KR101682907B1 - Adsorbent media, the preparation method thereof, circulation adsorption column for removing the nitrogen and phosphorus compounds - Google Patents

Abstract

Disclosed are an adsorption filter material for removing nitrogen and phosphorus, a method for manufacturing the same, and a circulation adsorption column containing the same. The adsorption filter material according to an embodiment of the present invention contains a plasticized mixture of 90-95 parts by weight of zeolite and 5-10 parts by weight of gamma-alumina. Accordingly, the present invention provides the adsorption filter material which improves sewage treatment efficiency by simultaneously removing nitrogen and phosphorus in polluted sewage.

Description

TECHNICAL FIELD [0001] The present invention relates to an adsorption filter material for simultaneous removal of nitrogen and phosphorus, a method for producing the same, and a circulation adsorption column containing the same. BACKGROUND ART [0002]

More particularly, the present invention relates to a sorbed material for simultaneous removal of nitrogen and phosphorus, a method for producing the sorbed material, and a circulating adsorption column comprising the sorbed material, the method for producing the same, and the circulating adsorption column .

Contaminated inflow water contains many nutrients such as organic matter and minerals (especially nitrogen and phosphorus), and thus proliferation of protozoan, algae, and bacteria is active. This causes eutrophication and causes green tide or red tide phenomenon, which greatly affects the environment. It is the reason why the water quality standards and regulations are set at the national level and the sewage treatment is required to satisfy these standards and regulations. Accordingly, various methods and apparatuses have been developed for treating nutrients including nitrogen and phosphorus.

Generally, in most sewage treatment plants, an activated sludge process for the purpose of removing organic matter is used. However, the removal efficiency of organic materials is good, but only the nutrients necessary for growth and growth of microorganisms are removed. Therefore, the removal rates of nitrogen and phosphorus, which are minerals, are remarkably low. Therefore, a tertiary treatment process such as an advanced sewage treatment is required, and various reaction vessels (anoxic tank, anaerobic tank, aerobic tank, etc.) are generally used for removing nitrogen and phosphorus by biological methods. However, in the case of the biological treatment method, when the pollutant load in the sewage inflow water is increased due to the nature of using the microorganisms, the treatment time is long and the treatment efficiency is low because the treatment plant is not operated smoothly.

As a result, researches on methods, materials and devices for simultaneous removal of nitrogen and phosphorus have been carried out in order to reduce the treatment time and increase the treatment efficiency in sewage treatment facilities. (See the following prior art documents).

Patent Document 1: Korean Patent No. 1,478,305 (registered on December 24, 2014) Patent Document 2: Korean Patent No. 1,167,488 (Registered on July 13, 2012) Patent Document 3: Korean Patent No. 1,135,011 (Registered on Apr. 03, 2012)

The present invention aims at providing an adsorbent filter material which simultaneously removes nitrogen and phosphorus in contaminated sewage to improve sewage treatment efficiency.

The present invention also provides a method for producing the adsorbent material.

Further, it is intended to provide a circulating adsorption column to which the adsorption filter medium is applied.

According to an aspect of the present invention, an adsorbent material composed of a mixture of zeolite and gamma alumina mixed with a mixture of 90 to 95 parts by weight of zeolite and 5 to 10 parts by weight of gamma alumina may be provided.

In addition, 5 to 10 parts by weight of titanium dioxide can be coated on the surface of the mixture.

According to another aspect of the present invention, there is provided a method for producing a zeolite comprising mixing zeolite and gamma alumina; Adding water and alumina boehmite sol to the mixture and kneading; Shaping the kneaded product into a spherical shape; Impregnating the workpiece with titanium dioxide sol to coat the surface of the workpiece with titanium dioxide; And a step of heat-treating the workpiece coated with the titanium dioxide on the surface thereof and firing the workpiece.

In this case, the zeolite may be mixed in an amount of 90 to 95 parts by weight and the gamma alumina may be added in an amount of 5 to 10 parts by weight.

Also, the ratio of the adsorbent material, alumina boehmite sol and water may be 8: 2: 1 to 9: 1: 1 based on the weight ratio.

The method may further comprise preparing the zeolite prior to mixing the zeolite and gamma alumina, wherein the step of preparing the zeolite comprises grinding the basalt mineral to a micrometer scale size, mixing it with sodium chloride or sodium carbonate step; Heat-treating the mixture, adding it to distilled water and stirring to elute the zeolite precursor; Adding NaAlO ₂ to the eluted zeolite precursor solution to form a reactant; And heat-treating the reactant to perform zeolite crystallization.

The step of eluting the zeolite precursor may further include the step of adding an acid solution to the distilled water to remove impurities from the zeolite precursor.

According to another aspect of the present invention, there is provided a circulating adsorption column installed at least one of a front end and a rear end of a reaction tank of a sewage treatment apparatus, wherein the circulating adsorption column includes a column body portion ; A plurality of adsorption media filled in the column body; A circulation unit for circulating the adsorption media discharged to the lower end of the column body to an upper end of the column body; And a washing unit located at an upper end of the column body and washing the adsorption media fed by the circulation unit, wherein the adsorption media is mixed with 90 to 95 parts by weight of zeolite and 5 to 10 parts by weight of gamma alumina A circulating adsorption column composed of the calcined product of the mixture may be provided.

In addition, the adsorption filter medium may further include an ultraviolet lamp, wherein 5 to 10 parts by weight of titanium dioxide is coated on the surface of the mixture, and the circulating adsorption column is installed inside the column body.

The adsorbent material produced by the adsorbent material according to embodiments of the present invention and the adsorbent material produced by the adsorbent material manufacturing method is a composite material composed of zeolite for removing nitrogen and gamma alumina for removing phosphor. Nitrogen and phosphorus simultaneously.

Further, the circulating adsorption column according to the embodiments of the present invention can be additionally provided in the reaction tank of the sewage treatment apparatus by filling the adsorption filter material according to the embodiments of the present invention, thereby improving the removal efficiency of nitrogen and phosphorus.

Fig. 1 is a flowchart of a method for manufacturing an adsorbent material according to one embodiment of the present invention.
FIG. 2 is a flowchart of steps before step S20 in FIG.
Fig. 3 is an FE-SEM image of zeolite precursor elution with or without acid treatment in the zeolite production process.
4 is an image of adsorbent material prepared according to one embodiment of the present invention.
5 is a schematic view of a circulating adsorption column according to an embodiment of the present invention.
6 is a graph showing nitrogen and phosphorus treatment times of the adsorbent material according to the present invention.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. It is to be understood that the following description is illustrative of the present invention, and the technical spirit of the present invention is not limited to the following description. BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention.

Adsorbed filter media

The present invention provides adsorptive filter media. The adsorbent material (hereinafter referred to as adsorbent material) according to the present invention can be used in a sewage treatment apparatus or the like to simultaneously remove nitrogen and phosphorus in contaminated sewage.

In one embodiment, the adsorptive filter media may consist of a calcined mixture of a mixture of zeolite and gamma alumina. That is, the adsorbent material is a composite material containing zeolite and gamma alumina. The specific manufacturing method of the adsorbent material will be described later. In this section, description is made on the material constituting the adsorbent material.

The zeolite may be natural zeolite; Zeolite 4A grade, zeolite 13X, zeolite Y and the like can be used. In one embodiment, the zeolite may be one produced according to the method according to the present invention, which will be described later on the basis of a basalt mineral. At this time, the basalt mineral may be a basalt mineral in the Cheolwon area, and may be a processed basalt mineral (stone) in an industry using basalt minerals. As a result, the crystallinity, specific surface area, and cation exchange capacity of zeolite were relatively higher than those of commercial zeolite. Since zeolite has a cation exchange capacity and is highly selective for NH ₄ ⁺ , it is widely used as a material for removing nitrogen in the sewage treatment field.

The gamma alumina may be a commercial gamma alumina or a gamma alumina prepared by a known method. Gamma alumina is a kind of metal oxide which is a carrier and can adsorb phosphorus.

The adsorbent material is composed of a calcined mixture of a mixture of zeolite and gamma alumina as described above. The zeolite may be mixed in an amount of 90 to 95 parts by weight and the gamma alumina may be mixed in an amount of 5 to 10 parts by weight ). This weight ratio may vary depending on the properties of the sewage / wastewater. However, when the adsorbing material has a mixing ratio of zeolite and gamma-alumina that is outside the range, it is not preferable from the viewpoint of the nitrogen removal rate, which will be confirmed in a test example described later.

In one embodiment, the adsorbent material may be formed into a spherical shape or a bead shape. The adsorbent material having a spherical or bead shape may be more preferable in terms of strength and degree of agglomeration of constituent materials. At this time, the spherical shape does not mean a complete spherical shape. In addition, the adsorbent material may have a size corresponding to a diameter of several millimeters. A spherical or bead type adsorbent filter material can be used to remove nitrogen and phosphorus in the sewage water filled in a plurality of reaction devices (column devices, etc.) disposed in the sewage treatment device.

In one embodiment, the surface of the sorbed media can be coated with titanium dioxide (TiO ₂ ). The titanium dioxide can be classified into rutile, anatase, titania and the like depending on the crystal structure, and in the present invention, an anatase having excellent photocatalytic activity is preferably used. Titanium dioxide is a typical material used as a photocatalyst, and it can impart a photocatalytic function to adsorbed filter media. That is, when an adsorption filter material coated with titanium dioxide is used, superoxide ions (O ₂ ^- ) and hydroxy radicals (-OH) can be generated by the reaction with irradiated light, Can be improved. Since the photocatalytic reaction is a known reaction, a detailed description of the reaction mechanism is omitted.

The titanium dioxide may be coated in an amount of 5 to 10 parts by weight based on the weight of the zeolite. The weight ratio may vary depending on the characteristics of the sewage / wastewater.

Adsorption filter material manufacturing method

The present invention further provides a method for producing adsorbent material. The adsorbent material produced according to the adsorbent material manufacturing method according to the present invention can be used in a sewage treatment apparatus and the like to simultaneously remove nitrogen and phosphorus in contaminated sewage.

Fig. 1 is a flowchart of a method for manufacturing an adsorbent material according to one embodiment of the present invention. Referring to FIG. 1, the adsorbent material manufacturing method includes a step S20 of mixing zeolite and gamma alumina, a step S30 of adding water and alumina boehmite sol to the mixture and kneading the mixture, a step S40 . ≪ / RTI > Further, the method may further include a step S50 of impregnating the titanium dioxide sol with the workpiece to coat the surface of the workpiece with titanium dioxide. Hereinafter, each step will be described in detail.

In step S20, zeolite and gamma alumina are mixed. Since zeolite and gamma alumina are the same as or similar to those described above, duplicate descriptions are omitted. Specifically, zeolite particles having a particle size of 500 nm to 3 占 퐉 and gamma alumina particles can be mixed using a 3D mixer, a ball mill or the like to form a mixture. The mixing time is not specified, and can be, for example, about 1 hour. The zeolite may be mixed in an amount of 90 to 95 parts by weight and the gamma alumina may be mixed in an amount of 5 to 10 parts by weight (based on the weight of the zeolite).

In step S30, water (NaOH-containing water is more preferable) and alumina bohemite sol are added to the mixture and kneaded to form a kneaded product. The kneaded product may be formed through a known method, for example, a conventional mixer may be used. On the other hand, the alumina boehmite sol and water may be added in an amount of 9: 1: 1 to 8: 2: 1 based on the weight of the adsorbent material, alumina boehmite sol and water. In one embodiment, when the amount of the alumina boehmite sol serving as the binder of the mixture is less than the above range, the mechanical strength of the adsorbent media is lowered and the shape of the adsorbent media is not maintained after the firing, When the addition amount of the mite sol is larger than the above range, the specific surface area of the adsorbed filter medium is reduced. Although it will be confirmed in a test example to be described later, it is preferable since the specific surface area of the adsorbent material is the largest when the ratio of the adsorbent material, alumina boehmite sol and water is 9: 1: 1.

One feature of the present invention is that alumina boehmite sol, which is an inorganic binder, is used in step S30. Alumina, boehmite sols can be reduced to the monohydrate _{(Al 2 O 3 · H 2} O) is due to the trihydrate _{(Al 2 O 3 · 3H 2} O) reduction of the mass is generated upon firing as compared to, in particular, zeolites and (-MOM-) or oligo (-M-OH-M-) bonds with metal oxides when hydration is easily carried out in a form that is easy to bond to gamma alumina. In addition, in the heat treatment, Phase transition, and thus has a merit of allowing a low-temperature heat treatment. In addition, since it is not an ordinary organic binder, it is also excellent in stability.

It is also possible to use an inorganic binder such as clay or blast furnace slag instead of alumina boehmite sol, but these alternatives contain a lot of other impurities such as magnesium, potassium, iron and the like, and the impurities act as an obstructing substance in nitrogen removal So that it is not preferable.

In step S40, the kneaded product is processed into a spherical shape (bead shape). This process can use known devices for spherical machining. For example, the kneaded product may be extruded through a conventional extruder and processed into a ring by using a conventional ringer.

In step S50, the workpiece is impregnated with titanium dioxide sol, and the surface of the workpiece is coated with titanium dioxide. The reason for coating the surface with titanium dioxide is to give a photocatalytic function to the adsorbed filter media. In one embodiment, the titanium dioxide sol solution of 10 nm in size is impregnated with the workpiece and dried at 100 DEG C for about 24 hours.

Thereafter, the adsorbent material can be produced by performing the heat treatment at a temperature in the range of more than 300 DEG C to 400 DEG C for about 1 hour. When the heat treatment is carried out at a temperature of 300 ° C or less, there is a disadvantage in that the adsorbed filter material can not maintain its shape after firing, and when the temperature is higher than necessary, the specific surface area is lowered. It is most preferable in terms of shape maintenance and specific surface area when the heat treatment temperature is about 350 캜.

Through the above steps, adsorbent material can be produced.

On the other hand, the zeolite used in step S20 can be produced based on basalt minerals. 2 is a flowchart of steps before step S20 in FIG. Referring to FIG. 2, the adsorbent material manufacturing method further includes a step of preparing a zeolite before the step S20, wherein the step of preparing the zeolite comprises pulverizing the basalt mineral into a micrometer size, and then mixing S12 step; S12: heat-treating the mixture, adding it to distilled water and stirring to elute the zeolite precursor; It was reacted by the addition of NaAlO ₂ in the eluted S13 zeolite precursor solution to form a reaction product; And performing a heat treatment on the reactant to perform zeolite crystallization. Hereinafter, each step will be described in detail.

In step S11, the basalt mineral is ground and mixed with sodium chloride or sodium carbonate to form a mixture. At this time, the basalt mineral may be a basalt mineral in the Cheolwon area, and may be a processed basalt mineral (stone) in an industry using basalt minerals. The crushing of the basalt mineral may be carried out using a conventional crusher (e.g., a jaw crusher), and the basalt mineral may be crushed to a size having a diameter of several tens of 탆 (e.g., 10 탆). Thereafter, the mixture may be mixed with sodium chloride or sodium carbonate at a ratio of 1: 1 and mixed for about 1 hour by a conventional mixing device such as a 3D mixer.

In step S12, the mixture may be primarily heat treated. The heat treatment may be performed using a conventional mixing / heat treating apparatus such as a rotary kiln (for example, heat treatment in a rotary kiln at a temperature of 500 DEG C for 30 minutes). The zeolite precursor may then be eluted by adding the mixture to the distilled water (for example 40 wt%) and stirring (for example 2 hours 300 rpm). At this time, an acid solution (for example, 2M HCl) may be added to the distilled water to remove impurities such as Fe and Ca in the release of the zeolite precursor. 3 is an FE-SEM image showing the presence or absence of an acid treatment. The left image is the case where the acid processing is performed, and the right image is the case where the acid processing is not performed. When the acid treatment is not carried out, it can be confirmed that the crystallinity of the produced zeolite is much lower.

NaAlO ₂ may be added to the eluted zeolite precursor solution in step S 13 to supplement the deficient Al or Na ⁺ in crystallization of the zeolite. At this time, other kinds of synthetic zeolite can be prepared by adjusting the total reaction molar ratio of Si: Al: Na. For example, when the ratio of Si: Al is 1 or less, zeolite 2.5A can be prepared, and when the ratio is 1 or more, zeolite 13X can be produced. In addition, the reaction yield can be improved when a certain amount (for example, 5 wt%) of the commercial zeolite 4A class is added in the above reaction.

In step S14, zeolite crystallization may be performed by heat-treating the reaction product at 80 DEG C (for example, 300 rpm for 3 hours). When crystallization is carried out at a temperature lower than 80 DEG C, crystallization is delayed more than necessary, which results in a long crystallization time. When the reaction temperature exceeds 80 DEG C, zeolite 13X may not be formed. On the other hand, when the reaction time exceeds 3 hours, zeolite 2.5A can be prepared.

The crystallized zeolite may then be washed in distilled water and dried (e.g. at 100 DEG C for 24 hours) and stabilized to complete the zeolite preparation.

Hereinafter, the present invention will be described more specifically with reference to test examples of adsorbent and adsorbent materials according to the present invention. However, it is apparent that the present invention is not limited to the following test examples.

Test Example

Adsorbent filter media were prepared according to the adsorbent filter manufacturing method according to the present invention.

A zeolite 4A grade (about 1 탆 particle size) and gamma alumina (about 1 탆 particle size) were mixed in a 3D mixer for about 1 hour. The mixing ratio of zeolite and gamma alumina was 9: 1 by weight. Then, water containing NaOH and alumina boehmite sol were added to form a kneaded product, which was extruded and recycled to prepare a bead-shaped adsorbent material. Then, the adsorption filter medium was impregnated with a 10 nm titanium dioxide sol solution (10 wt% of the adsorbent media weight) for 30 minutes and dried at 100 ° C for 24 hours. Thereafter, the adsorbent material was heat-treated for 1 hour to complete adsorption media having a diameter of about 5 mm. 3 is an image of the adsorbent material. The left image is the general image of the adsorbent media, and the right image is the FE-SEM image (Hitachi S-4800).

(1) Shape maintenance and specific surface area test according to the proportion of binder

In the process of preparing the adsorbent material, the adsorbent material was prepared by varying the mixing ratio of alumina boehmite sol and water. The specific surface area and the morphology of the adsorbent materials were observed. The blend ratio of zeolite, gamma alumina and titanium dioxide sol was 9: 1: 1 by weight. The specific surface area was measured by the BET method. The morphological observation was performed by adding 30wt% of the adsorbent material to distilled water, and then visually confirming the degree of loosening and breaking by stirring at 500rpm for 1 hour. The results are shown in Table 1 below.

Adsorbed filter material: alumina boehmite sol: ratio of water Specific surface area (m ² / g) Maintain shape One 9.5: 0.5: 1 250.7 × 2 9: 1: 1 233.9 O 3 8.5: 1.5: 1 184.3 O 4 8: 2: 1 150.5 O

Referring to Table 1, when the ratio of the adsorbent material: alumina bohemite sol: water is 9: 1: 1 (No. 2) to 8: 2: 1 (No. 4) When the blending ratio is 9.5: 0.5: 1 (no. 1), it can be confirmed that the shape is not maintained. As a result, the mixing ratio of the adsorbent material, alumina boehmite sol and water was determined. In particular, when the mixing ratio was 9: 1: 1, the specific surface area was the highest.

(2) Shape maintenance and specific surface area test according to heat treatment temperature (sintering temperature)

In the process of preparing the adsorbent material, the adsorbent material was manufactured by varying the heat treatment temperature (firing temperature) at the final stage (the heat treatment time was 1 hour), and the specific surface area and the post-calcination form of the adsorbent materials were observed. The mixing ratio of zeolite, gamma alumina and titanium dioxide sol was 9: 1: 1 by weight, and the mixing ratio of alumina boehmite sol and water was 1: 1, respectively, when the weight of adsorbed filter media was 8. The results are shown in Table 2 below.

Heat treatment temperature (sintering temperature, 占 폚) Specific surface area (m ² / g) Maintain shape One 250 273.8 × 2 300 250.1 × 3 350 233.9 O 4 400 198.3 O

Referring to Table 2, when the heat treatment temperature was 300 ° C or less, it was confirmed that the sintering temperature had to be higher than 300 ° C because it failed to maintain its shape. When considering the specific surface area, 350 ° C was the optimum sintering temperature .

(3) Measurement of nitrogen and phosphorus removal efficiency

In the process of preparing the adsorbent material, four kinds of adsorbent materials were prepared by varying the mixing ratio of zeolite and gamma alumina. Other manufacturing process conditions were controlled except for the mixing ratio. After that, the adsorbent was added to standard solutions (ammonia nitrogen 20 ppm and phosphorus 2 ppm) and actual wastewater (Kangwondo Jumunjin wastewater treatment plant wastewater sample, total nitrogen 18 ppm, total phosphorus 1.5 ppm), and nitrogen and phosphorus removal ratios were measured. The dose was 5 wt% for the standard solution and 1 wt% (w / v) for the actual wastewater, and the pH was adjusted to 3 in both cases. The results are shown in Table 3 below.

Mixing ratio of zeolite and gamma alumina Kinds Nitrogen removal rate
(The standard solution is the ammonia nitrogen removal rate, and the wastewater is the total nitrogen removal rate) Phosphorus removal rate
(The standard solution is the phosphorus removal rate, the wastewater is the total phosphorus removal rate) One
7: 3
Standard solution 84% 100% Wastewater 73% 100% 2
8: 2
Standard solution 90% 100% Wastewater 84% 100% 3
9: 1
Standard solution 91% 96% Wastewater 85% 100% 4
9.5: 0.5
Standard solution wastewater 92% 84% Wastewater 88% 100%

Referring to Table 3, when the mixing ratio of zeolite to gamma alumina was 8: 2, the removal efficiency of nitrogen and phosphorus was the best in the case of the standard solution. In the case of wastewater, the mixing ratio of zeolite and gamma- : 0.5 showed the best nitrogen and phosphorus removal rate. On the other hand, when the mixing ratio was 7: 3, the nitrogen and phosphorus removal rates were the lowest in both the standard solution and the wastewater, and thus it was not suitable for the scope of the present invention.

Circulating adsorption column

The present invention further provides a circulating adsorption column additionally provided in the sewage treatment apparatus. The circulating adsorption column according to the present invention is filled with the adsorbent material according to the present invention and the adsorbent material can be circulated to simplify the regeneration process and improve the treatment efficiency of removal of nitrogen and phosphorus . The circulating adsorption column may be installed at least one of the front end and the rear end of the reaction tank of the sewage treatment apparatus, thereby reducing the load of nitrogen and phosphorus contained in the sewage introduced.

5 is a schematic view of a circulating adsorption column 100 according to one embodiment of the present invention. The circulating adsorption column 100 may include a column body 110, a plurality of adsorption filter media 120, a circulating device 130, and a cleaning unit 140.

The column body 110 is constructed so that sewage can be input and output. A plurality of adsorption filter media (120) are filled in the inside of the column body part (110). The adsorbent material 120 is an adsorbent material prepared according to the above-described adsorbent material according to the present invention or the adsorbent material according to the present invention. Descriptions of the adsorbent material and the manufacturing method have been described above, so redundant description will be omitted. The amount to be filled is not specified, and can be filled to such an extent that about 40% of the column body portion 110 can be filled, for example.

The circulation unit 130 communicates with the lower end and the upper end of the column body 110 and circulates the adsorption media 120 discharged to the lower end of the column body 110 toward the upper end of the column body 110 Function. The circulation unit 130 includes a tube for connecting the upper end of the column body 110 to the upper end of the column body 110 and a driving source (not shown) for moving the adsorption filter medium 120 through the tube, And may be manufactured by combining conventional devices. Although not shown in FIG. 5, a recycling apparatus for regenerating the adsorbent material may be additionally installed in the circulation unit 130. The regenerating apparatus regenerates the adsorbent material used for the adsorbent material by a chemical method or a heat treatment method. That is, the used adsorbing material 120 is discharged to the lower end of the column body 110 and then injected into the upper end of the column body 110 through the circulation unit 130. In the course of the adsorption, Can be performed. The cleaning unit 140 may be coupled to the upper end of the column body 110 to perform a function of cleaning the adsorption media 120 supplied by the circulation unit 130.

5, a blower or the like for flowing the adsorption filter medium 120 may be further installed in the column body 110. [ The circulating adsorption column as described above has an advantage that it is higher in operation efficiency than the fixed adsorption column. In the case of a stationary adsorption column, when the adsorption of the adsorption filter medium is terminated, the operation of the adsorption column is stopped, and the adsorption filter medium is further recovered to recover the adsorbed adsorption media. In the case of the circulation adsorption column, The adsorbed filter medium is regenerated on the moving path from the inlet to the re-injection, and continuous sewage treatment is possible.

As described above, since the adsorbent material according to the present invention can be coated on the surface of the titanium dioxide functioning as a photocatalyst, the ultraviolet lamp 150 is disposed inside the column body 110 of the circulating adsorption column 100 Can be installed. The ultraviolet lamp 150 may be a conventional UV lamp that generates a photocatalytic reaction, and may be installed in the column body 110. In one embodiment, as shown in FIG. 5, a pair of ultraviolet lamps 150 may be installed in the column body 110 in the longitudinal direction. The titanium dioxide coated on the surface of the adsorbing filter medium 120 can be reacted by the light irradiated from the ultraviolet lamp 150 during the adsorption of the adsorption filter media 120 to generate hydroxy radicals, . 6 is a graph showing the nitrogen and phosphorus treatment times of adsorbent media according to the present invention. The adsorption filter material was a mixture of zeolite 4A: gamma alumina: titanium dioxide sol of 9: 1: 1, and the applied sample was actual wastewater (sample of wastewater from Kangwondo Jumunjin sewage treatment plant, total nitrogen 18ppm, total content 1.5ppm). The dose was 1 wt% (w / v), the pH was adjusted to 3, and the UV lamp installed was 30 W. Referring to FIG. 6, it can be seen that the adsorption filter material according to the present invention has a shorter photocatalytic function, and therefore, the time taken to remove total nitrogen or total phosphorus is shorter than that of the general filter media.

As described above, the adsorbent media produced by the adsorbent media according to the embodiments of the present invention and the adsorbent media produced by the adsorbent media production method are composite materials composed of zeolite for removing nitrogen and gamma alumina for removing phosphorus, When used for treatment, it is possible to remove nitrogen and phosphorus at the same time. Further, the circulating adsorption column according to the embodiments of the present invention can be additionally provided in the reaction tank of the sewage treatment apparatus by filling the adsorption filter material according to the embodiments of the present invention, thereby improving the removal efficiency of nitrogen and phosphorus.

Embodiments of the present invention have been described above. However, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the appended claims. It will be understood that various modifications may be made in the invention, and that such modifications are also included within the scope of the present invention.

100: circulating adsorption column 110: column body part
120: adsorption filter media 130: circulation device
140: Cleaning part 150: Ultraviolet lamp

Claims (9)

Zeolite, and gamma alumina,
Wherein the zeolite is mixed with 90 to 95 parts by weight and the gamma alumina with 5 to 10 parts by weight. The method according to claim 1,
5 to 10 parts by weight of titanium dioxide is coated on the surface of the mixture. Mixing zeolite and gamma alumina;
Adding water and alumina boehmite sol to the mixture and kneading;
Shaping the kneaded product into a spherical shape;
Impregnating the workpiece with titanium dioxide sol to coat the surface of the workpiece with titanium dioxide; And
Heat treating the workpiece coated with the titanium dioxide on the surface thereof and firing the workpiece;
Wherein the adsorbent material is adsorbed on the adsorbent. The method of claim 3,
Wherein the zeolite is mixed at 90 to 95 parts by weight and the gamma alumina is mixed at 5 to 10 parts by weight. The method of claim 4,
Wherein the ratio of the adsorbent material, alumina boehmite sol and water is 8: 2: 1 to 9: 1: 1 based on the weight ratio. The method of claim 3,
Further comprising the step of preparing the zeolite prior to mixing the zeolite and gamma alumina,
The step of preparing the zeolite comprises:
Pulverizing the basalt mineral to a micrometer-scale size, and then mixing with sodium chloride or sodium carbonate;
Heat-treating the mixture, adding it to distilled water and stirring to elute the zeolite precursor;
Adding NaAlO ₂ to the eluted zeolite precursor solution to form a reactant; And
And heat treating the reactant to perform zeolite crystallization. The method of claim 6,
The step of eluting the zeolite precursor comprises:
Further comprising the step of adding an acid solution to the distilled water to remove impurities from the zeolite precursor. A circulating adsorption column installed at least one of a front end and a rear end of a reaction tank of a sewage treatment apparatus,
Wherein the circulating adsorption column comprises:
A column body configured to allow sewage to flow in and out;
A plurality of adsorption media filled in the column body;
A circulation unit for circulating the adsorption media discharged to the lower end of the column body to an upper end of the column body; And
And a washing unit located at an upper end of the column body and washing the adsorption media fed by the circulation unit,
Wherein the adsorbing material is composed of a calcined mixture of 90 to 95 parts by weight of zeolite and 5 to 10 parts by weight of gamma alumina. The method of claim 8,
Wherein the adsorbing material is coated with 5 to 10 parts by weight of titanium dioxide on the surface of the mixture,
Wherein the circulating adsorption column further comprises an ultraviolet lamp installed inside the column body.

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