KR101570130B1

KR101570130B1 - Multiple odor absorbents by using mixing the natural zeolite and method of fabricating the same

Info

Publication number: KR101570130B1
Application number: KR1020150065702A
Authority: KR
Inventors: 박진희; 문장수; 송현준; 양고수
Original assignee: 동원중공업 주식회사; 전북대학교산학협력단
Priority date: 2015-05-12
Filing date: 2015-05-12
Publication date: 2015-11-18

Abstract

The present invention relates to a composite odor absorber using a mixture containing natural zeolite and a method for preparing the same, and more particularly, to a composite odor sorbent including natural zeolite, ash, yellow earth, bentonite and sodium hydrogen carbonate, Ammonia and trimethylamine, which are basic gases generated by use in facilities, and odor-causing substances such as hydrogen sulfide and methyl mercaptan, which are acidic gases, are adsorbed and removed. In addition, the complex odor sorbent using the contaminated mixed zeolite by adsorbing the odor-inducing substance has an excellent desorption efficiency by microwave, thereby enabling effective and rapid desorption of the sorbent material, thereby minimizing the energy required for the desorption process, And the ash is contained in the composite odor absorber using the mixture containing the natural zeolite, the waste to be buried is recycled to have useful applications in the industry to protect the environment and reduce the manufacturing cost.

Description

Technical Field [0001] The present invention relates to a composite odor absorber using a mixture containing a natural zeolite, and a method for producing the same. [0002]

The present invention relates to a composite odor absorber using a mixture containing natural zeolite and a method for preparing the same, and more particularly, to a composite odor sorbent including natural zeolite, ash, yellow earth, bentonite and sodium hydrogen carbonate, The present invention relates to a composite odor absorbing material using a mixture containing natural zeolite capable of effectively deodorizing odor generated in the facility by using the odor absorbing material in a facility where odor is generated, such as a facility, a sewage treatment plant, a manure treatment plant, an incinerator and a dyeing complex.

Recently, due to changes in the perception of environmental rights, odor problems are becoming serious as well as air pollution. Since Korea has a mixed population of residential area and industrial area for efficient use of the limited land area, the incidence of odor complaints is very high due to high population density, and there are many difficulties in efficient management due to the variety of types and sources of odorous substances .

In addition to the large number of substances causing these odors, it is difficult to uniformly express the extent of the damage or the degree of damage due to the complex action of odorous substances or individual differences in the smell, which is the most difficult and difficult to solve It is considered to be one of the problems. Odor is one of the sensory pollution causing mental and psychological damage rather than the harmfulness to the human body. Recently, the quality of life and environmental consciousness have improved, and civil complaints are increasing every year. The damage caused by the odor is mainly limited to the vicinity of the source, but it can affect far distances depending on the weather conditions, such as wind direction, wind speed, and temperature inversion, as well as the local features of the area.

In Korea, the amount of food waste generated due to the traditional food culture has raised the need for management measures. Among them, we are trying to use food waste as a resource as much as possible.

Food waste is discharged every day from households and restaurants. The amount of such garbage is gradually increasing from 13,672 tons / day in 2010 to 13,537 tons / day in 2011 and 13,209 tons / day in 2012. Food waste It has a different composition and content, and its protein content is relatively high in terms of nutrient composition. It has a useful value as feed and compost, but it has a high water content and is easily corrupted and malodorous. Therefore, when disposing of food waste, damage is increasing due to odor such as incessant complaints around environment basic facility due to odor generated.

Food waste recycling facilities, one of the abovementioned environmental facilities, have introduced waste disposal agents since 1995 and the amount of food waste has been rapidly increasing due to the separation and discharge of food waste mixed and discharged into the standard bags. It started to be installed in the room. However, this food waste disposal facility has been recognized as a disgusting facility due to the severe odor generated during transportation and processing of food waste, and it has become a subject of complaints of residents in the surrounding area, resulting in NIMBY ('Not In My BackYard') phenomenon. In the process, malodorous substances such as mercaptans, amines and the like are generated, causing discomfort and disgust to the residents in the surrounding area, making them subject to collective complaints, and it is difficult to install and operate a food waste recycling facility.

Accordingly, in order to remove the odor generated in food waste, in Registration No. 0837528 (2008 Registered Notice), it is possible to improve the efficiency of deodorization by decomposing and removing the substances causing the odor, and at the same time, A harmful odor deodorant composition has been proposed which is odorless and non-toxic even when contacted with the body.

Japanese Patent No. 1308156 (Registration Announcement dated Mar. 31, 2013) discloses a method of removing odors by passing odor, which has not been absorbed even after passing through the catalyst cartridge, through a cartridge filled with activated carbon.

However, the above-described conventional techniques have technical problems such as difficulty in deodorizing complex odors such as ammonia, trimethylamine, etc., which are basic gases including polar groups, and mercaptan, which is an acid gas.

Registered Patent No. 0837528 (Registered on Jun. 12, 2008) Registered Patent No. 1308156 (Registration Announcement on September 12, 2013)

In the present invention, ammonia, trimethylamine and the like, which are basic gases, and mercaptan (mercaptan), which is an acidic gas, are produced by preparing an adsorbent containing natural zeolite, ash, loess, bentonite and sodium hydrogencarbonate in order to remove odors generated in food waste. And to provide a composite odor absorbing material using the mixture containing natural zeolite adsorbing and removing odor and a method for producing the same.

In order to achieve the above-mentioned object, an embodiment of the present invention is a natural zeolite comprising 100 parts by weight of natural zeolite, 20 to 25 parts by weight of fly ash, 4 to 7 parts by weight of loess, 1 to 3 parts by weight of bentonite, And a composite zeolite-containing zeolite containing 1 to 5 parts by weight of an organic binder based on 100 parts by weight of the mixture, and 13 to 16 parts by weight of sodium (NaHCO ₃ ) The size of the pores is preferably 10 to 300 nm.
In another embodiment of the present invention, there is provided a natural zeolite comprising 100 parts by weight of natural zeolite, 20 to 25 parts by weight of fly ash, 4 to 7 parts by weight of loess, 1 to 3 parts by weight of bentonite and 13 to 16 parts by weight of sodium hydrogencarbonate (NaHCO ₃ ) Mixing parts by weight to prepare a first mixture; Adding 1 to 5 parts by weight of an organic binder to 100 parts by weight of the first mixture, and molding the resultant into a granule form; And a drying and calcining step of applying heat to the granulated mixture to form a composite zeolite adsorbent containing natural zeolite.
The method may further include, after the drying and firing step, selecting the mixture of the fired granule type to a size of 0.5 to 20 mm, 5 parts by weight, and the mixture is then rotated at 3 to 30 rpm to form a granule. In the drying and firing step, the granular mixture is heated to remove water on the surface of the granules step; A fine particle removing step of passing the mixture of granules through the drying step through a rotating screen including a perforation hole to remove fine particles; And a sintering step of applying heat to the granular mixture through the fine particle removing step; More preferably,
Also, it is preferable that the drying step is performed at a temperature of 80 to 150 ° C, and the sintering step is performed at a temperature of 250 to 800 ° C.

delete

The present invention relates to a composite odor sorbent material using a mixture containing natural zeolite and a method for producing the same, and more particularly, to a method for producing a composite odor sorbent material using natural zeolite, ) Is adsorbed and removed.

In addition, the complex odor sorbent material using the mixture containing the contaminated natural zeolite by adsorbing the odor-inducing substance has an excellent desorption efficiency by microwave, thereby enabling efficient and rapid desorption of the sorbent material, Energy efficiency is excellent.

By incorporating ash in a composite odor absorber using a mixture containing the natural zeolite, the waste to be buried is recycled to have useful applications in industry, thereby protecting the environment and reducing manufacturing costs.

1 is a photograph showing Example 2 produced according to an experimental example of the present invention.
FIG. 2 is a photograph showing the loosening phenomenon of water by conducting a hydrophobic test for T1 to T4 according to an experimental example of the present invention. FIG.
3 is a graph showing adsorption rates of mercaptans in Examples 1 to 3, Comparative Examples 1 to 4, and DW1 to DW4 of the present invention.
4 is a graph showing the adsorption ratios of formaldehyde of Examples 1 to 3, Comparative Examples 1 to 4, and DW1 to DW4 of the present invention.
5 is a graph showing ammonia adsorption ratios of Examples 1 to 3, Comparative Examples 1 to 4, and DW1 to 4 of the present invention.
6 is a graph showing the adsorption ratios of trimethylamine in Examples 1 to 3, Comparative Examples 1 to 4 and DW1 to 4 of the present invention.
7 is a scanning electron micrograph of Example 2 of the present invention.
8 is an electron micrograph of Comparative Example 3 of the present invention.
9 is an electron micrograph of Comparative Example 4 of the present invention.
10 is an electron micrograph of DW2 of the present invention.
11 is a graph showing XRD measurement results of Example 2 (a), Comparative Example 3 (b), Comparative Example 4 (c) and DW2 (d) of the present invention.
12 is a graph showing the adsorption heat of Example 2, Comparative Example 3, Comparative Example 4 and DW2 of the present invention.
13 is a graph showing the desorption rates of Example 2, Comparative Example 3, Comparative Example 4, and DW2 of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings. Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. As well as the fact that

Throughout this specification, when an element is referred to as "comprising ", it means that it can include other elements as well, without departing from the other elements unless specifically stated otherwise.

In each step, the identification code is used for convenience of explanation, and the identification code does not describe the order of the steps, and each step may be performed differently from the stated order unless clearly specified in the context. have. That is, each of the steps may be performed in the same order as described, or may be performed substantially concurrently or in the reverse order.

Hereinafter, the composite odor adsorbent using the mixture containing the natural zeolite of the present invention and the method for producing the same will be described in detail.

The composite odor sorbent material using the natural zeolite-containing mixture of the present invention may comprise a mixture comprising natural zeolite, fly ash, loess, bentonite and sodium hydrogencarbonate (NaHCO ₃ ) and an organic binder, Wherein the mixture contains 20 to 25 parts by weight of ash, 4 to 7 parts by weight of loess, 1 to 3 parts by weight of bentonite and 13 to 16 parts by weight of sodium hydrogencarbonate based on 100 parts by weight of natural zeolite, 1 to 5 parts by weight based on 100 parts by weight of the mixture.

The natural zeolite included in the odor absorbing material of the present invention is a natural mineral having various physico-chemical properties useful industrially because of a pore structure peculiar to the surface pore existing in the crystal. as one of the base units (Si, Al) O all of the oxygen in the ₄ tetrahedra are also shared by the other tetrahedron form the reticulated silicate (Tektosilicates) of structured type minerals are three-dimensionally linked. Also, the natural zeolite has a lattice structure (specific gravity: 2.0-2.3) which is large enough to form a large pore size of 2.3-7.5 Å in the crystal within the crystal, and the size of the pore is 4-12 The oxygen is determined by the shape of the oxygen ring at the entrance to the structural pore and by the number of intervening oxygen.

In particular, natural zeolites are collected in the form of "zeolitic tuff", which is mostly degraded to fine-grained tuff, and is a hydrated silicate containing a small amount of Na, K, Ca, Mg, As minerals, the types are clinoptilolite, mordenite, heulandite, phillipsite, erionite, chabazite and periorite ferrierite, etc. In the present invention, the type of the natural zeolite is not particularly limited, and natural zeolite extracted from nature can be selectively used. The natural zeolite has excellent cation exchange ability, And has an advantage of being excellent in heavy metal adsorption capacity.

The fly ash contained in the adsorbent of the present invention is economical because it has a large specific surface area and a large number of pores and thus has good adsorption power and reduces heat of hydration and can reduce the cost of manufacturing the adsorbent including the ash in terms of recycling waste materials . In addition, there is an excellent effect in increasing the porosity, improving the melting point, and lightening the weight of the composite odor absorbing material. The ash is preferably contained in 20 to 25 parts by weight of ash relative to 100 parts by weight of natural zeolite in the mixed odor absorber using mixed zeolite. If less than 20 parts by weight or more than 25 parts by weight of ash is used, . In addition, the particle size of the ash can be used without specifically proposed if the particle size is such that the compound odor absorber using the mixed zeolite is not problematic in the processability.

Yellow loess is a weakly alkaline soil collected from the lower layer of the ground, which is different from the normal surface layer. It is rich in calcium carbonate and consists of various mineral particles such as quartz, feldspar, mica and calcite. It is also known that loess is chemically composed of silica, iron, alumina, magnesium, sodium, potassium, lime, smectite, etc., emitting far infrared rays, generating oxygen and deodorizing function. And it has an advantage of lowering the melting point and increasing the strength of the adsorbent when producing the composite odor absorbent using the mixed zeolite including the yellow loess.

The particle size of the yellow loess contained in the composite odor absorber using the mixed zeolite of the present invention is not particularly limited as long as it does not cause any problems in the formability of the adsorbent, but it is preferably one having a particle size of 0.02 to 0.05 mm. In addition, the loess of the present invention may be contained in an amount of 4 to 7 parts by weight based on 100 parts by weight of the natural zeolite. If the loess component is less than 4 parts by weight, far-infrared ray irradiation and deodorization effects are difficult to expect. There is a problem that the moldability of the resin composition decreases.

Bentonite is a volcanic ash and rhyolite of the Neogene period, which is formed by stratification of volcanic rocks of Pelvic volcanism (rock formation) and formed stratification. The bentonite is composed of Montmorilllite-based expansive three- Si), and it can be expressed as Al ₂ Si ₄ (OH), which is a chemical structure of pyrophylite. In addition, the bentonite is gelled due to its swelling property by water in powder form. When the zeolite is included in the composite odor absorbent using the mixed zeolite of the present invention, the natural zeolite, fly ash, loess, bentonite, sodium hydrogencarbonate NaHCO ₃ ) and the organic binder so as to maintain the shape of the formed adsorbent to prevent deformation.

The bentonite is preferably contained in an amount of 1 to 3 parts by weight based on 100 parts by weight of the natural zeolite. When the amount of the bentonite is less than 1 part by weight, the strength of the adsorbent decreases and the granule shape tends to be broken. .

Sodium hydrogencarbonate generates pores or pores due to the generation of HCO ₃ gas during the decomposition process due to heat during drying, and Na ⁺ in the inorganic system remains in the adsorbent even after calcination and can help form the structural force. In addition, natural zeolite, ash, loess, and bentonite may be adhered or adhered to the adsorbent of the present invention in the process of forming the pores or pores. The sodium hydrogencarbonate is preferably contained in an amount of 13 to 16 parts by weight based on 100 parts by weight of the natural zeolite. If the amount is less than 13 parts by weight, the desired structural force can not be imparted to the adsorbent. If the amount is more than 16 parts by weight, There may be a problem that the strength is excessively deteriorated.

The organic binder which improves the adhesive strength between the materials of the complex odor absorber of the present invention and improves the adhesion is composed of carbon, hydrogen, and oxygen as chemical main components. In addition, there are a few inorganic substances such as sodium, magnesium, calcium and chlorine. As the organic binder, it is preferable to use at least one of molasses and carboxy methyl cellulose, and it may be a mixture of molasses and carboxymethyl cellulose, It can also be used. Preferably, the organic binder may be used by mixing water and molasses in a ratio of 1: 1 to 3: 1.

The amount of the organic binder is preferably 1 to 5 parts by weight based on 100 parts by weight of the mixture. If the amount of the organic binder is less than 1 part by weight, porosity may be insufficient due to oxidation of organic materials during firing, There is a problem that the shape of the adsorbent can not be maintained because the adhesive strength is lowered.

The complex odor sorbent material using the mixed zeolite of the present invention can be selected to optimize the adsorption of a substance causing odor to be adsorbed, preferably 10 to 300 nm. If the size of the pores is less than 10 nm, the size of the pores is too small, so that the adsorption rate of the basic gas and the acid gas, which are the substances causing the above-mentioned odor, is lowered and the effect of reducing the odor is poor. The porosity is too small to allow the adsorption rate to be lowered effectively.

On the other hand, a mixing step of preparing a mixture containing natural zeolite, ash and additive, a forming step of forming the mixture into a granule form further comprising an organic binder, a drying calcination step of applying heat to the mixture of the granular form, The mixed zeolite-based mixed odor absorber can be prepared through the step of selecting the mixture of the granule type in a size of 0.5 to 20 mm.

In the mixing step, natural zeolite, ash, loess, bentonite and sodium hydrogencarbonate are uniformly mixed. Preferably, 20 to 25 parts by weight of ash, 4 to 7 parts by weight of loess, 100 parts by weight of bentonite 1 to 3 parts by weight and sodium bicarbonate in an amount of 13 to 16 parts by weight.

In the molding step, a mixture containing natural zeolite, ash, loess, bentonite and sodium hydrogencarbonate and an organic binder is added to the rotating body and rotated to form granules. Preferably, 100 parts by weight of the mixture is mixed with organic 1 to 5 parts by weight of a binder may be contained and granulated into a granule through a granulation apparatus.

In the granule forming apparatus, a rotating body for forming the mixture into granules is connected perpendicularly to the driving shaft, and the driving shaft is rotated by the driving device to rotate the rotating body. The rotating body is inclined so that the dam is vertically formed to surround the rim of the disk. The dam is formed perpendicularly to the rim of the disk of the rotating body, and functions to prevent the powder from being released to the outside of the rotating body so as to be matured with granules having a predetermined size or more.

When the mixture is mixed with the organic binder in the rotating body and the powder grows in a granule shape having a certain size or more inside the rotating body, the centrifugal force due to rotation overcomes the resistance of frictional resistance and gravity, It is moved to the upper part of the small particles and the powder, and falls to the outside of the rotating body, so that only the mixture of the granule type having a certain size or more can be obtained. Since the time required for the mixture to grow in the form of granules in the powder is very short, the density of the granule-like mixture is low, so that the strength is not rigid and the specific gravity is light. In order to solve this problem, it is possible to rotate the granules in the rotating body even after the granules are grown to a predetermined size or more, so that a loop is further provided around the rotating body of the granulating device to obtain a mixture of a dense hard granular form .

The rotation speed of the rotating body is preferably 3 to 30 rpm. If the rotation exceeds 30 rpm, the granule size of the mixture becomes small, and when the rotation speed is less than 3 rpm, the mixture of the high- It is hard to get.

Also, it is preferable that the rotating body is adjusted at an angle of 30 to 55 from the ground. When the angle is close to vertical, the powdery mixture and granule type mixture may be mixed and released to the outside.

Wherein the drying and firing comprises applying a heat to the granular mixture to remove moisture on the surface by applying heat to the granular mixture, A fine particle removing step of passing the fine particles through a screen to remove fine particles and a granulated mixture in the form of fired granules through a firing step of applying heat to the mixture of granules through the fine particle removing step.

The drying step is a step of applying heat to the granular mixture at a temperature of 80 to 150 DEG C to dry only the surface thereof. The granular mixture is introduced into a cylindrical rotating screen and rotated to prevent the granular mixture from being broken Dry only the surface. If the temperature of the drying step is outside the range of 80 to 150 ° C, the granular mixture may be broken or cracked.

The mixture of granules in which the surface is dried through the drying step is passed through a rotating screen including perforated holes to remove fine particles. The granules are mixed with granules through the molding step And unnecessary energy waste is generated in drying and firing granule particles. Therefore, it is preferable that the fine powder excluding the granular mixture having a certain size or more is passed through a rotating screen including the perforated hole, discharged to the outside, and only the granular mixture is transferred to the firing step and fired.

The sintering step is a step of applying heat to the mixture of granules having passed through the step of removing fine particles, and as the sintering step proceeds, moisture in the mixture of granules is evaporated and humidity or humidity is increased in the air The evaporation of water vapor is further difficult to cause a phenomenon of adhesion between granules of the granule type mixture or a granule type mixture in the inside of the device, and therefore, the granule type mixture is subjected to co-current drying in which high temperature hot air is directly applied .

The calcining step is a step of calcining the granular mixture by adding hot air at a temperature of 250 to 800 DEG C, and more preferably, applying a hot air of 450 to 600 DEG C to the granular mixture. If the mixture is fired at a temperature of less than 450 ° C, the granule-type mixture may not be properly fired, so that the shape may not be maintained and may be flared or cracked. When fired at a temperature higher than 600 ° C, the zeolite The phase transition or phase collapse may occur and adsorption performance may be deteriorated.

Also, in order to allow the mixture of granules to be slowly heated to be dried and sintered, when the mixture is heated in the drying step and in the sintering step, the granular mixture is heated while being heated for a predetermined period of time, .

Only the mixture of granules in which the fine particles are removed in the firing step after the fine powder removing step can be fired, and the rotational resistance due to the fine powder can be removed, which enables efficient firing because the number of revolutions of the granule type mixture is increased. Thus, the finished granular mixture is more rounded and hardened to improve the quality, and the economy is improved due to the low volume and high density.

In addition, it is possible to prevent the scattering of the fine particles in the workplace by eliminating the fine powder in advance before the firing step, thereby making the workplace clean and safe.

Hereinafter, an embodiment of the present invention will be described. However, the scope of the present invention is not limited to the following preferred embodiments, and a person skilled in the art can carry out various modifications of the contents described in the present invention within the scope of the present invention.

[Experimental Example 1]

Preparation of complex odor adsorbents using mixed zeolite

The mixture was prepared by adding NaHCO ₃ to natural zeolite, fly ash, loess and bentonite having the composition ratios shown in Table 1 and mixing them uniformly through a paddle mixer.

The organic binder was prepared by mixing water and molasses (33 wt%) at a ratio of 2: 1 at 30 캜.

100 g of the mixture prepared in the same proportions as in the following Table 2 and 3.3 g of the organic binder were compressed and molded using a Rotary Gtor (Dongwon Engineering Co., Ltd.) as a molding machine to prepare a mixture of granules of 0.5 to 20 mm in size Respectively.

Constituent Natural zeolite Fly Ash ocher Bentonite SiO ₂ 71.0 54.1 52.9 68.57 Al ₂ O ₃ 11.4 14.4 23.4 14.79 K ₂ O 2.92 1.18 2.53 0.51 CaO 2.27 1.0 0.20 3.29 MgO 0.67 0.28 0.88 3.16 Na ₂ O 0.40 0.03 0.35 0.15 Fe ₂ O ₃ 0.74 4.84 8.70 3.95 TiO ₂ 0.08 0.86 1.11 0.03 MnO 0.06 - 0.07 0.07 P ₂ O ₃ - 0.29 0.12 0.08 Other 10.46 23.02 9.74 5.40

^{(unit :%)}

Zeolite Fly Ash ocher clay Starch Bentonite NaHCO ₃ Example 1 72.4
(100) 14.5
(20) 2.9
(4) - - 0.75
(One) 9.45
(13) Example 2
(S19) 70
(100) 15
(21.4) 4
(5.7) - - One
(1.4) 10
(14.3) Example 3 67
(100) 16.5
(24.6) 4.5
(6.7) - - 1.5
(2.2) 10.5
(15.7) Comparative Example 1 74
(100) 14
(18.9) 2.5
(3.4) - - 0.5
(0.7) 9
(12.2) Comparative Example 2 65
(100) 17
(26.2) 5
(7.7) - - 2
(3.1) 11
(16.9) Comparative Example 3
(S2) 70
(100) 15
(21.4) 4
(5.7) 10
(14.3) - One
(1.4) - Comparative Example 4
(S9) 60
(100) 20
(33.3) - - 15
(25) - 5
(8.3)

^{(Unit: g, in parentheses)} ^{Weight portion} ⁾

Performance evaluation according to drying temperature and firing temperature

In order to measure the maximum firing temperature at which no phase collapse of the zeolite occurs during the production of the composite odor adsorbent using the mixed zeolite, the natural zeolite is subjected to an organic acid precipitation and iodine adsorption Performance evaluation was conducted. The iodine adsorption performance was evaluated by weighing granular natural zeolite calcined in iodine solution for 24 hours.

Firing temperature (캜) 500 ℃ 600 ℃ 700 ℃ 800 ° C abandonment
Oxidation
Degree Before firing (g) 194.38 192.69 192.34 192.04 After firing (g) 170.30 165.95 165.47 163.69 Weight change (%) 12.4 13.9 14.0 14.5 iodine
absorption
Performance Before iodine impregnation (g) 50.06 50.11 50.32 50.19 After iodine impregnation (g) 62.5 63.57 61.81 61.18 Weight change (g) 12.44 13.46 11.49 10.99 Volume change (%) 46.15 49.94 42.63 40.77 Adsorption performance (%) 19.9 21.1 18.6 18.0

Table 3 shows the results of the evaluation of the degree of organic matter oxidation and iodine adsorption performance at the firing temperature measured by the firing test. The firing efficiency was the highest at the firing temperature of 500 to 700 ° C., It was found that the adsorption function was reduced due to the clogging of the micropores due to the collapse of the structural defects inside the natural zeolite. Therefore, it was found that when the maximum firing temperature is 500 to 700 ° C., the adsorption efficiency is excellent.

After setting the maximum sintering temperature to 500 to 700 ° C according to the results of Table 3, the granule-like mixture of Example 1 was subjected to drying under various conditions of heating time and duration, And fired to produce a sorbent material. The drying temperature was set to 80 to 150 ° C. The sintering temperature was set to 250 to 800 ° C while the total cumulative heating time was set to 90 minutes. Also, the experiment was carried out with a drying time> firing time for T1 or T2 and a firing time for T3 or T4.

division Set temperature
(° C) dry Plasticity Cumulative time
(min) Heating time (min) Duration (min) Heating time (min) Duration (min)
T1 80 10 20 - - 30 150 10 20 - - 60 450 - - 5 10 75 600 - - 5 10 90

T2 80 10 20 - - 30 150 - 30 - - 60 300 - - 5 5 70 450 - - 5 5 80 600 - - 5 5 90 T3
80 10 30 - - 40 600 - - 10 40 90
T4 80 10 10 - - 20 150 10 10 - - 40 450 - - 5 5 50 600 10 30 90

2, the hydrophobicity test was conducted on T1 to T4 prepared according to Table 4 to measure the release phenomenon against water. Experimental results showed that cracking or cracking of filter media occurred after firing and T1 and T3 showed water melting phenomenon in hydrophobic experiments. However, in case of T4, the strength was maintained and no cracking or cracking phenomenon could be observed. In the hydrophobic test, it was slightly dissolved in water but the shape did not change. Therefore, it was found that the drying temperature and the calcination temperature of the composite odor absorbing material using the mixed zeolite of the present invention are preferably 80 to 150 ° C. and 250 to 800 ° C., respectively.

Thus, the granular mixture in the same ratio as shown in Table 2 was put into a rotary kiln (Dongwon Engineering Co., Ltd.) through a transfer device and dried for 30 minutes while maintaining the temperature range between 100 and 120 ° C while rotating. The dried granular mixture was calcined by hot air at 500 to 700 ° C. for 60 minutes and then cooled to prepare a composite odor absorbing material using mixed zeolite. The prepared composite odor absorbing materials were placed in a vibration screen and only the particle size of the granules was selected from 0.5 to 20 mm to prepare Examples 1 to 3 and Comparative Examples 1 to 4.

[Experimental Example 2]

Iodine adsorption performance evaluation

Examples 1 to 3 and Comparative Examples 1 to 4 prepared in Experimental Example 1 were impregnated in an iodine solution for 24 hours, and weight and volume changes were measured.

Name of sample Precipitation (g) After impregnation (g) Weight change (g) Volume change (%) Adsorption performance (%) Example 1 15.52 22.50 6.98 28.94 32 Example 2 15.43 23.58 8.15 30.24 34 Example 3 15.39 22.46 7.07 29.99 33 Comparative Example 1 15.88 22.25 6.37 23.63 28 Comparative Example 2 15.71 22.09 6.38 23.67 29 Comparative Example 3 15.26 22.11 6.85 25.41 31 Comparative Example 4 15.81 23.11 7.30 27.08 31

From the results of Table 5, it can be seen that Examples 1 to 3 are superior in iodine adsorption performance to Comparative Examples 1 to 4. It was also confirmed that the adsorption performance of the composite odor adsorbent using the mixed zeolites of Examples 1 to 3 was superior to that of the natural zeolite of Experimental Example 1, in comparison with the iodine adsorption performance evaluation.

[Experimental Example 3]

Evaluation of compressive strength

The compressive strength was measured 10 times each by using a compressive strength meter after air cooling of Examples 1 to 3 and Comparative Examples 1 to 4 prepared in Experimental Example 1 and commercially available adsorbents DW1 to DW4 (KYOCERA CORPORATION) Respectively.

Name of sample Compressive strength (Kgf) Example 1 5.13 Example 2 5.90 Example 3 5.23 Comparative Example 1 4.21 Comparative Example 2 4.37 Comparative Example 3 0.83 Comparative Example 4 3.40 DW1 (Zeolite) 22.8 DW2 (multi-pore zeolite) 26.0 DW3 (loess ball) 4.90 DW4 (low temperature baked loam ball) 5.70

DW1 and DW2, which were produced by high temperature firing (600 to 1000 ° C), were superior to those of Examples 1 to 3, but DW3 to DW4 (200 to 600 ° C) manufactured by low temperature firing The compressive strength was similar.

It was also confirmed that the compressive strength of Comparative Example 3 containing no sodium hydrogencarbonate and Comparative Example 4 containing starch was significantly lower than that of Examples 1 to 3 and Comparative Examples 1 and 2.

[Experimental Example 4]

Evaluation of adsorption performance of odor-inducing substances

10 g of each of Examples 1 to 3, Comparative Examples 1 to 4 and commercially available adsorbents DW1 to DW4 prepared in Experimental Example 1 were sampled and injected into mercaptan, ammonia, acetaldehyde and trimethylamine solutions as malodorous substances And the adsorption rate of the malodorous substance was measured by measuring the weight by time.

2 hr 4 hr 6 hr 8 hr 12 hr 16 hr 20 hr 24 hr Example 1 0.372 0.321 0.302 0.289 0.261 0.227 0.206 0.187 Example 2 0.420 0.370 0.340 0.310 0.270 0.230 0.210 0.190 Example 3 0.396 0.372 0.354 0.304 0.291 0.209 0.199 0.192 Comparative Example 1 0.309 0.284 0.251 0.221 0.201 0.184 0.157 0.134 Comparative Example 2 0.333 0.301 0.276 0.244 0.205 0.192 0.179 0.167 Comparative Example 3 0.318 0.273 0.24 0.201 0.188 0.169 0.162 0.123 Comparative Example 4 0.299 0.287 0.261 0.236 0.204 0.191 0.191 0.146 DW1 0.287 0.210 0.198 0.186 0.180 0.174 0.174 0.156 DW2 0.382 0.382 0.342 0.296 0.25 0.217 0.211 0.197 DW3 0.345 0.331 0.317 0.296 0.268 0.254 0.246 0.232 DW4 0.228 0.222 0.204 0.173 0.154 0.136 0.111 0.093

^{(Unit: g / g)}

First, the results of Table 7 and FIG. 3 were obtained by evaluating the adsorption performance against mercaptan, which is one of the odor inducing substances, and it was confirmed that Example 2 exhibits the highest adsorption efficiency at 0.420 g / g. Next, it was found that the adsorption efficiency was 0.396 g / g in the order of DW2 commercially available in Example 3 and 0.382 g / g.

2 hr 4 hr 6 hr 8 hr 12 hr 16 hr 20 hr 24 hr Example 1 0.310 0.300 0.287 0.274 0.261 0.248 0.240 0.228 Example 2 0.314 0.304 0.284 0.275 0.265 0.255 0.245 0.245 Example 3 0.320 0.301 0.280 0.267 0.257 0.251 0.241 0.231 Comparative Example 1 0.259 0.259 0.259 0.259 0.247 0.240 0.231 0.218 Comparative Example 2 0.262 0.281 0.271 0.254 0.241 0.229 0.216 0.207 Comparative Example 3 0.258 0.251 0.246 0.241 0.234 0.234 0.234 0.234 Comparative Example 4 0.243 0.231 0.225 0.216 0.213 0.210 0.200 0.200 DW1 0.110 0.110 0.108 0.052 0.052 0.052 0.052 0.052 DW2 0.258 0.258 0.253 0.224 0.174 0.174 0.174 0.174 DW3 0.267 0.257 0.257 0.237 0.232 0.227 0.227 0.227 DW4 0.097 0.097 0.097 0.087 0.070 0.070 0.070 0.070

^{(G / g)}

Table 8 and FIG. 4 show the results of the adsorption rate test using formaldehyde, which is one of the odor inducing substances, that the best adsorption rate was 0.320 g / g in Example 3, 0.314 g / g in Example 2, 0.310 g / g, and DW3 was 0.267 g / g in that order.

2 hr 4 hr 6 hr 8 hr 12 hr 16 hr 20 hr 24 hr Example 1 0.310 0.281 0.251 0.222 0.204 0.184 0.174 0.173 Example 2 0.320 0.290 0.260 0.240 0.210 0.190 0.180 0.180 Example 3 0.318 0.289 0.257 0.231 0.208 0.181 0.177 0.177 Comparative Example 1 0.275 0.259 0.241 0.212 0.198 0.172 0.154 0.152 Comparative Example 2 0.277 0.261 0.242 0.201 0.178 0.161 0.143 0.134 Comparative Example 3 0.271 0.244 0.221 0.190 0.165 0.165 0.165 0.165 Comparative Example 4 0.280 0.270 0.254 0.200 0.170 0.140 0.120 0.120 DW1 0.128 0.128 0.122 0.118 0.115 0.109 0.109 0.109 DW2 0.263 0.258 0.253 0.234 0.194 0.154 0.119 0.119 DW3 0.252 0.247 0.247 0.227 0.217 0.168 0.128 0.128 DW4 0.099 0.096 0.094 0.091 0.089 0.089 0.070 0.070

^{(G / g)}

Table 9 and FIG. 5 show the results of adsorption experiments using ammonia among the odor inducing materials. Example 2 was 0.320 g / g, adsorption ratio was the highest, Example 3 was 0.318 g / g, 0.310 g / g, and Comparative Example 4 was 0.280 g / g.

2 hr 4 hr 6 hr 8 hr 12 hr 16 hr 20 hr 24 hr Example 1 0.302 0.265 0.241 0.215 0.176 0.157 0.129 0.118 Example 2 0.307 0.267 0.238 0.208 0.188 0.168 0.139 0.129 Example 3 0.305 0.261 0.241 0.207 0.185 0.170 0.135 0.123 Comparative Example 1 0.287 0.249 0.221 0.197 0.176 0.148 0.121 0.105 Comparative Example 2 0.291 0.254 0.232 0.211 0.171 0.137 0.112 0.091 Comparative Example 3 0.301 0.248 0.229 0.183 0.157 0.111 0.059 0.059 Comparative Example 4 0.340 0.307 0.267 0.227 0.187 0.147 0.127 0.093 DW1 0.139 0.099 0.079 0.053 0.033 0.020 0.007 0.007 DW2 0.191 0.151 0.125 0.099 0.072 0.046 0.033 0.026 DW3 0.250 0.204 0.164 0.125 0.092 0.059 0.039 0.026 DW4 0.145 0.099 0.079 0.059 0.039 0.026 0.020 0.013

^{(G / g)}

Table 10 and FIG. 6 show the results of adsorption experiments using trimethylamine among the odor inducing substances. As a result of the adsorption test, the best adsorption performance was obtained at 0.340 g / g in Comparative Example 4, 0.307 g / g in Example 2, 0.305 g / g, and 0.302 g / g, respectively.

The results of Tables 7 to 10 and FIGS. 3 to 6 of Experimental Example 4 show that adsorption ratios of mercaptan, ammonia and trimethylamine solution, which are odor inducing substances, The adsorbents of Examples 1 to 3 and Comparative Example 3, Comparative Example 4 and DW2 showed high adsorption rates.

[Experimental Example 5]

Physical and chemical performance evaluation of sorbent materials

SEM ( Electron scanning microscopy )analysis

The crystal structure was confirmed by SEM (electron scanning microscope) analysis of Example 2, Comparative Example 3, Comparative Example 4 and DW2 showing excellent adsorption power in Experimental Example 4 above.

7 to 10, it can be seen that the size of the mixed crystal structure and pore size on the surface of the zeolite is less than 200 nm in Example 2, and the size of pores in the zeolite surface is larger than that of Comparative Example 3 1 to 3 mu m, Comparative Example 4 is a pore state in which zeolite surfaces are mixed, the pore size is between 1 and 3 mu m, and DW2 is a cubic structure and a layer structure of crystals, It is confirmed that the surface particles have a size of ~ 1.5 nm.

XRD (X- ray diffraction )analysis

Example 2, Comparative Example 3, Comparative Example 4 and DW2 showing excellent adsorption power in Experimental Example 4 were subjected to XPD analysis using XPERT-PRO diffractometer of Philips using CuKα radiation.

11 shows the XRD diffract grams of DW2 in Example 2, FIG. 11B in Comparative Example 3, FIG. 11C in Comparative Example 4, and FIG. 11D show high density due to high intensity and peak I could. It was also found that there was no definite form of sodium aluminosilicate in the zeolite crystal structure due to the small peaks observed in the range of 20 to 35.

Adsorption heat Character rating

The heat of adsorption was measured by measuring the temperature rise over time while continuously applying a 500 W microwave.

12, it can be seen that the temperature changes with time in Examples 2 and DW2 rapidly progressed, and the temperature change in Comparative Example 3 and Comparative Example 4 changes slowly. The water molecules included in Example 2, Comparative Example 3, Comparative Example 4, and DW2 were polarized to absorb the microwaves, causing an exothermic reaction, resulting in a rise in temperature. Also, since the components such as iron and aluminum exhibit a high heat of adsorption due to electrical conductivity, the content of iron and aluminum in Examples 2 and DW2 is high, and the content of iron and aluminum in Comparative Example 3 and Comparative Example 4 is relatively low Could know.

Desorption performance evaluation

Evaluation of desorption performance for regenerating Formaldehyde contaminated Example 2, Comparative Example 3, Comparative Example 4 and DW2 using a microwave heating system was performed.

Formaldehyde were saturated in Example 2, Comparative Example 3, Comparative Example 4 and DW2, respectively, and then placed in a quartz tube and dried with a microwave of 500 W. During drying, the formaldehyde concentration in the exhaust gas was measured by gas chromatography by vaporizing from the opposite side with nitrogen gas at a flow rate of 50 ml / min.

Referring to FIG. 13, the desorption rate was in the order of Example 2, DW2, Comparative Example 3, and Comparative Example 4. In more detail, the desorption curve showed a desorption efficiency of almost 100% between 10 and 25 minutes, although the desorption time was different, and satisfactory desorption efficiency was obtained even at about 500 W of microwave. It can be confirmed that Example 2 resulted in 100% desorption within 10 minutes.

The results of Experimental Example 5 demonstrate that Example 2, which is a composite odor adsorbent using the mixed zeolite of the present invention, exhibited excellent adsorption and desorption rates in the adsorption rate and desorption performance evaluation as compared with DW2 that was commercialized in the past, The adsorption rate and the desorption rate of the adsorbent of Comparative Example 3 and the adsorbent of Comparative Example 4 containing starch were confirmed.

[Experimental Example 6]

Pilot - test Performance evaluation of adsorption tower

In order to evaluate the malodor removing performance of Example 2, which was rated excellent in Experimental Examples 4 and 5, adsorption experiments were carried out.

The gas phase gas which is volatilized after adding a solution containing hydrogen sulfide, acetaldehyde, trimethylamine and ammonia, which are the main odor inducing substances generated in the food processing facility, into lukewarm water is mixed with the mixed odor of the mixture containing natural zeolite of Example 2 The effluent concentration was measured 2 hours and 4 hours after passing through adsorption tower filled with adsorbent material.

division Influent concentration
(ppm) Effluent Concentration (ppm) Reduction rate (%) 2 hours 4 hours 2 hours 4 hours ammonia 2.865 0.454 1.937 84.2 32.4 Acetaldehyde 8.096 0.133 0.994 98.4 87.7 Trimethylamine 1.434 - 0.159 - 88.9 Complex odor 30,000 times 100 144 - -

As shown in Table 11, the ammonia concentration was measured to be 0.454 ppm and 1.937 ppm at the inlet concentration of 2.868 ppm after 2 hours and 4 hours, respectively, and the reduction rate was 84.2% and 32.4%, respectively. Acetaldehyde had an inlet concentration of 8.096 ppm , The reduction rate was measured as 98.4% and 87.7% at 0.133 ppm and 0.994 ppm after 2 hours and 4 hours, respectively, and trimethylamine was not detected at 0.159 ppm after 2 hours and 4 hours after the introduction at 1.434 ppm The reduction rate was measured as 88.9%.

The results of Experimental Examples 4 to 6 show that the complex odor sorbent using the natural zeolite-containing mixture according to the present invention adsorbs odor-causing substances such as ammonia, acetaldehyde, trimethylamine, and mercaptan, And it was confirmed that it is excellent in the efficiency of desorbing by microwave and the efficiency of renewable energy.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Should be understood.

Claims

A mixture comprising 100 parts by weight of natural zeolite, 20 to 25 parts by weight of fly ash, 4 to 7 parts by weight of loess, 1 to 3 parts by weight of bentonite and 13 to 16 parts by weight of sodium hydrogencarbonate (NaHCO ₃ ) And further comprising 1 to 5 parts by weight of an organic binder based on 100 parts by weight of the natural zeolite.

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The method according to claim 1,
Wherein the composite odor adsorbent has a pore size of 10 to 300 nm.

100 parts by weight of natural zeolite, 20 to 25 parts by weight of fly ash, 4 to 7 parts by weight of loess, 1 to 3 parts by weight of bentonite and 13 to 16 parts by weight of sodium hydrogencarbonate (NaHCO ₃ ) Mixing step;
Adding 1 to 5 parts by weight of an organic binder to 100 parts by weight of the first mixture, and molding the resultant into a granule form; And
And a drying and calcining step of applying heat to the granulated mixture to form a composite zeolite adsorbent.

5. The method of claim 4,
Further comprising, after the drying and calcining step, selecting a mixture of the fired granule type to a size of 0.5 to 20 mm.

delete

5. The method of claim 4,
Wherein the molding step is carried out by adding 1 to 5 parts by weight of an organic binder to 100 parts by weight of the mixture in the rotating body and then rotating the mixture at 3 to 30 rpm to form a granule. (JP) METHOD FOR MANUFACTURING COMBINED.

5. The method of claim 4,
In the drying and firing step,
A drying step of applying heat to the granular mixture to remove moisture on the granular surface;
A fine particle removing step of passing the mixture of granules through the drying step through a rotating screen including a perforation hole to remove fine particles; And
A sintering step of applying heat to the granular mixture through the fine particle removal step;
Wherein the natural odor absorbing material comprises a natural zeolite.

9. The method of claim 8,
Wherein the drying step is performed at a temperature of 80 to 150 ° C.

9. The method of claim 8,
Wherein the calcining step is performed at a temperature of 250 to 800 ° C.