KR101695486B1 - Removal method of Iron from Concentrated Cu Ore through Selective Chlorination Using Cuprous Chloride - Google Patents

Abstract

Disclosed is a selective chloridizing method using CuCl to obtain high-quality chalcocite by selectively removing iron from concentrated Cu ore. To investigate a mechanism of the selective chloridizing method, a thermochemical analysis using a chemical potential diagram is performed, and iron is confirmed to be removed from concentrated Cu ore to be changed to gaseous FeCl_2 under an argon gas atmosphere at 1100 K by a selective chloridizing response. In this experiment, as a result of reacting CuCl with concentrated Cu ore for five hours under argon gas atmosphere in which 800-1100 K of sulfur exist; iron content in concentrated Cu ore is reduced from 23.6 mass% to equal to or less than 0.37 mass%, Cu content increased from 39.8 mass% to equal to or greater than 58.7 mass%, and high-quality chalcocite is obtained. Accordingly, iron is able to selectively be removed from concentrated Cu ore in a single process, and high quality chalcocite is able to be produced as a result.

Description

{Removal method of Iron from Concentrated Cu Ore through Selective Chlorination Using Cuprous Chloride}

The present invention relates to a method for removing iron in identification light by a selective chlorination method using copper chloride.

Currently, commercial copper copper smelting (blister copper, 99%) production is done by dry process using sulfur hexane concentrate as raw material. Cofactor is produced by a two step reaction of matte smelting and converting, in which iron and sulfur are removed by slag (mainly Fe ₂ SiO ₄ ) and sulfur dioxide gas (SO ₂ ), respectively.

Iron is removed by a two-stage high temperature reaction, a 1493 K bake process and a 1473 K bake process to reduce the copper loss involved in slag formation. Nonetheless, the slag produced in both processes will contain about 1 - 8% copper. Therefore, the copper contained in the slag is recovered through the slag treatment process, and the copper concentration in the slag after the slag treatment process is reduced to 0.4 - 1.3%. However, although the slag produced by the slag treatment process contains a large amount of iron, it is difficult to use the slag as a raw material for the steelmaking process due to the copper remaining in the slag.

Also, as described above, in the present copper smelting process, a large amount of sulfur dioxide gas is discharged by the oxidation reaction of sulfur in the sulfur sulphide concentrate. These sulfur dioxide gases are collected and used for sulfuric acid production. However, in spite of the improvement of the capture technology of sulfur dioxide gas, the emission of sulfur dioxide gas as a byproduct is one of the problems to be solved from the viewpoint of environmental friendliness.

Various studies have been done in the past to solve the problems in the copper smelting process. Among them, a method of recovering copper from sulfide light using a chlorination method has been proposed as an alternative.

For most chlorination methods chlorine gas (Cl ₂ ) was used as a chlorinating agent at a temperature of 573 - 1023 K under an inert gas atmosphere.

Kanari et al ., For example, reported a chlorination reaction between chlorine gas and identification light containing mainly chalcopyrite at 573 K. (Non-Patent Document 1.) As a result of the experiment, Most of the elements were chlorinated and copper chloride was separated from iron chloride and sulfur chloride at 573 K according to the difference in vapor pressure of the metal chloride. This method has the advantage that copper can be recovered as copper chloride at low temperature, but the use of chlorine gas is pointed out as a disadvantage because it has safety and environmental issues.

Various studies have been made on a method of recovering copper from the hydrofluoric acid (Cu ₂ S) by a molten salt electrolysis method using a metal chloride as a molten salt as well as a chlorination method. Garbee et al . Used copper chloride as a molten salt at 723 - 873 K to obtain copper and sulfur from the phosphorus by the molten salt electrolysis method. (Non-Patent Document 2). Interestingly, copper was obtained when FeS-Cu ₂ S synthetic mat was used as a raw material, and FeS was expected to be removed with iron chloride (FeCl ₂ ) by reaction with copper chloride Respectively. However, no thermodynamic analysis of chlorination reactions taking into account the sulfur and chlorine chemical potentials has been made and no results have been reported when the identification light is used as the raw material.

Therefore, in order to develop an environmentally friendly and efficient new copper smelting process using the molten salt electrolytic process, it is required to develop a method for producing high-quality hydride by selectively removing iron in the identification light without using chlorine gas.

Non-Patent Document 1. N. Kanari, I. Gaballah, and E. Allain, Thermochimica Acta 373, 75-93 (2001). Non-Patent Document 2. A.K. Garbee and S.N. Flengas, Journal of the Electrochemical Society 119, 631-641 (1972).

Accordingly, the present invention provides a method of selectively removing iron in the light of identification by the reaction of copper chloride with a copper chloride using a selective chlorination method using copper chloride (CuCl) as a chlorinating agent, and producing a high- There is a purpose to provide a method that can be done.

The problems to be solved by the present invention are not limited to the above-mentioned problem (s), and another problem (s) not mentioned can be understood by those skilled in the art from the following description.

According to an aspect of the present invention, (b) adding a chlorinating agent to the identified light, mixing and placing the chlorinated agent in a quartz tube, and then injecting an inert gas to form an inert atmosphere; (c) heating the quartz tube to react the identification light with the chlorinating agent; And (d) recovering and washing the resulting residue, followed by drying. The present invention also provides a method for removing iron in a light by a selective chlorination method using copper chloride.

According to the present invention, it is possible to produce high-quality focused light in the identified light by a single process. Conventionally, two steps are required at a reaction temperature of about 1500 K to remove iron from identification light. However, when copper chloride is used as a chlorinating agent, iron can be selectively removed at a temperature of 800 to 1100 K And as a result, a high-quality hydride can be produced.

In addition, it is possible to greatly increase the stability of the process by not using chlorine gas, which is difficult to handle, such as chlorine gas.

1 is a flow chart showing a process of a method for removing iron in identification light by a selective chlorination method using copper chloride according to an embodiment of the present invention.
2 is a schematic view showing a high-temperature reaction apparatus in a method for removing iron in identification light by a selective chlorination method using copper chloride according to an embodiment of the present invention.
3 is a diagram in which chemical potential diagrams of Cu-S-Cl and Fe-S-Cl systems are superimposed at 1100 K. FIG.
FIG. 4 is a graph showing the results of a heat treatment of an identification light sample (I), an identification light sample (II), and an identification light sample (I) in a method of selectively removing iron in the identification light by a selective chlorination method using copper chloride according to an embodiment of the present invention Hereinafter, the X-ray diffraction analysis graph is shown.
Fig. 5 is a graph showing the results of the field emission scanning (SEM) showing the microstructure of the sample (I) subjected to the heat treatment and the case without heat treatment in the method of removing iron in the optical fiber by the selective chlorination method using copper chloride according to the embodiment of the present invention It is an electron microscope photograph.
FIG. 6 is a graph showing the results of X-ray diffraction analysis of the condensate recovered at the low temperature part of the quartz tube in the experiment for confirming the mechanism of the selective chlorination method using copper chloride.
FIG. 7 is an X-ray diffraction analysis graph of the residue produced according to the average particle size in the iron removal method in the identified light by the selective chlorination method using copper chloride according to the embodiment of the present invention.
8 is a field emission scanning electron micrograph of a surface of a product residue in a method for removing iron in identification light by a selective chlorination method using copper chloride according to an embodiment of the present invention.
9 is a graph showing the results of X-ray diffraction analysis of the product residue according to the reaction temperature change in the method for removing iron in the identified light by the selective chlorination method using copper chloride according to the embodiment of the present invention.
10 is a graph showing the results of X-ray diffraction analysis of a residue after reaction by a selective chlorination method in the case where sulfur powder is not present in the reaction system in the iron removal method by the selective chlorination method using copper chloride according to the embodiment of the present invention FIG.
FIG. 11 is a graph showing the results of a selective chlorination method using an identification light sample (II) having an average particle size of less than 45 μm as a raw material in a method for removing iron in identification light by a selective chlorination method using copper chloride according to an embodiment of the present invention X-ray diffraction analysis of the product residues after the reaction by < RTI ID = 0.0 >

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving it will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings.

The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. To fully disclose the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.

In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail.

Hereinafter, the present invention will be described in detail.

1 is a flow chart showing a process of a method for removing iron in identification light by a selective chlorination method using copper chloride according to an embodiment of the present invention.

Referring to FIG. 1, the method for removing iron in identification light by the selective chlorination method using copper chloride according to the present invention comprises the steps of: (a) preparing a concentrated copper ore; (b) adding a chlorinating agent to the identified light, mixing and placing the chlorinated agent in a quartz tube, and then injecting an inert gas to form an inert atmosphere; (c) heating the quartz tube to react the identification light with the chlorinating agent; And (d) recovering and washing the product residues and drying.

In the step of preparing the identification light, the identification light, which is a raw sample, is crushed to obtain an arbitrary range selected from the group consisting of average particle sizes of 45-75 탆, 75-105 탆, 105-150 탆, and 150-300 탆 (I) having a mean particle size of less than 45 mu m (excluding 0 mu m) can be produced by crushing the identification light as a raw sample (S100 ).

The identified optical sample (Ⅰ) mainly comprises a chalcopyrite (CuFeS _2), and the recoil seat (Cu ₅ FeS _4), iron sulfide (FeS _2), and comprise a silicon dioxide least one from the group consisting of (SiO ₂₎ .

The identification optical specimen (II) mainly contains iron sulfide (FeS ₂ ), and may contain chalcopyrite (CuFeS ₂ ) or silicon dioxide (SiO ₂ ), or may contain both chalcopyrite and silicon dioxide.

When the identified optical sample (I) is reacted with the chlorinating agent, it may be recovered as a stranded copper having a copper content of 58.7 mass% to 66.6 mass%. When the identified optical sample (II) is reacted with a chlorinating agent And the copper content can be recovered as a driven light having 61.7 mass% to 67.7 mass%.

A chloride may be added to the identified light, mixed and placed in a quartz tube, and then an inert gas may be introduced to form an inert atmosphere (S200).

The chlorinating agent may be cuprous chloride (CuCl).

When the chlorinating agent is copper chloride, chlorination can be performed safely differently from chlorine gas, and high-grade sulfurized copper can be produced by a chemical reaction of two or more steps in a single process.

Meanwhile, sulfur (S) may be further added to the step (b).

When the sulfur (S) is further added, the chemical potential of sulfur in the reaction system can be positively controlled in the reaction between the identification light and the chlorinating agent in the step (c). However, Water is not changed by the addition of sulfur.

3 is a diagram in which chemical potential diagrams of Cu-S-Cl and Fe-S-Cl systems are superimposed at 1100 K. FIG.

Referring to FIG. 3, when a large amount of copper chloride is used at a reaction temperature of 1100 K and sulfur is additionally added, the sulfur and chlorine chemical potentials in the reaction system can be fixed at point a in FIG.

In the step (b), an inert gas may be introduced into the quartz tube at a flow rate of 200 sccm to form an inert atmosphere, and the internal pressure may be maintained at 1 atm (S200).

When the above condition is exceeded, it is difficult to recover high-quality pulsed light by selectively removing iron from the identified light by controlling the sulfur and chlorine chemical potentials in the reaction system by the high-temperature chlorination reaction.

The inert gas may be any one selected from the group consisting of helium (He), neon (Ne) and argon (Ar), and it is highly preferable to select argon.

There is a possibility that the sulfur and chlorine chemical potentials in the reaction system other than the inert gas may be influenced.

In the step (c), the quartz tube may be heated at 800 K to 1100 K for 5 hours to react the identification light with the chlorinating agent (S300).

If the temperature does not reach the above range, the reaction does not proceed. Particularly, when the melting point of copper chloride is below 696 K, sufficient reaction does not proceed, thereby selectively removing iron from the identification light and increasing the content of copper, It is difficult to manufacture.

Here, the quartz tube can be heated and reacted to release iron in the identification light into gaseous iron chloride (FeCl ₂ ).

The iron in the identification light can be selectively removed by gaseous iron chloride to increase the copper content in the raw material, so that a high-quality hydrodynamic light can be produced.

 (I) having an average particle size of 45 - 300 탆 has a copper content of 39.8 mass% to 58.7 mass% - 66.6 mass%, which is a product residue recovered in the reaction in the temperature range of 800 to 1100 K, Can be increased by mass%.

Also, when the average particle size of the identified optical sample (I) is 45-75 탆, the copper content of the hydrofluoric acid recovered in the reaction in the temperature range of 800 - 1100 K in which sulfur is not present is 39.8 mass% to 59.8 Mass% - 63.2 mass%.

Therefore, it is possible to produce a high-quality hydride directly from the identified optical sample (I).

On the other hand, in the case of the phosphor (Ⅱ) having an average particle size of less than 45 ㎛, the copper content of the recovered phosphorus in the reaction in the temperature range of 800 - 1100 K containing sulfur is 34.6 mass% to 66.9 mass% - 67.7 mass% Lt; / RTI >

Also, in the case of an identification optical sample (II) having an average particle size of less than 45 탆, the copper content of the recovered remainder in the 800 K reaction in which sulfur is not present can be increased from 34.6 mass% to 61.7 mass%.

Thus, a high-quality hydride can be produced directly from the identified optical sample (II).

In step (d), the generated residue may be recovered, washed and dried (S400).

The generating may be the step of cleaning to recover a residue, generated and remove the remaining 10% hydrochloric acid and water was recovered (HCl) and 8.6% unreacted residual copper chloride with ammonium hydroxide (NH ₄ OH) leaching.

The residue produced after leaching can be washed with distilled water and then dried to recover high-quality pulsed light from the product residue.

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

< Example  1> Using copper chloride Sympathetic Selective chlorination method

Quartz crucibles were prepared, and homogenized light was pulverized to obtain a homogeneous light sample (I) having an average particle size of 45 to 75 mu m, 75 to 105 mu m, 105 to 150 mu m, and 150 to 300 mu m and an average particle size of 45 Mu] m, were prepared.

Copper chloride powder (CuCl, anhydrous, purity 99.9%, Wako Pure Chemical Industries, Ltd.) and powdered sulfur (purity ≥99%, Kojundo Chemical Laboratory Co., Ltd.) were prepared.

2 is a schematic view showing an apparatus for selective chlorination in a method for removing iron in identification light by a selective chlorination method using copper chloride according to an embodiment of the present invention.

Referring to FIG. 2, the identification light was pulverized into a mortar and poured into a beaker before use. To prepare the experiment, 0.20 g of the identified light sample, 2.00 g of copper chloride and sulfur were mixed in a glove box and placed in a quartz crucible (= 24 mm, I.D. = 50 mm). Thereafter, 6.00 g of copper chloride was added to the mixture, and the quartz crucible was placed inside a quartz tube (= 44 mm, l = 900 mm) and closed with a silicone rubber stopper.

After quenching the air for 5 minutes, the quartz tube was purged with argon gas (purity ≥ 99.999%) until the internal pressure of the tube was 1 atm. After the second argon gas filling, 200 sccm of gas was introduced using a mass flow controller (MFC, Model no .: 5400S, Kojima Instruments Inc.) and the pressure inside the quartz tube was maintained at 1 atm . After the inert atmosphere adjustment was completed, it was placed in a horizontal path preheated to 800 - 1100 K.

The product residue obtained after the reaction was pulverized using a mortar, leached with 10% hydrochloric acid solution for 30 minutes, and further leached with 8.6% ammonium hydroxide solution for 30 minutes twice.

The residue produced after the leaching process was again washed with distilled water and dried at 323 K under atmospheric conditions.

< Experimental Example  1> Chemical composition analysis method

The chemical composition of the residue produced in Example 1 was analyzed using inductively coupled plasma atomic emission spectroscopy (ICP-AES, Perkin Elmer, Optima 5300DV, Thermo Fisher Scientific, ICAP 6500).

The crystal phase was identified by X-ray diffraction (XRD: Rigaku, SmartLab, Cu-K radiation), and the microstructure of the reactant light sample and the resulting residue was analyzed by field emission scanning electron microscopy (FE-SEM, Hitachi, SU8230).

< Experimental Example  2> Sympathetic In the selective chlorination method  Thermodynamic analysis for

 The selective removal of iron was confirmed at 1100 K using the chemical potential diagram of Cu-S-Cl and Fe-S-Cl system for the thermodynamic analysis of the selective chlorination method.

Figure 3 is a chemical potential of chlorine (Cl) on the horizontal axis (hereinafter referred to as 'p _Cl2') and the vertical axis as sulfur (S) chemical potential (hereinafter _'S2 p') having a Cu-S-Cl and Fe- at 1100 K for S-Cl system chemical potential diagrams.

Referring to FIG. 3, the obliquely processed region is a region in which Cu ₂ S ( s ) and FeCl ₂ ( 1 ) exist in a stable phase.

Therefore situ p _Cl2 And p _S2 Is present in the region, iron is converted to FeCl ₂ ( 1 ) and copper can be obtained as Cu ₂ S ( s ). At this time, since the vapor pressure of from 1100 K only one FeCl ₂ (l) is negligible vapor pressure of Cu ₂ S (s) is high as 0.09 atm FeCl ₂ (l) is evaporated as a gas. For this reason, the shaded region is defined as a potential region where the selective chlorination reaction of iron can occur.

In the experiment, because the excess amount of copper used in the reaction system p _Cl2 And p _S2 Is controlled by the equilibrium of Cu ₂ S ( s ) / CuCl ₂ ( 1 ). Sulfur in the reaction system exists and p _S2 If the reaction system be higher control p _S2 Because be considered to be controlled at about 1 atm, the reaction system within a p _Cl2 under two conditions And p _S2 is fixed at point a in Fig. Since the point a is located at the boundary of the potential region where the selective chlorination occurs, the iron in the identification light is chlorinated with FeCl ₂ according to the following Schemes 1, 2, and 3.

[Reaction Scheme 1]

CuFeS ₂ ( s ) + 2 CuCl ( l ) = 3/2 Cu ₂ S ( s ) + FeCl ₂ ( l, g ) + 1/4 S ₂ ( g )

Δ G ° _r = - 24.4 kJ @ 1100 K

[Reaction Scheme 2]

FeS ( s ) + 2 CuCl ( l ) = Cu ₂ S ( s ) + FeCl ₂ ( l, g )

Δ G ° _r = - 41.3 kJ @ 1100 K

[Reaction Scheme 3]

Cu ₅ FeS ₄ ( s ) + 2 CuCl ( l ) = 7/2 Cu ₂ S ( s ) + FeCl ₂ ( l , g ) + 1/4 S ₂ ( g )

Δ G ° _r = - 5.53 kJ @ 1100 K

A thermodynamic study on selective chlorination using copper chloride was carried out when sulfur was not present in the reaction system. When using a large excess of copper, as shown in the previous described reaction system p _Cl2 And p _S2 Is controlled by the equilibrium of Cu ₂ S ( s ) / CuCl ₂ ( 1 ). Considering the redox potential of Cu ₂ S ( s ), even though there is no sulfur in the reaction system, p _S2 in the reaction system is considered to have a value between the y-axis value at point b in FIG. 3 and the y- . Therefore under the two conditions p _Cl2 And p _S2 Is located between point b and point a on the equilibrium line of Cu ₂ S ( s ) / CuCl ₂ ( l ) and is located on the right border of the potential region where the selective chlorination occurs. Therefore, even if sulfur is not present in the reaction system, iron in the identification light is chlorinated with FeCl ₂ in accordance with the above Schemes 1, 2, and 3.

< Experimental Example  3> At 1100 K Symmetrical photolysis  Confirm

In order to confirm the behavior of the identification light at high temperature, the identification light sample (I) was heat-treated for 5 hours under an argon gas atmosphere containing 1100 K sulfur.

FIG. 4 is a graph showing the results of a heat treatment of an identification light sample (I), an identification light sample (II), and an identification light sample (I) in a method of selectively removing iron in the identification light by a selective chlorination method using copper chloride according to an embodiment of the present invention Hereinafter, the X-ray diffraction analysis graph is shown.

4, (a) shows the result of X-ray diffraction analysis of the untreated optical sample (I), (b) shows the result of X-ray diffraction analysis of the unidentified optical sample (II) ) Is a graph of an X-ray diffraction analysis result of the identified optical sample (I) obtained after heat treatment of the identified optical sample (I) for 5 hours at a temperature of 1100 K in a reaction system containing sulfur.

4 (a), the identification light sample (I) is mainly composed of CuFeS ₂ And Cu ₅ FeS ₄ , FeS ₂ , and SiO ₂ are partially present.

Referring to FIG. 4 (b), the identified optical sample (II) mainly consists of FeS ₂ And CuFeS ₂ and SiO ₂ are partially present.

Referring to FIG. 4 (c), when the identification optical sample (I) is heated at 1100 K, CuFeS ₂ And Cu ₉ Fe ₉ S ₁₆ and Cu _{5 . 433} Fe _{1 . 087} S ₄ (bornite, Cu ₅ FeS ₄ ), and SiO ₂ .

From the above results, it can be seen that CuFeS ₂ in the identification light sample (I) undergoes a decomposition reaction of the following reaction formula 4 at a reaction of 1100 K.

As can be seen from FIG. 4 (a), the identification light sample (I) contains a trace amount of FeS ₂ .

On the other hand, as shown in FIG. 3, since the FeS is present as a stable phase at 1100 K, it is expected that the decomposition reaction of the following Reaction Formula 5 would occur, but it is considered that it is not shown in FIG. 4 (c) because the peak intensity is weak.

[Reaction Scheme 4]

14 CuFeS ₂ ( s ) = Cu ₅ FeS ₄ ( s ) + Cu ₉ Fe ₉ S ₁₆ ( s ) + 4 FeS ( s ) + 2 S ₂ ( g )

[Reaction Scheme 5]

_{FeS 2 (s) = FeS (} s) + 1/2 S 2 (g)

Δ G ° _r = - 2.84 kJ @ 1100 K

Fig. 5 is a graph showing the results of the field emission scanning (SEM) showing the microstructure of the sample (I) subjected to the heat treatment and the case without heat treatment in the method of removing iron in the optical fiber by the selective chlorination method using copper chloride according to the embodiment of the present invention It is an electron microscope photograph.

Fig. 5 (a) is a photograph of the surface of the specimen I without heat treatment, and Fig. 16 (b) is a photograph of the surface of the specimen when the specimen I is heat-treated under the condition of sulfur at 1100 K. Fig.

Referring to FIG. 5, after heat treatment at 1100 K, it was confirmed that sharp edges were formed on the particle surface of the identification light sample (I), but void formation due to evaporation of sulfur was not observed.

< Experimental Example  4> Of the selective chlorination method  Mechanism identification

Experiments were conducted to confirm the mechanism of selective chlorination using copper chloride. 5.00 g of the identified optical sample (I) having an average particle size in the range of 150-300 μm was mixed with 0.3 g of copper chloride to prepare a mixture. The mixture was then filtered through a quartz crucible (Φ = 26 mm, d = 24 mm , depth). A quartz crucible was placed in a quartz tube, the atmosphere in the quartz tube was controlled by the method of Example 1, and the reaction was conducted at 1100 K for 5 hours under an argon gas atmosphere.

After the experiment, the resultant residue obtained in the quartz crucible was mixed with 0.6 g of copper chloride without adding sulfur, and the atmosphere was controlled by the method of Example 1 and reacted at 1100 K for 5 hours under an argon gas atmosphere.

At the end of the reaction, the condensed deposits at the low temperature section of the quartz tube were analyzed by X-ray diffraction analysis.

6 is a graph showing the X-ray diffraction analysis results of the condensate condensed at the low temperature part of the quartz tube in the experiment for confirming the mechanism of the selective chlorination method using copper chloride.

Referring to FIG. 6, FeCl ₂ .2 (H ₂ O) was confirmed, and it was confirmed that iron in the identification light was removed as gaseous FeCl ₂ by selective chlorination using copper chloride as predicted according to thermodynamic considerations.

Water molecules in FeCl ₂ · 2 (H ₂ O) were predicted to be bound to FeCl ₂ when the silicon plug of the quartz tube was opened to recover the deposit.

< Experimental Example  5> Identified photon particle size  effect

The degree of iron removal by the particle size of the identified optical sample was confirmed.

Experiment number ^a Sympathetic light
Sample type Average particle size d _ore / 탆 Amount of sulfur added Ws / g Reaction temperature T / K element i concentration, C (mass%) ^b Remarks Cu Fe Al Ca Reactant The sample (I)
39.8 23.6 1.16 0.62 SiO ₂ = 8.75% by weight The sample (II) 34.6 23.7 1.20 0.03 SiO ₂ = 5.31% by weight 150812 The sample (I) 45 - 75 0.10 1100 65.5 0.28 0.54 0.13 150813 The sample (I) 75 - 105 0.10 1100 63.5 0.34 0.64 0.04 150814 The sample (I) 105 - 150 0.10 1100 62.1 0.36 0.64 0.05 150815 The sample (I) 150 - 300 0.10 1100 62.0 0.37 0.79 0.05 150816 The sample (I) 45 - 75 0.10 1100 66.6 0.21 0.41 0.04 150907 The sample (I) 150 - 300 0.10 1100 61.0 0.29 0.8 0.07 150902 The sample (I) 45 - 75 0.10 900 63.7 0.12 0.49 0.07 150908 The sample (I) 150 - 300 0.10 900 60.5 0.17 0.8 0.04 160316 The sample (I) 45 - 75 0.10 800 62.9 N / A 0.5 N / A 160317 The sample (I) 150 - 300 0.10 800 58.7 0.08 0.75 N / A 150904 The sample (I) 45 - 75 - 1100 63.2 0.31 0.61 0.06 150903 The sample (I) 45 - 75 - 900 63.5 0.12 0.51 0.08 160309 The sample (I) 45 - 75 - 800 59.8 0.12 0.55 N / A 150913 The sample (II) <45 0.10 1100 67.7 0.29 0.81 N / A 160314 The sample (II) <45 0.10 800 66.9 N / A 0.88 N / A 160318 The sample (II) <45 - 800 61.7 0.37 0.81 N / A

Table 1 shows the experimental conditions of the selective chlorination reaction of the identified light and the analysis results of the produced light.

Here, a is the experimental condition, and the identification light is pulverized by using a mortar bowl before the experiment. The reaction time is 5 hours, the mass of the identification light is 0.20 g, and the mass of copper chloride is 8.00 g. The sample and the chlorinating agent were mixed in a glove box under an argon gas atmosphere. The reaction was carried out in an argon gas (purity 99.999%) atmosphere and argon gas was introduced at a flow rate of 200 sccm.

and b is a result of measurement by inductively coupled plasma atomic emission spectrometry. N / A is the result measured below the analysis limit (<0.030 mass%).

Referring to Table 1, the average particle size of the identified light sample (I) was 45 to 75 μm, 75 to 105 μm, 105 to 150 μm, and 150 to 300 μm. Under the atmosphere of argon gas containing 1100 K of sulfur And reacted with copper chloride for 5 hours.

As a result of the recovery of the product residues, the mass% of copper was 39.8 mass% for the reactant raw material, but increased to 62.0 - 65.5 mass% for the produced residue.

The mass% of iron was 23.6 mass% for reactant raw material but decreased to 0.28 - 0.37 mass% for all particles.

FIG. 7 is an X-ray diffraction analysis graph of the residue produced according to the average particle size in the iron removal method in the identified light by the selective chlorination method using copper chloride according to the embodiment of the present invention.

7 (a) shows average particle size of 45 to 75 μm, (b) shows 75 to 105 μm, (c) shows 105 to 150 μm, and (d) shows 150 to 300 μm.

Referring to FIG. 7, high-quality pulsed light was obtained when the identified optical sample (I) having various particle sizes was used as a raw material.

Referring to FIG. 7, it can be seen that in addition to the fluorescence, silicon dioxide remains in the generated residue. The silicon dioxide is a material mixed in the identification light used as the raw material. From the result of FIG. 7, it can be seen that the silicon dioxide does not cause a chlorination reaction with copper chloride and is not removed as a chloride.

8 is a field emission scanning electron micrograph of a surface of a product residue in a method for removing iron in identification light by a selective chlorination method using copper chloride according to an embodiment of the present invention.

8 (a) shows the average particle size of 45-75 μm (Experiment No. 150812) and (b) 75-105 μm (Experiment No. 150814).

Referring to FIG. 8, it can be seen that pores are formed on the surface of the high-quality hydrated phosphor particles obtained after the reaction by the selective chlorination method of the identification light sample (I). It can be confirmed by the reaction with copper chloride at 1100 K ) Were selectively removed as FeCl ₂ .

Therefore, iron is selectively removed as FeCl ₂ in the identification light through the reaction with copper chloride under the condition of 1100 K of sulfur, so that high-quality pulsed light can be obtained.

< Experimental Example  6> Effect according to reaction temperature

The effect of reaction temperature was evaluated by performing a selective chlorination method at 1000 K, 900 K, and 800 K, respectively, using an identification optical sample (I) having an average particle size of 45 - 75 μm and 150 - 300 μm in the presence of sulfur Respectively.

Referring to Table 1, the mass% of copper was 39.8 mass% in the case of the raw material but increased to 58.7-66.6 mass% in the case of the produced residue. In addition, the mass% of iron was 23.6 mass% for the raw material, but was found to be a value of less than 0.05 mass% to 0.29 mass% at the temperature of the produced residue.

9 is a graph showing the results of X-ray diffraction analysis of the product residue according to the reaction temperature change in the method for removing iron in the identified light by the selective chlorination method using copper chloride according to the embodiment of the present invention.

Here, the reaction is carried out in the presence of sulfur, and (a) represents 900 K for 1000 K (b) and 800 K for (c).

Referring to FIG. 9, it was confirmed that a high quality pulsed light could be obtained when the reaction was carried out in an argon gas atmosphere containing 800 to 1100 K of sulfur for 5 hours.

< Experimental Example  7> Sulfur chemistry On potential  Influence of

Referring to Table 1, the influence of p _S2 on the selective chlorination of the identification light using copper chloride was examined. In Experiment Nos. 150904, 150903, and 160309, the selective chlorination method was performed for 5 hours under an argon gas atmosphere in which no sulfur was present at 800 - 1100 K.

Referring to Table 1, in the case of the selective chlorination method in which sulfur was not used, the mass% of copper was 39.8 mass% in the case of the raw material as the iron was selectively removed from the identification light sample (I), but 59.8 - 63.5 Mass%.

FIG. 10 is a graph showing the results of X-ray diffraction analysis of a residue after reaction by selective chlorination in the case where sulfur powder is not present in the reaction system in the iron removal method by the selective chlorination method using copper chloride according to the embodiment of the present invention FIG.

Referring to FIG. 10, it was confirmed that a high quality pulsed light was produced from the residue produced when the reaction was carried out under an argon gas atmosphere of 800 to 1100 K in the absence of sulfur for 5 hours.

< Experimental Example  8> Sympathetic light  Influence by kind

The influence of the type of identification light on the selective chlorination of identification light using copper chloride was investigated.

Referring to Table 1, in Experiment Nos. 150913 and 160314, the selective chlorination method was performed for 5 hours under an argon gas atmosphere in which 800-1100 K of sulfur was present as a raw material for the identification optical sample (II). In Experiment No. 160318 The selective chlorination method was carried out for 5 hours under the atmosphere of argon gas in which no sulfur was present at 800 K using the optical sample (II).

As shown in Table 1, in the case of the selective chlorination method using the identification light sample (II) as a raw material, the mass% of copper was selectively removed from the identification light sample (II), and thus 34.6 mass% In the case of water, it increased to 61.7 - 67.7 mass%.

Fig. 11 is a graph showing the results of a selective chlorination method using an identification light sample (II) having an average particle size of less than 45 [mu] m as a raw material in the method for removing iron in identification light by a selective chlorination method using copper chloride according to an embodiment of the present invention X-ray diffraction analysis of the product residues after the reaction by &lt; RTI ID = 0.0 &gt;

Referring to FIG. 11, when the identified optical sample (II) is used as a raw material and reacted for 5 hours under an argon gas atmosphere of 800 to 1100 K, high-quality pulsed light is generated from the generated residue regardless of the presence or absence of sulfur in the reaction system Respectively.

Therefore, the iron removal method in the optical fiber by the selective chlorination method using the copper chloride according to the present invention can remove the iron by the single high temperature chemical process using the copper chloride as the chlorinating agent regardless of the presence or absence of the sulfur, A new selective chlorination method that can be prepared is provided.

It was performed using the chemical potential diagram thermodynamic study on the mechanism of the pick chloride method, in the case of reacting the identified light for 5 hours using a copper chloride under an argon gas atmosphere at 1100 K, in the iron FeCl ₂ Identification light , Which is consistent with the thermodynamic prediction.

It should be understood that the present invention has been described with respect to a specific embodiment of a method for removing iron in identification light by a selective chlorination method using copper chloride according to the present invention. However, it is obvious that various modifications are possible within the scope of the present invention .

Therefore, the scope of the present invention should not be construed as being limited to the embodiments described, but should be determined by equivalents to the appended claims, as well as the following claims.

It is to be understood that the foregoing embodiments are illustrative and not restrictive in all respects and that the scope of the present invention is indicated by the appended claims rather than the foregoing description, It is intended that all changes and modifications derived from the equivalent concept be included within the scope of the present invention.

Claims (13)

(a) preparing a concentrated Cu ore;
(b) adding cuprous chloride (CuCl) to the identification light, placing the mixture in a quartz tube, and then introducing an inert gas to form an inert atmosphere;
(c) heating the quartz tube to react the identification light with the chlorinating agent; And
(d) recovering the product residues, washing and drying, thereby removing iron in the identified light by the selective chlorination method.
The method according to claim 1,
The step (a)
The identification sample, which is a raw sample, is ground to obtain an identification light sample (I) in any one range selected from the group consisting of average particle sizes of 45-75 μm, 75-105 μm, 105-150 μm, and 150-300 μm A method for removing iron in identification light by selective chlorination using copper chloride.
The method according to claim 1,
The step (a)
(II) having an average particle size of less than 45 탆 (excluding 0 탆) is produced by pulverizing the identification light which is the original sample. The identification of the iron in the light by the selective chlorination method using copper chloride Removal method.
delete The method according to claim 1,
The step (b)
And further adding sulfur (S) to the copper chloride.
6. The method of claim 5,
When sulfur (S) is further added
Wherein the chemical potential of sulfur in the reaction system can be controlled in the reaction between the identification light and the chlorinating agent by the selective chlorination method using copper chloride.
The method according to claim 1,
The step (b)
Wherein an inert gas is introduced into the quartz tube at a flow rate of 200 sccm to form an inert atmosphere and the internal pressure is maintained at 1 atm.
8. The method of claim 7,
Wherein the inert gas is any one selected from the group consisting of helium (He), neon (Ne), and argon (Ar)
The method according to claim 1,
The step (c)
And the quartz tube is heated at 800 K to 1100 K for 5 hours to react the identification light with the chlorinating agent.
The method according to claim 1,
The step (c)
Heating the quartz tube to react the identification light and the chlorinating agent,
(Fe) in the identification light is vaporized with gaseous iron chloride (FeCl ₂ ) to remove the copper.
3. The method of claim 2,
The identification optical sample (I)
Wherein the copper chloride is recovered in a phosphorus content of 58.7 mass% to 66.6 mass% when reacted with a chlorinating agent.
The method of claim 3,
The identified optical sample (II)
Wherein the copper is recovered in a phosphorus content of 61.7 mass% to 67.7 mass% when reacted with a chlorinating agent.
The method according to claim 1,
The step (d)
The resulting residue with 10% hydrochloric acid (HCl) and 8.6% was recovered ammonium hydroxide (NH ₄ OH) to the leaching and methods within the iron removing sympathetic light by selecting chloride method using a copper chloride, characterized in that for cleaning use.

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