KR102059860B1 - Porous absorbent granule and method for producing the same - Google Patents

Abstract

The objective of the present invention is to provide a porous absorption molded body which can prevent valuable metal ion absorption performance from reducing by mixing absorbent powder with a binder material in a powder form, and ensure superior durability. The present invention provides the porous absorption molded body manufactured by mixing the absorbent powder and the binder powder and thermally treating the mixture.

Description

POROUS ABSORBENT GRANULE AND METHOD FOR PRODUCING THE SAME}

The present invention relates to a porous adsorptive molded article and a method for manufacturing the same, and more particularly, to a porous adsorptive molded article and a method for manufacturing the same, which are excellent in durability and can maintain adsorptive performance even in repeated adsorption and desorption processes.

In order to cope with the recent resource depletion crisis, the issue of resource recycling has emerged as a global issue. The discovery of new resources is approaching its limit, and it is necessary to find fundamental means such as using alternative materials or waste resources to cope with the crisis of resource depletion. As an alternative to overcome this, technology development for recovering valuable metals from seawater, brine, and wastewater is actively underway.

Lithium, one of such valuable metals, is used in a wide range of fields such as ceramics, secondary battery materials, refrigerant adsorbents, catalysts, and pharmaceuticals, and has attracted attention as a nuclear fusion energy source. If large-capacity batteries and electric vehicles are put to practical use, demand for lithium and lithium compounds is expected to increase further.

Considering that the world reserves of commercially available lithium land resources are only around 4 million tons, it is urgent to develop new technologies to secure lithium resources at this point. To this end, studies are being conducted to effectively collect a small amount of lithium dissolved in an aqueous solution such as seawater, brine, and lithium battery wastewater, and the main key of these studies is high selectivity to lithium ions and excellent adsorption and desorption performance. To develop high performance adsorbents.

On the other hand, as a method of recovering valuable metal ions present in water, a chemical precipitation method, a solvent extraction method, and an adsorption method are used.

The chemical precipitation method recovers by precipitating metal ions through pH adjustment using a precipitant such as an alkali solvent, or by precipitating metal ions using a coprecipitation agent such as an aluminum compound. The chemical precipitation method is used as the most common recovery method, but has a disadvantage in that selective recovery is difficult because various metal ions can be precipitated together due to low selectivity for a specific target material.

Solvent extraction is a method of selectively extracting metal ions using an organic solvent having selectivity to specific metal ions. However, there is a problem that the organic solvent used in the process is expensive, and the selectivity for the specific target material is somewhat low, so that it is difficult to separate and recover the target material. In addition, there is a disadvantage that compatibility is difficult due to the problem of low efficiency in the condition of low metal ion concentration.

Adsorption is a method of selectively separating target substances using an adsorbent having selectivity for a particular ion. This adsorption method is the most practical method that is excellent in operability and recovery efficiency even under low ionic concentration and does not cause environmental pollution.

Adsorbents used in the adsorption method are difficult to recover in the form of powder and are used in the form of a molded article using a binder material. However, the binder material surrounds the surface of the adsorbent in the manufacture of the molded article, and in this process, the adsorption performance of the adsorbent is deteriorated.

Binder materials include organic / inorganic binders. Water glass widely used as an inorganic binder has an advantage of being easily molded by mixing with an adsorbent powder, but high temperature heat treatment at 500 ° C. or higher is required to maintain durability of the molded body. As a result, there is a problem in that the specific surface area of the adsorbent is lowered, and when the binder solution and the adsorbent powder are mixed, there is a problem in that the binder solution surrounds the adsorbent and the adsorption performance is lowered.

The organic binder is used by dissolving organic materials such as polyvinyl chloride (PVC) and polyvinyl alcohol (PVA) in an organic solvent and water. After mixing the adsorbent powder and the organic binder solution, a separate curing process is required, and even after curing, the durability of the molded body is low, so that the adsorbent powder is lost. In addition, there is a problem in that the binder solution surrounds the adsorbent powder and the adsorption performance is deteriorated and environmental pollution is caused by the use of the organic solvent.

Meanwhile, Korean Patent Publication No. 10-1910403 discloses an HTO lithium adsorbent for lithium ion adsorption as a related art. However, as in the present invention, the adsorbent body composition is obtained by mixing a binder material in powder form with an adsorbent. There is no disclosure.

Republic of Korea Patent Publication No. 10-1910403 (August 22, 2018 notification)

An object of the present invention is to prevent the valuable metal ion adsorption performance of the adsorbent from being lowered by the binder material.

Another object of the present invention is to provide a porous adsorption molded body having excellent durability while maintaining the adsorption performance of the adsorbent.

In order to achieve the above object, the present invention provides a porous adsorption molded body prepared by heat treatment after mixing the adsorbent powder and binder powder.

The binder powder is polyethylene (PE), polypropylene (PP), polyvinylidene fluoride (PVdF), polyvinyl chloride (PVC), nylon, polycarbonate (PC), polyethylene terephthalate (PET), polymethyl methacryl At least one thermoplastic resin powder selected from the group consisting of latex (PMMA), polyoxymethylene (POM), and polystyrene (PS).

The adsorbent powder and the binder powder may be mixed in a weight ratio of 3: 7 to 9: 1.

The adsorbent powder and the binder powder may be heat treated at 90 to 250 ° C. for 30 minutes to 120 hours.

The invention also comprises the steps of (a) mixing the lithium reactant and the titanium reactant to produce a lithium-titanium precursor; (b) heat treating the lithium-titanium precursor to prepare an adsorbent powder; And (c) mixing the adsorbent powder with the binder powder and performing heat treatment.

It may be mixed so that the molar ratio of Li and Ti of the lithium-titanium precursor of step (a) is 0.5 to 2.5: 1.

The lithium reactant of step (a) is any selected from the group consisting of Li ₂ CO ₃ , LiOH, LiF, Li ₂ SO ₄ , LiNO ₃ , LiCl, Li ₂ O, C ₂ H ₃ LiO ₂ , and combinations thereof It can be one.

The titanium reactant of step (a) may be any one selected from the group consisting of TiO ₂ , TiCl ₄ , TiOCl ₂ , TiOSO ₄ , TiO (OH) ₂ , and combinations thereof.

The heat treatment of step (b) may be performed at 500 to 1000 ℃.

The binder powder of step (c) is polyethylene (PE), polypropylene (PP), polyvinylidene fluoride (PVdF), polyvinyl chloride (PVC), nylon, polycarbonate (PC), polyethylene terephthalate (PET ), Polymethylmethacrylate (PMMA), polyoxymethylene (POM), and polystyrene (PS) may be at least one thermoplastic resin powder selected from the group consisting of.

Heat treatment of step (c) may be performed at 90 to 250 ℃ for 30 minutes to 120 hours.

Porous adsorption molded body according to the present invention has the effect that the adsorbent's valuable metal ion adsorption capacity is not lowered by the binder material surrounding the adsorbent.

In addition, according to the present invention has the effect of increasing the durability of the adsorption molded body by the binder material in the form of a powder.

1 is a view showing a conventional porous adsorption molded body prepared by mixing the adsorbent powder and the binder solution.
2 is a view showing a porous adsorption molded body prepared by mixing the adsorbent powder and the binder powder according to an embodiment of the present invention.
Figure 3 is a flow chart of the process of manufacturing a porous adsorptive molded article according to an embodiment of the present invention.
Figure 4 is a graph comparing the lithium ion elution performance of the porous adsorption molded body of Examples 1 to 5 when converting LTO to HTO adsorbent.
5 is a graph comparing lithium ion adsorption performance of the HTO adsorbent powder, the porous adsorbing bodies of Example 1, and Example 2. FIG.

In the following description, only parts necessary for understanding the embodiments of the present invention will be described, it should be noted that the description of other parts will be omitted in a range that does not distract from the gist of the present invention.

The terms or words used in the specification and claims described below should not be construed as being limited to the ordinary or dictionary meanings, and the inventors are appropriate to the concept of terms in order to explain their invention in the best way. It should be interpreted as meanings and concepts in accordance with the technical spirit of the present invention based on the principle that it can be defined. Therefore, the embodiments described in the present specification and the configuration shown in the drawings are only preferred embodiments of the present invention, and do not represent all of the technical idea of the present invention, and various equivalents may be substituted for them at the time of the present application. It should be understood that there may be variations and variations.

Porous Adsorption Molded Body

Hereinafter, a porous adsorptive molded article according to an embodiment of the present invention will be described in detail.

1 is a view showing a conventional porous adsorption molded body prepared by mixing the adsorbent powder and binder solution, Figure 2 is a view showing a porous adsorption molded body prepared by mixing the adsorbent powder and binder powder according to an embodiment of the present invention. to be.

Porous adsorption molded body according to an embodiment of the present invention is prepared by heat treatment of the adsorbent powder and binder powder.

The adsorbent is a substance capable of adsorbing and desorbing valuable metal ions contained in seawater, brine, and wastewater to recover valuable metals.

According to an embodiment of the present invention, the adsorbent may be lithium titanium oxide (LTO) represented by Chemical Formula 1 below.

[Formula 1]

Li _x Ti _y O _z

In Formula 1, x, y, and z satisfy 0.1 ≦ x ≦ 4, 1 ≦ y ≦ 5, and 2 ≦ z ≦ 12.

Specifically, the lithium titanium oxide represented by Chemical Formula 1 may be represented by Li ₄ Ti ₅ O ₁₂ , LiTi ₂ O ₄ , Li ₂ TiO ₃ , Li ₂ Ti ₃ O ₇ , or the like, and a spinel structure Or it may be a layered structure (layered structure), the lithium titanium oxide is not limited to the above examples.

The adsorbent in powder form may be prepared by mixing the lithium reactant and the titanium reactant in a predetermined ratio and then heat treatment.

At this time, it is preferable to mix the lithium reactant and the titanium reactant so that the molar ratio of Li and Ti is 0.5 to 2.5: 1, and more preferably, 2: 1.

The lithium reactant may use any one selected from the group consisting of Li ₂ CO ₃ , LiOH, LiF, Li ₂ SO ₄ , LiNO ₃ , LiCl, Li ₂ O, C ₂ H ₃ LiO ₂ , and a combination thereof. The titanium reactant may use any one selected from the group consisting of TiO ₂ , TiCl ₄ , TiOCl ₂ , TiOSO ₄ , TiO (OH) ₂ , and combinations thereof.

After mixing the lithium reactant and the titanium reactant, it may be heat treated for 3 to 5 hours at a temperature of 500 to 1000 ℃, it is preferable to heat treatment for 4 hours at 600 ℃.

The binder is added to the adsorbent powder for imparting surface coating property to the adsorbent and for easy recovery of the adsorbed molded body after adsorbing valuable metals.

The binder is preferably in the form of a powder so that the adsorption molded body may have a porous structure.

Specifically, the particle size of the binder powder may be 1 to 500 μm. Thus, by using a binder powder of various sizes, it is possible to easily control the internal pore size of the porous adsorption molded body.

Referring to FIG. 1, conventionally, a binder material was dissolved in an organic solvent or water, and a binder in a solution form was mixed with an adsorbent powder to prepare an adsorption molded body. However, this requires a separate curing process, the durability of the adsorption molded body is lowered after curing, there is a problem that the adsorbent powder is lost from the molded body. In addition, the binder solution surrounds the adsorbent powder to reduce the specific surface area of the adsorbent, thereby degrading the adsorption performance and causing environmental pollution due to the use of organic solvents.

However, according to the present invention, when the binder in powder form is mixed with the adsorbent powder, an adsorbed molded article having high durability while maintaining the adsorbent performance of the adsorbent can be prepared. 2, the porous adsorptive molded body according to the present invention is in the form of a mixture of adsorbent powder and binder powder. Compared to the molded article of FIG. 1 in which the binder solution and the adsorbent powder are mixed, the molded article of FIG. 2 can maintain the adsorption performance because the degree of decrease in the specific surface area of the adsorbent due to the binder material is significantly lower. In addition, by adsorbing the adsorbent powder and the binder powder to heat treatment, it is possible to provide an adsorption molded body having high durability while maintaining the adsorption performance.

It is preferable to use a thermoplastic resin powder for the binder powder.

The thermoplastic resin powder that can be used as the binder powder is polyethylene (PE), polypropylene (PP), polyvinylidene fluoride (PVdF), polyvinyl chloride (PVC), nylon, polycarbonate (PC), polyethylene terephthalate ( PET), polymethylmethacrylate (PMMA), polyoxymethylene (POM), and polystyrene (PS) can be used one or more selected from the group consisting of.

The binder powder is preferably mixed with the adsorbent powder in a weight ratio of 3: 7 to 9: 1, and most preferably in a weight ratio of 7: 3.

The weight ratio is out of the numerical limit range, there is a problem that the durability of the adsorption molded body is reduced when the adsorbent is excessively mixed with the binder, and the adsorption performance of the adsorption molded body is reduced when the binder is excessively mixed with the adsorbent, the above range It is desirable to mix to satisfy

After mixing the adsorbent powder and the binder powder may be heat-treated at 90 to 250 ℃. If the heat treatment is performed at less than 90 ℃ do not come out of the desired hardness and the durability of the adsorbing molded body may be lowered, if it exceeds 250 ℃ because the binder powder may be burned or cracks in the adsorbed molded body may be heat treated within the above range desirable.

In addition, the heat treatment is preferably performed for 30 minutes to 120 hours.

Method for Manufacturing Porous Adsorption Molded Body

Hereinafter, a method of manufacturing a porous adsorptive molded article according to an embodiment of the present invention will be described.

3 is a process flowchart of a method for preparing a porous adsorptive molded article according to an embodiment of the present invention.

Referring to Figure 3, the porous adsorptive molded article manufacturing method according to an embodiment of the present invention

 (a) mixing a lithium reactant and a titanium reactant to produce a lithium-titanium precursor;

(b) heat treating the lithium-titanium precursor to prepare an adsorbent powder; And

(c) mixing the adsorbent powder with the binder powder and performing heat treatment.

First, a lithium reactant and a titanium reactant are mixed to prepare a lithium-titanium precursor (S10).

The lithium-titanium precursor may be prepared by uniformly mixing the lithium reactant and the titanium reactant in a powder at a predetermined ratio.

The mixing may use various methods such as ball milling. In the example of the ball milling process, the lithium reactant and the titanium reactant are charged into a ball milling machine to uniformly mix and grind the lithium reactant and the titanium reactant, and rotate at a constant speed using the ball mill to mechanically react the lithium reactant and the titanium reactant. Can be mixed uniformly.

Balls used for ball milling may use balls made of ceramics such as alumina and zirconia, and the balls may be all the same size, and balls having two or more sizes may be used together.

When the lithium reactant and the titanium reactant are mixed, the molar ratio of Li and Ti is preferably 0.5 to 2.5: 1, more preferably 2: 1.

The lithium reactant may use any one selected from the group consisting of Li ₂ CO ₃ , LiOH, LiF, Li ₂ SO ₄ , LiNO ₃ , LiCl, Li ₂ O, C ₂ H ₃ LiO ₂ , and a combination thereof. The titanium reactant may use any one selected from the group consisting of TiO ₂ , TiCl ₄ , TiOCl ₂ , TiOSO ₄ , TiO (OH) ₂ , and combinations thereof.

Next, the lithium-titanium precursor is heat-treated to prepare an adsorbent powder (S20).

Charge the lithium-titanium precursor into an electric furnace and raise the temperature. At this time, the temperature increase rate of the electric furnace is preferably about 5 to 20 ℃ / min. If the temperature rising speed of the furnace is too slow, productivity decreases due to a long time, and if the temperature rising speed of the furnace is too fast, thermal stress may be applied due to a rapid temperature rise, and thus the temperature of the furnace at the temperature rising rate in the above range. It is desirable to raise. At this time, the pressure in the electric furnace is preferably maintained at normal pressure.

The lithium-titanium precursor may be heat-treated for 3 to 5 hours at a temperature of 500 to 1000 ℃, it is preferable that the heat treatment for 4 hours at 600 ℃.

If the heat treatment temperature is too high, there is a possibility that lithium is volatilized, and if the heat treatment temperature is too low, the reaction does not occur between the lithium reactant and the titanium reactant and thus may not be converted into an adsorbent. It is preferable.

The heat treatment is preferably maintained for a certain time. The heat treatment is preferably performed in an oxidizing atmosphere such as air or oxygen (O ₂ ).

Finally, the adsorbent powder is mixed with the binder powder for heat treatment (S30).

The binder is added to give the surface coating property to the adsorbent and for easy recovery of the adsorbed molded body after the valuable metal adsorption.

The binder is preferably in the form of a powder so that the adsorption molded body may have a porous structure. Specifically, the particle size of the binder powder may be 1 to 500 um. Thus, by using a binder powder of various sizes, it is possible to easily control the internal pore size of the porous adsorption molded body.

Referring to FIG. 1, conventionally, a binder material was dissolved in an organic solvent or water, and a binder in a solution form was mixed with an adsorbent powder to prepare an adsorption molded body. However, this requires a separate curing process, the durability of the adsorption molded body is lowered after curing, there is a problem that the adsorbent powder is lost from the molded body. In addition, the binder solution surrounds the adsorbent powder to reduce the specific surface area of the adsorbent, thereby degrading the adsorption performance and causing environmental pollution due to the use of organic solvents.

However, according to the present invention, when the binder in powder form is mixed with the adsorbent powder, an adsorbed molded article having high durability while maintaining the adsorbent performance of the adsorbent can be prepared. 2, the porous adsorptive molded body according to the present invention is in the form of a mixture of adsorbent powder and binder powder. Compared to the molded article of FIG. 1 in which the binder solution and the adsorbent powder are mixed, the molded article of FIG. 2 can maintain the adsorption performance because the degree of decrease in the specific surface area of the adsorbent due to the binder material is significantly lower. In addition, by adsorbing the adsorbent powder and the binder powder to heat treatment, it is possible to provide an adsorption molded body having high durability while maintaining the adsorption performance.

It is preferable to use a thermoplastic resin powder for the binder powder.

The thermoplastic resin powder that can be used as the binder powder is polyethylene (PE), polypropylene (PP), polyvinylidene fluoride (PVdF), polyvinyl chloride (PVC), nylon, polycarbonate (PC), polyethylene terephthalate ( PET), polymethylmethacrylate (PMMA), polyoxymethylene (POM), and polystyrene (PS) can be used one or more selected from the group consisting of.

The binder powder is preferably mixed with the adsorbent powder in a weight ratio of 3: 7 to 9: 1, and most preferably in a weight ratio of 7: 3.

When the weight ratio is outside the numerical limit range, excessive mixing of the adsorbent with respect to the binder has a problem of decreasing durability of the adsorbent, and excessive mixing of the binder with the adsorbent has a problem of decreasing the adsorption performance of the adsorbent with the above-mentioned range. It is desirable to mix to satisfy

After mixing the adsorbent powder and the binder powder may be heat-treated at 90 to 250 ℃. If the heat treatment is performed at less than 90 ℃ do not come out of the desired hardness and the durability of the adsorbing molded body may be lowered, if it exceeds 250 ℃ because the binder powder may be burned or cracks in the adsorbed molded body may be heat treated within the above range desirable.

In addition, the heat treatment is preferably performed for 30 minutes to 120 hours.

Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Preparation Example 1 Preparation of Adsorbent Powder

LiOH.H ₂ O and TiO ₂ were quantified to have a Li and Ti molar ratio of 2: 1, uniformly mixed by ball milling, and calcined and dried at 600 ° C. for 4 hours to prepare a Li ₂ TiO ₃ adsorbent powder. .

<Example>

The adsorbent powder and the binder powder prepared in Preparation Example 1 were mixed at various weight ratios to prepare an adsorbed molded body.

Example 1

An adsorption molded body obtained by mixing the Li ₂ TiO ₃ adsorbent (hereinafter, LTO) powder and the binder powder of Preparation Example 1 was prepared. Low density polyethylene (LDPE) powder was used as the binder. At the time of mixing, the weight ratio of the adsorbent powder and the binder powder was mixed to be 8: 2. The mixture was heat treated at 150 ° C. for 1 hour to prepare an adsorption molded body.

Example 2

Adsorption molded bodies were prepared in the same manner as in Example 1, except that the LTO and LDPE powders had a weight ratio of 7: 3.

Example 3

Adsorption molded bodies were prepared in the same manner as in Example 1, except that the LTO and LDPE powders had a weight ratio of 6: 4.

Example 4

Adsorption molded bodies were prepared in the same manner as in Example 1, except that the LTO and LDPE powders had a weight ratio of 5: 5.

Example 5

Adsorption molded bodies were prepared in the same manner as in Example 1, except that the LTO and LDPE powders had a weight ratio of 4: 6.

Experimental Example 1 Measurement Results of Loss Ratio of Adsorption Molded Body

In order to measure the degree of loss of the adsorbent powder from the molded product mixed with the adsorbent powder and the binder powder, 5 g of the molded product was carried in 1 L of water and stirred for 7 days using a mechanical shaker. After stirring, the molded body was separated from the aqueous solution, and the weight after drying was measured, and the weight change of the molded body before and after stirring was measured. The loss rate was calculated as follows.

Loss rate (%) = (weight change of molding after stirring (g) / weight of molding before stirring (g))

LTO (g) LDPE (g) % Lost Example 1 (LTO: LDPE = 8: 2) 16 4 7 Example 2 (LTO: LDPE = 7: 3) 14 6 1.3 Example 3 (LTO: LDPE = 6: 4) 12 8 0.7 Example 4 (LTO: LDPE = 5: 5) 10 10 0.4 Example 5 (LTO: LDPE = 4: 6) 8 12 0.3

Table 1 is a table comparing the loss ratio of the adsorption molded bodies prepared from Examples 1 to 5. Referring to Table 1, the loss ratio of Example 1 having a weight ratio of LTO: LDPE of 8: 2 is the highest, and in Examples 3 to 5, it can be seen that the change in the loss ratio is insignificant. Accordingly, it can be seen that as the content of the binder increases in manufacturing the molded article, the adsorbent is not lost from the adsorbed molded article, and the durability of the adsorbed molded article is excellent.

In addition, as described above, it is most preferable to use the molded article of Example 2 (LTO: LDPE = 7: 3) so that the binder powder can maintain the adsorption performance while maintaining the adsorption performance when considering the adsorption performance of the adsorbent. It is considered to be preferable.

Experimental Example 2: Evaluation of Lithium Elution Performance of Adsorption Molded Body

In order to switch to a lithium ion adsorbent, the lithium ion elution performance of the molded object which mixed the adsorbent powder and binder powder was evaluated.

In the case of LTO adsorbent, it is a general method to convert Li of LTO structure into H and convert it to HTO through acid solution treatment before lithium ion adsorption process. In order to ion exchange Li ⁺ and H ⁺ in the porous adsorption body, HTO was prepared after dispersing the porous adsorption body in 0.3 M HCl solution at 25 ° C. for 5 days.

For Li-ion elution performance experiment, it was loaded in a 2 L beaker under the condition of 1 g / 0.3 M HCl 1 L of a molded product, and stirred for 5 days at a stirring speed of 100 rpm using a mechanical stirrer for smooth elution.

Figure 4 is a graph comparing the lithium ion elution performance of the porous adsorption molded body of Examples 1 to 5 when converting LTO to HTO adsorbent.

Referring to FIG. 4, Example 1 (LTO: LDPE = 8: 2) having the lowest binder powder content was found to have a lithium ion dissolution rate similar to that of LTO powder. In addition, the dissolution rate of lithium ions decreased as the binder powder content increased.

This result seems to be because the binder powder surrounds the adsorbent and prevents hydrogen ions in the aqueous solution from penetrating into the molded body during the elution of the adsorbent as described above. Therefore, it will be necessary to control the content of the appropriate binder powder to suppress this.

Referring to FIG. 4, Example 2 (LTO: LDPE = 7: 3) showed no significant difference with the LTO powder in the elution performance. The dissolution performance of Example 1 (LTO: LDPE = 8: 2) was similar to that of LTO powder, but the content of the binder powder was so small that the durability of the molded body was not considered to be good. It would be desirable to use shaped bodies.

Experimental Example 3: Evaluation of Lithium Ion Adsorption Performance of Adsorption Molded Body

After lithium ion elution, the lithium ion adsorption performance of the porous adsorption molded body was evaluated.

Filtered seawater was used as the adsorption mother liquor, and LiCl was added to the filtered seawater to adjust the concentration of lithium ions in the seawater to about 30 ppm. Adsorption performance experiment was carried out under the condition of 1 L Lg / 30 ppm Li spiked seawater, and was mixed for 3 days at a speed of 100 rpm using a mechanical shaker. After mixing, the adsorption mother liquor was separated and filtered to measure the concentration of lithium ions.

5 is a graph comparing lithium ion adsorption performance of the HTO adsorbent powder, the porous adsorbing bodies of Example 1, and Example 2. FIG.

Referring to FIG. 5, the LTO powder showed the highest lithium ion adsorption performance of about 11 mg / g, and the Example 1 and Example 2 molded bodies showed the lithium ion adsorption performance of about 9 mg / g. Comparing the LTO powder with Example 2 (LTO: LDPE = 7: 3), it can be seen that the molded article of Example 2 had a decrease in lithium ion adsorption performance by about 17%. As the content of the binder powder was increased, the adsorption performance of lithium ions did not decrease significantly. Therefore, it is preferable to use the molded article of Example 2 (LTO: LDPE = 7: 3) having excellent durability while maintaining the adsorption performance. will be.

So far it has been described with respect to the porous adsorption molded article according to an embodiment of the present invention and specific embodiments of the manufacturing method thereof, it is obvious that various embodiments can be modified within the scope of the present invention.

Therefore, the scope of the present invention should not be limited to the described embodiments, but should be determined not only by the claims below but also by the equivalents of the claims.

In other words, the foregoing embodiments are to be understood in all respects as illustrative and not restrictive, the scope of the invention being indicated by the following claims rather than the detailed description, and the meaning and scope of the claims and All changes or modifications derived from the equivalent concept should be interpreted as being included in the scope of the present invention.

Claims (11)

A porous adsorption molded body prepared by mixing and then heat treating a powder form adsorbent and a binder in powder form,
The adsorbing molded body has a form in which adsorbent powder and binder powder are mixed.
The adsorbent in powder form is prepared by (a) mixing a lithium reactant and a titanium reactant to prepare a lithium-titanium precursor, and (b) heat treating the lithium-titanium precursor.
The binder powder is polyethylene (PE), polypropylene (PP), polyvinylidene fluoride (PVdF), polyvinyl chloride (PVC), nylon, polycarbonate (PC), polyethylene terephthalate (PET), polymethyl methacryl At least one thermoplastic resin powder selected from the group consisting of latex (PMMA), polyoxymethylene (POM), and polystyrene (PS),
The adsorbent powder and the binder powder is a porous adsorption molded body, characterized in that mixed in a weight ratio of 3: 7 to 9: 1. delete delete The method of claim 1,
Porous adsorption molded body, characterized in that the adsorbent powder and the binder powder is heat-treated at 90 to 250 ℃ for 30 minutes to 120 hours. (a) mixing a lithium reactant and a titanium reactant to produce a lithium-titanium precursor;
(b) heat treating the lithium-titanium precursor to prepare an adsorbent in powder form; And
(c) mixing the heat-treated adsorbent in powder form with a binder in powder form;
The binder powder is polyethylene (PE), polypropylene (PP), polyvinylidene fluoride (PVdF), polyvinyl chloride (PVC), nylon, polycarbonate (PC), polyethylene terephthalate (PET), polymethyl methacryl At least one thermoplastic resin powder selected from the group consisting of latex (PMMA), polyoxymethylene (POM), and polystyrene (PS),
The adsorbent powder and the binder powder is a method for producing a porous adsorption molded body, characterized in that mixed in a weight ratio of 3: 7 to 9: 1. The method of claim 5,
Of step (a)
Method for producing a porous adsorption molded body, characterized in that the mixing ratio of the lithium-titanium precursor of Li and Ti is 0.5 to 2.5: 1. The method of claim 5,
Of step (a)
The lithium reactant is any one selected from the group consisting of Li ₂ CO ₃ , LiOH, LiF, Li ₂ SO ₄ , LiNO ₃ , LiCl, Li ₂ O, C ₂ H ₃ LiO ₂ , and combinations thereof Method for producing a porous adsorption molded body. The method of claim 5,
Of step (a)
The titanium reactant is any one selected from the group consisting of TiO ₂ , TiCl ₄ , TiOCl ₂ , TiOSO ₄ , TiO (OH) ₂ , and combinations thereof. The method of claim 5,
The heat treatment of step (b) is a method for producing a porous adsorption molded body, characterized in that performed at 500 to 1000 ℃. delete The method of claim 5,
The heat treatment of step (c) is carried out for 30 minutes to 120 hours at 90 to 250 ℃ method for producing a porous adsorption molded body.

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