KR101701172B1 - Hydrogen fluoride adsorbent and selective removal of hydrogen fluoride using the same - Google Patents

Abstract

The present invention provides a hydrogen fluoride adsorbent which comprises a porous polymer functionalized with an amine group and adsorbs hydrogen fluoride in an aqueous solution containing a hydrofluoric acid salt and hydrogen fluoride. The hydrogen fluoride adsorbent according to the present invention can selectively remove only hydrogen fluoride in an aqueous solution containing a hydrofluoric acid salt and hydrogen fluoride including a porous polymer whose surface is functionalized with an amine group. The method of removing hydrogen fluoride using the method is capable of selectively removing hydrogen fluoride contained in an aqueous solution containing a fluoric acid salt. Thus, the alkali metal fluoride finally obtained in the step of producing an alkali metal fluoride is high in purity, Since the large hydrogen fluoride is selectively removed from the aqueous solution in advance, the device can be protected during the recrystallization and drying process.

Description

FIELD OF THE INVENTION The present invention relates to a hydrogen fluoride adsorbent and a method for selectively removing hydrogen fluoride using the same.

The present invention relates to a hydrogen fluoride adsorbent and a method for selectively removing hydrogen fluoride using the hydrogen fluoride adsorbent. More particularly, the present invention relates to a process for selectively removing hydrogen fluoride contained in an excess amount of hydrogen fluoride in an alkali metal fluoride or the like, It is possible to reduce the amount of hydrogen fluoride generated in the drying process of the alkali metal fluoride by removing the hydrogen fluoride by using the adsorbent capable of obtaining high purity alkali metal fluoride and removing the hydrogen fluoride having high corrosivity from the aqueous solution, And to a method for protecting the same.

Fluorides of alkali metals have been used in various industries. In particular, fluorides of sodium (Na), potassium (K) and cesium (Cs) are used as main raw materials for synthesizing organic fluorine compounds. The fluoride of the alkali metal is generally prepared by reacting a hydrate of an alkali metal or a carbonate with hydrogen fluoride or hydrogen fluoride (see the following chemical reaction formula).

<Chemical reaction formula>

MOH + HF? MF + H ₂ O (M = Na, K, Rb, Cs)

M ₂ CO ₃ + 2HF? 2MF + CO _2? + H ₂ O (M = Na, K, Rb, Cs)

MF + HF? MHF ₂ (M = Na, K, Rb, Cs)

For example, sodium fluoride (NaF) is produced by reacting sodium hydroxide or sodium carbonate with hydrogen fluoride. However, since an excessive amount of hydrogen fluoride is generally used, the metal fluoride actually obtained contains a considerable amount of sodium fluoride (NaHF ₂ ).

The above alkali metal fluoride synthesis step is usually carried out in an aqueous solution. Therefore, the produced alkali metal fluoride is separated from the aqueous solution by a method such as recrystallization and finally a drying process is required. When excess hydrogen fluoride is present in the aqueous solution together with the alkali metal fluoride, the solubility of the metal fluoride becomes high and recrystallization is not easy, and the resultant hydrogen fluoride compound also exists in the metal fluoride obtained by recrystallization from the aqueous solution. The hydrogen fluoride compound is decomposed into alkali metal fluoride and hydrogen fluoride at a high temperature, so it is corrosive in the drying process and there is a possibility that a large amount of harmful hydrogen fluoride is generated.

The best way to solve these problems is to precisely match the theoretical equivalents of alkali metal compounds with hydrogen fluoride, but it is not easy in practical terms. It is a practical method to remove hydrogen fluoride as much as possible from an aqueous solution of metal fluoride synthesized before recrystallization, while using excess hydrogen fluoride which is relatively easy to remove instead.

As a method for removing hydrogen fluoride from an aqueous solution, processes such as chemical precipitation and coagulation, separation membrane, and electrodialysis are used. Chemical precipitation and aggregation combine with fluorine ions to remove fluorine ions from the aqueous solution by adding calcium or magnesium compounds which form products with very low solubility in water and to remove the remaining fine particles and fluorine ions, use.

As a specific example, in Korean Patent Laid-Open No. 10-2009-0131823 (Patent Document 1), in order to treat acidic wastewater containing fluorine, acidic wastewater containing fluorine is introduced into the reaction tank, and the amount of calcium A step of adding fluorine to a part or the whole of calcium chloride in the form of calcium chloride, a neutralizing treatment by adding an alkali neutralizing agent after fluorine treatment, and a step of finally adding a polymer flocculant to form a sludge to precipitate the fluorine have.

Korean Patent Laid-Open No. 10-2010-0112741 (Patent Document 2) discloses a hydrofluoric acid wastewater treatment system comprising a membrane capable of stably treating hydrofluoric acid (HF) -containing wastewater at a level lower than the discharged water quality standard .

However, in these processes, it is practically impossible to selectively remove fluorine ions of alkali metal fluorides and fluorine hydrogen fluoride mixed in an aqueous solution as a method for removing fluorine ions from an aqueous solution.

Accordingly, the present inventors have found that, while studying a method for selectively removing hydrogen fluoride contained in an aqueous solution containing a hydrofluoric acid salt and hydrogen fluoride, the present inventors have found that, in an aqueous solution containing a hydrofluoric acid salt containing a porous polymer functionalized with an amine group and hydrogen fluoride An adsorbent capable of adsorbing hydrogen fluoride has been developed and the present invention has been completed.

Korean Patent Publication No. 10-2009-0131823 (December 28, 2009) Korean Patent Publication No. 10-2010-0112741 (November 12, 2010)

An object of the present invention is to provide a hydrogen fluoride adsorbent and a method for selectively removing hydrogen fluoride using the same.

In order to achieve the above object,

A porous polymer functionalized with an amine group,

A hydrogen fluoride adsorbent characterized by adsorbing hydrogen fluoride in an aqueous solution containing a fluoric salt and hydrogen fluoride.

In addition,

A method for removing hydrogen fluoride comprising the steps of: introducing the hydrogen fluoride adsorbent according to claim 1 into an aqueous solution containing hydrofluoric acid and hydrogen fluoride to adsorb hydrogen fluoride, the porous hydrogen polymer having an amine function.

The hydrogen fluoride adsorbent according to the present invention can selectively remove only hydrogen fluoride in an aqueous solution containing a hydrofluoric acid salt and hydrogen fluoride including a porous polymer whose surface is functionalized with an amine group. The method of removing hydrogen fluoride using the method is capable of selectively removing hydrogen fluoride contained in an aqueous solution containing a fluoric acid salt. Thus, the alkali metal fluoride finally obtained in the step of producing an alkali metal fluoride is high in purity, Since the large hydrogen fluoride is selectively removed from the aqueous solution in advance, the device can be protected during the recrystallization and drying process.

The present invention

A porous polymer functionalized with an amine group,

A hydrogen fluoride adsorbent characterized by adsorbing hydrogen fluoride in an aqueous solution containing a fluoric salt and hydrogen fluoride.

Hereinafter, the hydrogen fluoride adsorbent according to the present invention will be described in detail.

It has been impossible to selectively remove fluorine ions of hydrofluoric acid and hydrogen fluoride mixed in the aqueous solution. Accordingly, the present invention provides a hydrogen fluoride adsorbent comprising a porous polymer functionalized with an amine group as an adsorbent for selectively removing hydrogen fluoride in an aqueous solution containing hydrofluoric acid and hydrogen fluoride.

In the hydrogen fluoride adsorbent according to the present invention, it is preferable that the porous polymer is in the form of a spherical powder, and the particle size of the particles is 10 μm to 2 mm. Also, the porous polymer has a large amount of pores, and preferably has a surface area of from 0.1 m ² / g to 400 m ² / g.

The porous polymer may be a styrenic polymer, an acrylic polymer, a methacrylic polymer, a vinyl polymer, a urethane polymer, or an epoxyamine polymer. Specific examples of the polymer include an acrylic monomer having an epoxy group, And a cross-linkable monomer having at least two possible reactors. Further, it may be a polymer prepared by copolymerizing a monomer such as a styrene-based monomer or an acrylic monomer.

In addition, the amine functional group-containing porous polymer preferably has an amine group concentration of 1.0 mmol / g to 4.0 mmol / g, more preferably 2.0 mmol / g to 3.7 mmol / g, mmol / g. If the amine group concentration of the amine-functionalized polymer is less than 1.0 mmol / g, the hydrogen fluoride removal efficiency is lowered. If the amine group concentration exceeds 4.0 mmol / g, an excess amount Since the reaction is required to be carried out using an amine compound, not only the separation and purification load after the reaction is large but also the degree of swelling of the porous resin in the aqueous solution increases when the concentration of the amine group is excessively high. This is not easy.

Further, the hydrofluoric acid salt may be an alkali metal fluoride or ammonium fluoride. In this case, the alkali metal fluoride may be an alkali metal fluoride such as sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs), ammonium fluoride is _{NH 4 F, NH 4 HF 2} , CH 3 NH ₃ F, (CH ₃ ) ₂ NH ₂ F, (CH ₃ ) ₃ NHF, (CH ₃ ) ₄ NF, and the like.

In addition,

A method for removing hydrogen fluoride comprising the steps of: introducing the hydrogen fluoride adsorbent according to claim 1 into an aqueous solution containing hydrofluoric acid and hydrogen fluoride to adsorb hydrogen fluoride, the porous hydrogen polymer having an amine function.

Hereinafter, a method for removing hydrogen fluoride according to the present invention will be described in detail.

The method for removing hydrogen fluoride according to the present invention includes the step of adsorbing hydrogen fluoride by introducing the hydrogen fluoride adsorbent of claim 1, which comprises a porous polymer functionalized with an amine group, into an aqueous solution containing a hydrofluoric acid salt and hydrogen fluoride.

It has been impossible to selectively remove fluorine ions of hydrofluoric acid and hydrogen fluoride mixed in the aqueous solution. Accordingly, in the present invention, as the adsorbent for selectively removing hydrogen fluoride in an aqueous solution containing hydrofluoric acid and hydrogen fluoride, a hydrogen fluoride adsorbent containing a porous polymer functionalized with an amine group is used. This is put into an aqueous solution containing hydrofluoric acid and hydrogen fluoride to bring the aqueous solution and the adsorbent into contact with each other to adsorb hydrogen fluoride.

Specifically, the porous polymer is in the form of a spherical powder, and the particle size of the particles is preferably 10 μm to 2 mm. Also, the porous polymer has a large amount of pores, and preferably has a surface area of from 0.1 m ² / g to 400 m ² / g.

The porous polymer may be a styrenic polymer, an acrylic polymer, a methacrylic polymer, a vinyl polymer, a urethane polymer, or an epoxyamine polymer. Specific examples of the polymer include an acrylic monomer having an epoxy group and a polymerization reaction And a cross-linkable monomer having at least two possible reactors. Further, it may be a polymer prepared by copolymerizing a monomer such as a styrene-based monomer or an acrylic monomer.

Furthermore, the amine functional group-containing porous polymer preferably has an amine group concentration of 1.0 mmol / g to 4.0 mmol / g, more preferably 2.0 mmol / g to 3.7 mmol / g, mmol / g. If the amine group concentration of the amine-functionalized polymer is less than 1.0 mmol / g, the hydrogen fluoride removal efficiency is lowered. If the amine group concentration exceeds 4.0 mmol / g, an excess amount Since the reaction is required to be carried out using an amine compound, not only the separation and purification load after the reaction is large but also the degree of swelling of the porous resin in the aqueous solution increases when the concentration of the amine group is excessively high. This is not easy.

In addition, the porous polymer functionalized with an amine group in the above step may be, for example,

Preparing a porous polymer (step a); And

And a step (b) of mixing the porous polymer and the amine compound prepared in the step (a) and reacting them to prepare a porous polymer functionalized with an amine group (step b).

First, step (a) is a step of preparing a porous polymer.

In step a, a porous polymer capable of functionalizing an amine group is prepared.

Specifically, the porous polymer in step (a) preferably contains an epoxy group. In the subsequent step, the functional group can be functionalized by reacting an amine compound with an epoxy group contained in the porous polymer.

As a specific example, the porous polymer of step a) may be prepared by suspension polymerization,

Adding a monomer containing an epoxy group, a monomer containing two or more double bonds and an organic solvent to an aqueous solution containing a dispersion stabilizer (step a-1); And

Heating the mixture of step a), adding an initiator and stirring to prepare a porous polymer (step a-2).

In the step a-1, an aqueous solution containing a dispersion stabilizer is prepared in order to perform suspension polymerization using a dispersion stabilizer, and the monomer and the organic solvent to be prepared from the porous polymer are mixed into an aqueous solution containing the dispersion stabilizer.

Specifically, the dispersion stabilizer of step a-1 may be a water-soluble polymer such as poly (vinylpyrrolidone), polyvinyl alcohol, a chemical derivative of cellulose, a polyacrylic acid polymer, a hydrophobically modified polyacrylic acid polymer, A polymer or a hydrophobically modified polymethacrylic acid polymer may be used. Further, inorganic particles such as calcium triphosphate, magnesium hydroxide, calcium carbonate and silica, or a mixture of these inorganic particles with a surfactant, or a mixture of inorganic particles and the water-soluble polymer may be used.

The monomer containing an epoxy group in the step a-1 is preferably a monomer containing an epoxy group, which is a functional group capable of functionalizing with an amine group. Specific examples thereof include glycidyl methacrylate, glycidyl acrylate And the like can be used.

Further, the monomer containing at least two double bonds of the above-mentioned step a-1 may be selected from divinylbenzene, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, propylene glycol dimethacrylate, polypropylene glycol dimethacrylate , Trimethylolpropane trimethacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, and trimethylolpropane triacrylate.

The organic solvent used in step (a-1) is not limited as long as it is an organic solvent used for forming pores in suspension polymerization. Specific examples thereof include aromatic organic solvents such as toluene, benzene and xylene and derivatives thereof, Aliphatic alcohols such as alcohol, decyl alcohol, dodecyl alcohol and tetradecyl alcohol, and organic solvents such as cyclohexyl alcohol.

At this time, various monomers may be additionally used as the monomer of the step a-1 to control the mechanical properties of the porous resin. As a specific example, styrene, chloromethylstyrene, vinyltoluene, alpha-methylstyrene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, acrylonitrile and the like can be used.

The step a-2 is a step of heating the mixture of the step a-1, adding an initiator and stirring to prepare a porous polymer. In the step a-2, in order to polymerize the mixture of the step a) And then stirred to prepare a porous polymer.

Specifically, the temperature at which the mixture is heated in step a-2 may be from 50 캜 to 90 캜. Polymerization can proceed by adjusting the temperature appropriately according to the reactivity of the polymer.

After carrying out the step a-2, the porous polymer can be prepared by washing and drying.

Next, the step (b) is a step of mixing the porous polymer and the amine compound prepared in the step (a) and reacting them to prepare a porous polymer functionalized with an amine group.

The porous polymer prepared in step a may be functionalized through reaction of an epoxy group with an amine compound.

Specifically, the mixing ratio of the porous polymer and the amine compound in the step (b) is preferably 1: 0.1 to 5.0, more preferably 1: 0.4 to 1.0. The reaction ratio of the epoxy group and the amine compound contained in the porous polymer is preferably 1: 1 to 5. If it is outside the above range, there is a problem in that it is difficult to remove hydrogen fluoride when the hydrogen fluoride is used for removing hydrogen fluoride due to the lack of amine groups functionalized in the porous polymer, or an excessive amount of hydrogen fluoride is excessively used in comparison with the epoxy group, have.

The amine compound of step b may be a primary amine compound, a secondary amine compound or a tertiary amine compound. Specific examples of the amine compound include ethylamine, butylamine, hexylamine, octylamine, decylamine, dodecylamine , having Tra decyl amine, hexadecyl amine, octadecyl amine, ethylene diamine _{(NH 2 CH 2 CH 2 NH} 2), tetramethylenediamine _{(NH 2 (CH 2) 4} NH 2), hexamethylene diamine (NH ₂ (CH ₂ ) ₆ NH ₂ ), N-ethylethylenediamine (NH ₂ CH ₂ CH ₂ NHCH ₂ CH ₃ ), N, N'-dimethylethylenediamine (NH ₂ CH ₂ CH ₂ N (CH ₃ ) ₂ ) Diethylethylenediamine (NH ₂ CH ₂ CH ₂ N (CH ₂ CH ₃ ) ₂ ), diethylenetriamine (NH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ ), triethylenetetraamine (NH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ ), polyethyleneimine and the like can be used.

Further, the reaction of step b) may be carried out at a temperature of 50 ° C to 120 ° C for 1 hour to 48 hours.

After the step (b), the porous polymer functionalized with an amine group may be prepared by washing and drying.

As described above, the adsorbent containing the prepared porous polymer functionalized with an amine group is introduced into an aqueous solution containing hydrofluoric acid and hydrogen fluoride to adsorb hydrogen fluoride.

Specifically, the hydrofluoric acid salt may be an alkali metal fluoride or ammonium fluoride. In this case, the alkali metal fluoride may be an alkali metal fluoride such as sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs), ammonium fluoride is _{NH 4 F, NH 4 HF 2} , CH 3 NH ₃ F, (CH ₃ ) ₂ NH ₂ F, (CH ₃ ) ₃ NHF, (CH ₃ ) ₄ NF, and the like.

The amount of the porous polymer functionalized with the amine group is preferably 2 g or more, more preferably 2 g to 20 g, and most preferably 6 g to 15 g with respect to 1 L of the aqueous solution. If the amount of the porous polymer functionalized with the amine group is less than 2 g per 1 L of the aqueous solution, there is a problem that the hydrogen fluoride removal rate drops.

Further, the temperature at which the above step is carried out is preferably 5 ° C to 50 ° C, more preferably 10 ° C to 30 ° C. The adsorption of hydrogen fluoride is advantageous as the temperature is lower, but the solubility of the hydrofluoric acid salt in the aqueous solution is lowered.

As a specific example, it is possible to use a batch type reactor for contacting the porous polymer particles functionalized with an emulsifier and an aqueous solution containing hydrofluoric acid and hydrogen fluoride, or a method in which an aqueous solution is continuously introduced into a filled column filled with porous particles.

In addition, the method may further include the step of bringing the porous polymer functionalized with hydrogen fluoride-adsorbed amine groups into contact with an aqueous solution containing a cation after performing the above step.

The porous polymer adsorbed by hydrogen fluoride can be regenerated by contacting with an aqueous solution containing a cation. That is, when the porous polymer is brought into contact with an aqueous solution containing an alkali metal salt or an ammonium ion, the porous polymer is returned to its state before hydrogen fluoride is adsorbed, and the hydrogen fluoride adsorbed on the porous polymer reacts with the alkali metal salt or ammonium ion contained in the aqueous solution, Fluoride or ammonium fluoride.

Accordingly, the aqueous solution can be reused in the course of producing an alkali metal fluoride as a mixture of an alkali metal salt, ammonium fluoride, alkali metal fluoride and the like.

Specifically, the cation may be an alkali metal ion or an ammonium ion. In addition, various salts of alkali metals such as hydroxides, sulfates, phosphates and nitrates can be used, but it is most preferable to select hydroxides in consideration of the byproducts of the regeneration process.

Furthermore, the concentration of the cation in the aqueous solution containing the cation is preferably 0.1 M to 5 M, more preferably 0.1 M to 2 M. If the concentration of the cation in the aqueous solution containing the cation is less than 0.1 M, a large amount of aqueous solution is required, and if the concentration exceeds 5 M, the porous polymer may be chemically deteriorated.

Further, the temperature for performing the above step may be 25 ° C to 95 ° C, and may be a temperature of 30 ° C to 80 ° C. If the temperature for performing the above step is less than 25 ° C, desorption of hydrogen fluoride may not be performed smoothly. If the temperature exceeds 95 ° C, the swelling of the porous polymer may occur severely, It is not desirable because there is a possibility.

Hereinafter, the present invention will be described in detail with reference to the following examples and experimental examples.

It should be noted, however, that the following examples and experimental examples are illustrative of the present invention, but the scope of the invention is not limited by the examples and the experimental examples.

PREPARATION EXAMPLE 1 Preparation of Porous Polymer 1

Step 1: First, 7.5 g of poly (vinylpyrrolidone) (PVP55, Sigma-Aldrich) having a weight average molecular weight of 55,000 as a dispersion stabilizer was dissolved in 500 g of water, and a 1 L glass reaction Lt; / RTI &gt;

50 g of trimethylolpropane trimethacrylate (TMPTMA, TCI), which is a cross-linkable monomer, with 50 g of glycidyl methacrylate (GMA, Sejon Chemical) having an epoxy group as an organic solvent for pore formation Mixed with 130 g of toluene, and charged into the reactor. The reactants were mixed at a speed of 500 rpm using a mechanical stirrer equipped with a stirring rod of a turbine type.

Step 2: The mixture of step 2 was stirred and warm water having a temperature of 75 캜 was circulated through the jacket of the reactor to raise the temperature of the reaction product. Then, 1.0 g of azobisisobutyronitrile (AIBN, Junsei) 20 g of toluene was added thereto. After the reaction was initiated for 4 hours after the initiator was added, the stirring was stopped, and the temperature of the reaction was gradually lowered. Then, the porous polymer was separated through filtration.

The separated porous polymer was washed with water, and toluene and unreacted monomers were removed using methanol. The polymer was dried in a vacuum oven at 70 ° C for 24 hours and recovered in powder form.

&Lt; Preparation Example 2 > Preparation of porous polymer 2

Except that 70 g of glycidyl methacrylate as a monomer having an epoxy group in Step 1 of Production Example 1 was used and 30 g of trimethylolpropane trimethacrylate as a crosslinkable monomer was used, To prepare a porous polymer.

PREPARATION EXAMPLE 3 Preparation of Porous Polymer 3

Except that 85 g of glycidyl methacrylate as a monomer having an epoxy group in Step 1 of Production Example 1 and 15 g of trimethylolpropane trimethacrylate as a crosslinkable monomer were used, To prepare a porous polymer.

The polymerization yield, specific surface area, pore size and particle size of the porous polymer prepared in Preparation Examples 1 to 3 were analyzed by BET adsorption method and electron microscope, and the results are shown in Table 1 below.

GMA
(g) TMPTMA
(g) Polymerization yield
(%) Particle size
(mm) Specific surface area
(m ² / g) Pore size
(nm) Production Example 1 50 50 99.7 0.54 160 21.8 Production Example 2 70 30 98.1 0.37 80 19.1 Production Example 3 85 15 97.2 0.35 50 11.3

&Lt; Preparation Example 4 > Preparation of porous polymer functionalized with an amine group 1

In a 500-mL flask, 20 g of the porous polymer prepared in Preparation Example 1 was dispersed in 100 g of water, and 13.6 g of ethylamine (NH ₂ CH ₂ CH ₃ , 70% by weight aqueous solution, Sigma-Aldrich) After the addition, the reaction was carried out at a temperature of 90 ° C for 16 hours.

After completion of the reaction, the resultant was filtered to separate the functionalized porous polymer with amine groups, washed sequentially with water and methanol, and then dried in a vacuum oven at 70 ° C to prepare a porous polymer functionalized with an amine group.

&Lt; Preparation Examples 5 to 9 > Preparation of porous polymer functionalized with amine groups 2 to 6

The porous polymer functionalized with an amine group was prepared in the same manner as in Preparation Example 4, except that the kind of the porous polymer, the amount of the porous polymer, the type of the amine, and the content of the amine were changed as shown in Table 2 below .

At this time, the porous polymer functionalized with an amine group and having an amine group concentration of 0.2 g of an amine group was added to 50 mL of 0.1 M hydrochloric acid aqueous solution and stirred for 3 hours. Then, And the filtrate was measured by titration using 0.1 M TTKSGHKSKXMFBA aqueous solution. The results are shown in Table 2 below.

Porous resin Amine (g) Amine group concentration
(mmole / g) Production Example 4 Production Example 1 NH ₂ CH ₂ CH ₃ 13.6 2.25 Production Example 5 Production Example 1 NH ₂ CH ₂ CH ₂ NH ₂ 12.7 2.32 Production Example 6 Production Example 1 NH ₂ CH ₂ CH ₂ NHCH ₂ CH ₃ 18.6 2.23 Production Example 7 Production Example 1 _{NH 2 CH 2 CH 2 N (} CH 3) 2 18.6 2.00 Production Example 8 Production Example 2 NH ₂ CH ₂ CH ₃ 13.3 3.00 Production Example 9 Production Example 3 NH ₂ CH ₂ CH ₃ 16.2 3.28

&Lt; Examples 1 to 15 & gt; Removal of hydrogen fluoride from aqueous solution

50 mL of a hydrogen fluoride aqueous solution having a concentration of 100 mg / L was added to a 100 mL PP flask, and 0.10 g of the porous polymer functionalized with the amine group prepared in Preparation Example 4 was added thereto. And the concentration of hydrogen fluoride was measured by taking 5 mL of the aqueous solution from which the porous polymer was removed using a 0.45 m syringe filter.

The hydrogen fluoride was removed from the aqueous solution by varying the amount and type of the porous polymer functionalized with an amine group in the same manner as above, and the results are shown in Table 3.

Example Porous polymer
Kinds Resin amount
(g) Initial concentration of hydrogen fluoride (mg / L) Hydrogen fluoride removal rate
(%) One Production Example 4 0.10 100 59.9 2 Production Example 4 0.30 100 95.5 3 Production Example 4 0.50 100 98.0 4 Production Example 5 0.10 100 72.8 5 Production Example 5 0.30 100 98.7 6 Production Example 5 0.50 100 98.9 7 Production Example 6 0.10 100 69.3 8 Production Example 6 0.30 100 97.8 9 Production Example 6 0.50 100 97.2 10 Production Example 7 0.10 100 28.6 11 Production Example 7 0.30 100 74.1 12 Production Example 7 0.50 100 85.8 13 Production Example 8 0.10 100 69.8 14 Production Example 8 0.30 100 96.4 15 Production Example 8 0.50 100 98.1 13 Production Example 9 0.10 100 81.8 14 Production Example 9 0.30 100 97.7 15 Production Example 9 0.50 100 97.8

As shown in Table 3, it can be seen that the porous polymer functionalized with an amine group removes hydrogen fluoride contained in the aqueous solution very efficiently.

&Lt; Examples 16 to 24 & gt ; Removal of sodium fluoride from aqueous solution

50 mL of a sodium fluoride aqueous solution having a concentration of 100 mg / L was added to a 100 mL PP flask, and 0.10 g of a porous polymer functionalized with an amine group was added thereto. The mixture was stirred at a temperature of 20 ° C for 3 hours and filtered through a 0.45 μm syringe filter Was used to collect 5 mL of the aqueous solution from which the porous polymer had been removed and mixed with the same amount of TISABII solution. The concentration of sodium fluoride was measured using a fluorine ion meter (Thermo-Orion, A214 ISE meter).

The sodium fluoride was removed from the aqueous solution by varying the amount and type of the porous polymer functionalized with an amine group in the same manner as above, and the results are shown in Table 4.

Example Porous polymer
Kinds Resin amount
(g) Initial concentration of sodium fluoride (mg / L) Sodium fluoride removal rate
(%) 16 Production Example 4 0.10 100 0.3 17 Production Example 4 0.30 100 0.2 18 Production Example 4 0.50 100 0.7 19 Production Example 7 0.10 100 0.5 20 Production Example 7 0.30 100 0.3 21 Production Example 7 0.50 100 0.8 22 Production Example 9 0.10 100 0.2 23 Production Example 9 0.30 100 0.6 24 Production Example 9 0.50 100 0.5

As shown in Table 4, it was confirmed that the effect of removing the fluorine ions contained in the alkali metal fluoride was insignificant in the porous polymer functionalized with an amine group.

&Lt; Examples 25 to 33 & gt; Removal of hydrogen fluoride from aqueous solution of alkali metal fluoride

40 mL of an aqueous solution of sodium fluoride at a concentration of 100 mg / L and 10 mL of a hydrogen fluoride aqueous solution at a concentration of 100 mg / L were added to a 100 mL PP flask, and 0.25 g of a porous polymer functionalized with an amine group was added thereto. , And 5 mL of the aqueous solution with the porous polymer removed using a 0.45 μm syringe filter was mixed with the same amount of TISABII solution. The mixture was mixed with the same amount of TISABII solution, and then sodium fluoride was added thereto using a fluorine ion meter (Thermo-Orion, A214 ISE meter) .

The hydrogen fluoride was selectively removed by varying the concentration of the alkali metal fluoride and hydrogen fluoride in the aqueous solution in the same manner as above, and the results are shown in Table 5.

Example Alkali metal
Fluoride Alkali metal fluoride:
Hydrogen fluoride Fluoride ion concentration (mg / L) Hydrofluoric acid removal rate (%) 25 NaF 8: 2 81.2 98 26 NaF 6: 4 60.4 99 27 NaF 5: 5 51.0 98 28 NaF 4: 6 39.7 98 29 NaF 2: 8 20.4 95 30 NaF 9: 1 10.8 99 31 KF 9: 1 10.2 99 32 KF 9.5: 0.5 5.3 96 33 CsF 9: 1 9.8 97

As shown in Table 5, it can be confirmed that the porous polymer functionalized with an amine group can selectively separate hydrogen fluoride from a mixture of an alkali metal fluoride salt and hydrogen fluoride, and the hydrogen fluoride removal rate is excellent at 95% or more I could confirm.

&Lt; Comparative Examples 1 to 3 >

In a 100 mL PP flask, 40 mL of an aqueous sodium fluoride solution having a concentration of 100 mg / L and 10 mL of an aqueous hydrogen fluoride solution having a concentration of 100 mg / L were added thereto, and 0.25 g of calcium hydroxide was added thereto. The mixture was stirred at a temperature of 20 ° C for 3 hours 5 mL of the aqueous solution from which calcium hydroxide was removed using a 0.45 μm syringe filter was mixed with the same amount of TISABII solution and the concentration of sodium fluoride was measured using a fluorine ion meter (Thermo-Orion, A214 ISE meter).

Hydrogen fluoride was selectively removed using activated alumina and anion exchange resin (Amberlite IRA-400) instead of calcium hydroxide in the same manner as above, and the results are shown in Table 6.

Comparative Example absorbent NaF: hydrogen fluoride Fluoride ion concentration (mg / L) Hydrofluoric acid removal rate (%) One Calcium hydroxide 8: 2 11.4 87.5 2 Activated alumina 8: 2 23.3 70.9 3 IRA-400 8: 2 69.4 25.0

As shown in Tables 3 to 6, it can be seen that the porous polymer resin functionalized with an amine group removes hydrogen fluoride contained in the aqueous solution very efficiently, as shown in Examples 1-15 of Table 3. However, as shown in Examples 16 to 24 of Table 4, it is confirmed that the effect of removing the fluorine ions contained in the alkali metal fluoride is almost insignificant. This means that hydrogen fluoride can be selectively separated from a mixture of an alkali metal fluoride and hydrogen fluoride as shown in Examples 25-33 of Table 5, and it was confirmed that the hydrogen fluoride removal rate is excellent.

On the other hand, as shown in Table 6, in Comparative Example 1, calcium hydroxide which is generally used for removing fluorine ions contained in an aqueous solution by chemical precipitation is used. As a result, fluorine ion removal efficiency is high, but alkali metal fluoride and hydrogen fluoride It can be seen that there is no selectivity between them. In Comparative Example 2, active alumina generally used for removing fluorine ions contained in an aqueous solution by physical adsorption was used. As a result, fluorine ion removal efficiency was high, but there was no selectivity between alkali metal fluoride and hydrogen fluoride Able to know. Furthermore, Comparative Example 3 shows that the selectivity between alkali metal fluoride and hydrogen fluoride is very low as compared with the examples using an anion exchange resin as a polymer material.

&Lt; Examples 34 to 42 > The hydrogen fluoride-adsorbed porous polymer

In a 250 mL PP flask, add 1 g of porous resin with 45 mg of hydrogen fluoride per g to 100 mL of 0.1 M aqueous sodium hydroxide solution, stir at 50 ° C for 3 hours, and use a 0.45 μm syringe filter The concentration of sodium fluoride was measured using a fluorine ion meter (Thermo-Orion, A214 ISE meter) after mixing 5 mL of the aqueous solution from which the porous polymer had been removed and mixing with the same amount of TISABII solution.

The porous polymer was regenerated in the same manner as described above, and the results of the experiment with different kinds, concentrations, amounts and reaction temperatures of the alkali metal ions contained in the solution are shown in Table 7.

Example The type, concentration and amount of alkali metal ions in solution Reaction temperature
(° C) Fluoride ion concentration (mg / L) Regeneration rate of hydrogen fluoride (%) 34 NaOH 0.1 M 100 mL 50 424 94 35 NaOH 0.1 M 100 mL 60 433 96 36 NaOH 0.1 M 100 mL 70 441 98 37 NaOH 0.1 M 100 mL 20 387 86 38 KOH 0.1M 100 mL 70 432 96 39 CsOH 0.1M 100 mL 70 438 97 40 NaOH 0.2M 50 mL 70 399 89 41 NaOH 0.2M 100 mL 60 442 98 42 NaOH 1 M 100 mL 70 449 100

As shown in Examples 34-42 of Table 7, the porous polymer can be easily regenerated using an aqueous solution of a hydroxide compound of an alkali metal, and the higher the concentration of the solution and the higher the reaction temperature, the higher the regeneration efficiency .

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Various modifications and variations are possible in light of the above teachings.

Claims (16)

A porous polymer which is functionalized with an amine group and does not contain a metal ion,
A hydrogen fluoride adsorbent characterized by selectively adsorbing hydrogen fluoride in an aqueous solution containing a fluoric salt and hydrogen fluoride,
Wherein the functionalized amine group is a secondary or tertiary amine group.
The method according to claim 1,
Wherein the porous polymer is in the form of a spherical powder, and the particle diameter of the particles is 10 [mu] m to 2 mm.
The method according to claim 1,
Wherein the surface area of the porous polymer is 0.1 m ² / g to 400 m ² / g.
The method according to claim 1,
Wherein the porous polymer is at least one polymer selected from the group consisting of a styrenic polymer, an acrylic polymer, a methacrylic polymer, a vinyl polymer, a urethane polymer, and an epoxyamine polymer, or a copolymer thereof.
The method according to claim 1,
Wherein the porous polymer functionalized with the amine group has an amine group concentration of 1.0 mmol / g to 4.0 mmol / g.
The method according to claim 1,
Wherein the fluoric acid salt is an alkali metal fluoride or ammonium fluoride.
The method according to claim 6,
Wherein the alkali metal fluoride is one kind of alkali metal fluoride selected from the group consisting of sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs).
A method for removing hydrogen fluoride comprising the step of selectively adsorbing hydrogen fluoride by introducing the hydrogen fluoride adsorbent of claim 1 into an aqueous solution containing a fluoric acid salt and hydrogen fluoride.
9. The method of claim 8,
The porous polymer functionalized with an amine group in the above-
Preparing a porous polymer (step a);
(B) a step of mixing the porous polymer and the amine compound prepared in the step (a) and reacting them to prepare a porous polymer functionalized with an amine group (step b).
10. The method of claim 9,
Wherein the porous polymer of step (a) comprises an epoxy group.
10. The method of claim 9,
Wherein the mixing ratio of the porous polymer and the amine compound in the step (b) is 1: 0.1 to 1.5.
10. The method of claim 9,
The amine compound of step b may be selected from the group consisting of ethylamine, butylamine, hexylamine, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, ethylenediamine (NH2CH2CH2NH2), tetramethylenediamine (CH2) 4NH2), hexamethylenediamine (NH2 (CH2) 6NH2), N-ethylethylenediamine (NH2CH2CH2NHCH2CH3), N, N'- dimethylethylenediamine (NH2CH2CH2N (CH3) Wherein the hydrogen fluoride is at least one selected from the group consisting of diamine (NH2CH2CH2N (CH2CH3) 2), diethylenetriamine (NH2CH2CH2NHCH2CH2NH2), triethylenetetramine (NH2CH2CH2NHCH2CH2NHCH2CH2NH2), and polyethyleneimine.
10. The method of claim 9,
Wherein the reaction of step (b) is carried out at a temperature of 50 ° C to 120 ° C for 1 hour to 48 hours.
9. The method of claim 8,
Wherein the amount of the porous polymer functionalized with the amine group is 2 g to 20 g based on 1 L of an aqueous solution containing hydrofluoric acid and hydrogen fluoride.
9. The method of claim 8,
Wherein the temperature at which the step is carried out is 5 ° C to 50 ° C.
9. The method of claim 8,
Contacting the porous polymer functionalized with hydrogen fluoride-adsorbed amine groups with an aqueous solution comprising a cation, after performing the above steps.