KR101629910B1 - Manufacturing method for deodorant compounding using the waste coal ash - Google Patents

Abstract

A method for producing a composite deodorant using waste coal ash is disclosed. In the present invention, odorous substances to be deodorized are selected for the zeolite obtained by converting the clay minerals into alpine-based clay minerals by the acid treatment of fly ash, adding an alkali aqueous solution, dewatering and washing with water, It is expected that by adding 1 to 50 wt% of one or two selected from strontianite (SrCO 3), it is possible to selectively produce a deodorant according to the type and use of the odor removing type.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for manufacturing a composite deodorant using waste coal ash,

The present invention relates to a method for producing a composite deodorant using waste coal, and more particularly, to a method for producing a nanocomposite deodorant having high use stability and odor removal efficiency by using waste coal ash.

When coal is burned in coal-fired power plants or steel mills (1,400 to 1,700 ° C), clay minerals that are non-combustible are not burned but are melted by energy and are scattered along with the exhaust gas. Cooled and collected and discharged in the state of spherical particles in a fine state. As shown in Table 1, the chemical composition of domestic coal fly ash is about 70 wt% or more of silica (SiO ₂ ) and alumina (Al ₂ O ₃ ), about 5 wt% of iron oxide (Fe ₂ O ₃ ) (MgO), sodium oxide (Na ₂ O), potassium oxide (K ₂ O), SO ₃ , and TiO ₂ , P ₂ O ₃ and the like, and anhydrous amorphous aluminum silicate Non-crystalline aluminosilicate).

Chemical composition of domestic coal fly ash division SiO ₂ Al ₂ O ₃ Fe ₂ O ₃ CaO MgO Na ₂ O K ₂ O SO ₃ lg.loss F.A. 49.5 29.9 4.7 0.6 0.6 - 3.8 0.1 9.0 B.A. 47.7 25.4 5.7 0.6 0.7 - 3.3 0.1 15.3

F.A: Fly Ash B.A: Bottom Ash (The constituents of fly ash generated in a power plant may vary depending on the method of power generation, fuel used, etc.)

As shown in Table 2 below, the trend of recycling of fly ash from thermal power plants has increased from 20 ~ 30% in the middle and late 1990s to around 60 ~ 70% after 2010 The amount of coal ash is still abundant, environmental pollution is serious and the recycling rate of waste coal ash is still insufficient. Effective recycling of wastes is known to reduce the cost of waste disposal by more than 30%, as well as extend the life time of resources by more than 40% by utilizing waste resources.

Category / Year 1997 1998 1999 2000 2004 2006 2008 2009 Fly ash generation (10,000 tons) 320 366 395 443 561 584 761 835 Recycled (10,000 tons) 87 116 168 242 434 389 513 525 Recycling rate (%) 27.2 32.2 42.5 54.6 77.4 66.6 67.4 62.8

Source: Kim, Chang-hyun, Electric Power Industry and Environmental Impact (2009)

Unusual is that artificial zeolite can be synthesized from fly ash, which has high value-added recyclability. Since zeolite has a high cation exchange capacity (CEC), it has excellent adsorption ability of cations such as nitrogen and heavy metals and plays a role of carrier in the growth of microorganisms. Therefore, nitrogen and heavy metals It is also used as a soil remediation agent because it has excellent bibbing power and excellent soil improvement effect. The zeolite consists of alumino-silicates in which the basic structure of AlO ₄ and SiO ₄ tetrahedra, each structurally linked by oxygen, is bounded in three dimensions infinitely. The basic structure consists of a sodalite unit. In the case of the A type zeolite, the D4R structure is formed. The X and Y types have a three-dimensional shape of the D6R structure.

Research papers on the synthesis of zeolites using the principle of zeolite formation by fly ash treatment are described in International Journal of Microporous and Mesoporous Materials (Marion Gross et al., Vol.104, page 67-76, 2007., available online , And 'Chemical Engineering', Theory and Applications of Chemical Engineering, Vol. 10, No. 2 (Cho, Hun-Ho, (Investigation of Ammonia Nitrogen Adsorption Characteristics on Zeolite Synthesized by Fly Ash, 41, 4, pp. 537 ~ 541, 2003).

Allophane, which is an amorphous silicate aluminum salt, is produced by warming the fly ash (pH = 4-6). When the pH is lower than 2, the anion exchange capacity (AEC) Imogolite, which is a crystalline aluminum silicate salt of high water content, is produced and warmed in an alkali state to produce a zeolite having a high cation exchange capacity (CEC).

Alphalane clay minerals are mainly composed of silanol groups (Si-OH), silicon (Si), aluminum (Al), oxygen (O) and hydrogen (H) (Aluminosilicate) clay mineral with a structure in which silicic acid is condensed (dehydrically bonded) to a site of Al (OH) H2O group of active aluminum and each of hollow spherical particles Spherical particles) are also called amorphous clay because they are randomly bound to silicon, aluminum, oxygen, and hydrogen without X-ray diffraction and appear as amorphous in X-ray diffraction.

The fly ash is an amorphous anhydrous aluminum silicate, which is an amorphous aluminum silicate, the difference being that the fly ash is anhydrous, whereas alafane is a volatile. When it reacts with alkali, alafane is converted into zeolite by crystallization, and anhydride coal ash is converted into zeolite by crystallization when it reacts with alkali.

Using the above-described generation principle of zeolite, Korean Unexamined Patent Application Publication Nos. 10-1999-0065036, 10-2007-0046294, 10-2008-0112620 and Japanese Unexamined Patent Publication Nos. 59-86687, 9-255324, 2001 -146417, 2001-220132, and 10-2007-0046294 disclose methods for artificially preparing zeolite by alkali treatment of fly ash. For example, zeolite low-temperature granulation of fly ash, production of artificial zeolite from coal fly ash, synthesis of A- and P-type zeolites using microwave heat source, synthesis of fly ash zeolite using Y-type fly ash zeolite seed powder, (Acrylonitrile) or poly (furfuryl alcohol) formed in the pupil using a Y-zeolite as a carbon / zeolite composite, or a colloid-imprinted carbon (CIC) Of ZSM-5.

On the other hand, an adsorbent used for removing air and water contaminants, separation and purification of a mixture from zeolite synthesis using the properties of fly ash can be produced. The adsorbent thus prepared has high selectivity for specific components These results were obtained by hydrothermal treatment of coal fly ash with alkali at high temperature or synthesis of zeolite by hydrothermal treatment of fly ash with aqueous alkaline solution. These zeolites have high cation exchange capacity Zeolite is used for various purposes such as ion exchangers, catalysts, adsorbents and dehydrating agents, and is widely used in the separation process due to the adsorption and separation characteristics of zeolite. The industrial application is also used as a raw material for various kinds of pharmaceuticals including odor treating agent, drying, adsorption, catalyst and dehumidifying agent of wastewater. The main application fields currently being used in domestic and foreign countries are the use as a soil and water quality improving agent, Treatment of radioactive waste, use of synthetic detergent as a cleaning aid, and the like.

A proposal related to the application of zeolite has been proposed as an antibacterial mask utilizing zeolite of Korean Patent Application No. 10-2004-0093358, a polymer resin composite for antibacterial and deodorization utilizing zeolite of Korean Patent Application No. 10-2011-0074952 The zeolite component used is closer to natural zeolite than zeolite produced from fly ash. That is, the use of natural zeolite is recommended for deodorants and pharmaceutical raw materials of articles which are contacted with human body, classified as soil improving agent or everyday household goods, and the like because stability is a problem rather than zeolite produced from fly ash.

Most of the fly ash contains a large amount of water-soluble minerals that are activated by energy when the minerals are burned, and harmful heavy metals such as copper, cadmium, and chromium are harmful to the human body. When a zeolite product in which a harmful heavy metal component is not removed is used for medical products such as an everyday household article and an antibacterial mask which are in contact with a human body, the harmful action to the human body can be given.

Patent Document 1. Korean Patent Laid-Open Publication No. 10-1999-0065036 Patent Document 2: Korean Patent Laid-open Publication No. 10-2007-0046294 Patent Document 3. Korean Patent Application No. 10-2011-0074952

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art, and an object of the present invention is to provide a deodorant having high stability, which can be used as a deodorant of human contact household goods by removing the harmful heavy metals contained in fly ash during the synthesis of zeolite And a deodorizing performance is controlled according to a substance to be removed.

According to another aspect of the present invention, there is provided a method of manufacturing a composite deodorant using waste coal ash, comprising the steps of: heating coal fly ash, adding hydrochloric acid (HCl) Aluminum chloride is converted to clay minerals, which are aluminum salts. The harmful heavy metal components of the alpine-in clay minerals are dehydrated and washed, and an alkali aqueous solution of 50 to 80 wt% is added to the allophane clay minerals. To a stirring reaction for 6 hours or more, followed by dewatering, washing with water and drying; Analyzing the Al and Si composition ratios of the zeolite and adding alumina (Al ₂ O ₃ ) and silicic acid (SiO ₂ ) to the composition ratio of Al and Si to adjust the composition of the zeolite; Adding magnesium (MgO) selected as deodorizing center material to the zeolite whose constituent composition has been adjusted from the above step; Selecting a substance to be deodorized as a malodor substance to be deodorized from one of toluene, xylene, or a compound thereof; Adding 1 to 30 wt% of one or two selected from platinum chloride (PtCl ₆ ), strontianite (SrCO ₃ ) to the zeolite according to the selected odor substances; Mixing the zeolite and the additives in a vacuum mixer and mixing them uniformly; Adding the mixed zeolite and the additive to the particle accelerator and pulverizing the mixed zeolite for 1 to 3 hours to powderize the particle size into nanosize; And the zeolite and the additive stirred mixture and acceleration then pulverized concrete or film solidified comprising: processing control shaping of the shape according to the application onto the large annular pellets of; H ₂ on magnesium is selected to be made, including, removing the odor center material O, Fe ₂ O ₃ , and SiO ₂ , to induce catalytic activity at room temperature. The present invention also provides a method for producing a composite deodorant using the waste coal ash.
Composite deodorant method using waste coal ash according to an embodiment of the present invention, an alkaline aqueous solution of a zeolite is a salt of an alkali metal _{(NaCl, Na 2 SO 4,} KCl, K 2 SO 4) and salts of alkaline earth metals (MgCl _2, MgSO ₄ , CaCl ₂ ), or a mixture of two or more thereof.
Composite deodorant method using waste coal ash according to an embodiment of the present invention, the zeolite an aqueous alkaline solution is sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca (OH) _2), sodium carbonate (Na ₂ CO ₃₎ , Potassium carbonate (K ₂ CO ₃ ), and the like.
The method of producing a composite deodorant using waste coal ash according to an embodiment of the present invention is characterized in that zeolite is a dehydrated and dried powder state in which the amount of bentonite is 1 to 10 wt% as an inorganic binder based on the weight of zeolite of 100 wt% 1 to 10 wt% of cellulose is mixed and 1 to 10 wt% of ammonium chloride (NH ₄ Cl) is mixed. Water is added to the pellet to facilitate molding, By weight and 55% by weight.
The method of manufacturing a composite deodorant using waste coal ash according to an embodiment of the present invention is characterized in that magnesium selected as the deodorizing center material is adjusted to 5 to 20 wt% based on 100 wt% of zeolite and the magnesium particle size is adjusted to 1000 mesh or less .
In the method of manufacturing a composite deodorant using waste coal ash according to an embodiment of the present invention, the zeolite and the additives are stirred and mixed, and after the accelerated pulverization, the shape of the spherical or annular pellet is adjusted to a desired shape, And dried in a heating furnace at 900 to 1400 ° C to produce a porous composite deodorant.

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According to the method for producing a composite deodorant using waste coal ash according to an embodiment of the present invention, the waste treatment cost can be drastically reduced by recycling waste coal ash, and a large amount of zeolite having antibacterial and deodorizing function can be produced using waste coal ash It is expected to be.

According to the method for producing a composite deodorant using waste coal ash according to an embodiment of the present invention, it is expected that mass production of zeolite by using a raw fly ash as a raw material for disposal can be suppressed, which is essential for obtaining natural zeolite.

According to the method for producing a composite deodorant using waste coal ash according to an embodiment of the present invention, a highly toxic deodorant that can be used as a deodorant of human contact household goods can be manufactured by removing the harmful heavy metals in the process of zeolite synthesis.

According to the method for producing a composite deodorant using waste coal ash according to an embodiment of the present invention, it is possible to provide a high-efficiency nano-composite deodorizer using waste coal as a deodorant with high efficiency for removing odor having a removal efficiency of 50% .

Zeolites contain large amounts of water in the structural cavities, but can easily be dehydrated by heating for several hours at 200-300 degrees. This dewatered zeolite has the characteristic of molecular sieving that selectively adsorbs inorganic and organic molecules of a suitable size and shape and consequently separates the other molecules mixed with each other. This is the same function as sieving sand with various particle sizes and separating them by size. The selective adsorption characteristics of the zeolite associated with the molecular sieve function vary depending on the size and shape of the zeolite cavity. The size of the effective pore size also depends on the nature of the cations in the cavities of the same zeolite. For example, in the case of zeolite A, which is a synthetic zeolite, substitution with K has a diameter of 3, whereas substitution with Na and Ca has a size of 4 and 5, respectively. In addition, the selective adsorption capacity and propensity of zeolite depend not only on the pore structure of the mineral but also on the shape, size and polarity of the molecules acting on the mineral. When all of the adsorbable molecules react with each other, the zeolite selectively adsorbs only the more polar molecules. Therefore, under normal conditions, water molecules which are added polar substances always exist in the zeolite. The degree of saturation for a specific molecule is also considered as a major factor affecting the selective adsorption of zeolite. The adsorption capacity varies somewhat depending on the mineral species. Synthetic zeolites, which can be adsorbed up to about 30% of the dry weight presently, have been developed and distributed. In applications related to absorption and molecular sieve properties of the zeolite is the application of drying agent for dewatering purposes of various gases, SO _2, and in the application to the generator of the specific gas (O _2, N _2, etc.), natural gas and LPG Applications to the removal of impure gases such as CO ₂ , and applications to the extraction of paraffinic hydrocarbons. On the other hand, since the zeolite produced from the coal ash of the discarded waste coal ash contains a harmful substance component, when the zeolite is used as a deodorant for everyday household goods or the like, the stability of the human body is low and the zeolite is used as a deodorant for deodorization It is difficult to alternatively produce a deodorant having high deodorizing power for the removal of a specific odor or odor. According to the embodiment of the present invention, a nanocomposite deodorant having high stability and high deodorizing ability with respect to a specific odor can be mass-produced.

Hereinafter, a method for producing a composite deodorant using waste coal ash according to an embodiment of the present invention will be described in detail.

≪ Example 1 >

Preparation of zeolite and deodorant additive selection compound deodorant

First, the fly ash of the waste coal ash is put in a waste coal ash, and hydrochloric acid (HCl) is added in a weakly acidic pH range of 4 to 6, and the mixture is stirred to produce clay minerals Switch. Then, hydrochloric acid is added to the fly ash, acid treated, and heat is applied to obtain clay minerals of amorphous aluminum silicate, alafane. Concentration of hydrochloric acid (HCl) pH 4 to 6 corresponds to slightly acidic treatment. After adding 50 to 80 wt% of an alkali aqueous solution to 100 wt% of allophane clay minerals obtained by weak acid treatment of coal fly ash, the mixture is stirred at a temperature of 100 to 200 ° C for 6 hours or more, dehydrated and washed, The zeolite thus obtained is converted into clay minerals such as copper, cadmium and chromium which are harmful to the human body, and then the mixture is stirred in an aqueous alkali solution for 6 hours at a temperature of 100 to 200 ° C. Processing, and dehydration-rinsing-drying processes. Therefore, according to the embodiment of the present invention, the zeolite produced from coal fly ash is a state in which harmful heavy metal components are mostly removed, and when the zeolite product is used in medicinal products such as antibacterial mask, I hardly give it.

The dried zeolite is selected from the odor materials to be deodorized again, and the deodorizing material is selected and classified into nickel-zirconium ferrite, tungsten (WO ₃ ), platinum chloride (PtCl ₆ ), molybdenum (MoO ₃ ) And strontianite (SrCO ₃ ) are added to zeolite at 1 to 30 wt% to prepare a composite deodorant. The method of adding the deodorant to the zeolite may be selected from stirring blending, vacuum blending, and the like, preferably a composite deodorizer in a nano powder state.

For example, as shown in Table 3 below, a deodorizing material is selectively selected and added according to the deodorization target material.

division Type of substance to be deodorized Types of Corresponding Additives
Zeolite ammonia Tungsten (WO ₃ ) Hydrogen sulfide Nickel-zirconium ferrite (Ni-ZrFerrite) toluene Platinum chloride (Ptcl ₆ ) Xylene Strontia nite (SrCO ₃ )

The zeolite / tungsten composite deodorant showed good odor removal performance when the deodorization target material was ammonia.

The zeolite / nickel - zirconium ferrite composite deodorant showed excellent odor removal performance when the deodorization target material was hydrogen sulfide.

The zeolite / chlorinated platinum complex deodorant was excellent in odor removal performance when the deodorization target substance was toluene.

The zeolite / strontanite composite deodorant had excellent odor removal performance when the deodorization target substance was xylene.

In addition, zeolite / molybdenum composite deodorant showed similar odor removal performance in odor generating substances such as ammonia, hydrogen sulfide, toluene, and xylene.

However, the composite deodorant selectively produced according to the odorous substance is not limited to zeolite / tungsten-ammonia, zeolite / nickel-zirconium ferrite-hydrogen sulfide, zeolite / platinum-toluene, zeolite / strontanite-xylene Or may be made of a composite deodorant containing a variety or variant. For example, zeolite / tungsten, nickel zirconium ferrite-ammonia, zeolite / nickel zirconium ferrite, platinum chloride-ammonia, and the like.

Therefore, the nickel-zirconium ferrite, tungsten (WO ₃ ), platinum chloride (PtCl ₆ ), molybdenum (MoO ₃ ), strontianite (SrCO ₃ ) Although the odor removal performance may be excellent in the odor type, it is expected that better odor removal performance can be expected when one or more substances are further mixed together, and also, there is a variable depending on the degree of mixture between materials.

It is important to note that when adding a substance selected from these odor eliminating substances to zeolite in an amount of 1 to 30 wt%, it may or may not have the ability to remove a specific odor. In view of this, The material is selected for a specific use, the amount thereof is weighed, and the added amount is adjusted to produce a synthetic zeolite composite deodorant.

According to the preparation of the additive-selective composite deodorant corresponding to the zeolite and the offensive odor removing material of the example 1, the zeolite produced from the fly ash can be manufactured to have human stability and the odor removing material can be selectively In a relatively simple manner.

≪ Example 2 >

Zeolite and composition ratio adjustment and odor removing substance additive selection manufacturing of composite deodorant

The zeolite obtained in Example 2 is the same as the zeolite obtained in Example 1 described above, and a specific method for producing zeolite is omitted.

The zeolites obtained by the process of the present invention have different Al and Si composition ratios. For example, the composition ratio of Al: Si other than the other materials constituting the zeolite may be 1: 2. Referring to Table 1, it can be seen that the content of Si is generally about 1 time larger than that of Al. Alumina (Al ₂ O ₃ ) and silicic acid (SiO ₂ ) may be added to adjust the composition ratio of the zeolite in accordance with the composition ratio of Al and Si. When alumina or silicate is further added to the zeolite, the content of the zeolite can be made into a suitable composite deodorizer by supplementing insufficient alumina or silicate or by reducing the content of the excess material. In fact, the excess of either Al or Si degrades the functional groups of the zeolite.

Magnesium (MgO) is added as a deodorizing center material after appropriately adjusting the composition ratio of the zeolite. Magnesium is the central substance of deodorization, and when magnesium is added, odor removal of the zeolite is activated.

Then, the odor substances to be deodorized are selected and nickel-zirconium ferrite, tungsten (WO ₃ ), platinum chloride (PtCl ₆ ), molybdenum (MoO ₃ ), strontianite (SrCO ₃ ) And 1 to 30 wt% of the zeolite is added to the zeolite to prepare a composite deodorizer.

According to the preparation of the additive-selective composite deodorant corresponding to the zeolite and the offensive odor removing material of Example 2, the zeolite produced from the fly ash can be made to have human stability, and the composition ratio of Al and Si of the zeolite It is possible to manufacture a composite deodorant having a malodor removing material selectively added according to a substance to be removed, in a relatively simple manner.

≪ Example 3 >

Selection of zeolite and composition ratio and odor removing substance additive and manufacture of nanocomposite deodorant

The zeolite obtained in Example 3 is the same as the zeolite obtained in Example 1 described above, and the specific method for producing zeolite is omitted. The method for adjusting the composition ratio of the produced zeolite and the selection of the additive for the malodor removing material are as described in the second embodiment. As in Examples 2 to 3, zeolite having the human body stability, the composition ratio of zeolite, and the zeolite selectively added with the object to remove odor and the additives were uniformly mixed in a vacuum blender, Are mixed evenly. When the mixing is completed, the mixture is collected and charged into a particle accelerator to be pulverized for 1 to 3 hours, and the particle size of the constituent material is powdered to a nanosize size. Additive Synthesized in Nano-Size The zeolite enables to obtain a well-formulated crystal state so as to improve the moldability in the shaping process suitable for the use, and to prevent the lack of specific substances, unevenness or unevenness, The synthetic additive zeolite can be formed into a pellet-shaped solidification and shape that is convenient for use.

According to the above-described Examples 1-3, the aqueous alkali solution of a zeolite is a salt of an alkali metal _{(NaCl, Na 2 SO 4,} KCl, K 2 SO 4) and salts of alkaline earth metals _{(MgCl 2, MgSO 4, CaCl} 2) may be mixed alone or two kinds, also from the caustic soda (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca (OH) _2), sodium carbonate (Na ₂ CO _3), potassium carbonate (K ₂ CO ₃₎ The alkaline aqueous solution influences the cation exchange ability in the production of zeolite by heating the clay minerals in the alkaline environment in the alkaline aqueous solution.

As a result, the fly ash was converted into clay minerals, which are amorphous aluminum silicate clay minerals, by heating at slightly acidic condition of hydrochloric acid concentration of pH 4 ~ 6, and then converted into alkali clay minerals such as NaCl, Na ₂ SO ₄ , KCl, K ₂ SO ₄ ) stirring the reaction process at a temperature of more than 6 hours 100~200 ℃ in an aqueous alkaline solution is a zeolite cation exchange ability was evaluated as relatively good, a salt of an alkaline earth metal is selected as the alkaline aqueous solution similar to (MgCl _2, Mg _s O _4, the CaCl _2), or caustic soda (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca (OH) _2), sodium carbonate (Na ₂ CO _3), potassium carbonate (K ₂ CO ₃₎ one of which is selected or two or The cation exchange capacity of the zeolite was similar to that of the former as shown in Table 4 below.

division Alkaline component Cation exchange capacity (pass / failure)


Aqueous alkaline solution



Alkali metal yeomyeom _{(NaCl, Na 2 SO 4,} KCl, K 2 SO 4)
pass Alkaline earth metal salts _{(MgCl 2, MgSO 4, CaCl} 2)
pass Caustic soda (NaOH) pass Potassium hydroxide (KOH) pass Soda (Na ₂ CO ₃ ) pass Calcium hydroxide (Ca (OH) ₂ ) pass Potassium carbonate (K ₂ CO ₃ ) pass

According to the above-described Examples 1 to 3, the additive-synthesized zeolite is in a powdery state in which the zeolite is dehydrated and dried, wherein the total additive synthetic zeolite is contained in an amount of 1 to 10 wt% as an inorganic binder, ) System, 1 to 10 wt% of ammonium chloride (NH4Cl) was mixed, and water was added to the pellet so as to facilitate molding, thereby adjusting the water content of the whole mixture to 40 to 55 wt% When mixed, a compound deodorant which is easy to use can be obtained.

According to the above-described Examples 2 and 3, the magnesium selected as the deodorizing center material is 5 to 20 wt% based on 100 wt% of the zeolite and the magnesium particle size is preferably adjusted to 1000 mesh or less and mixed as the deodorizing center material magnesium H2O, the combination of _{Fe 2 O 3, Al 2 O} 3, SiO 2 or any one of two or more active substances in it is preferable to induce the activity of the catalyst at room temperature. Here, the deodorization reaction center is magnesium, and the activation of oxygen generation is by H ₂ O. [ The catalytic activity depends on Fe ₂ O ₃ , and the activation of HC adsorption and the activation of hydrogenation are activated by Al ₂ O ₃ , SiO ₂ .
In the solidification step of Example 3 described above, the zeolite and additives were stirred and mixed, and after accelerated pulverization, spherical or rod-shaped pellets were pelletized to form a shape suitable for the intended use. The mixture was naturally dried at room temperature and then calcined at 900 to 1400 ° C To obtain a porous dried composite deodorant.

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As a result of verifying the deodorizing effect during the production process, the deodorizing ability of odorant (NH ₃ , HS, etc.), which is a basic odorant, was evaluated as follows.

1) Experimental conditions (experimental room)

Room temperature: 18 ± 3 ° C, relative humidity: 44 ± 5%, container for deodorization test: 400mm * 400mm * 400mm, amount of deodorizing composition sample: 20g

2) Experimental method

100 g of the nanocomposite deodorant prepared according to Example 2 of the present invention was placed in the device for deodorization test, and 1 liter of a deodorant solution containing 5 ppm of deodorant concentration (NH ₃ , HS, etc.) was injected into the device through the injector. Natural evaporation or exhaust of odor was carried out under the sealing conditions of the apparatus. The concentration of odor concentration 5PPM was injected into the apparatus, and after 1 hour, the concentration was measured with a MiniRAE 3000 VOC analyzer. As a result, the odor concentration was changed as shown in <Table 5> as the time elapsed from the initial 5PPM, and the odor concentration was decreased in proportion to the time elapsed, and it was assumed that the odor concentration was absorbed or removed by the compound deodorant.

Example 2 Odor concentration Elapsed Time (Hour) Primary measurement 5.0ppm One Secondary measurement 4.5 ppm 2 Third measurement 3.5ppm 3 Fourth measurement 2.1 ppm 4

The deodorizing performance of general synthetic zeolite was measured according to the same experimental method as that of Example 2 so that the odor removing performance according to Example 2 can be compared with the control group.

Control group Odor concentration Elapsed Time (Hour) Primary measurement 5.0ppm One Secondary measurement 4.9 ppm 2 Third measurement 4.6 ppm 3 Fourth measurement 4.1 ppm 4

The sensory test on the nanocomposite deodorant prepared according to the third embodiment of the present invention was performed.

The sensory test was carried out by sensory test.

The panel (judge) was made up of ten (quitting box). The panel is very reliable and reproducible, and the results of the panel can be obtained. To determine the effect, ten people are required to take a pitcher (two healthy men in their twenties, two men in their 30s, two women in their twenties, women in their twenties 2 women, 2 women in their 40s).

The sensory test was carried out under the following conditions.

100 g of the nanocomposite deodorant sample prepared according to Example 3 of the present invention was placed in a device for deodorizing test 400 mm * 400 mm * 400 mm and the concentration of the odorant (NH3, HS, etc.) 1 liter was sprayed. After lapse of time every 1 hour interval for 1 to 5 hours, the nose was put on a 10mm long 6cm transparent tube connected to 400mm * 400mm * 400mm, the data was collected through this and the panel judged the odor. Table 7 shows the results obtained by applying the step method.

Number of measurements The compound deodorant of the present invention Control deodorant Rating 1 hours There is a bit of smell. It smells strong. ③ / ⑤ 2 hours Have a fairly low odor The smell does not change ② / ④ 3 hours Very low odor There is a bit of smell. ① / ③ 4 hours Very low odor There is a bit of smell. ① / ③ 5 hours Very low odor Have a fairly low odor ① / ②

Very little odor ①, little odor ② ②, little odor ③, odor does not change ④, strong odor ⑤.

As a result of the sensory evaluation, it was found that the deodorizing performance of the nanocomposite deodorant using the waste coal ash produced according to the embodiment of the present invention is twice as high as that of the conventional deodorant, which is a control group, over time.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of illustration, .

Claims (10)

The fly ash is heated and hydrochloric acid (HCl) is added in a weakly acidic pH range of 4 to 6, and the mixture is stirred to convert the clay minerals of alafene, which is an aluminum silicate salt of amorphous water, to dehydrate and wash the harmful heavy metal components of the alafinin clay mineral A zeolite obtained by adding a 50 to 80 wt% alkali aqueous solution to the alpine-in clay mineral and stirring the mixture at a temperature of 100 to 200 캜 for 6 hours or more, followed by dewatering, washing with water and drying;
Analyzing the Al and Si composition ratios of the zeolite and adding alumina (Al ₂ O ₃ ) and silicic acid (SiO ₂ ) to the composition ratio of Al and Si to adjust the composition of the zeolite;
Adding magnesium (MgO) selected as deodorizing center material to the zeolite whose constituent composition has been adjusted from the above step;
Selecting a substance to be deodorized as a malodor substance to be deodorized from one of toluene, xylene, or a compound thereof;
Adding 1 to 30 wt% of one or two selected from platinum chloride (PtCl ₆ ), strontianite (SrCO ₃ ) to the zeolite according to the selected odor substances;
Mixing the zeolite and the additives in a vacuum mixer and mixing them uniformly;
Adding the mixed zeolite and the additive to the particle accelerator and pulverizing the mixed zeolite for 1 to 3 hours to powderize the particle size into nanosize; And
And a solidifying step of shaping and shaping the zeolite and additives in accordance with the intended use in the form of spherical or rod-shaped annular pellets after agitated mixing and accelerated pulverization,
Combining at least one activating material selected from the group consisting of H ₂ O, Fe ₂ O ₃ , and SiO _{2 with} magnesium selected as the deodorizing center material to induce catalytic activity at room temperature; A method for manufacturing a deodorant. delete delete The method according to claim 1,
The alkali aqueous solution of the zeolite may be a waste coal ash mixed with a salt of an alkali metal (NaCl, Na ₂ SO ₄ , KCl, K ₂ SO ₄ ) or a salt of an alkaline earth metal (MgCl ₂ , MgSO ₄ , CaCl ₂ ) A method for manufacturing a composite deodorant using the method. The method according to claim 1,
The zeolite an aqueous alkaline solution is sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca (OH) 2), sodium carbonate (Na ₂ CO _3), potassium carbonate (K ₂ CO ₃₎ one of which is selected or two or A method for producing a composite deodorant using waste coal ash mixed with. The method according to claim 1,
Bentonite and 1-10 wt% of bentonite and cellulose are mixed as an inorganic binder and an organic binder, respectively, based on 100 wt% of zeolite as a powdery state in which the zeolite is dehydrated and dried, (NH4Cl), and then water is added to the pellet so as to facilitate the shaping process. The moisture content of the whole mixture is adjusted by 40 to 55 wt%, and the mixture is stirred and mixed, thereby producing a composite deodorant. delete The method according to claim 1,
Wherein the magnesium selected as the deodorizing center material is adjusted to 5 to 20 wt% based on 100 wt% of the zeolite and the magnesium particle size is adjusted to 1000 mesh or less, thereby producing a composite deodorant. delete The method according to claim 1,
In the solidification step, zeolite and additives are stirred and mixed, and after accelerated pulverization, spherical or rod-shaped annular pellets are formed in a shape suitable for the purpose of use. The formed product is naturally dried at room temperature and then dried at 900 to 1400 ° C A method for manufacturing a composite deodorant using waste coal ash produced from a dried composite deodorant.