KR20190052244A - Method for producing granular adsorbent for removing ionic pollutants using alum sludge and granular adsorbent produced thereby - Google Patents

Abstract

Disclosed are a manufacturing method of a granular adsorbent for removing harmful ions using an alum sludge, and a granular adsorbent manufactured thereby. According to the present invention, the manufacturing method of an adsorbent and a granular adsorbent manufactured thereby form an adsorbent as a granular. Accordingly, when the adsorbent is applied and used in a field, there is no phenomenon that adsorbents are agglomerated such that a channeling of water can be prevented, and a flow path of a product having an adsorbent installed therein can be prevented from being clogged. In addition, since the adsorbent is formed as a granular, the present invention may prevent the adsorbent from being leaked to the outside of a product having the adsorbent installed therein. Accordingly, since there is no operation for treating leaked adsorbent, the present invention provides effect of convenience.

Description

Technical Field [0001] The present invention relates to a method for producing a granular adsorbent for removing harmful ions using an alum sludge, and a granular adsorbent prepared by the method,

The present invention relates to a method for producing a granular adsorbent for removing harmful ions present in water using an alum sludge and a granular adsorbent produced thereby.

Harmful substances contained in drinking water are removed by various methods such as reverse osmosis, agglomeration, oxidation, precipitation, electrodialysis or adsorption. And, the adsorption method is simple, effective, and economical, so it is widely used.

Alum is widely used for drinking water purification and is added as a coagulant to remove suspended matter and natural organic matter. When the alum is added to water, an amorphous aluminum hydroxide, which is a type of sludge, can be formed, and aluminum hydroxide is used as a soil remover or soil remover since it is a porous material.

As the amount of water used increases, the amount of the alum used in the water treatment process also increases. Then, since a large amount of sludge is generated, a method for treating the sludge is also needed.

The present applicants have made a great effort in the development of a technology capable of processing the sludge, and as a result obtained a patent right (Registration No. 10-1344235) for "Adsorbent for removing harmful ions using Alum sludge and its production method" .

The adsorbent disclosed in Registration No. 10-1344235 is in powder form.

However, when the powdery adsorbent is applied to a field and used, aggregation occurs.

In this case, channeling phenomenon of water occurs due to the aggregated adsorbent, and the flow path of the product in which the adsorbent is installed is clogged.

Since the adsorbent in the form of powder may leak out of the area of the product where the adsorbent is installed, it is necessary to limit the flow rate or to treat the adsorbent discharged. Therefore, there is an uncomfortable problem.

It is an object of the present invention to provide a method for producing a granular adsorbent for removing harmful ions using an Alum sludge capable of solving all the problems of the prior art as described above and a granular adsorbent produced thereby.

Another object of the present invention is to provide a method for producing a granular adsorbent for removing harmful ions using an alum sludge capable of preventing channeling of water by forming an adsorbent in a granular form and blocking the flow path of a product installed with the adsorbent, And to provide the granular adsorbent thus prepared.

Another object of the present invention is to provide a method for producing a granular adsorbent for removing harmful ions by using an alum sludge which can be conveniently used by preventing the adsorbent from leaking out of a part of a product in which the adsorbent is installed and a granular adsorbent . ≪ / RTI >

A method for producing an adsorbent for adsorbing and removing arsenic (As) ions, fluorine (F) ions and selenium (Se) ions according to the present invention, And iron (Fe), drying the alum sludge from which impurities have been removed at 80 to 130 ° C for 2 to 6 hours, and then pulverizing the sludge; Firing the pulverized alum sludge; Mixing the fired sludge and a binder into water and stirring the mixture; Curing the stirred solution to form granules; Washing and drying the cured granules may be performed.

Further, the granular adsorbent according to the present invention may be one produced by the process according to any one of claims 1 to 8.

In the method for producing a granular adsorbent for removing harmful ions using the alum sludge according to the present embodiment and the granular adsorbent produced by the method, the adsorbent is formed in a granular form. Therefore, the phenomenon of accumulation of the adsorbent does not occur even when the adsorbent is used in the field, so that the channeling phenomenon of water can be prevented, and the effect of preventing the flow path of the product in which the adsorbent is installed can be prevented .

Further, since the adsorbent is formed in a granular form, it is possible to prevent the adsorbent from leaking out of the site of the product in which the adsorbent is installed. Then, there is no need for an operation to treat the leached adsorbent, so that a convenient effect may be obtained.

1 is a photograph showing a granular adsorbent produced by a manufacturing method according to an embodiment of the present invention.
Fig. 2 is an enlarged photograph taken from a portion of Fig. 1; Fig.
3 is a flow diagram illustrating a method of making a granular adsorbent in accordance with an embodiment of the present invention.
Figures 4 (a) and 4 (b) are graphs showing Langmuir adsorption isotherms and Freundlich adsorption isotherms of adsorbents.

The meaning of the terms described herein should be understood as follows.

The word " first, " " second, " and the like, used to distinguish one element from another, are to be understood to include plural representations unless the context clearly dictates otherwise. The scope of the right should not be limited by these terms.

It should be understood that the terms "comprises" or "having" does not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

It should be understood that the term " at least one " includes all possible combinations from one or more related items. For example, the meaning of " at least one of the first item, the second item and the third item " means not only the first item, the second item or the third item, but also the second item and the second item among the first item, Means any combination of items that can be presented from more than one.

It should be understood that the term " and / or " includes all possible combinations from one or more related items. For example, the meaning of " first item, second item and / or third item " may include not only the first item, the second item or the third item but also two of the first item, Means a combination of all items that can be presented from the above.

It is to be understood that when an element is referred to as being " connected or installed " to another element, it may be directly connected or installed with the other element, although other elements may be present in between. On the other hand, when an element is referred to as being " directly connected or installed " to another element, it should be understood that there are no other elements in between. On the other hand, other expressions that describe the relationship between components, such as "between" and "between" or "neighboring to" and "directly adjacent to" should be interpreted as well.

On the other hand, when an element is referred to as being " formed, combined, or installed " with another element, it is to be understood that any element and other elements may be provided separately, formed, It should be interpreted that the other components are integrally formed as a single body.

In each step, the identification codes (for example, S100, S110, S120, etc.) are used for convenience of explanation, and the identification codes do not describe and explain the order of each step, Unless the order is described, it may happen differently from the stated order. That is, each step may occur in the same order as described, may be performed substantially concurrently, or may be performed in reverse order.

Hereinafter, a method for producing a granular adsorbent for removing harmful ions using the alum sludge according to an embodiment of the present invention and a granular adsorbent produced by the method will be described in detail.

FIG. 1 is a photograph showing a granular adsorbent produced by a production method according to an embodiment of the present invention, and FIG. 2 is an enlarged photograph taken from a part of FIG.

As shown, the adsorbent according to an embodiment of the present invention can adsorb and remove arsenic (As), which is a harmful substance contained in drinking water. The adsorbent according to the embodiment of the present invention may be formed into a granular form using the adsorbent disclosed in Registration No. 10-1344235 registered and filed by the present applicants .

The adsorbent of the present invention is used to produce the adsorbent according to the embodiment of the present invention, so that the content disclosed in the above patent publication is included in the content of the present invention.

The adsorbent disclosed in the above patent publication uses an Alum sludge generated in a water treatment process to produce an adsorbent.

In the water treatment process, Alum (Al ₂ (SO ₄ ) _{3 ·} 14H ₂ O) is added to remove the solid suspended matter and the organic matter, thereby aggregating the contaminants. The addition of alum to water produces amorphous Aluminum Hydroxide (Al (OH) ₃ ). Aluminum hydroxide has high voids and can be used as an adsorbent for harmful substances.

The adsorbent disclosed in the above patent publication removes the impurities of the sludge from the sludge, dries the sludge from which the impurities have been removed at 80 to 130 ° C. for 2 to 6 hours, and pulverizes the dried sludge into powder . At this time, the surface area of the adsorbent is 30 m ² / g to 50 m ² / g, and the diameter is 50 μm to 200 μm.

The adsorbent disclosed in the above patent publication has an adsorption amount of not less than 8.89 mg / g for trivalent arsenic (As) at a room temperature and a maximum adsorption amount of not less than 5.15 mg / g for pentavalent arsenic. Therefore, the adsorption effect of arsenic is excellent.

Most of the adsorbent disclosed in the above patent publication is adsorbed within 30 minutes to 60 minutes. In addition, since harmful ions adsorbed on the adsorbent can be easily removed, they can be recycled.

Alum as well as various materials are added during the water treatment process. As a result, aluminum (Al), silicon (Si), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), copper (Cu) , Zirconium (Zr), tin (Sn), and the like.

A method of manufacturing an adsorbent according to an embodiment of the present invention will be described with reference to FIG. 3 is a flowchart illustrating a method of manufacturing a granular adsorbent according to an embodiment of the present invention.

As shown in the figure, in step S110, an aluminum sludge can be obtained in a water treatment plant. Alum, Si, Ti, V, Cr, Mn, Fe, Cu, Zn, Zr and Sn.

At this time, the aluminum sludge may contain only aluminum (Al), manganese (Mn) and iron (Fe).

Then, the step (S120) in the can to remove the impurities in the alum sludge, step (S130) in the alum sludge impurities are removed 80 ℃ - 2 eseo 130 ℃ - dried for 6 hours, a surface area of 30m ² / g to 50 m < ² > / g and a diameter of 50 mu m to 200 mu m.

Thereafter, in step S140, the crushed alum sludge can be fired. Applicants have found through experimentation that the adsorbed amount of the adsorbent according to this embodiment is high when the crushed alum sludge is calcined at a predetermined temperature. Through these experimental results, the crushed sludge can be calcined at 290 ° C - 310 ° C for 23 - 25 hours in step S140.

Thereafter, in step S150, the fired sludge and the binder may be stirred into the water. The binder is an additive for forming alum sludge in the form of powder in the form of granules.

The method of preparing an adsorbent according to an embodiment of the present invention may use sodium alginate as a binder or sodium alginate and polyvinyl alcohol as a binder.

Sodium alginate exists in association with sodium cations and is a long macromolecule composed of molecules connected in series. Sodium alginate is water-insoluble, but the alkali salt of sodium alginate dissolves in water and forms a solution with a very high viscosity.

And, polyvinyl alcohol has the function of an adhesive.

The step (S151) of adding sintered alum sludge and sodium alginate, which is a binder, to water is carried out by adding 5 to 15 g of the sludge sludge and 1 to 3 g of the sodium alginate to 100 ml of water and stirring at 45 to 55 ° C for 1 hour or more Stirring can be carried out.

The step (S155) of stirring the sintered sludge with sodium alginate and polyvinyl alcohol as a binder (S155) is performed by adding 5 to 15 g of sludge sludge, 1 to 3 g of sodium alginate, 1 to 3 g of polynnyl alcohol - 3 g, and stir at 45 캜 - 55 캜 for 1 hour or more.

Thereafter, in step S160, the solution in which the alum sludge and the binder are stirred may be cured to form granules. In detail, the solution in which the alum sludge and the binder are stirred is sucked by using a syringe or the like, and then dipped in 0.5 M (Mole) of calcium chloride (CaCl ₂ ) solution by one drop. The stirred solution is then immersed in a calcium chloride (CaCl ₂ ) solution in the form of droplets and cured, preferably immersed for 36-48 hours to maintain proper hardness and cured.

Thereafter, in step S170, the cured granules can be washed with distilled water, and in step S180, the dried granules can be dried at 24 ° C to 26 ° C for more than 24 hours.

Then, a granular adsorbent is prepared. At this time, the size of the granular adsorbent is preferably approximately 1-2 mm in diameter.

Experimental Example

The results of Isotherm Experiment performed with the adsorbent produced by the production method according to the embodiment of the present invention will be described.

)를 각각 5, 10, 20, 50, 100, 300, 500 및 800mg를 넣어서 16시간동안 실험을 진행하였다.In order to investigate the adsorption capacity of adsorbents according to the concentration of arsenic,

) Were added for 5, 10, 20, 50, 100, 300, 500 and 800 mg, respectively, for 16 hours.

In this case, 0.2 g of the adsorbent (hereinafter referred to as " first adsorbent ") according to the embodiment of the present invention in which the binder is sodium alginate was placed in 40 ml of the arsenic solution with the respective concentrations of the pentavalent arsenic dissolved therein, (Hereinafter referred to as " second adsorbent ") according to the embodiment of the present invention, which is a polyvinyl alcohol, was placed in 40 ml of arsenic solution of each concentration in which pentavalent arsenic was dissolved, 0.2 g of the adsorbent disclosed herein (hereinafter referred to as "registered adsorbent") was placed in 40 ml of the arsenic solution of each concentration in which the pentavalent arsenic was dissolved. Then, Bayoxide (hereinafter referred to as "conventional adsorbent" Were added to 40 ml of the arsenic solution of each concentration in which the pentavalent arsenic was dissolved.

Each solution was stirred at 30 rpm with an overhead shaker at 25 ° C, and analyzed using ICP-OES (Agilent 7200, USA).

As a result, as shown in FIGS. 4 (a) and 4 (b) and Table 1, when the first adsorbent and the second adsorbent according to the embodiment of the present invention are judged to have a correlation coefficient r ² , The first adsorbent appeared to follow Langmuir Isotherm and the second adsorbent followed all of Langmuir Isotherm and Freundlich Isotherm.

And, in the maximum adsorption capacity (q _max ), the first adsorbent was similar to the existing adsorbent, and the second adsorbent was superior to the existing adsorbent.

division
Langmuir Isotherm Freundlich Isotherm q _max (mg / g) K _L (L / mg) r ² K _F (mol / gxL) n r ² The first adsorbent 16.419 0.030 0.965 2.537 3.416 0.871 The second adsorbent 20.901 0.016 0.977 2.117 2.829 0.977 Registered adsorbent 33.013 1.042 0.957 10.935 5.192 0.915 Conventional adsorbent 16.106 0.017 0.964 2.086 3.208 0.962

The granular adsorbent produced by the production method according to the embodiment of the present invention can adsorb not only arsenic (As) ions but also fluorine (F) and selenium (Se) ions. The isotherm experiment results for fluorine (F) and selenium (Se) ions were similar to those of isotherms for arsenic ions.

The method for producing a granular adsorbent for removing harmful ions using the alum sludge according to an embodiment of the present invention and the granular adsorbent produced thereby form an adsorbent in a granular form. Therefore, the phenomenon of accumulation of the adsorbent does not occur even when the adsorbent is applied to the field, so that the channeling phenomenon of the water can be prevented and the flow path of the product in which the adsorbent is installed can be prevented from being clogged.

Further, since the adsorbent is formed in a granular form, it is possible to prevent the adsorbent from leaking out of the site of the product in which the adsorbent is installed. Then, it is convenient because there is no need to work out the treated adsorbent.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. Will be clear to those who have knowledge of. Therefore, the scope of the present invention is defined by the appended claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be interpreted as being included in the scope of the present invention.

Claims (9)

A method for preparing an adsorbent for adsorbing and removing arsenic (As) ions, fluorine (F) ions and selenium (Se)
The impurities of the aluminum sludge containing aluminum (Al), manganese (Mn) and iron (Fe) are removed, the impurities are removed from the sludge, the sludge is dried at 80 - 130 ° C for 2 - 6 hours, ;
Firing the pulverized alum sludge;
Mixing the fired sludge and a binder into water and stirring the mixture;
Curing the stirred solution to form granules;
And washing and drying the cured granules is carried out. The method according to claim 1,
Wherein the pulverized alum sludge is calcined at 290 - 310 캜 for 23 - 25 hours. The method according to claim 1,
Wherein the binder is sodium alginate. ≪ RTI ID = 0.0 > 21. < / RTI > The method according to claim 1,
And 5 to 15 g of the alum sludge and 1 to 3 g of the sodium alginate are added to 100 ml of water and the mixture is stirred at 45 to 55 ° C for 1 hour or more. The method according to claim 1,
Wherein the binder is sodium alginate and polyvinyl alcohol. ≪ RTI ID = 0.0 > 21. < / RTI > The method according to claim 1,
5 to 15 g of the alum sludge, 1 to 3 g of the sodium alginate and 1 to 3 g of the polyvinyl alcohol are added to 100 ml of water, and the mixture is stirred at 45 to 55 ° C for 1 hour or more. Way. The method according to claim 1,
Wherein the agitated solution is immersed in a solution of 0.1-0.5 M (Mole) of calcium chloride (CaCl ₂ ) in water droplets for 36-48 hours to cure. The method according to claim 1,
Characterized in that the cured granules are washed with distilled water and dried at 24 - 26 占 폚 for more than 24 hours. A granular adsorbent produced by a process according to any one of claims 1 to 8.

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