throw in the granulated material was also implemented, and it confirmed that the hydrogen sulfide concentration was 100 ppm.
(3) The deodorization rate was calculated by the following formula.
Deodorization rate (%) = (100− (measured value)) / 100 × 100

(ammonia)
The deodorization rate was determined by setting the initial ammonia concentration to 800 ppm as in the case of hydrogen sulfide.

(Methyl sulfide)
The deodorization rate was determined in the same manner as hydrogen sulfide, with an initial methyl sulfide concentration of 10 ppm.

Examples 1-5 and Comparative Examples 1-4
The amount of activated carbon, slaked lime, humic soil and additives shown in Table 1 are put into a saucer of a small mixer (made by MARUI), and the aqueous solution of iron sulfate and binder solution shown in Table 1 are added while stirring. I put it in. After the addition, the mixture was stirred for 5 minutes to obtain a granulating powder. The total amount of the solid content of the deodorant composition was 100, and 2% by weight of the solid content was added in an external number.

  The whole amount of the obtained granulating powder was put into a disk pelleter (F-5 / 11 type manufactured by Fuji Powder Co., Ltd.) to obtain a cylindrical granulated product having a diameter of 5 mm. Thereafter, the obtained granulated product was dried for 2 hours with a constant temperature dryer at 105 ° C. to obtain a granulated product for evaluation. Table 1 shows the physical properties (pH, hardness and particle size) of the obtained granulated product. Moreover, the deodorization rate of hydrogen sulfide, ammonia, and methyl sulfide of the obtained granulated product was evaluated. The results are shown in Tables 2, 3 and 4, respectively.

  The detail of each raw material used in Examples 1-6 and Comparative Examples 1-4 is shown below.

<Iron sulfate>
a) Aqueous polyferric sulfate aqueous solution (trade name: Polytetsu (registered trademark), manufactured by Nittetsu Mining Co., Ltd., solid content concentration: 40% by weight)
b) Ferric sulfate aqueous solution (concentration: 40% by weight)
c) Ferric sulfate aqueous solution (concentration: 30% by weight)

<Slaked lime>
Slaked lime (special slaked lime (manufactured by Yumihashi Kogyo Co., Ltd.))

<Activated carbon>
a) Coconut shell activated carbon: specific surface area 800 m ² / g, average particle size 120 μm, moisture 8%
b) Coal-based activated carbon: specific surface area 600 m ² / g, average particle size 100 μm, moisture 10%
c) Wood-based activated carbon: specific surface area 500 m ² / g, average particle size 130 μm, moisture 6%

<Humus soil>
a) Humic soil with 17% organic content: Kagoshima Prefecture b) Humic soil with 10% organic component: Mie Prefecture c) Humic soil with 5% organic component: Yamagata Prefecture

<Additives>
a) Attapulgite (trade name: SGB (manufactured by Zemex Attapulgite LLC))
b) Sepiolite (trade name: Milen SP (manufactured by Showa Mining Co., Ltd.))

<Binder>
a) 7.7 wt% aqueous solution of polyvinyl alcohol (PVA) (trade name: Gozenol KH-17 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)) b) water-based urethane resin (trade name: Superflex 860 (Daiichi Kogyo Seiyaku) 13) of polyester-based anionic water-based urethane resin) 40% by weight aqueous solution c) polyester-based biodegradable resin (trade name: Prasema L110 (Daiichi Kogyo Seiyaku Co., Ltd.), polylactic acid emulsion) % By weight aqueous solution

  As is apparent from Table 2, it can be seen that there is an effect of sufficiently deodorizing hydrogen sulfide regardless of the blending amount of humic soil.

  As can be seen from Table 3, when no humic soil is added (Comparative Examples 1 to 3), the deodorization rate of ammonia is low, and it is understood that a sufficient deodorizing effect cannot be obtained. In addition, it can be seen that ammonia increases the deodorization rate when the humic soil increases.

  As can be seen from Table 4, when activated carbon is not blended (Comparative Example 3), the deodorization rate of methyl sulfide is low and the deodorizing effect is not sufficient.

Example 6
In a small mixer (made by MARUI), 30 parts by weight of activated carbon, 12 parts by weight of slaked lime, 30 parts by weight of humic soil (17% by weight of organic components) and 4 parts by weight of attapulgite are added, and while stirring, 60 parts by weight of a ferric sulfate aqueous solution and a polyvinyl alcohol aqueous solution as a binder were added. After the addition, the mixture was stirred for 5 minutes to obtain a granulating powder. The total amount of the solid content of the deodorant composition in the polyvinyl alcohol aqueous solution was 100, and 2% by weight of the solid content was added in an external number.

  The whole amount of the obtained granulating powder was put into a disk pelleter (F-5 / 11 type manufactured by Fuji Powder Co., Ltd.) to obtain a cylindrical granulated product having a diameter of 5 mm. Thereafter, the obtained granulated product was dried for 2 hours with a constant temperature dryer at 105 ° C. to obtain a granulated product for evaluation. The obtained granulated material was used for the following tests.

Test example 1
The entrance odor of the activated carbon deodorization tower in the sewage treatment plant (containing the odor components shown in Table 4) was passed through a small deodorization device (diameter 20 cm, filling height of solid deodorization composition 1.5 m) at a gas passage speed of 0.116 m / s. Then, aeration was conducted for 1 year under the condition of a contact time of about 13 seconds, and the malodor concentration at the inlet and outlet was measured. Each odor component was measured according to Environmental Agency Notification No. 9.

  The results are shown in Table 5.

  From Table 5, it turns out that the solid deodorizing composition of this invention can deodorize several odor of acidic gas, basic gas, and neutral gas simultaneously.

Claims (8)

A solid deodorizing composition comprising iron sulfate, slaked lime, activated carbon and humic soil, wherein the content of the iron sulfate is 10 to 50% by weight as a solid content in the total amount of the solid deodorizing composition, and the pH is 6 to 8 . The solid deodorizing composition according to claim 1, wherein the iron sulfate is at least one compound selected from the group consisting of ferrous sulfate, ferric sulfate and polyferric sulfate. The solid deodorizing composition according to claim 1 or 2, wherein the activated carbon is activated carbon composed of one or more raw materials selected from the group consisting of woody material, coconut husk and coal. The solid deodorizing composition according to any one of claims 1 to 3, wherein the humic soil is a soil containing 10 wt% or more of humic substances. The solid deodorizing composition according to any one of claims 1 to 4, wherein the content of the humic soil is 10 to 30% by weight in the total amount of the solid deodorizing composition. Furthermore, the solid deodorizing composition in any one of Claims 1-5 containing a binder. The manufacturing method of the solid deodorizing composition in any one of Claims 1-6 including the process of granulating and drying, after previously mix | blending slaked lime, activated carbon, and humic soil, adding and mixing an iron sulfate solution. The manufacturing method according to claim 7, further comprising a step of adding and mixing a binder after adding and mixing the iron sulfate solution.