KR20110046024A - Leaching method of impurities contained in molybdenum oxide product - Google Patents

Abstract

PURPOSE: A method for leaching impurities contained in molybdenum oxide concentrates is provided to economically produce the molybdenum oxide concentrates with the superior quality by selectively leaching impurities from the molybdenum oxide concentrates using leachate. CONSTITUTION: A method for leaching impurities contained in molybdenum oxide concentrates includes an impurity leaching process with respect to the molybdenum oxide concentrates using leachate selected from a group including a first leachate, a second leachate, and a third leachate. The first leachate includes ammonium chloride, sodium chloride, hydrochloric acid, and water. The second leachate includes ammonium chloride, calcium chloride, hydrochloric acid, and water. The third leachate includes ammonium chloride, sodium chloride, calcium chloride, hydrochloric acid, and water.

Description

Leaching method of impurities contained in concentrate of molybdenum oxide {LEACHING METHOD OF IMPURITIES CONTAINED IN MOLYBDENUM OXIDE PRODUCT}

The present invention relates to a method for leaching impurities contained in a molybdenum oxide concentrate. Specifically, high quality molybdenum oxide can be leached by selectively leaching impurities such as copper, iron, lead, and zinc contained in the roasted molybdenum oxide concentrate using a leaching solution. It relates to a leaching method that can produce concentrate.

Molybdenum has high heat resistance, corrosion resistance and weldability, and is used as a material for making stainless steel, alloy steel and special steel. Molybdenum is also used as a substitute for tungsten for aircraft components, electrical materials, industrial motors and filaments.

Molybdenum's global mining capacity is 8,600 thousand tons, which can be used for about 50 years compared with 2005's annual demand of about 180 thousand tons. About 88% of molybdenum's global mined light is located in four countries: China, the United States, Chile and Canada. In the global molybdenum market, demand growth rate of 5.2% and supply growth rate of 3.8% in the last 10 years, the demand growth rate is higher than the supply growth rate, and supply shortage began to appear in 2002. At present, the production of molybdenum concentrates in the world's mines is increasing, but there is a shortage of supply due to the lack of production capacity of the roasting plant for processing.

Molybdenum is produced from molybdenum (Molybdenite), which is an ore, which is mostly produced together with other emulsified minerals. In order to use molybdenum as a subsidiary material added during steelmaking, the molybdenum emulsified concentrate is obtained by concentrate processing by mineral processing such as flotation and then roasting. Roasting in a roaster Thereafter, in the leaching process, metal impurities other than molybdenum are dissolved and separated.

Conventional leachate reagents for leaching metal impurities such as copper, iron, lead and zinc, which are contained in the roasted molybdenum oxide concentrate, include hydrochloric acid, nitric acid, sulfuric acid, ammonium hydroxide, iron chloride, sodium cyanide and caustic soda. There were a lot of chemicals.

Most of these leaching reagents dissolve impurities, but at the same time dissolve large amounts of molybdenum together. Therefore, the necessity of recovering molybdenum dissolved in the leachate has been raised, and a solvent extraction method, an ion exchange resin method, and an adsorption method with activated carbon have been used for recovery purposes. However, such a conventional method requires many additional processes such as a process of recovering and desorbing molybdenum, and there is a problem in that loss of molybdenum occurs in every process.

In order to solve this problem, the present inventors have conducted a continuous study on the leaching method of molybdenum oxide concentrate. As a prior study, it is noted that when ammonium chloride and hydrochloric acid are used together as the leachate, most of the metallic impurities in the molybdenum oxide concentrate are dissolved, but molybdenum is not dissolved but is mostly in the solid state. Korean Patent Application No. 10-2009-0009382 Issue (filed February 5, 2009) was held.

Subsequently, better results were obtained by using a leachate containing sodium chloride and ammonium chloride and hydrochloric acid, using a leachate containing calcium chloride and ammonium chloride and hydrochloric acid, or using a leachate containing sodium chloride, calcium chloride, ammonium chloride and hydrochloric acid. .

The leaching method of impurities contained in the molybdenum oxide concentrate according to the present invention aims to solve the following problems.

First, to minimize molybdenum dissolved in the leachate, it is intended to minimize or unnecessary the subsequent recovery process of molybdenum.

Second, to reduce the amount of chemicals such as ammonium chloride.

Third, make relatively cheap drugs available.

Fourth, to minimize environmental pollution caused by discharged wastewater.

The solution to the problem of the present invention is not limited to those mentioned above, and other solutions not mentioned can be clearly understood by those skilled in the art from the following description.

The method of leaching the impurities contained in the molybdenum oxide concentrate according to the present invention preferably includes leaching impurities of the molybdenum oxide concentrate using a first leaching solution containing ammonium chloride, sodium chloride and hydrochloric acid.

The method of leaching the impurities contained in the molybdenum oxide concentrate according to the present invention preferably includes leaching the impurities of the molybdenum oxide concentrate using a second leaching solution containing ammonium chloride, calcium chloride and hydrochloric acid.

The leaching method of impurities contained in the molybdenum oxide concentrate according to the present invention preferably comprises leaching the impurities of molybdenum oxide concentrate using a third leaching solution containing ammonium chloride, sodium chloride, calcium chloride and hydrochloric acid.

In the method for leaching impurities contained in the molybdenum oxide concentrate according to the present invention, the molybdenum oxide concentrate is preferably obtained by roasting ore of molybdenum.

In the leaching method of impurities contained in the molybdenum oxide concentrate according to the present invention, the first leachate is 3 to 10 parts by weight of ammonium chloride, 3 to 10 parts by weight of sodium chloride, and 8 to 20 hydrochloric acid based on 100 parts by weight of molybdenum oxide concentrate. Preference is given to using parts by weight and 50 to 300 parts by weight of water.

In the leaching method of impurities contained in the molybdenum oxide concentrate according to the present invention, the second leachate is 3 to 10 parts by weight of ammonium chloride, 3 to 10 parts by weight of calcium chloride, and 8 to 20 parts by weight of hydrochloric acid based on 100 parts by weight of molybdenum oxide concentrate. Preference is given to using from 50 to 300 parts by weight of water and water.

In the leaching method of impurities contained in the molybdenum oxide concentrate according to the present invention, the third leaching liquid is 3 to 10 parts by weight of ammonium chloride, 3 to 10 parts by weight of sodium chloride, and 3 to 10 parts of calcium chloride based on 100 parts by weight of molybdenum oxide concentrate. Preference is given to using parts by weight, 8 to 20 parts by weight of hydrochloric acid and 50 to 300 parts by weight of water.

In the method for leaching impurities contained in the molybdenum oxide concentrate according to the present invention, it is preferable that the ratio of the weight (g) of the molybdenum oxide concentrate and the volume (mL) of the leach solution is 1: 1 to 1: 2.

In the method for leaching impurities contained in the molybdenum oxide concentrate according to the present invention, the leaching temperature is preferably 20 ^° C. to 90 ° C., more preferably 60 ^° C. to 80 ° C.

In the leaching method of impurities contained in the molybdenum oxide concentrate according to the present invention, the leaching time is preferably 30 minutes to 180 minutes.

In the leaching method of the impurities contained in the molybdenum oxide concentrate according to the present invention, it is preferable to further include separating the leach solution and the molybdenum oxide concentrate after the leaching is completed.

In the method for leaching impurities contained in the molybdenum oxide concentrate according to the present invention, after the separation step, it is preferable to further include the step of washing the separated molybdenum oxide concentrate with washing water.

In the leaching method of impurities contained in the molybdenum oxide concentrate according to the present invention, in the washing step, the volume of the washing water is preferably 1/3 to 1 of the leaching liquid volume.

According to the leaching method according to the present invention, since most of the molybdenum oxide concentrate is in a solid state after the leaching is completed, there is an effect that the process for recovering molybdenum dissolved in the leaching solution is unnecessary or minimized.

According to the leaching method according to the present invention, since the amount of ammonium chloride used is reduced, there is an effect of reducing the total amount of nitrogen in the discharged wastewater can be expected to improve the water quality.

According to the leaching method according to the present invention, since the amount of chemicals used is also reduced and relatively inexpensive chemicals can be used, productivity is improved and economics are secured.

The effects of the present invention are not limited to those mentioned above, and other effects not mentioned can be clearly understood by those skilled in the art from the following description.

Hereinafter will be described in detail with respect to the leaching method according to the present invention.

The leaching method according to the present invention provides a method for more effectively leaching impurity copper (lead), lead (lead), iron (iron) and zinc (zinc) contained in the molybdenum oxide concentrate. In the leaching method according to the present invention, since molybdenum dissolution is suppressed, molybdenum oxide is not dissolved but is present in a solid state. Meanwhile, the molybdenum oxide concentrate (MoO ₃ : Molybdenum Trioxide) according to the present invention means obtained by roasting an emulsified molybdenum concentrate (MoS ₂ : Molybdenite Concentrate).

The leaching solution according to the present invention is an aqueous solution used for leaching metal impurities in molybdenum oxide concentrate. Water, ammonium chloride and hydrochloric acid or water, sodium chloride, ammonium chloride and hydrochloric acid or water, calcium chloride, ammonium chloride and hydrochloric acid or water, sodium chloride, calcium chloride, ammonium chloride and hydrochloric acid. It is preferable that such a leach solution can sufficiently moisten molybdenum oxide concentrate.

The leaching method according to the present invention uses a first leachate containing sodium chloride, ammonium chloride and hydrochloric acid, or a second leachate containing calcium chloride, ammonium chloride and hydrochloric acid, or comprises sodium chloride, calcium chloride, ammonium chloride and hydrochloric acid. The third leachate can be used to proceed.

Here, ammonium chloride, sodium chloride or calcium chloride serves as a dissolution inhibiting agent to dissolve molybdenum. In addition, sodium chloride and calcium chloride reduce the amount of ammonium chloride used. And hydrochloric acid plays a role in dissolving copper, iron zinc and molybdenum.

The content of ammonium chloride and hydrochloric acid in the leachate according to the present invention will vary depending on the quality of the molybdenum oxide concentrate. For example, if the iron content is high, or if the copper grade is high, the amount of hydrochloric acid will be increased relatively.

Ores, such as copper, iron, lead, and zinc are not uniform in quality, but vary in particular, depending on the origin of the ore. The molybdenum oxide ore displaced by this is first leached with hydrochloric acid. After analyzing the amount of molybdenum dissolved, the amount of ammonium chloride that can form the molybdenum dissolved in the complex salt is calculated and added.

According to the test results, the use of sodium chloride has a low effect of inhibiting the dissolution of molybdenum, and it is shown that the use of a predetermined amount of ammonium chloride together has a good effect of inhibiting the dissolution of molybdenum.

In the leaching solution according to the present invention, the amount of hydrochloric acid is preferably used in an amount of about 20 to 30% with respect to the amount corresponding to the chemical equivalent of the impurities to be leached.

In the leachate according to the present invention, the amount of ammonium chloride is preferably added in an amount corresponding to a chemical equivalent corresponding to the amount of molybdenum dissolved in the leaching test using only hydrochloric acid without using ammonium chloride. Do.

The first leachate according to the present invention includes ammonium chloride, sodium chloride and hydrochloric acid and water. Specifically, the first leachate according to the present invention uses 3 to 10 parts by weight of ammonium chloride, 3 to 10 parts by weight of sodium chloride, 8 to 20 parts by weight of hydrochloric acid and 50 to 300 parts by weight of water based on 100 parts by weight of molybdenum concentrate. It is preferable.

In the first leachate according to the present invention, if the ammonium chloride is less than 3 parts by weight, the ammonium ion is insufficient, and the molybdenum oxide ions dissolved by hydrochloric acid cannot be sufficiently made into the complex salt of ammonium molybdenum oxide. Therefore, there is a problem that the quality of molybdenum is increased in the leach solution. When the ammonium chloride exceeds 10 parts by weight, since the ammonium ions and molybdenum oxide ions remain after the complex salt is formed, there is a problem that is not economical. Therefore, the amount of other ammonium chloride used in the present invention is preferably 3 to 10 parts by weight.

In the first leachate according to the present invention, the amount of sodium chloride used is to obtain the effect of replacing the amount of ammonium chloride used. If sodium chloride is less than 3 parts by weight, there is a problem that the amount of molybdenum dissolved. If sodium chloride exceeds 10 parts by weight, there is a problem in that it is not economical because it is a waste of chemicals. The amount of the sodium chloride according to the present invention can be determined by experiment, an appropriate amount, preferably 3 to 10 parts by weight. Usually about 5 parts by weight is an appropriate amount.

In the first leachate according to the present invention, the amount of hydrochloric acid may be further used about 20 to 30% with respect to the amount corresponding to the chemical equivalent of the impurities to be leached. In general, it is preferable to use a minimum amount to dissolve copper, iron, lead, zinc, and the like to allow an acceptable quality (Cu 0.5% or less, Pb 0.05% or less) in the solid by performing a riching experiment. More preferably, parts by weight are used.

If the hydrochloric acid is less than 8 parts by weight, impurities in the solid may be higher than the acceptable grade. If the amount of hydrochloric acid exceeds 20 parts by weight to dissolve a large amount of molybdenum, there is a problem to use a lot of ammonium chloride or sodium chloride, the use of a lot of chemicals, the cost and corrosion and wear of the equipment will be derived. Therefore, the amount of hydrochloric acid according to the present invention is preferably 8 to 20 parts by weight.

In the first leachate according to the present invention, when the amount of water used is less than 50 parts by weight, there is a fear that the ore is not sufficiently wetted by the leachate, and the machine may be overloaded. If the water exceeds 300 parts by weight, there is an uneconomical problem because the facility is large and requires a lot of chemicals. Therefore, the water content is preferably 50 to 300 parts by weight. Usually about 100 parts by weight is an appropriate amount.

In the second and third leaching liquors according to the present invention, the amount of calcium chloride used is to obtain the effect of replacing the amount of ammonium chloride used. If calcium chloride is less than 3 parts by weight, there is a problem in that the amount of ammonium chloride is increased. If the calcium chloride exceeds 10 parts by weight, it is a waste of chemicals, there is a problem that is not economical. Therefore, the amount of calcium chloride used according to the present invention is preferably 3 to 10 parts by weight. Usually, about 5 weight part is a suitable quantity.

In the leaching method according to the present invention, the ratio of the weight (g) of molybdenum oxide concentrate and the volume of the leachate (mL) depends on the concentration of the chemical and the viscosity of the leachate, but is approximately 1: 1 to 1: 2. Preferred, approximately 1: 1.

If the ratio is less than 1: 1, there is a lack of contact between the leachate and the ore, so leaching may not be performed smoothly, and the machine may be overloaded.If the ratio exceeds 1: 2, the facility may be over-invested and the overuse of chemicals may occur. to be.

Hereinafter, the leaching method according to the present invention will be described in more detail while presenting a chemical reaction formula.

The hydrochloric acid contained in the leaching solution according to the present invention not only dissolves copper, iron, lead and zinc by reacting with molybdenum oxide concentrate, but also dissolves molybdenum oxide with molybdenum oxide ions (MoO ₄ ^-2 ) as shown in Scheme 1 below. Let's do it.

HCl + MoO _{3 + H 2 O -> MoO 4} -2 + 3H + + Cl -

The molybdenum oxide ions react with ammonium chloride and change to a solid state. This change can be seen from the ionization behavior in the Eh-pH diagram of the ammonium ions and molybdenum oxide ions of FIG. 1. This change in the molybdenum oxide pH 6.0 or higher, but is ionized with MoO ₄ ^-2, pH 5.0 or less consistent with that present in the form of MoO ₃ as a solid.

That is, as shown in Scheme 2, when ammonium chloride is added, molybdenum oxide becomes a solid salt of ammonium molybdenum oxide containing crystallized water at low pH, preferably pH 5.0 or less, so that molybdenum dissolution is suppressed. will be.

^{_{2NH 4 Cl + MoO 4 -2 +}} 3H + + Cl - -> (NH 3) 2 _and MoO _{3 and} H ₂ O + 3HCl

As shown in Scheme 2, the use of ammonium chloride increases the weight of the molybdenum oxide concentrate and maintains the solid state because crystal water is included in the formation of the molybdenum oxide complex salt.

In the leaching method according to the present invention, since the reaction between hydrochloric acid and metal oxides (Cu, Zn, Fe, Pb, Mo etc) is exothermic, it does not significantly affect the reaction rate even if the temperature of the leaching liquid is not high. However, the temperature of the immersion liquid can be improved to some extent when the reaction rate be high and that the NH ₄ ⁺ ion and MoO ₄ ^-2 ion bonded form a complex salt.

Therefore, the leaching temperature according to the present invention is preferably 20 to 90 ℃. This is because if the leaching temperature is less than 20 ° C, the leaching reaction may have a slow rate.

In addition, when considering the effect of the temperature of the leaching solution at approximately 60 ^o C dissolution inhibiting side and the effect of the temperature rise on the reaction rate, the leaching temperature according to the present invention is 60 ℃ It is more preferable that it is -80 degreeC.

On the other hand, the leaching time is related to the reaction rate, the reaction rate is affected by the particle size distribution. That is, when the particle size distribution of the particles is coarse, a large reaction time is required, and when the particle size distribution is fine, the reaction time may be relatively small. The reaction rate is also affected by the degree of agitation.

In consideration of these various matters, the leaching time according to the present invention is preferably 30 minutes to 180 minutes. This is because if the leaching time is less than 30 minutes, the leaching reaction may not occur properly, and if it exceeds 180 minutes there is a risk of unnecessary expense loss and excess mechanical equipment. And according to the experimental results, considering the side of the leaching reaction and the side of the excess mechanical equipment, it can be seen that the leaching time is more appropriate 60 minutes.

In the leaching method, the initial pH of the leaching solution should be sufficiently low, and usually 1.0 or less, and preferably 2.0 or less after the leaching.

The present invention may further comprise the step of separating the leaching solution and the molybdenum oxide concentrate after the leaching is finished. The method for separating the leach liquor and the molybdenum oxide concentrate is not particularly limited, and general methods such as filtration separation and centrifugation such as gravity filtration, pressure filtration, reduced pressure filtration and filter press can be used.

The leaching method according to the present invention may further comprise the step of washing the molybdenum oxide concentrate separated from the leach solution with washing water.

The washing step according to the present invention is a step for removing impurities physically remaining in the molybdenum oxide concentrate separated from the leachate, preferably impurities including residual chemical components. The washing step can minimize the chemicals remaining in the molybdenum oxide concentrate and can safely lower the grade of copper produced in the molybdenum oxide concentrate.

Washing water according to the present invention means the water to filter the leachate to separate the leachate and the solid, and then wash the filtered solid. Washing liquid according to the present invention refers to the liquid filtered by washing with washing water. The cleaning liquid may include various metal ions such as copper, molybdenum, iron, and zinc.

Washing water is used to wash away the residual chemicals, and also to remove the dissolved copper. If the pH of the liquid is increased by using a lot of washing water, molybdenum may dissolve and be careful.

Washing water is preferably selected in consideration of the use and solubility of molybdenum oxide concentrate, it is preferable to use water.

The volume of the wash water according to the invention is preferably from 1/3 to 1 of the volume of the leachate, more preferably about 1/2.

If the volume of the wash water is less than 1/3 of the volume of the leachate, it is difficult to remove all impurities and residual chemicals remaining in the molybdenum oxide concentrate, and if it exceeds 1, the molybdenum oxide may be dissolved in the wash solution.

The pH of the washing water after the washing step according to the present invention is preferably 3.0 or less. The molybdenum oxide concentrate completed by the washing step is dried through a calcination process in the temperature range of 300 ℃ to 350 ℃. Drying apparatus is not particularly limited, it is common to use a rotary drying furnace.

On the other hand, copper, a valuable metal present in the leachate, can be recovered by a copper substitution reaction by waste iron.

Hereinafter, the present invention will be described in detail through examples. However, the following examples are only for illustrating the present invention in detail and are not intended to limit the scope of the present invention by these examples.

Example 1

100 g of the roasted molybdenum oxide concentrate was leached at 70 ° C. for 60 minutes using 100 mL of water, 5 g of sodium chloride, 5 g of ammonium chloride, and 15 mL of hydrochloric acid, and then the leachate and the molybdenum oxide concentrate were separated by filtration. The leaching solution and molybdenum oxide concentrate were separated and washed again with 50 mL of water to obtain a washing solution and molybdenum oxide concentrate (see Table 1). After leaching, the molybdenum oxide concentrate was dried and dried in a drier and analyzed by an ICP analyzer [Perkin-Elmers, USA]. Leachate and wash solution were also sampled and analyzed by ICP analyzer.

As a result, the volume of the leaching liquid was 75 mL, and the volume of the washing liquid was 49 mL. The weight of the molybdenum oxide concentrate separated after leaching was 94.93 g. The grade of molybdenum oxide concentrate was 54.33% for molybdenum and 2.80% for copper before leaching. After the leaching was completed, molybdenum was 55.23% and copper was 0.146%. The quality of the leachate was 0.01 g / L for molybdenum and 23.25 g / L for copper. The quality of the wash liquid was 0.01 g / L for molybdenum and 18.69 g / L for copper.

Example 2

The same procedure as in Example 1 was carried out, except that 12 g of sodium chloride, 5 g of ammonium chloride, and 15 mL of hydrochloric acid were used (see Table 1).

As a result, the volume of the leaching liquid was 51 mL for the 71 mL washing liquid. The weight of the molybdenum oxide concentrate separated after leaching was 95.66 g. The grade of molybdenum oxide concentrate was 54.86% molybdenum and 2.83% copper before leaching. After the leaching was completed, molybdenum was 57.34% and copper was 0.174%. The quality of the leachate was 0.135 g / L for molybdenum and 23.6 g / L for copper. The quality of the wash liquid was 0.058 g / L for molybdenum and 19.37 g / L for copper.

Example 3

The same procedure as in Example 1 was conducted, except that 5 g of sodium chloride, 3 g of ammonium chloride, and 15 mL of hydrochloric acid were used (see Table 1).

As a result, the volume of the leaching liquid was 73.5 mL, and the volume of the washing liquid was 47 mL. The weight of the molybdenum oxide concentrate separated after leaching was 95.93 g. The quality of the molybdenum oxide concentrate was 55.22% for molybdenum and 2.88% for copper before leaching. After the leaching was completed, molybdenum was 57.54% and copper was 0.193%. The quality of the leachate was 0.19 g / L for molybdenum and 24.32 g / L for copper. The quality of the wash liquid was 0.171 g / L for molybdenum and 19.31 g / L for copper.

Example 4

The same procedure as in Example 1 was performed except leaching using 5 g of sodium chloride, 5 g of ammonium chloride, and 15 mL of hydrochloric acid (see Table 1).

As a result, the volume of the leaching liquid was 80 mL, and the volume of the washing liquid was 49.5 mL. The weight of the molybdenum oxide concentrate separated after leaching was 94.93 g. The quality of the molybdenum oxide concentrate was 54.14% for molybdenum and 2.98% for copper before leaching. After the leaching was completed, molybdenum was 57.44% and copper was 0.23%. The quality of the leachate was 0.234 g / L for molybdenum and 25.28 g / L for copper. The quality of the wash liquid was 0.235 g / L for molybdenum and 14.92 g / L for copper.

Example 5

The same procedure as in Example 1 was conducted, but leached using 5 g of calcium chloride, 5 g of ammonium chloride, and 15 mL of hydrochloric acid (see Table 1).

As a result, the volume of the leaching liquid was 76 mL, and the volume of the washing liquid was 49 mL. The weight of the molybdenum oxide concentrate separated after leaching was 95.52 g. The quality of the molybdenum oxide concentrate was 54.24% for molybdenum and 2.76% for copper before leaching. After the leaching was completed, molybdenum was 56.78% and copper was 0.212%. The quality of the leachate was 0.01 g / L for molybdenum and 23.36 g / L for copper. The quality of the wash liquid was 0.01 g / L for molybdenum and 15.95 g / L for copper.

Example 6

In the same manner as in Example 1, but leached using 10 g of calcium chloride, 5 g of ammonium chloride and 15 mL of hydrochloric acid (see Table 1).

As a result, the volume of the leaching liquid was 70 mL, and the volume of the washing liquid was 51.5 mL. The weight of the molybdenum oxide concentrate separated after leaching was 96.66 g. The grade of molybdenum oxide concentrate was 55.20% for molybdenum and 2.78% for copper before leaching. After the leaching was completed, molybdenum was 57.10% and copper was 0.254%. The quality of the leachate was 0.026 g / L for molybdenum and 23.24 g / L for copper. The quality of the wash liquid was 0.01 g / L for molybdenum and 17.56 g / L for copper.

Example 7

In the same manner as in Example 1, but leached using 5 g of calcium chloride, 3 g of ammonium chloride and 15 mL of hydrochloric acid (see Table 1).

As a result, the volume of the leaching liquid was 77 mL and the volume of the washing liquid was 50 mL. The weight of the molybdenum oxide concentrate separated after leaching was 95.87 g. The grade of molybdenum oxide concentrate was 55.17% for molybdenum and 2.82% for copper before leaching. After the leaching was completed, molybdenum was 57.52% and copper was 0.218%. The quality of the leachate was 0.207 g / L for molybdenum and 23.64 g / L for copper. The quality of the wash liquid was 0.165 g / L for molybdenum and 15.84 g / L for copper.

Example 8

In the same manner as in Example 1, but leached using 5 g of calcium chloride, 3 g of ammonium chloride and 12 mL of hydrochloric acid (see Table 1).

As a result, the volume of the leaching liquid was 71 mL, and the volume of the washing liquid was 50 mL. The weight of the molybdenum oxide concentrate separated after leaching was 94.35 g. The grade of molybdenum oxide concentrate was 55.09% for molybdenum and 2.82% for copper before leaching. After the leaching was completed, molybdenum was 57.46% and copper was 0.20%. The quality of the leachate was 7.696 g / L for molybdenum and 23.87 g / L for copper. The quality of the wash liquid was 6.59 g / L for molybdenum and 18.82 g / L for copper.

Example 9

In the same manner as in Example 1, it was leached using 3 g of sodium chloride, 3 g of calcium chloride, 4 g of ammonium chloride, and 15 mL of hydrochloric acid (see Table 1).

As a result, the volume of the leaching liquid was 75 mL, and the volume of the washing liquid was 50 mL. The weight of the molybdenum oxide concentrate separated after leaching was 93.55 g. The grade of molybdenum oxide concentrate was 55.60% for molybdenum and 3.03% for copper before leaching. After the leaching was completed, molybdenum was 58.16% and copper was 0.22%. The quality of the leachate was 0.256 g / L for molybdenum and 25.58 g / L for copper. The quality of the wash liquid was 0.215 g / L for molybdenum and 17.97 g / L for copper.

Comparative Example 1

In the same manner as in Example 1, but leached using 12 g of ammonium chloride and 15 mL of hydrochloric acid (see Table 1).

As a result, the volume of the leaching liquid was 72.5 mL, and the volume of the washing liquid was 50 mL. The weight of the molybdenum oxide concentrate separated after leaching was 98.08 g. The quality of molybdenum oxide concentrate was 55.44% for molybdenum and 2.72% for copper before leaching. After the leaching was completed, molybdenum was 56.52% and copper was 0.44%. The quality of the leachate was 0.01 g / L for molybdenum and 19.18 g / L for copper. The quality of the wash liquid was 0.01 g / L for molybdenum and 12.23 g / L for copper.

Comparative Example 2

In the same manner as in Example 1, but leached using 15 mL of hydrochloric acid (see Table 1).

As a result, the volume of the leaching liquid was 81 mL, and the volume of the washing liquid was 50 mL. The weight of the molybdenum oxide concentrate separated after leaching was 90.34 g. The quality of the molybdenum oxide concentrate was 54.73% for molybdenum and 2.89% for copper before leaching. After the leaching was completed, molybdenum was 57.76% and copper was 0.258%. The quality of the leachate was 22.25 g / L for molybdenum and 23.97 g / L for copper. The quality of the wash liquid was 15.04 g / L for molybdenum and 14.23 g / L for copper.

Comparative Example 3

In the same manner as in Example 1, 2 mL of sulfuric acid was added and the leaching was performed at room temperature (see Table 1).

As a result, the volume of the leaching liquid was 88 mL and the volume of the washing liquid was 50 mL. The weight of the molybdenum oxide concentrate separated after leaching was 86.27 g. The quality of the molybdenum oxide concentrate was 55.49% for molybdenum and 2.90% for copper before leaching. After the leaching was completed, molybdenum was 56.93% and copper was 0.30%. The quality of the leachate was 59.87 g / L for molybdenum and 25.36 g / L for copper. The quality of the wash liquid was 22.14 g / L for molybdenum and 8.28 g / L for copper.

Comparative Example 4

In the same manner as in Example 1, but leached using 12 g of sodium chloride and 15 mL of hydrochloric acid (see Table 1).

As a result, the volume of the leaching liquid was 77 mL and the volume of the washing liquid was 51.5 mL. The weight of the molybdenum oxide concentrate separated after leaching was 94.33 g. The grade of molybdenum oxide concentrate was 55.93% for molybdenum and 2.82% for copper before leaching. After the leaching was completed, molybdenum was 57.47% and copper was 0.17%. The quality of the leachate was 6.13 g / L for molybdenum and 24.03 g / L for copper. The quality of the wash liquid was 4.81 g / L for molybdenum and 15.71 g / L for copper.

Comparative Example 5

In the same manner as in Example 1, but leached using 15 g of sodium chloride and 15 mL of hydrochloric acid (see Table 1).

As a result, the volume of the leaching liquid was 82 mL, and the volume of the washing liquid was 50 mL. The weight of the molybdenum oxide concentrate separated after leaching was 94.51 g. The quality of molybdenum oxide concentrate was 54.63% for molybdenum and 2.92% for copper before leaching. After the leaching was completed, molybdenum was 56.98% and copper was 0.196%. The quality of the leachate was 6.53 g / L for molybdenum and 24.41 g / L for copper. The quality of the wash liquid was 4.83 g / L for molybdenum and 14.73 g / L for copper.

Comparative Example 6

In the same manner as in Example 1, but leached using 12 g of calcium chloride and 15 mL of hydrochloric acid (see Table 1).

As a result, the volume of the leaching liquid was 82.5 mL, and the volume of the washing liquid was 50 mL. The weight of the molybdenum oxide concentrate separated after leaching was 94.33 g. The grade of molybdenum oxide concentrate was 55.33% for molybdenum and 2.81% for copper before leaching. After the leaching was completed, molybdenum was 57.43% and copper was 0.196%. The quality of the leachate was 9.89 g / L for molybdenum and 23.38 g / L for copper. The quality of the wash liquid was 6.71 g / L for molybdenum and 12.55 g / L for copper.

Comparative Example 7

In the same manner as in Example 1, but leached using 15 g of calcium chloride and 15 mL of hydrochloric acid (see Table 1).

As a result, the volume of the leaching liquid was 84.5 mL, and the volume of the washing liquid was 51 mL. The weight of the molybdenum oxide concentrate separated after leaching was 93.1 g. The quality of the molybdenum oxide concentrate was 54.92% for molybdenum and 2.84% for copper before leaching. After the leaching was completed, molybdenum was 57.82% and copper was 0.21%. The quality of the leachate was 9.03 g / L for molybdenum and 23.73 g / L for copper. The quality of the wash liquid was 6.45 g / L for molybdenum and 12.57 g / L for copper.

Composition of materials used in the test Molybdenum Oxide Concentrate
(g) water
(mL) Chloride
Sodium (g) Chloride
calcium
(g) Chloride
Ammonium (g) Hydrochloric acid
(mL) Wash solution (mL) Sulfuric acid
(mL)
Temperature
( ^o C) Example 1 100 100 5 - 5 15 50 - 70 Example 2 100 100 12 - 5 15 50 - 70 Example 3 100 100 5 - 3 15 50 - 70 Example 4 100 100 5 - 4 15 50 - 70 Example 5 100 100 - 5 5 15 50 - 70 Example 6 100 100 - 10 5 15 50 - 70 Example 7 100 100 - 5 3 15 50 - 70 Example 8 100 100 - 5 3 12 50 - 70 Example 9 100 100 3 3 4 15 50 - 70 Comparative Example 1 100 100 - - 12 15 50 - 70 Comparative Example 2 100 100 - - - 15 50 - 70 Comparative Example 3 100 100 - - - - 50 2 Room temperature Comparative Example 4 100 100 12 - - 15 50 - 70 Comparative Example 5 100 100 15 15 50 70 Comparative Example 6 100 100 12 15 50 70 Comparative Example 7 100 100 15 15 50 70

Wherein the leaching time of the entire test is 60 minutes, the room temperature means 25 ℃. The molybdenum oxide concentrate is [concentrate which roasted the molybdenum emulsified concentrate of Codelco mine in roasting furnace of Kwangyang alloy, Kwangyang alloy, Korea], the sodium chloride is 99.5% or more of sodium chloride, [WAKO, Japan], and the calcium chloride is calcium chloride 95.0% or more, [JUNSEI, Japan], the ammonium chloride is 99.5% or more of ammonium chloride, [JUNSEI, Japan], the hydrochloric acid is hydrochloric acid 36%, specific gravity = 1.18, [Dongwoo Fine Chem, Korea], The sulfuric acid is sulfuric acid 96%, specific gravity = 1.84, [Dongwoo Fine Chem, South Korea].

Recovery rate according to Examples and Comparative Examples of the present invention
In leachate
% Recovery In the wash solution
% Recovery In concentrate
% Recovery molybdenum copper molybdenum copper molybdenum copper Example 1 0.00 62.32 0.00 32.73 100 4.95 Example 2 0.02 59.21 0.01 34.91 99.98 5.88 Example 3 0.03 62.06 0.01 31.51 99.96 6.43 Example 4 0.03 67.83 0.02 24.77 99.94 7.40 Example 5 0.00 64.34 0.00 28.32 100 7.34 Example 6 0.00 58.59 0.00 32.57 100 8.84 Example 7 0.03 64.52 0.01 28.07 99.96 7.41 Example 8 0.99 60.00 0.60 33.32 98.41 6.68 Example 9 0.03 63.38 0.02 29.68 99.95 6.94 Comparative Example 1 0.00 61.70 0.00 22.45 100 15.84 Comparative Example 2 3.29 67.27 1.37 24.65 95.33 8.08 Comparative Example 3 9.49 76.84 1.99 14.25 88.51 8.91 Comparative Example 4 0.86 65.62 0.45 28.69 98.69 5.69 Comparative Example 5 0.98 68.47 0.44 25.19 98.58 6.34 Comparative Example 6 1.48 68.69 0.61 22.34 97.92 8.97 Comparative Example 7 1.39 70.56 0.60 22.56 98.01 6.88

In Comparative Example 1, using 12 g of ammonium chloride and 15 mL of hydrochloric acid, leaching of copper in the molybdenum oxide concentrate was 85.15%, and no leaching of molybdenum occurred, resulting in an inhibitory effect of 100%. Compared with Example 1 it can be seen that when using sodium chloride 5g and ammonium chloride 5g instead of 12g ammonium chloride showed better results. In this case, due to the effect of reducing chemicals and reducing the amount of ammonium chloride used, it helps to improve the water environment.

In Comparative Example 2, when molybdenum oxide concentrate was leached using only hydrochloric acid without adding ammonium chloride, copper showed good results because 91.92% of the copper was eluted. However, molybdenum dissolves in 3.66% of the leachate, resulting in a significant loss of molybdenum.

In Comparative Example 3, even when sulfuric acid was used, copper eluted 91.09%, showing good results. Molybdenum, however, dissolves 11.48% in leachate, resulting in a significant loss of molybdenum.

In Comparative Example 4, when molybdenum oxide concentrate was leached using 12 g of sodium chloride and 15 mL of hydrochloric acid without adding ammonium chloride, copper showed a good result because 94.31% was eluted. However, molybdenum dissolves 1.31% in leachate, resulting in huge molybdenum loss.

In Comparative Example 5, even when ammonium chloride was added to 15 g of sodium chloride and 15 mL of hydrochloric acid was used, the results were not improved.

In Comparative Example 6, when molybdenum oxide concentrate was leached using 12 g of calcium chloride and 15 mL of hydrochloric acid without adding ammonium chloride, copper eluted 91.03%, and showed good results. However, molybdenum dissolves 2.09% in leachate, resulting in a huge loss of molybdenum.

In Comparative Example 7, there was no improvement in results even if calcium chloride was increased to 15 g without adding ammonium chloride and 15 mL of hydrochloric acid was used.

The results of the above comparative tests show that the use of sodium chloride or calcium chloride alone without the use of ammonium chloride is not able to completely inhibit the dissolution of molybdenum oxide, and when sodium chloride or calcium chloride is used together with ammonium chloride, there is an effect of inhibiting the dissolution of molybdenum oxide. It can be seen.

In Example 1, 5 g of sodium chloride and 5 g of ammonium chloride were added, or 5 g of calcium chloride and 5 g of ammonium chloride were added in Example 5, reducing the use of chemicals while performing the same results as adding 12 g of ammonium chloride of Comparative Example 1. It works.

In Example 2, increasing the use of sodium chloride to 12 g did not help to improve the results. Excessively reducing the amount of ammonium chloride used in Examples 3 and 4 reduced the dissolution inhibition of molybdenum oxide. can see.

In Example 6, the change in performance is not significant when used from 5 g of calcium chloride of Example 5 to 10 g of calcium chloride, but the amount of chemicals used is excessive.

In Example 7, when the amount of ammonium chloride used is reduced from 5 g to 3 g, the dissolution inhibiting effect of molybdenum oxide appears to be reduced as in Examples 3 and 4.

In Example 8, when using the amount of 3 g of ammonium chloride and hydrochloric acid to 12 mL, molybdenum oxide is largely dissolved.

In Example 9, even when leaching using 3 g of sodium chloride, 3 g of calcium chloride, and 4 g of ammonium chloride, the same results as in Example 3 and Example 4 were obtained.

The embodiments and the accompanying drawings described in the present specification are merely illustrative of some of the technical ideas included in the present invention. Accordingly, the embodiments disclosed herein are for the purpose of describing rather than limiting the technical spirit of the present invention, and it is apparent that the scope of the technical idea of the present invention is not limited by these embodiments. It will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

1 shows an Eh-pH diagram of ammonium ions and molybdenum oxide ions.

Claims (12)

In the method of leaching impurities contained in molybdenum oxide, Leachate of any one selected from the group consisting of a first leachate containing ammonium chloride, sodium chloride and hydrochloric acid, a second leachate containing ammonium chloride, calcium chloride and hydrochloric acid and a third leachate containing ammonium chloride, sodium chloride, calcium chloride and hydrochloric acid Leaching impurities of the molybdenum oxide concentrate using Method for leaching impurities contained in molybdenum oxide concentrate. The method of claim 1, The molybdenum oxide concentrate is leaching method of impurities contained in the molybdenum oxide concentrate, characterized in that obtained by roasting the ore of molybdenum. The method of claim 1, The first leachate is characterized in that the oxidation is characterized in that 3 to 10 parts by weight of ammonium chloride, 3 to 10 parts by weight of sodium chloride, 8 to 20 parts by weight of hydrochloric acid and 50 to 300 parts by weight of water based on 100 parts by weight of molybdenum oxide concentrate. Method for leaching impurities contained in molybdenum concentrate. The method of claim 1, The second leaching solution is based on 100 parts by weight of molybdenum oxide concentrate, 3 to 10 parts by weight of ammonium chloride, 3 to 10 parts by weight of calcium chloride, 8 to 20 parts by weight of hydrochloric acid and 50 to 300 parts by weight of water. Method of leaching impurities contained in concentrate. The method of claim 1, The third leachate is based on 100 parts by weight of molybdenum oxide concentrate, 3 to 10 parts by weight of ammonium chloride, 3 to 10 parts by weight of sodium chloride, 3 to 10 parts by weight of calcium chloride, 8 to 20 parts by weight of hydrochloric acid and 50 to 300 parts by weight of water. A method for leaching impurities contained in a molybdenum oxide concentrate, which is used. The method of claim 1, A ratio of the weight (g) of the molybdenum oxide concentrate and the volume (mL) of the leachate is 1: 1 to 1: 2 leaching method of impurities contained in the molybdenum oxide concentrate. The method of claim 1, The leaching temperature is leached method of impurities contained in molybdenum oxide concentrate, it characterized in that a 20 ^o C to 90 ℃. The method of claim 7, wherein The leaching temperature is 60 ^o C to 80 ℃ leaching method of impurities contained in the molybdenum oxide concentrate. The method of claim 1, The leaching time is a leaching method of impurities contained in the molybdenum oxide concentrate, characterized in that 30 minutes to 180 minutes. The method of claim 1, After the leaching is finished, the leaching method of the impurities contained in the molybdenum oxide concentrate further comprising the step of separating the leach liquid and molybdenum oxide concentrate. The method of claim 10, After the separation step, the method of leaching impurities contained in the molybdenum oxide concentrate further comprising the step of washing the separated molybdenum oxide concentrate with washing water. The method of claim 10, In the washing step, the volume of the wash water leaching method of impurities contained in the molybdenum oxide concentrate, characterized in that 1/3 to 1 of the leachate volume.

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