KR101322340B1 - Method for removing hydrogen fluoride gas by stabilization to source material of making fluorine - Google Patents

Abstract

The present invention relates to a method for removing fluorine gas through stabilization with a source material for producing fluorine. More specifically, in recent years, a number of deaths and injuries have been caused by the successive hydrofluoric acid leakage accidents at semiconductor factories, etc., and a means of removing the hydrofluoric acid by a simple manufacturing method has been manufactured. By using this method, most of hydrofluoric acid gas can be removed in a short time by using a simple process. Sodium compound and potassium compound are supported by natural mordenite having excellent cation exchange capacity, many pore structures, and excellent adsorption function. Ion-substituted, etc., to solidify and adsorb fluorine gas to reduce and stabilize the fluorine source, such as fluorspar, cryolite, fluorite apatite, to stabilize the fluorine gas by combining the chemical method with the physical method. Fluoride gas removal through stabilization of fluorine source It relates to the law.
To this end, the present invention comprises the steps of (a) pulverizing natural mordenite having a cation substitution capacity (CEC) of at least 160 meq / 100g or more; (b) dissolving any one of sodium compound, potassium compound, calcium salt compound, silicate compound, aluminum salt compound and phosphate compound in distilled water; (c) reacting the natural mordenite powder obtained in the step (a) and the solution of the step (b) into a reaction tank, and reacting the sodium and potassium compounds in the pores of the natural mordenite by using the natural mordenite as a carrier. Impregnating any one of a calcium salt compound, a silicate compound, an aluminum salt compound and a phosphate compound; (d) solidifying the resultant of step (c); (e) mixing the natural adhesive to the resultant of step (d) to form a powder type, granule type, ball type, filter type, block type, honeycomb type, and drying them; And (f) adsorbing fluorine gas to the resultant of step (e) to stabilize the fluorine manufacturing source material, comprising reducing and stabilizing the fluorine production source material, including fluorite, cryolite and fluorite apatite. It provides a method for removing fluorine gas through.

Description

Method for removing Hydrogen Fluoride gas by stabilization to source material of making Fluorine

The present invention relates to a method for removing fluorine gas through stabilization with a source material for producing fluorine. More specifically, in recent years, a number of deaths and injuries have been caused by the successive hydrofluoric acid leakage accidents at semiconductor factories, etc., and a means of removing the hydrofluoric acid by a simple manufacturing method has been manufactured. By using this method, most of hydrofluoric acid gas can be removed in a short time by using a simple process. Sodium compound and potassium compound are supported by natural mordenite having excellent cation exchange capacity, many pore structures, and excellent adsorption function. Ion-substituted, etc., to solidify and adsorb fluorine gas to reduce and stabilize the fluorine source, such as fluorspar, cryolite, fluorite apatite, to stabilize the fluorine gas by combining the chemical method with the physical method. Fluoride gas removal through stabilization of fluorine source It relates to the law.

Hydrofluoric acid (hydrofluoric acid) gas is widely used in various fields including semiconductor manufacturing processes. Hydrogen fluoride (HF) is a colorless gas, but it is mixed with water contained in the air to form hydrofluoric acid.

Hydrogen fluoride is prepared by reacting calcium fluoride (fluorite, CaF ₂ ) with concentrated sulfuric acid (H ₂ SO ₄ ). Cooling the hydrogen fluoride into a liquid produces pure hydrofluoric acid. In the process of producing phosphoric acid by reacting calcium phosphate with sulfuric acid, hydrogen fluoride can be obtained as a by-product when calcium phosphate is used because fluorine is combined as an impurity.

The chemical reaction for each case is shown below.

CaF ₂ (s) + H ₂ SO ₄ (l) → 2HF (g) + CaSO ₄ (s)

Ca ₅ (PO ₄ ) 3 F + 5H ₂ SO ₄ + 10H ₂ O → 3H ₃ PO ₄ + 5CaSO ₄ 2H ₂ O + HF

Folic acid is particularly dangerous to humans due to its penetration into skin tissue. Fluorine ion (F ^-) is another halogen ion size ^{(Cl -, Br -, I} -) less than the amount of hydrofluoric acid is readily penetrate into the skin. Other halogen ions, except for fluorine ions, are strong acids (HCl, HBr, HI) that combine with hydrogen ions to dissociate completely in aqueous solution. However, hydrofluoric acid is a weak acid (pKa = 3.17) that does not dissociate completely. Therefore, in most cases, hydrofluoric acid molecules are absorbed even when penetrated into the skin. The degree to which hydrofluoric acid dissociates into cations (H ⁺ ) and anions (F ⁻ ) also varies with concentration, and even undissociated molecules are small and can be easily absorbed by the skin.

Some of the hydrofluoric acid once absorbed into the human body will be dissociated, resulting in the generation of fluorine ions (F ⁻ ), which is a problem. This is because fluorine ions react with calcium ions (Ca ²⁺ ) or magnesium ions (Mg ²⁺ ) present in the body to form CaF ₂ (s) or MgF ₂ (s), which are insoluble salts. When the concentration of calcium and magnesium ions in the electrolyte is lower than the normal level due to the chemical reaction, the balance of the electrolyte is broken. In addition, fluorine ions react with the bones and damage the bones.

Moreover, since hydrofluoric acid has a low boiling point and easily turns into a gas at room temperature, even if hydrofluoric acid leaks into the liquid, the temperature is about 20 degrees Celsius, so that the problem becomes very serious. When vaporized hydrogen fluoride enters the lungs through respiration, hydrofluoric acid will react with the water contained in the mucus, causing necrosis of lung tissue. Even weaker forms of blisters in the lungs are dangerous enough to cause death if breathing is difficult.

In recent years, a number of deaths and injuries have been reported as a result of a hydrofluoric acid leak at a semiconductor factory, etc., and secondary damage is still ongoing.

Therefore, there is a need for the development of a technology capable of removing fluorine gas by using a simple manufacturing method and removing the fluorine gas by using a simple process.

The present invention has been made to solve the above problems, in particular, in recent years, a number of deaths and injuries continue to occur as a result of a hydrofluoric acid gas leakage accident in a semiconductor factory, etc., and in the situation where the second damage still continues, It is an object of the present invention to manufacture a means for removing hydrofluoric acid by a manufacturing method, and to provide a hydrofluoric acid gas removing method capable of removing most of hydrofluoric acid gas in a short time using a simple process.

In order to achieve the above object, a method for removing fluorine gas through stabilization of fluorine manufacturing source material according to the present invention includes: (a) pulverizing natural mordenite having a cation substitution capacity (CEC) of at least 160 meq / 100g or more; (b) dissolving any one of sodium compound, potassium compound, calcium salt compound, silicate compound, aluminum salt compound and phosphate compound in distilled water; (c) reacting the natural mordenite powder obtained in the step (a) and the solution of the step (b) into a reaction tank, and reacting the sodium and potassium compounds in the pores of the natural mordenite by using the natural mordenite as a carrier. Impregnating any one of a calcium salt compound, a silicate compound, an aluminum salt compound and a phosphate compound; (d) solidifying the resultant of step (c); (e) mixing the natural adhesive to the resultant of step (d) to form a powder type, granule type, ball type, filter type, block type, honeycomb type, and drying them; And (f) adsorbing fluorine gas to the resultant of step (e) to reduce fluorine, cryolite, and fluorine to a source of fluorine production, including fluorite, and stabilizing it.

In addition, the natural mordenite of step (a) has a cation substitution capacity of 171 meq / 100g or more, and purity may be 80% or more.

In addition, in step (f), the deodorization rate relative to the initial concentration according to the adsorption of the hydrofluoric acid gas may be 99% or more.

According to the present invention, a number of deaths and injuries have been continuously made in recent years due to a fluorine gas leakage accident in a semiconductor factory, etc., and a means for removing the fluorine gas by a simple manufacturing method is prepared in a situation where secondary damage is still occurring. And, it is effective to remove most of the fluorine gas in a short time by using a simple process.

In addition, according to the present invention, a natural mordenite having excellent cation exchange ability, a large number of pore structures, and an excellent adsorption function is used as a carrier to be ion-substituted with sodium compounds, potassium compounds, etc., and then solidified and adsorbed hydrofluoric acid thereon. By reducing and stabilizing with fluorine-prepared source materials such as fluorite, cryolite and fluorite apatite, it is possible to maximize the efficiency of removing fluorine gas by incorporating a chemical method into a physical method.

1 is a crystal structure diagram of a natural mordenite powder used as a carrier in a method for removing fluorine gas through stabilization to a source of fluorine production according to a preferred embodiment of the present invention;
2 is a chemical structural diagram showing an atomic skeleton of natural mordenite substituted with sodium ions,
3 is a graph showing a concentration curve of hydrofluoric acid gas over time using the hydrofluoric acid gas remover according to the present invention;
4 is a test report of the cation substitution ability (CEC) of the natural mordenite used for the production of hydrofluoric acid gas remover according to the present invention,
5 is a main component table of natural mordenite used for the production of hydrofluoric acid gas remover according to the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the drawings, the same reference numerals are used to designate the same or similar components throughout the drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear. In addition, the preferred embodiments of the present invention will be described below, but it is needless to say that the technical idea of the present invention is not limited thereto and can be variously modified by those skilled in the art.

1 is a crystal structure diagram of a natural mordenite powder used as a carrier in a method for removing fluorine gas through stabilization to a source of fluorine production according to a preferred embodiment of the present invention. 2 is a chemical structural diagram showing the atomic skeleton of natural mordenite substituted with sodium ions.

Natural mordenite has a structure in which silicon (Si) and aluminum (Al) are bonded through oxygen (O). In order to share oxygen with + 3-valent aluminum and + 4-valent silicon in the skeleton, -2 is electrically neutral around silicon and -1 is around aluminum. To compensate for this negative charge, cations such as sodium ions (Na ⁺ ) are required in the backbone. These cations are provided by sodium or potassium compounds.

Referring to FIG. 1, in the skeleton of natural mordenite, many pores 10 are approximately 30 times larger than pores of activated carbon, so that these pores not only perform a physical filter function but also a sodium compound or a potassium compound. It is suitable to impregnate a metal compound with high ion exchangeability.

Referring to FIG. 2, natural mordenite is formed by three-dimensional combination of Si—O—Al—O—Si structures. Molecular pores are provided in the three-dimensional structure to adsorb water, organic molecules, and metal ions. It is also used to control the humidity of the room by using the moisture adsorption capacity.

Fluoride gas scavenger through stabilization of fluorine production source according to a preferred embodiment of the present invention utilizes such a natural mordenite powder as a basic carrier. This carrier is a mineral with large pores and excellent ion exchangeability (CEC), and utilizes a physical filter function using pores and a cation impregnation function into pores. In order to remove and stabilize the cation, these pores are impregnated with a high dissociation compound among the carbonate compounds.

The impregnated powder is ion-substituted under appropriate conditions. For example, it is substituted with sodium having high ion exchangeability in the compound on the powder. The powder is used as a hydrofluoric acid gas remover as it is, or mixed with a natural adhesive, and shaped into granule type, ball type, filter type, block type, honey cup type, etc. It will remove the gas.

Natural mordenite forms a homogeneous honeycomb structure corresponding to 20 to 40 nanometers and has multi-porosity. For example, the ability to remove ammonium gas is approximately 10 to 30 times that of palm activated carbon. In addition, it has a humidity control function that absorbs moisture when the humidity in the air is high and discharges moisture when it is dried, and the cation exchange capacity (CEC) is at least about 160 meq / 100g, specifically about 171 meq / 100g. Is reached. In addition, the crystal structure has a trace amount of polarity corresponding to van der Waals forces, so that harmful substances including basic substances, acidic substances, polar substances and active substances are adsorbed and removed.

As mentioned in [Background Art of the Invention], hydrogen fluoride is prepared by reacting calcium fluoride (fluorite, CaF ₂ ) with concentrated sulfuric acid (H ₂ SO ₄ ). Cooling the hydrogen fluoride into a liquid produces pure hydrofluoric acid. In the process of producing phosphoric acid by reacting calcium phosphate with sulfuric acid, hydrogen fluoride can be obtained as a by-product when calcium phosphate is used because fluorine is combined as an impurity.

The chemical reaction formula of the process for producing fluorine gas from fluorite (calcium fluoride) is as follows.

CaF ₂ (s) + H ₂ SO ₄ (l) → 2HF (g) + CaSO ₄ (s)

The chemical reaction of the process for producing fluorine gas from calcium phosphate salt (Fluorapatite) is shown below.

Ca ₅ (PO ₄ ) 3 F + 5H ₂ SO ₄ + 10H ₂ O → 3H ₃ PO ₄ + 5CaSO ₄ 2H ₂ O + HF

In addition, hydrofluoric acid gas can be prepared from cryolite (Na ₃ AlF ₆ ).

Such fluorite, cryolite, fluorite apatite, etc. are used in the production of fluorine gas, as well as the source material for producing fluorine (Fluorine).

In the present invention, the hydrofluoric acid gas is reacted with sodium compounds, potassium compounds, calcium salt compounds, silicate compounds, aluminum compounds, phosphate compounds, and the like in the process of producing fluorine gas from such fluorine-producing raw materials. Remove This reaction removes the hydrofluoric acid gas and produces a stable source of hydrofluoric acid.

In order to speed up the reaction, sodium fluorine, potassium ions, calcium ions, silicon ions, aluminum ions, phosphorus ions, and the like are impregnated into the pores of natural mordenite and ion-exchanged to solidify into a molding to prepare a fluorine gas remover. .

The hydrofluoric acid gas remover to which the hydrofluoric acid gas removing method is applied through stabilization to a source of fluorine production according to a preferred embodiment of the present invention is prepared by the following process.

1. The first step

Natural mordenite ore is pulverized to produce natural mordenite powder. At this time, the natural mordenite powder is preferably as fine as possible in terms of surface area increase. For example, it is preferable that it is 325 mesh or more, and it is more preferable that a particle diameter is 1 micrometer or less. As the natural mordenite is finely pulverized, the surface area is increased to increase the reaction speed and improve the impregnation efficiency.

At this time, the natural mordenite is preferably at least 160 meq / 100g, more preferably 170 meq / 100g or more cation substitution capacity (CEC). As the cation substitution ability is excellent, sodium ions such as sodium compounds, potassium compounds and calcium compounds, potassium ions and calcium ions are easily adsorbed to natural mordenite. In the present invention, natural mordenite having a cation substitution capacity of 171 meq / 100g and a purity of 80% or more was used.

2. Second Step

Sodium compound, potassium compound, calcium salt compound, silicate compound, aluminum salt compound or phosphate compound is dissolved in distilled water. As the sodium compound, sodium carbonate may be used as the potassium compound, but is not limited thereto.

3. The third step

The natural mordenite powder obtained in the first step and the solution of the second step are added to the reaction tank and reacted with sodium mortar, potassium compound, calcium salt compound, silicate compound and aluminum salt in the pores of the natural mordenite using the natural mordenite as a carrier. Impregnated with either the compound or the phosphate compound. Through this reaction, at least one of sodium compound, potassium compound, calcium salt compound, silicate compound, aluminum salt compound, and phosphate compound is impregnated into the pores of the natural mordenite using the natural mordenite as a carrier. In this case, the second step and the third step may be performed at the same time. That is, any one of natural mordenite powder, sodium compound, potassium compound, calcium salt compound, silicate compound, aluminum salt compound, and phosphate compound may be liquefied in distilled water, and then reacted under certain conditions.

4. Fourth Step

The resultant of the third step is solidified. Solidification can be made of any one of powder type, granule type, ball type, filter type, block type, honeycomb type, and is preferably formed into a ball type for convenient use by inserting into a filter. It is also possible to form in other shapes.

In order to mold into any one of the ball type, granule type, filter type, block type, and honey cup type, the natural adhesive of any one of protein-based, carbohydrate-based and complex polysaccharide-based systems may be mixed and molded into the result of the third step.

5. The fifth step

After the resultant of the fourth step is dried at 180 ~ 250 ° C, a filter is prepared and passed through hydrofluoric acid (HF).

The hydrofluoric acid removal mechanism by the sodium compound is as follows.

2HF + 2Na ⁺ → 2NaF + H ₂

The hydrofluoric acid removal mechanism by the potassium compound is as follows.

2HF + 2K ⁺ → 2KF + H ₂

The fluorine gas removal mechanism by the calcium compound is as follows.

2HF + Ca ²⁺ → CaF ₂ + H ₂

The hydrofluoric acid gas removal mechanism by the silicate compound is as follows.

2HF + Si ²⁺ → SiF ₂ + H ₂

The hydrofluoric acid gas removal mechanism by the aluminum salt compound is as follows.

2HF + Al ²⁺ → AlF ₂ + H ₂

The hydrofluoric acid removal mechanism by the phosphate compound is as follows.

2HF + P ²⁺ → PF ₂ + H ₂

As such, sodium ions, potassium ions, calcium ions, silicon ions, aluminium ions, phosphorus ions, etc., such as sodium compounds, potassium compounds, calcium salt compounds, silicate compounds, aluminum salt compounds, and phosphate compounds impregnated in the pores of natural mordenite The fluoride is combined with the fluoride to reduce and stabilize the fluorine gas while reducing and stabilizing it with a material similar to fluorine-producing materials such as fluorite, cryolite, and fluorite apatite.

Examples in which sodium carbonate is used as the sodium compound are as follows.

Grind natural mordenite ore into 325 mesh.

Add 20-45 g of sodium carbonate to 100 mL of distilled water and dissolve it in 60-80 degrees Celsius.

30-50 mL of sodium carbonate solution is added to the reactor with 100 g of crushed mordenite powder and reacted at 60-80 ° C. at a speed of 1000-3000 rpm for 8-10 hours.

When the reaction is complete, a protein-based natural adhesive and an appropriate amount of acetic acid or potassium permanganate are mixed and molded into a ball shape having a diameter of 1 to 30 mm using a dehydrator, and dried at 200 ° C.

When the hydrofluoric acid gas remover and the hydrofluoric acid gas prepared as described above react with each other, the fluorine ions in the hydrofluoric acid gas and the sodium ions in the hydrofluoric acid gas remover react with each other to stabilize the chemical bond.

Table 1 below is a result of measuring the deodorization rate of the hydrofluoric acid gas using the hydrofluoric acid gas remover prepared in this way, Figure 3 is a graph showing the concentration curve of hydrofluoric acid gas over time using the hydrofluoric acid gas remover according to the present invention to be.

As the sample, 20g of solid fluorine gas remover was used, and FT-IR was used as MIDAC I1801 model. The temperature, pressure, and path length of FT-IR gas cell were 130 ° C, 14.57psi, and 20m, respectively. The size was 5L.

Deodorization rate was calculated according to the following formula.

Deodorization rate = [(blank concentration by time zone-sample concentration by time zone) / blank concentration by time zone] × 100

Referring to Table 1 and FIG. 3, the deodorization rate was 98.0% after 30 minutes, indicating that most of the fluorine gas was removed, and the deodorization rate was 99% or more after 90 minutes, indicating that most of the fluorine gas was deodorized. .

Figure 4 is a test report of the cation substitution capacity (CEC) of the natural mordenite used for the production of hydrofluoric acid gas remover according to the present invention, Figure 5 is a natural mordenite used for the production of hydrofluoric acid gas remover according to the present invention Main ingredient list.

Referring to Figure 4, it can be seen that the cation substitution capacity of the natural mordenite used for the production of hydrofluoric acid gas remover according to the present invention reaches 170 meq / 100g.

Referring to Figure 5, it can be seen that the natural mordenite used for the production of fluorine gas remover is composed of Si oxide, Al oxide, Fe oxide, Ca oxide, Mg oxide, K oxide, and Na oxide.

It will be apparent to those skilled in the art that various modifications, substitutions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. will be. Accordingly, the embodiments disclosed in the present invention and the accompanying drawings are not intended to limit the technical spirit of the present invention but to describe the present invention, and the scope of the technical idea of the present invention is not limited by the embodiments and the accompanying drawings. . The protection scope of the present invention should be interpreted by the following claims, and all technical ideas within the equivalent scope should be interpreted as being included in the scope of the present invention.

10-pore

Claims (3)

(a) milling natural mordenite having a cation substitution capacity (CEC) of at least 160 meq / 100g or more;
(b) dissolving any one of sodium compound, potassium compound, calcium salt compound, silicate compound, aluminum salt compound and phosphate compound in distilled water;
(c) reacting the natural mordenite powder obtained in the step (a) and the solution of the step (b) into a reaction tank, and reacting the sodium and potassium compounds in the pores of the natural mordenite by using the natural mordenite as a carrier. Impregnating any one of a calcium salt compound, a silicate compound, an aluminum salt compound and a phosphate compound;
(d) solidifying the resultant of step (c);
(e) mixing the natural adhesive to the resultant of step (d) to form a powder type, granule type, ball type, filter type, block type, honeycomb type, and drying them; And
(f) adsorbing fluorine gas to the resultant of step (e) to reduce fluorine, cryolite, and fluorine to a source of fluorine production, including fluorite and stabilization;
Fluorine gas removal method through the stabilization of the fluorine manufacturing source material comprising a. The method of claim 1,
The natural mordenite of step (a) has a cation substitution capacity of 171 meq / 100g or more, purity of 80% or more, characterized in that the fluorine gas removal method through the stabilization to the source of fluorine manufacturing. The method of claim 1,
In the step (f), the deodorization rate relative to the initial concentration according to the adsorption of the fluorine gas is 99% or more, characterized in that the fluorine gas removal method through stabilization to the fluorine manufacturing source material.

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