KR20150064258A - Method of treating molybdenite containing copper - Google Patents

Abstract

The present invention relates to a method for pretreating molybdenite containing copper and, more specifically, to a method for pretreating molybdenite containing copper, which comprises steps of: mixing molybdenite containing copper and sulfuric acid; carrying out a sulfation reaction as heating molybdenite containing copper and sulfuric acid after a mixture; water leaching by stirring with water after the sulfation reaction; separating solid and liquid after water leaching; and drying the separated solid.

Description

TECHNICAL FIELD The present invention relates to a method for treating copper containing fluorine,

The present invention relates to a pretreatment method of copper-containing flue gas which removes copper contained in low-grade flue gas.

Molybdenum improves the hot creep properties of steel, prevents temper embrittlement and increases the corrosion resistance of steel, which is a very important element in the manufacture of heat resistant steel and in the manufacture of corrosion resistant steel as an alloying element. The copper content in the ferromolybdenum for steelmaking is usually limited to 0.5% or less.

Molybdenite (MoS ₂ ) is an economical raw material of molybdenum. The concentration of molybdenum in the ore is usually only about 0.05 to 0.1% by weight. The concentration of molybdenite is lower than that of molybdenite. However, The sulfide can be easily recovered and concentrated.

Lowering the copper content to 0.5% or less in the flourescent light only by the beneficiation process is difficult because the copper ore is also the sulfide light and it may be difficult to lower the copper content of the fluorine-rich copper having a high copper content because the recovery rate of the molybdenum may be lowered. Nevertheless, it is being produced and sold.

Ferromolybdenum for steelmaking can be ferromolybdenum produced by roasting and oxidizing ferrofumenite and then leaching with dilute sulfuric acid solution to remove copper, followed by filtration, drying and thermal reduction. However, since the molybdenum is dissolved in the aqueous solution due to the sulfuric acid leaching, a process for recovering the molybdenum is required. Therefore, MoO ₃ reacts with water to leach out and is present as molybdic acid. Therefore, A lot of energy is consumed. To overcome these disadvantages, methods have been developed to remove leaching before roasting, i.e., in the sulfide state. U.S. Patent No. 1,895,811 (published on Jan. 31, 1933) discloses a process for treating ores, which does not require a high-pressure vessel and has a simple process. However, when molybdenum light is added with concentrated sulfuric acid, The higher the temperature, the higher the reaction rate and reaction rate with the copper sulfide, and the fluorophore surface is also oxidized and leached into the aqueous solution together with copper. Therefore, it is necessary to develop a process capable of minimizing the oxidation of molybdenum while increasing the removal rate of copper.

Accordingly, the present invention is to provide a pretreatment method of copper-containing flue gas which can remove only copper while minimizing the oxidation of molybdenum when reacted with sulfuric acid of low-boiling flour containing copper sulfide.

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.

SUMMARY OF THE INVENTION In order to solve the above problems, the present invention provides a method of manufacturing a semiconductor device, Adding sulfuric acid to the reaction mixture; Adding water after the sulfation reaction and stirring the mixture to form water; Separating the solid and liquid after the water leaching; And a step of drying the separated solid.

At this time, the sulfation reaction is performed at 180 - 240 캜 for 20 - 80 minutes.

And the sulfuric acid is mixed at an equivalent ratio of 0.9 to 1.8 with respect to the flow of water.

Also, the sulfation reaction is performed at 210 - 240 캜 for 40 - 80 minutes.

The water is characterized in that it is at least one selected from the group consisting of distilled water, deionized water, light water and heavy water.

Further, the pretreatment method of copper-containing flame hydrothermal according to the present invention may further include a step of flotation prior to mixing the flue gas with the sulfuric acid.

According to the present invention, it is possible to prevent the conventional problem of leaching molybdenum into an aqueous solution by adjusting the temperature and time of the sulfation reaction during the flood-rich treatment for the production of ferromolybdenum for producing steel from low- The removal rate can be improved.

In addition, since only copper sulfide is formed by copper sulfate and is removed by leaching into water, the solid-liquid separation is easier than conventional sulfuric acid leaching after roasting and the cost of recovering molybdenum from waste acid can be reduced.

FIG. 1 is a flow chart showing a pre-treatment method of copper-containing fl uorescent light according to the present invention.
FIG. 2 is a graph showing boiling points according to sulfuric acid concentration in a water-sulfuric acid system.
FIG. 3 is a graph showing the removal rate of copper according to the amount of sulfuric acid added in the pretreatment method of copper-containing fl ow water according to the present invention.
FIG. 4 is a result of X-ray diffraction analysis of the flue gas according to the addition amount of sulfuric acid in the pretreatment method of copper-containing flue gas according to the present invention.
FIG. 5 is a graph showing the change in copper concentration in the flue gas according to the sulfurization reaction temperature and the reaction time in the pretreatment method of copper-containing flue gas according to the present invention.
FIG. 6 is a graph showing the change of the dissolution rate of molybdenum according to the sulfurization reaction temperature and time in the pretreatment method of the copper-containing flame hydrothermal according to the present invention.

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.

The present invention relates to a process for the production of copper-containing flame hydrothermal fluids,

Adding sulfuric acid to the reaction mixture;

Adding water after the sulfation reaction and stirring the mixture to form water;

Separating the solid and liquid after the water leaching; And

And a step of drying the separated solid.

The pretreatment method of the copper-containing flue gas according to the present invention can be carried out by reacting low-grade flue gas containing copper sulfide with sulfuric acid to make copper contained in the flue gas into copper sulfate, By adjusting the temperature and time, copper removal rate can be increased and oxidation of molybdenum can be minimized.

FIG. 1 is a flow chart showing a pre-treatment method of copper-containing fl uorescent light according to the present invention. Hereinafter, the present invention will be described in detail with reference to Fig.

The method for pretreatment of copper-containing flame hydrothermal according to the present invention includes a step (S100) of mixing copper-containing flue gas with sulfuric acid.

In the pretreatment method of copper-containing flame hydrothermal according to the present invention, the copper-containing flue gas includes chalcopyrite (CuFeS ₂ ), chalcocite (Cu ₂ S), and bornite (Cu ₅ FeS ₄ ) , And these minerals can be made into copper sulfate by reacting with sulfuric acid. In this case, the flue gas may further include a step of performing a flotation process before mixing with the sulfuric acid. In the flue gas, the mineral having the hydrophobic surface is attached to the surface of the bubbles to float to the surface of the solution, So that it can be separated. In addition, the flue gas may further include crushing and pulverizing steps to further improve the reactivity with sulfuric acid.

In addition, when the total flourescent water is not sufficiently wetted by sulfuric acid to uniformly mix the flourescent water and sulfuric acid, water can be added and mixed uniformly.

The method for pretreatment of copper-containing flame hydrothermal according to the present invention includes a step (S200) of performing sulfation reaction by heating after mixing.

At this time, the amount of sulfuric acid to be added needs to be such that it can react with all the elements capable of reacting with sulfuric acid, such as alkali metals or alkaline earth metal oxides contained in low-grade fluorinated water, as well as Cu, Fe and Zn present as sulfides , The reactivity varies depending on the type of sulfuric acid and impurities to be lost due to evaporation, so it can be added or subtracted depending on the raw material or the reaction apparatus. In the pretreatment method according to the present invention, sulfuric acid is preferably mixed in an equivalent ratio of 0.9 to 1.8 with respect to water vapor. When the sulfuric acid is mixed in an amount less than 0.9 equivalent, there is a problem in that the removal rate of copper contained in the flue gas is low. When the equivalent ratio exceeds 1.8, molybdenum contained in the flue gas is leached.

2 is a graph showing the boiling point according to the sulfuric acid concentration in the water-sulfuric acid system. As shown in FIG. 2, it can be seen that the maximum temperature that can be treated with sulfuric acid at atmospheric pressure is 330 캜, which is an eutectic point between sulfuric acid and water near 98.3% by weight, and the boiling point of 90% 255 ° C.

When the hydrofluoric acid is subjected to sulfuric acid and sulfuric acid, the copper contained in the flue gas is formed of copper sulfate as shown in the following reaction formulas 1, 2 and 3.

[Reaction Scheme 1]

1 / 2CuFeS ₂ + 2H ₂ SO ₄ ? 1/2 CuSO ₄ + 1 / 2FeSO ₄ + S + 2H ₂ O + SO ₂ ↑

[Reaction Scheme 2]

1 / 2CuS ₂ + 2H ₂ SO ₄ ? CuSO ₄ + 1 / 2S + 2H ₂ O + SO _2?

[Reaction Scheme 3]

_{1 / 4Cu 5 FeS 4 + 3H} 2 SO 4 → 5 / 4CuSO 4 + 1 / 4FeSO 4 + S + 3H 2 O + 3 / 2SO 2 ↑

Table 1 shows the reaction heat (? H), Gibbs free energy (? G) and equilibrium constant (K) generated when CuFeS ₂ , Cu ₂ S and Cu ₅ FeS ₄ contained in the flue gas are reacted with sulfuric acid will be. As shown in Table 1, as the temperature increases, the reaction rate (equilibrium constant) increases and the reaction heat shows a weak endothermic reaction (ΔH is a positive number).

Temperature (℃) 180 210 225 240 300 CuFeS ₂ ? H (Kcal / mole) 1.072 1.063 1.066 1.078 1.301 ? G (Kcal / mole) -16.078 -17.214 -17.781 -18.349 -20.629 Equilibrium constant (K) 5.7E07 6.1E07 6.3E07 6.5E07 7.4E07 Cu ₂ S ? H (Kcal / mole) 5.59 5.48 5.43 5.4 5.49 ? G (Kcal / mole) -8.18 -9.09 -9.54 -9.99 -11.79 Equilibrium constant (K) 8.8E07 1.3E07 1.5E07 1.8E07 3.1E07 Cu ₅ FeS ₄ ? H (Kcal / mole) 8.644 8.579 8.135 8.043 8.019 ? G (Kcal / mole) -14.613 -16.151 -16.908 -17.66 -20.656 Equilibrium constant (K) 1.1E07 2.0E07 2.6E07 3.3E07 7.5E07

The reaction of sulfuric acid with hydrogen fluoride can also oxidize the surface according to equation (4) or (5), and the oxidized hydrogen fluoride is dissolved in water in a considerable amount.

[Reaction Scheme 4]

_{MoS 2 + 2H 2 SO 4 →} MoO 2 + 2S + 2H 2 O + 2SO 2 ↑

[Reaction Scheme 5]

MoS ₂ + 3H ₂ SO ₄ ? MoO ₃ + 2S + 3H ₂ O + 3SO _2?

Table 2 below shows the heat of reaction (ΔH), the Gibbs free energy (ΔG) and the equilibrium constant (K) for the oxidation reaction of the flue gas with sulfuric acid. It is also found that the reaction rate of the oxidation of sulfuric acid is increased with increasing temperature.

Temperature (℃) 180 210 225 240 300 MoS ₂ + 2H ₂ SO ₄ ? H (Kcal / mole) 36.79 36.88 36.92 36.97 37.28 ? G (Kcal / mole) -4.13 -6.84 -8.20 -9.56 -15.01 Equilibrium constant (K) 9.8E01 1.2E03 3.9E03 1.2E04 5.3E05 MoS ₂ + 3H ₂ SO ₄ ? H (Kcal / mole) 54.15 54.13 54.13 54.13 54.37 ? G (Kcal / mole) -7.04 -11.09 -13.11 -15.14 -23.24 Equilibrium constant (K) 2.5E03 1.0E05 5.7E05 2.8E06 7.3E08

As described above, it can be seen that the reaction rate increases with increasing temperature in both the copper sulfide and the flue gas. However, Cu and Mo differ in reactivity with concentrated sulfuric acid. In other words, oxides such as Cu and Fe are basic oxides and are easily reacted with sulfuric acid. On the other hand, the oxide of Mo is an acidic oxide and does not react well with sulfuric acid. Similarly, sulfides also react with sulfuric acid more readily than sulfides of Mo. Therefore, when the reaction conditions with sulfuric acid are properly adjusted, most of the copper sulfides are formed of copper sulfate and MoS ₂ may not react. Therefore, the sulfation reaction is preferably performed at 180 - 240 캜 for 20 - 80 minutes. If the sulfation reaction is lower than 180 ° C, the copper removal rate is lowered. If it exceeds 240 ° C, the leaching rate of molybdenum is increased and molybdenum should be recovered from the leaching solution. When the reaction time is less than 20 minutes, copper contained in the flue gas can not be sufficiently removed. When the reaction time exceeds 80 minutes, molybdenum is leached.

The sulfation reactor can be either batch or continuous, but in the case of a batch reactor, the reactant layer is thinned and the reactant is maintained at a uniform temperature throughout. Even in the continuous mode, the flow of the reactants is kept in a plug flow so that the temperature of the whole reactor is uniform and the residence time of the reactants in the reactor is the same. It is preferable that the reaction product after the sulfation reaction is discharged and cooled to 100 캜 or lower.

The pretreatment method of copper-containing flame hydrothermal according to the present invention includes a step (S300) in which water is added after the sulfation reaction and water is leached by stirring.

In the pretreatment method of copper-containing flue gas according to the present invention, the flue gas having the sulfated reaction can be removed by leaching water, copper sulfate and other impurities in a batch or continuous manner in a precipitation tank equipped with a stirrer. The water may be at least one selected from the group consisting of distilled water, deionized water, light water and heavy water.

Next, a pretreatment method of copper-containing flame hydrothermal according to the present invention includes a step (S400) of separating solid and liquid after the water leaching.

In the pretreatment method of copper-containing flue gas according to the present invention, solid-liquid separation for separating solid and liquid present in the solution after the water leaching is carried out. At this time, the solid-liquid separation can be performed in a filtration apparatus such as a belt filter or a drum filter.

The method for pretreatment of copper-containing flame hydrothermal according to the present invention comprises drying the separated solid (S500).

The separated solid may be subjected to a drying process to dry the moisture present in the solid.

The present invention also relates to a method for producing copper-containing flood-rich strand, Heating the mixture to a temperature of 210 to 240 ° C. to perform a sulfation reaction; Adding water after the sulfation reaction and stirring the mixture to form water; And separating the solid and liquid after the water leaching; And a step of drying the separated solid.

In the pretreatment method of copper-containing flame hydrothermal according to the present invention, the sulfation reaction may be performed at 210-240 ° C. for 40-80 minutes to remove 99% or more of copper and recover molybdenum to 99.7% or more Experimental Examples 2 and 3). At this time, it is preferable that the sulfuric acid is mixed at an equivalent ratio of 0.9 to 1.8 to the flourescent light, and the reason for the limitation is as described above.

Example 1: Pretreatment of Copper-containing Flux

Table 3 shows constituent elements and contents of the concentrates of the flue-hydrothermal extracts collected at the Kimmo mine in Uljin-ku, Gyeongbuk province. 20 g of the hydrogen fluoride in Table 3 and sulfuric acid-dissolved concentrated sulfuric acid solution were placed in a 50 ml material crucible and mixed with a glass rod. After the sulfation reaction, samples were taken out and cooled. Then, 200 ml of distilled water was added to a 1000 ml flask, and the mixture was stirred at 300 rpm for 60 minutes at 90 ° C. and leached. The thus prepared sample was filtered using a glass fiber filter paper and dried at 112 ° C for 24 hours.

element Mo S Cu Fe Pb Zn MgO SiO ₂ Al ₂ O ₃ CaO Average diameter
(탆) content
(weight%) 39.1 24.9 7.66 8.48 0.97 0.73 0.10 1.94 7.52 0.32 32.1

Experimental Example 1: Analysis of copper concentration and removal rate according to the amount of sulfuric acid added

The copper concentration and the removal rate according to the addition amount of sulfuric acid in the pretreatment method of the copper-containing flue gas according to the present invention were analyzed, and the results are shown in Tables 4, 3 and 4.

Sulfuric acid addition amount
(g) 180 DEG C 225 ° C Copper content
(weight%) Copper removal rate
(%) Copper content
(weight%) Copper removal rate
(%) 2 7.4 3.4 7.51 4.5 4 7.23 6 7.05 8 8 6.7 13 5.1 22 16 3.61 49 0.16 97 32 2.53 85 0.05 99 64 0.53 95.4 0.03 99.6

As shown in Table 4 and FIG. 3, the removal rate of copper was increased (sulfurization reaction time: 40 minutes) as the addition amount of sulfuric acid was increased in both the sulfuric oxidation reaction temperatures of 180 ° C and 225 ° C. When the sulfuric acid addition temperature was 225 ℃, the copper removal rate was 97% at 16g of sulfuric acid addition. Copper removal rate increased with increasing sulfuric acid addition. In addition, although the sulfuric acid addition amount is the same, the copper removal rate is higher than the sulfation reaction temperature 180 ° C when the sulfation reaction temperature is 225 ° C.

FIG. 4 is a result of X-ray diffraction analysis of the flue gas according to the addition amount of sulfuric acid in the pretreatment method of copper-containing flue gas according to the present invention. Referring to FIG. 5, it was confirmed that water quenching and quartz were observed in the flue hydrothermal before the sulfation reaction, but the presence of flue hydrothermal, sulfur and quartz was observed after the sulfation reaction.

EXPERIMENTAL EXAMPLE 2 Analysis of Copper Concentration by Sulfation Temperature and Time

The concentration of copper in the flue gas was analyzed according to the sulfurization reaction temperature and the reaction time in the pretreatment method of the copper-containing flame hydrothermal according to the present invention, and the results are shown in Table 5 and FIG.

Sulfation reaction 180 DEG C 210 ℃ 225 ° C 240 ℃ 270 ℃ 300 ° C 10 minutes 7.64 3.5 2.15 1.76 0.22 0.14 20 minutes 6.03 2.12 0.54 0.34 0.18 0.14 30 minutes 2.7 0.81 0.33 0.05 0.058 0.043 40 minutes 1.38 0.65 0.074 0.045 0.042 0.031 80 minutes 0.76 0.06 0.031 0.032 0.031 0.029

As shown in Table 5 and FIG. 5, it can be seen that 0.06% by weight of copper remains when the sulfation reaction time is 80 minutes when the sulfation reaction temperature is 210 ° C, and 0.33% Copper remains only at 0.degree. C. at 240.degree. C. and 0.34 weight% copper remains at 20.degree. C. When the reaction time is set at 270.degree. C. and 300.degree. C. for 10 minutes, only 0.22 weight% and 0.14 weight% (Addition amount of H ₂ SO ₄ : 32 g). Therefore, the copper content in the flue gas can be lowered to 0.5% by weight or less at a reaction temperature of 210 ° C for 80 minutes, 30 minutes at 225 ° C, 20 minutes at 240 ° C, 10 minutes at 270 ° C and 300 ° C, Minute, the copper content in the flue gas can be reduced to 0.5 wt% or less.

Experimental Example 3: Analysis of molybdenum dissolution rate according to the sulfurization reaction temperature and time

The dissolution rate of molybdenum was analyzed according to the sulfation reaction temperature and time in the pretreatment method of copper-containing flame hydrothermal according to the present invention, and the results are shown in Table 6 and FIG.

Sulfation reaction 180 DEG C 210 ℃ 225 ° C 240 ℃ 270 ℃ 300 ° C 10 minutes 0.11 0.1 0.2 0.15 0.23 0.27 20 minutes 0.13 0.12 0.19 0.16 0.15 0.21 30 minutes 0.18 0.14 0.18 0.16 1.17 5.88 40 minutes 0.21 0.18 0.23 0.15 3 8.1 80 minutes 0.18 0.22 0.15 3.49 3.58 8.6

As shown in Table 6 and FIG. 6, it can be seen that the dissolution rate of molybdenum increases with an increase in the sulfurization reaction temperature and time (H ₂ SO ₄ : 32 g, flow rate: 20 g). That is, when the reaction is carried out at 240 ° C for at least 80 minutes and at 270 ° C for at least 30 minutes, oxidation occurs on the surface of the flue gas. Therefore, it is considered that copper can be completely removed without loss of molybdenum by adjusting the sulfation reaction time in the range of the sulfation temperature of 210 - 240 ° C. That is, it can be seen that copper can be removed by 99% or more and molybdenum can be recovered by 99.7% or more when the reaction is carried out at a temperature of 210-240 ° C. for 40-80 minutes.

It should be understood that the present invention has been described with respect to a specific embodiment of a pretreatment method for copper-containing flame hydrothermal fluids according to the present invention, but various modifications may be made without departing from the scope of the present invention.

Therefore, the scope of the present invention should not be limited to the above-described embodiments, but should be determined by the scope of the appended claims and equivalents thereof.

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 (11)

Mixing copper rich water and sulfuric acid;
Adding sulfuric acid to the reaction mixture;
Adding water after the sulfation reaction and stirring the mixture to form water;
Separating the solid and liquid after the water leaching; And
And drying the separated solid.
The method according to claim 1,
Wherein the sulfation reaction is carried out at a temperature of 180 to 240 캜.
The method according to claim 1,
Wherein the sulfation reaction is carried out for 20 to 80 minutes.
The method according to claim 1,
Wherein the sulfuric acid is mixed at an equivalent ratio of 0.9 to 1.8 to the flame hydrothermal light.
The method according to claim 1,
Wherein the sulfuric acid oxidation reaction is carried out at 180-240 ° C for 20-80 minutes by mixing sulfuric acid at an equivalent ratio of 0.9-1.8.
The method according to claim 1,
Wherein the sulfation reaction is performed at 210-240 < 0 > C.
The method according to claim 6,
Wherein the sulfation reaction is carried out for 40 to 80 minutes.
The method according to claim 6,
Wherein the sulfuric acid is mixed at an equivalent ratio of 0.9 to 1.8 to the flame hydrothermal light.
The method according to claim 1,
Wherein the sulfuric acid reaction is carried out at 210-240 ° C for 40-80 minutes by mixing sulfuric acid at an equivalent ratio of 0.9-1.8.
The method according to claim 1,
Wherein the water is at least one selected from the group consisting of distilled water, deionized water, light water and heavy water.
The method according to claim 1,
Further comprising the step of pre-mixing the flue gas with the sulfuric acid before mixing the flue gas with the sulfuric acid.

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