KR100418997B1 - An absorbant of eliminating posphorus and It's manufacturing method - Google Patents

Abstract

The present invention relates to a phosphorus removal adsorbent used in a process for simultaneously treating nitrogen (N) and phosphorus (P) contained in sewage, manure, livestock wastewater, etc., which is 60 to 70 parts by weight of hard calcium carbonate and ferric oxide After mixing the composition mixed at a ratio of 30 to 40 parts by weight in a pulverizer for 24 hours, 5 parts by weight of 3% polyvinyl alcohol was added to the dried composition, and formed into particles having a diameter of 2 to 3 mm, and the molded product was 1.100 to 1.200 It is a porous form of adsorbent prepared by performing heat treatment at 2 ℃ for 2 hours and then slowly cooling to room temperature. Filling the filter with the adsorbent of the present invention in a filter, it is possible to simply remove the phosphorus in the water by passing the waste water. While purifying without the aid of neutralizing agent, it has a strong ability to treat sewage and wastewater than existing treatment methods. The present invention relates to a phosphorus removing adsorbent and a method for producing the same.

Description

Phosphorus removal adsorbent and its manufacturing method {An absorbant of eliminating posphorus and It's manufacturing method}

The present invention relates to an adsorbent for removing phosphorus contained in waste water and a method of manufacturing the same, and more particularly, to a composition using a mixture of hard calcium carbonate and ferric oxide powder as an adsorbent, to which a binder is added and molded and calcined. By forming the outer wall of the glass on the adsorbent surface and activating the voids to maximize the surface area, it is possible to increase the treatment efficiency for phosphorus and to maintain the phosphorus treatment performance of the adsorbent, while minimizing the amount of sludge generated to reduce operation management and maintenance costs. It relates to an adsorbent for removing phosphorus and a method for producing the same.

Recently, with the increase of population, industrial development, and the improvement of living standards, the discharge of living sewage, industrial wastewater, livestock wastewater and various organic wastewaters has increased rapidly, resulting in serious water pollution. Above all, when excessive discharge of nitrogen and phosphorus in the natural world causes eutrophication, which increases water pollution by algae growth, deteriorates the taste of water and makes bad smells too bad, making it unsuitable for water supply. Reduction of oxygen adversely affects the self-cleaning of rivers, jeopardizing even habitats of aquatic organisms such as fish. Therefore, environmental groups such as the government regulate the discharge of clean and treated water after the treatment by using physicochemical or biological methods at the wastewater source.

Currently, biological treatment processes that are widely used for advanced treatment of sewage have been established to treat nitrogen and phosphorus simultaneously by combining anaerobic and aerobic tanks in series. Since the growth conditions of the phosphorus-removing microorganisms are opposite, it requires a separate reaction tank and a reactor operation for each, which has a disadvantage of high facility and maintenance costs. In addition, during the rainy season, when the dissolved oxygen in the sewage and wastewater becomes high, phosphorus emission from the anaerobic tank becomes difficult, and it is difficult to operate because it requires high technology to adjust the concentration of microorganisms in the reaction tank corresponding to organic matter.

Recently, due to various problems described above, nitrogen is biologically treated, and in the case of phosphorus, chemical treatment using an adsorbent has been commonly used to combine independent processes for each.

Wastewater treatment adsorbents used in the process include porous zeolites, bentonite and ocher, etc. In recent years, waste shells have been used as adsorbents because of their excellent environmental friendliness and adsorption performance. By doing so, it was able to obtain great effects in terms of economics and efficiency.

However, since most of the currently used adsorbents are used in powder form, the sedimentation rate is slow and the reaction time is long, and the amount of adsorbent per unit volume is small. In addition, the excessive use of the adsorbent causes some particles of the adsorbent to float in the colloidal form, causing secondary pollution due to increased turbidity, decreased light transmittance, and reduced supply of dissolved oxygen. Since a second process is required for treatment, the burden of facility and maintenance costs is brought about.

In order to improve this, Korean Patent Application No. 2000-60530 is shell shell powder processed and pulverized at a high temperature; Porous natural inorganic powder consisting of at least one of ocher, montmorillonite, elite, bentonite, elvan or zeolite; And it introduces a porous adsorbent for water treatment to granulate by adding a mixture of chitosan and water as a binder to a composition consisting mainly of carbon made of porous charcoal or activated carbon as a main component.

The adsorbent of the above technique is to adjust the specific gravity of each adsorbent having a certain strength by varying the specific gravity so that it is possible to adjust the suspension time until precipitation and to maintain the proper form by using a binder to increase the settling speed and treatment efficiency will be.

However, since the adsorbent is formed by agglomeration of various adsorbents with voids formed by a binder, the specific surface area of the adsorbent is reduced and the amount of adsorption per unit weight does not increase significantly. Since the removal efficiency is low and the amount of calcium to remove phosphorus in the adsorbent is relatively small, a large amount of adsorbent has to be added, which does not improve the problem of increased turbidity.

The present invention has been prepared to solve the above problems, the specific surface area is wider than the conventional adsorbent and excellent adsorptivity, so that the removal efficiency for phosphorus can be increased even in a small amount, and precipitated in the form of sludge that is not dissolved in water after treatment. Therefore, there is no increase in turbidity, the amount of sludge precipitated is small, and the separation is easy, so that it can be processed without special separation process, thereby providing a porous ball-type phosphorus removal adsorbent which can reduce the overall operating cost and treatment cost. There is a purpose.

1 is the solubility of apatite according to the concentration and pH of phosphorus of the present invention

2a to 2d is a state diagram of phosphorus removal efficiency and turbidity according to the adsorbent composition and firing temperature of the present invention

Figure 3a to Figure 3b is a state diagram showing the pH change with time when the adsorbent of the present invention added

The present invention for solving the above object is granulated by adding a binder to a composition in which 20 to 40 parts by weight of ferric oxide (Fe ₂ O ₃ ) is mixed with respect to 60 to 80 parts by weight of calcium oxide (CaO) component. In the method for producing a phosphorus removal adsorbent for drying and calcination of the molded article, it can be achieved by providing a method for producing a phosphorus removal adsorbent, characterized in that using a hard calcium carbonate as the calcium oxide component.

The present invention will be described in more detail as follows.

According to the above method, the adsorbent components are mixed and a binder is added. At this time, the ferric oxide powder used as the adsorbent component is dried at 400 ° C. for 24 hours, and the hard calcium carbonate powder is dried at 380 ° C. for 16 hours. Cooled in desiccator, it is made of pure hard calcium carbonate powder and ferric oxide powder.

In general, the calcium oxide components include hard calcium carbonate, heavy calcium carbonate, calcium hydroxide, calcium oxide, and the like, but the present invention is characterized by the use of hard calcium carbonate that is excellent in terms of commercial and processing effects.

First, the chemical composition of the hard calcium carbonate powder is shown in Table 1 below. When the hard calcium carbonate is calcined, carbon dioxide evaporates as much as the loss in ignition shown in Table 1 to form a porous calcium oxide (CaO), which expands the specific surface area and distributes a large number of highly reactive calcium charges on the molecular surface. This can improve the removal performance for phosphorus. In addition, the hard calcium carbonate functions as an inorganic solidifying agent, even when the adsorbent of the present invention is sprayed in powder form, the hard calcium carbonate absorbs water and causes a swollen swelling phenomenon so that turbidity does not exist in the colloidal state. Secondary pollution due to the like can be prevented.

Furtherance CaO MgO SiO ₂ R ₂ O ₃ Ignition loss Etc Content (wt.%) 53.0 0.3 0.2 0.3 43.0 3.2

In the case of ferric oxide, another adsorbent component, ferrous ions (Fe ²⁺ ) and ferric ions present in ferric oxide are formed at the same time as the glass wall with calcium carbonate is formed on the outer wall of the adsorbent during plastic working. (Fe ³⁺ ) combines with phosphate ions in the wastewater to form poorly soluble phosphate compounds. Therefore, when the adsorbent is used in the adsorption process, when the ferric oxide, which is in the form of glass, is separated from the adsorbent outer wall in the form of a phosphate compound, wastewater containing phosphorus penetrates into the pores of the adsorbent, and calcium is present in the pores. Phosphorus secondary removal of phosphorus can increase the removal efficiency of phosphorus, and because a certain amount of calcium is continuously discharged to act as a factor to increase the duration of the adsorption capacity. In addition, the ferric oxide serves to form a porous form by forming pores by reacting with silicon dioxide present in a small amount of hard calcium carbonate as shown in Table 1.

The adsorbents are mixed for 24 hours in a grinder with a composition ratio of 60 to 80 parts by weight of hard calcium carbonate and 20 to 40 parts by weight of ferric oxide, and then completely mixed in an alcohol phase for 30 minutes. This is the most appropriate range where removal takes place most efficiently but no increase in turbidity. In the composition ratio, if the ratio of ferric oxide to the total adsorbent is reduced, the solidification of the adsorbent becomes poor during plastic working, and the turbidity due to the turbidity during the phosphorus removal process increases, and conversely, the total adsorbent in the composition ratio When the ratio of ferric oxide to is increased, since the organic film of ferric oxide is formed too thick on the outer wall of the adsorbent prepared after plastic working, the internal permeation of the wastewater is not easy and the phosphorus removal efficiency is lowered.

Phosphorus removal efficiency shows similar removal efficiencies in all cases having a composition ratio of 20 to 40 parts by weight of ferric oxide with respect to 60 to 80 parts by weight of hard calcium carbonate, and since the turbidity is generated within the currently regulated range, If used as an adsorbent, but turbidity is rapidly increased when 20 parts by weight of ferric oxide is mixed with 80 parts by weight of hard calcium carbonate. Therefore, it may be considered that the composition ratio of the two adsorbent components is best mixed with 30 to 40 parts by weight of ferric oxide based on 60 to 70 parts by weight of hard calcium carbonate.

Before firing the mixed composition by the above method, a binder for forming into a certain shape, ie, ball form, is required. As a binder commonly used for the above applications, natural polymers such as chitosan, cellulose, and starch and synthetic water-soluble polymers such as polyvinyl alcohol and polyethylene oxide are used, and 5 parts by weight of the binder is added to 100 parts by weight of the composition. By making it possible to form a sufficient dough can be controlled constant formation. In the present invention, a polyvinyl alcohol (PVA) aqueous solution having a concentration of 3% is used as a binder. When the binder is added and subjected to plastic processing, the water produced during the heat treatment is solidified through the hydration reaction with the binder, thereby polyvinyl alcohol. Most of them are blown with carbon dioxide and water vapor and only the adsorbent allows the shape of the ball to be controlled. In addition, since the polymer material such as polyvinyl alcohol has a characteristic of forming a porous membrane on its own, it is more effective because it can simultaneously perform a function as a modifier.

According to the present invention, the plastic working is heated to 1.100 ° C. while adjusting the temperature increase rate by 3 ° C. per minute, and then subjected to heat treatment for 2 hours in a range of 1.100 to 1.200 ° C., and then the temperature reduction rate to room temperature is 1 minute. It is preferable to cool slowly by 5 degreeC. Hard calcium carbonate used in the composition is slightly different in physical properties depending on the conditions such as time, including the firing temperature, when calcined under the above conditions has a white porous form, specific gravity is about 2.5, Mohs hardness is 2-3 This results in hard calcium carbonate with a small refractive index. However, when heated for more than 1200 ℃ for a long time, the melting of hard calcium carbonate occurs and becomes a hard white crystalline material in the porous material, so the specific surface area is reduced and the specific gravity is increased significantly, which is not suitable as an adsorbent. On the other hand, when the plastic working is less than 1.100 ℃, the temperature is low, so it is not easy to hydrolyze the hard calcium carbonate, so it is difficult to form hard calcium carbonate with sufficient porosity due to poor porosity due to evaporation of carbon dioxide.

When the content of hard calcium carbonate is in the range of 60 to 70% and the sintering temperature is in the range of 1.100 to 1.200 ° C. with respect to the total content of hard calcium carbonate and ferric oxide, as in the adsorbent prepared by the present invention, the hard outer wall is formed. Particles having calcium oxide (CaO) adhered to the surface of the compound (2CaO.Fe ₂ O ₃ ) of calcium carbonate and ferric oxide. This is supported by the data on the crystal phase according to the composition ratio and the firing temperature of the conventional calcium carbonate and iron oxide.

Using the adsorbent of the crystal form in the adsorption process, first, a light calcium carbonate attached to the surface are dissolved in the solvent is a calcium ion dissociation me of water hydroxide ions (OH ^-) and the reaction of calcium hydroxide (Ca (OH) ₂₎ It is generated as a result of repeated dissociation with calcium and hydroxide ions. In the initial stage of the reaction, calcium ions produced from hard calcium carbonate adhering to the surface are treated with phosphorus in the wastewater and treated with poorly soluble phosphate compounds, and the calcium ions of the hard calcium carbonate are sufficiently consumed in the form of phosphate compounds. When the time has elapsed as is to be a light calcium carbonate as the oxidant ferric compound vitreous outer wall of (2CaO · Fe ₂ O ₃₎ crystals occurs within the causal split by continuous reaction becomes possible waste water from penetrating into the absorbent. Therefore, when the wastewater penetrates into the adsorbent, activated calcium in the adsorbent pores cannot be removed in the wastewater, causing secondary reactions with the remaining phosphorus, and also causing precipitation in the form of poorly soluble phosphate compounds. It can play a decisive role in increasing and increasing the duration of adsorption capacity.

The phosphorus removal by the adsorbent in the above process is based on the crystallization dephosphorization method which precipitates crystals in the supersaturated solution. The crystallization dephosphorization method applies the principle that the solute is precipitated by crystallization as the nucleus when the crystal of the substance is put in the supersaturated solution. pH and supersaturation are formed so that apatite crystallization proceeds using calcium hydroxide as a nucleus.

Referring to more detail with reference to the solubility of apatite according to the concentration and pH of phosphorus of Figure 1 attached to the drawings it can be seen that pH plays an important role in the crystallization. Since the adsorbent of the present invention continuously discharges a certain amount of calcium, the adsorbent may continuously produce calcium hydroxide by reacting with water, which is a solvent, and thus the supersaturation may be maintained. Crystalline dephosphorization due to the nuclei can be stable within the quasi-stable zone, and the phosphate compound produced by the above process does not exceed 10.5 even though the pH in waste water is always over 9 even after time of precipitation. The reaction is performed within the solubility range of the quasi-stable zone state, thereby maintaining the crystallization phenomenon. In particular, hydroxyapatite (Ca ₁₀ (OH) ₂ (PO ₄ ) ₆ ), a phosphoric acid compound produced by crystallization and dephosphorization, is poorly soluble crystal having the characteristic of growing the calcium hydroxide around the nucleus, and thus is not suspended in water. It does not increase turbidity because it is deposited on the bottom.

Therefore, when the adsorbent prepared by the method of the present invention is added to the filtration and the reactor by applying the fluid type or the filling type, as a result, the poorly soluble phosphate compound does not become a slurry state, but maintains the hard state of the first ball state as it is. It is easy and can be said to be efficient at the point of nature recycling because it can be immediately used as a phosphate fertilizer by grinding the recovered material.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited only to the following examples.

<Examples 1 to 4>

3% polyvinyl alcohol aqueous solution as a binder in 100 parts by weight of a composition containing a mixture of hard calcium carbonate powder and ferric oxide powder as an adsorbent and mixing 80 parts by weight and 20 parts by weight of hard calcium carbonate and ferric oxide. 5 parts by weight was added to form a ball particle having a diameter of 2 to 3mm, dried, and then the firing temperature is as shown in Table 2 and heat-treated for 2 hours to prepare an adsorbent.

100 mg of the adsorbent prepared by the above method was added to 1 L of wastewater containing 10 mg / L of phosphoric acid, and the phosphorus removal efficiency according to the reaction time was measured and shown in Table 2 together with FIG. 2A. The turbidity of the wastewater was measured by the Nephlo method and shown in Table 2 below.

Firing temperature (℃) Phosphorus removal efficiency (%) over time (H) Turbidity (NTU) 5 10 20 40 80 160 200 Example 1 1100 88 92.4 94.1 96.6 98.4 98.5 98.6 10.2 Example 2 1200 80.2 86.5 89.5 91.9 95.3 95.9 96 9.0 Example 3 1300 75.6 79.5 84.3 87.6 93.5 94.9 94.7 7.9 Example 4 1400 71.2 73.6 79.9 83.5 88.4 91.7 90.4 7.2

<Examples 5 to 8>

3% polyvinyl alcohol aqueous solution as a binder in 100 parts by weight of a mixture of hard calcium carbonate powder and ferric oxide powder as a component of the adsorbent, and a mixing ratio of hard calcium carbonate and ferric oxide to 70 parts by weight and 30 parts by weight. 5 parts by weight was added to form a ball particle having a diameter of 2 to 3mm, dried, and then the firing temperature is as shown in Table 3 and heat-treated for 2 hours to prepare an adsorbent.

100 mg of the adsorbent prepared by the above method was added to 1 L of wastewater containing 10 mg / L of phosphoric acid, and the phosphorus removal efficiency was measured according to the reaction time. The turbidity of the wastewater was measured by the Nephel method and is shown in Table 3 below.

Firing temperature (℃) Phosphorus removal efficiency with time (H) Turbidity (NTU) 5 10 20 40 80 160 200 Example 5 1100 83.9 87.1 91.3 95 97.1 98.9 99 6.6 6 1200 72.3 77.7 81.6 89.6 94.8 96.2 96.3 6.0 Example 7 1300 64.2 72.2 75 81.2 89.9 93.6 94.7 5.5 Example 8 1400 58.6 63.6 71.2 78.5 84.9 88.6 90.4 4.7

<Example 9 to Example 12>

3% polyvinyl alcohol aqueous solution as a binder in 100 parts by weight of a mixture of hard calcium carbonate powder and ferric oxide powder as a component of the adsorbent and mixing 60 parts by weight and 40 parts by weight of hard calcium carbonate and ferric oxide. 5 parts by weight was added to form a ball particle having a diameter of 2 to 3 mm, dried, and then the firing temperature is as shown in Table 4, followed by heat treatment for 2 hours to prepare an adsorbent.

100 mg of the adsorbent prepared by the above method was added to 1 L of wastewater containing 10 mg / L of phosphoric acid, and the phosphorus removal efficiency according to the reaction time was measured and shown in Table 4 together with FIG. 2C. The turbidity of the waste water was measured by the Nefel method and is shown in Table 4 below.

Firing temperature (℃) Phosphorus removal efficiency (%) over time (H) Turbidity (NTU) 5 10 20 40 80 160 200 Example 9 1100 72.9 74.9 79.8 84.9 91.3 96.2 99 4.5 Example 10 1200 60.1 67.1 71.5 78.2 87.9 95 96.3 3.7 Example 11 1300 49.6 52.5 59.7 68.5 75.2 88.8 91.7 3.3 Example 12 1400 44.6 46.1 53.1 59.6 69.2 78.3 84.4 2.8

<Examples 13 to 16>

3% polyvinyl alcohol aqueous solution as a binder in 100 parts by weight of a composition containing a mixture of hard calcium carbonate powder and ferric oxide powder as a component of the adsorbent and mixing 50 parts by weight and 50 parts by weight of hard calcium carbonate and ferric oxide. 5 parts by weight was added to form a ball particle having a diameter of 2 to 3 mm and dried, and then the firing temperature is as shown in Table 5 and heat-treated for 2 hours to prepare an adsorbent.

100 mg of the adsorbent prepared by the above method was added to 1 L of wastewater containing 10 mg / L of phosphoric acid, and the phosphorus removal efficiency according to the reaction time was measured and shown in Table 5 together with FIG. 2D. The turbidity of the wastewater was measured by the Nefel method and is shown in Table 5 below.

Firing temperature (℃) Phosphorus removal efficiency (%) over time (H) Turbidity (NTU) 5 10 20 40 80 160 200 Example 13 1100 37.5 39.9 47.2 55.1 67.4 79.5 84.2 4.1 Example 14 1200 26.7 30.1 37.2 44.2 55.8 69.7 71.1 3.3 Example 15 1300 8.1 10.5 16.3 22.7 29.7 36.9 37.9 2.7 Example 16 1400 5.6 8.5 12.9 17.8 23.5 30.2 32.2 2.0

(In the above embodiment, the phosphorus removal efficiency was measured by (content of phosphorus in raw water-content of phosphorus in treated water / content of phosphorus in raw water) × 100, and the content of phosphorus is When the absorbance was measured by applying the molybdate method (Vanadomolybdophasphoric acid colorietric method), potassium dihydrogen phosphate (KH ₂ PO ₄ ) was used as a standard solution, and as a coloring reagent, an oxidate of ammonium oxide ((NH ₄ ) 6Mo ₇ O was used. _A calibration curve was prepared using a mixture of ₄ · 4H ₂ O) and vanadium ammonium (NH ₄ VO ₃ ), and the absorbance was measured at 400 to 470 wavelength to describe the content of each phosphorus.)

As a result of the above Examples 1 to 16, it can be seen that as the amount of hard calcium carbonate increases in the composition, phosphorus removal efficiency is increased but at the same time, turbidity is increased. On the other hand, as the amount of hard calcium carbonate in the composition decreases, the turbidity is lower but the phosphorus removal rate is also lower. In addition, the firing temperature shows that the lower the temperature, the higher the phosphorus removal efficiency.

When the adsorbent components were composed of 60 to 80 parts by weight of calcium carbonate and 20 to 40 parts by weight of ferric oxide and the firing temperature was 1.100 to 1.200 ° C., the measured phosphorus removal efficiency was similar. As can be seen, it can be observed that the turbidity was sharply increased in the case of Examples 1 to 4, which is a composition mixed with 80 parts by weight and 20 parts by weight of hard calcium carbonate and ferric oxide. Therefore, in consideration of the phosphorus removal efficiency and turbidity, it can be seen that it is preferable to formulate at a ratio of 60 to 70 parts by weight of calcium oxide and 30 to 40 parts by weight of ferric oxide.

<Example 17 to Example 18>

The mixture of calcium carbonate powder and ferric oxide powder was used as an adsorbent, and the mixing ratio of calcium carbonate and ferric oxide was 70 parts by weight and 30 parts by weight. After the addition by weight to form a ball-shaped particles of 2 ~ 3mm in diameter and dried, the firing temperature is as shown in Table 6 and heat-treated for 2 hours to prepare an adsorbent.

100 mg of the adsorbent prepared by the above method was added to 1 L of wastewater containing 10 mg / L of phosphoric acid, and the pH was measured according to the reaction time.

Firing temperature (℃) PH over time (H) One 2 7 20 50 70 100 200 Example 17 1100 10.138 10.223 10.273 10.417 10.370 1011. 10.214 10.328 Example 18 1200 9.334 9.420 9.850 10.280 9.960 9.883 10.067 10.139

<Examples 19 to 20>

The mixture of calcium carbonate powder and ferric oxide powder was used as an adsorbent, and the mixing ratio of calcium carbonate and ferric oxide was 60 parts by weight and 40 parts by weight. By weight parts are added to form a ball-shaped particles of 2-3mm in diameter and dried, and then the firing temperature as shown in Table 7 and heat-treated for 2 hours to prepare an adsorbent.

100 mg of the adsorbent prepared by the above method was added to 1 L of wastewater containing 10 mg / L of phosphoric acid, and the pH was measured according to the reaction time.

Firing temperature (℃) PH over time (S) One 2 7 20 50 70 100 200 Example 19 1100 9.489 9.989 10.158 10.217 10.154 9.78 10.128 10.283 Example 20 1200 9.11 10.105 10.100 10.280 10.208 10.014 10.106 10.428

As can be seen from Tables 6 and 7 above, the results of Examples 17 to 20 were confirmed to have pH of 9 or more and not exceeding 10.5 after sufficient time had elapsed. That is, when the adsorbent of the present invention is used, calcium ions and phosphorus are combined to generate phosphorus compounds within the solubility boundary of the apatite, so it can be seen that the removal reaction of calcium to phosphorus is performed by crystallization.

As described above, the adsorbent of the present invention is capable of processing wastewater and wastewater, which is stronger than conventional treatment methods without special aids, by activating the voids and maximizing the surface area by firing the composition mixed with a powder containing hard calcium carbonate and iron in a constant ratio. It can keep the processing time and maintain the processing time, and it is possible to remove the phosphorus in the water simply by filling the filter with the adsorbent and passing the waste water, and also because the amount of sludge generated after the treatment is small and easy to separate, It is easy to treat the sludge without the process, which brings the effect of reducing the overall operating cost.

Claims (8)

delete delete A binder is added to granulate 20 to 40 parts by weight of ferric oxide (Fe ₂ O ₃ ) based on 60 to 80 parts by weight of the calcium oxide (CaO) component, and granulated by drying the granulated molded product, followed by plastic working. In the method for preparing a phosphorus removal adsorbent, hard calcium carbonate is used as the calcium oxide component. The method according to claim 3, wherein the binder is selected from natural polymers such as chitosan, cellulose, starch, and synthetic water-soluble polymers such as polyvinyl alcohol or polyethylene oxide. The method of claim 4, wherein the binder is an aqueous solution of 3% by weight. The method according to claim 4, wherein the binder is added in an amount of 5 parts by weight based on 100 parts by weight of the composition of the calcium oxide component and the ferric oxide. The method according to claim 3, wherein the plastic working method is heated to 1.100 ℃ while adjusting the temperature increase rate by 3 ℃ per minute, and then subjected to heat treatment for 2 hours in the range of 1.100 ~ 1.200 ℃ and then the temperature reduction rate to room temperature Method for producing a phosphorus removal adsorbent, characterized in that the slow cooling by 5 ℃ per minute An adsorbent for phosphorus removal, which is produced by the method of claim 3 to 7.