WO2010090478A2

WO2010090478A2 - Method for leaching impurities contained in molybdenum oxide concentrates

Info

Publication number: WO2010090478A2
Application number: PCT/KR2010/000728
Authority: WO
Inventors: 송진곤; 허천회; 임경미
Original assignee: (주)광양합금철
Priority date: 2009-02-05
Filing date: 2010-02-05
Publication date: 2010-08-12
Also published as: WO2010090478A3; KR20100090094A; KR101037655B1

Abstract

The present invention relates to a leaching method that enables the production of good quality molybdenum oxide concentrates by selectively leaching impurities such as copper, iron, lead and zinc from roasted molybdenum oxide concentrates using a leach liquor comprising ammonium chloride and hydrochloric acid. As molybdenum oxide concentrates produced by the leaching method of the present invention are mostly present in the solid state, a process for recovering molybdenum dissolved in the leach liquor is not required.

Description

Leaching method of impurities contained in molybdenum oxide concentrate

The present invention relates to a leaching method of impurities contained in a molybdenum oxide concentrate, by selectively leaching impurities such as copper, iron, lead and zinc from roasted molybdenum oxide concentrate by using a leaching solution containing ammonium chloride and hydrochloric acid. It relates to a leaching method that can produce molybdenum oxide 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. In addition, the molybdenum is used as a substitute for tungsten used in airplane parts, 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 distributed in four countries: China, the United States, Chile and Canada. In the global molybdenum market, the demand growth rate of 5.2% and the supply growth rate of 3.8% over the past 10 years, the demand growth rate is higher than the supply growth rate. Currently, the production of molybdenum concentrates in the world's mines is increasing, but there is a shortage of bottlenecks due to the lack of production capacity of roasting plants for processing.

Molybdenum is produced from molybdenum (Molybdenite), which is ore, which is mostly produced with other emulsified minerals. In order to use molybdenum as a subsidiary material added during steelmaking, molybdenum emulsified concentrate is roasted in a roasting furnace after concentrate production by flotation. Thereafter, in the leaching process, metal impurities other than molybdenum are dissolved and separated.

Reagents for leaching metal impurities such as copper, iron, lead and zinc which are impurities contained in the molybdenum oxide concentrate roasted in the leaching of molybdenum include hydrochloric acid, nitric acid, sulfuric acid, ammonium hydroxide, iron chloride, sodium cyanide and caustic. There are many chemicals such as soda. Most of the reagents dissolve impurities, but simultaneously dissolve a large amount of molybdenum. To recover molybdenum dissolved in the leachate, the molybdenum is recovered by using a solvent extraction method, an ion exchange resin method, and an adsorption method with activated carbon. Many processes, such as desorption, are required and loss of molybdenum occurs at every process.

Therefore, the present inventors continue to study the leaching method of molybdenum oxide concentrate to overcome the above-mentioned problems, and when ammonium chloride and hydrochloric acid are used together as the leaching solution, most of the metal impurities in the molybdenum oxide concentrate are dissolved but molybdenum is dissolved. The present invention has been completed by focusing on the fact that most of them exist in the solid state.

The present invention was derived to overcome the above-described problems, and since most of the molybdenum oxide concentrate is in a solid state after the leaching is completed, it does not require a process for recovering molybdenum dissolved in the leach solution and improve productivity. It provides a method for leaching the impurities contained in the molybdenum oxide concentrate.

The present invention provides a method for leaching impurities contained in molybdenum oxide concentrate, including a method of leaching impurities of molybdenum oxide concentrate using a leaching solution containing ammonium chloride and hydrochloric acid as a means for solving the above problems.

According to the present invention, since most of the molybdenum oxide concentrate is in a solid state after the leaching is completed, it does not require a process for recovering molybdenum dissolved in the leach solution, and has an effect of improving productivity.

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

The present invention relates to a method for leaching impurities contained in a molybdenum oxide concentrate comprising leaching impurities of molybdenum oxide concentrate using a leaching solution containing ammonium chloride and hydrochloric acid.

Molybdenum oxide concentrate according to the present invention means that obtained by roasting the ore of molybdenum.

The method for leaching the impurities of the molybdenum oxide concentrate according to the present invention is carried out using a leaching solution containing ammonium chloride and hydrochloric acid, copper, lead, iron and zinc contained in the molybdenum oxide concentrate ( leaching zinc). At this time, since the dissolution of molybdenum is suppressed, the molybdenum oxide is not dissolved but exists in a solid state.

The leaching solution is an aqueous solution used for leaching metal impurities in the molybdenum oxide concentrate, and includes water, ammonium chloride and hydrochloric acid. The leaching solution is preferably so as to sufficiently wet the molybdenum oxide concentrate.

The ratio of the weight of molybdenum oxide concentrate (g) to the volume of the leach liquor (mL) depends on the amount of impurities in the molybdenum oxide concentrate, the concentration of ammonium chloride in the leach liquor, the concentration of hydrochloric acid and the viscosity of the leach liquor. 2 is preferred, and about 1: 1 is more preferred.

If the ratio is less than 1: 1, there is a lack of contact between the leaching solution and the ore, so leaching may not be performed smoothly, and the machine may be overloaded.

Hydrochloric acid contained in the leaching solution reacts with molybdenum oxide concentrate to dissolve copper, iron, lead, and zinc, as well as dissolve molybdenum oxide with molybdenum oxide ions (MoO ₄ ^-2 ) as shown in Scheme 1 below.

Scheme 1

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

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

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.

Scheme 2

_{_{^{2NH 4 Cl + MoO 4 -2 +}}} 3H + + Cl - -> (NH 3) 2 · MoO 3 · 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 forming the molybdenum oxide complex salt.

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, high iron content or high copper grade increases the amount of hydrochloric acid used.

The amount of hydrochloric acid is preferably used more than 20 to 30% with respect to the amount corresponding to the chemical equivalent of the impurities to be leached.

The amount of ammonium chloride should be added in consideration of the amount of molybdenum dissolved in the leaching test using only hydrochloric acid without using ammonium chloride.

The amount of ammonium chloride and hydrochloric acid is preferably 5 to 20 parts by weight of ammonium chloride and 8 to 20 parts by weight of hydrochloric acid based on 100 parts by weight of molybdenum oxide concentrate.

If the ammonium chloride is less than 5 parts by weight of ammonium ions, the molybdenum oxide ions dissolved by hydrochloric acid cannot be sufficiently made into a complex salt of ammonium molybdenum oxide, so the quality of molybdenum in the leachate may be increased, and more than 20 parts by weight. When the ammonium ions and molybdenum oxide ions form, the ammonium ions remain after the complex salt is not economical.

In the present invention, the leaching temperature is preferably 20 to 90 ℃, 60It is more preferable that it is -80 degreeC.

If the leaching temperature is less than 20 ℃ there is a fear that the rate of leaching reaction is slowed, if it exceeds 90 ℃ there is a fear that the cost used to heat the leaching liquid is excessive.

In the present invention, the leaching time is preferably 30 minutes to 180 minutes, more preferably about 60 minutes.

If the leaching time is less than 30 minutes, the leaching reaction may not occur properly, if it exceeds 180 minutes there is a risk of unnecessary expense loss and excess mechanical equipment.

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 of separating the leachate 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, and centrifugation is preferable.

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 is performed to remove impurities physically remaining in the molybdenum oxide concentrate separated from the leachate, preferably impurities including residual chemical components, and may minimize chemicals remaining in the molybdenum oxide concentrate. The grade of copper in the molybdenum oxide concentrate produced can be safely lowered.

The washing liquid is preferably selected in consideration of the use and solubility of molybdenum oxide concentrate, and water is preferably used.

The amount of the washing liquid is preferably 1/3 to 1 of the leaching liquid, more preferably about 1/2.

If the amount of the washing liquid is less than 1/3 of the amount of the leaching liquid, it is difficult to remove all impurities and residual chemicals remaining in the molybdenum oxide concentrate, and if it exceeds 1, molybdenum oxide may be dissolved in the washing liquid.

After the washing step is completed, the pH of the washing water 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 ℃. The drying apparatus is not particularly limited, and it is preferable 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 for 60 minutes at 70 ° C using a leaching solution containing 100 mL of water, 10 g of ammonium chloride and 10 mL of hydrochloric acid (see Table 1). After leaching, the leachate and the molybdenum oxide concentrate were separated by filtration. After the leaching, the molybdenum oxide concentrate was dried and dried in a drier and analyzed by ICP analyzer [Perkin-Elmers, USA]. Leachate samples were also analyzed and analyzed by ICP analyzer.

As a result, the volume of the leachate was 84 mL, and the weight of the molybdenum oxide concentrate separated after leaching was 102.3 g. The grades of molybdenum oxide concentrates were 57.09% molybdenum and 2.21% copper before leaching, and 55.77% molybdenum and 0.47% copper after leaching. The quality of the leachate was 0.49 g / L for molybdenum and 20.57 g / L for copper.

Example 2

The same procedure as in Example 1 was carried out except that 5 g of ammonium chloride was added (see Table 1).

As a result, the volume of the leachate was 78.5 mL, and the weight of the molybdenum oxide concentrate separated after leaching was 99.9 g. The grades of molybdenum oxide concentrate were 56.78% molybdenum and 2.11% copper before leaching, and 56.76% molybdenum and 0.41% copper after leaching. The quality of the leachate was 0.98 g / L for molybdenum and 21.68 g / L for copper.

It carried out in the same manner as in Example 1, the ammonium chloride content was 5g, and leached at room temperature (see Table 1).

As a result, the volume of the leachate was 81 mL, and the weight of the molybdenum oxide concentrate separated after leaching was 89.4 g. The grades of molybdenum oxide concentrate were 56.81% of molybdenum and 1.90% of copper before leaching, and 56.94% of molybdenum and 0.38% of copper after leaching. The quality of the leachate was 2.64 g / L for molybdenum and 18.76 g / L for copper.

In the same manner as in Example 1, the ammonium chloride content was 5g, and leached at room temperature for 40 minutes (see Table 1).

As a result, the volume of the leachate was 85 mL, and the weight of the molybdenum oxide concentrate separated after leaching was 102.0 g. The quality of molybdenum oxide concentrate was 58.01% of molybdenum and 2.32% of copper before leaching, and 56.52% of molybdenum and 0.67% of copper after leaching. The quality of the leachate was 4.22 g / L for molybdenum and 19.20 g / L for copper.

Example 5

In the same manner as in Example 1, the ammonium chloride content was 5g and leached at room temperature for 80 minutes (see Table 1).

As a result, the volume of the leachate was 75 mL, and the weight of the molybdenum oxide concentrate separated after leaching was 101.1 g. The grades of molybdenum oxide concentrate were 58.60% molybdenum and 1.98% copper before leaching. After leaching, molybdenum was 57.82% and copper was 0.48%. The quality of the leachate was 1.93 g / L for molybdenum and 19.91 g / L for copper.

Example 6

In the same manner as in Example 1, the content of hydrochloric acid was 12mL, after the leaching was completed, the leachate and the molybdenum oxide concentrate was separated and the molybdenum oxide concentrate was washed with 50mL of wash water (see Table 1).

As a result, the volume of the leaching liquid was 90 mL, the weight of the molybdenum oxide concentrate separated after leaching was 96.5 g, and the volume of the washing liquid was 50 mL. The grades of molybdenum oxide concentrate were 56.61% molybdenum and 2.41% copper before leaching. After leaching, molybdenum was 58.66% and copper was 0.17%. The quality of the leachate was 0.05g / L molybdenum and 19.88g / L copper, and the wash liquid was 0.04g / L molybdenum and 9.11g / L copper.

Example 7

A leaching test was conducted in the same manner as in Example 1 (see Table 1).

As a result, the volume of the leachate was 84 mL, and the weight of the molybdenum oxide concentrate separated after leaching was 102.3 g. The grade of molybdenum oxide concentrate was 57.09% of molybdenum before leaching, 2.21% of copper, 0.04% of lead, 0.99% of iron and 0.07% of zinc.After the leaching, molybdenum was 55.77%, copper of 0.47%, lead of 0.03%. %, 0.46% iron and 0.01% zinc. The quality of the leachate was 0.49 g / L for molybdenum, 20.57 g / L for copper, 0.12 g / L for lead, 6.18 g / L for iron, and 0.71 g / L for zinc.

Example 8

The same method as in Example 1, but the leaching test at room temperature (see Table 1).

As a result, the volume of the leachate was 76 mL, and the weight of the molybdenum oxide concentrate separated after leaching was 102.0 g. The grade of molybdenum oxide concentrate was 56.88% molybdenum before leaching, 2.14% copper, 0.04% lead, 1.32% iron and 0.07% zinc.After the leaching, molybdenum 55.77%, copper 0.47%, lead 0.03 %, 0.46% iron and 0.01% zinc. The quality of the leachate was 2.19 g / L for molybdenum, 20.54 g / L for copper, 0.14 g / L for lead, 7.34 g / L for iron, and 0.68 g / L for zinc.

Comparative Example 1

The same method as in Example 1, but the leaching test at room temperature without the addition of ammonium chloride (see Table 1).

As a result, the volume of the leachate was 96 mL, and the weight of the molybdenum oxide concentrate separated after leaching was 89.3 g. The grade of molybdenum oxide concentrate was 56.77% of molybdenum and 2.18% of copper before leaching. After leaching, molybdenum was 57.55% and copper was 0.32%. The quality of the leachate was 56.27 g / L for molybdenum and 19.69 g / L for copper.

Comparative Example 2

In the same manner as in Example 1, leaching was performed by adding 7 g of ammonium sulfate instead of ammonium chloride and 2 mL of sulfuric acid instead of hydrochloric acid (see Table 1).

As a result, the volume of the leachate was 83 mL, and the weight of the molybdenum oxide concentrate separated after leaching was 95.7 g. The grade of molybdenum oxide concentrate was 59.31% of molybdenum and 2.25% of copper before leaching. After leaching, molybdenum was 57.28% and copper was 0.50%. The quality of the leachate was 54.16 g / L for molybdenum and 21.26 g / L for copper.

Table 1

here

The room temperature is 25 ℃,

The molybdenum oxide concentrate is [concentrate that roasted the molybdenum emulsified concentrate of Codelco mine in the roasting furnace of Kwangyang alloy iron, Kwangyang alloy iron, Korea],

Ammonium chloride is at least 99.5% ammonium chloride, [JUNSEI, Japan],

The hydrochloric acid is hydrochloric acid 36%, specific gravity = 1.18, [Dongwoo Fine Chem, Korea],

The ammonium sulfate is ammonium sulfateAt least 99.5%, [JUNSEI, Japan],

The sulfuric acid is sulfuric acid 96%, specific gravity = 1.84, [Dongwoo Fine Chem, South Korea].

TABLE 2

TABLE 3

If ammonium sulfate and sulfuric acid are used in place of ammonium chloride and hydrochloric acid in Comparative Example 2, leaching of copper in the molybdenum oxide concentrate is possible, but the effect of inhibiting the leaching of molybdenum is not seen.

In Comparative Example 1, when molybdenum oxide concentrate was leached using only hydrochloric acid without addition of ammonium chloride, copper eluted 86.84%, showing good results. However, molybdenum was dissolved in 9.52% leachate, resulting in enormous loss of molybdenum. However, when 10 g of ammonium chloride was added in Example 8, the recovery rate was increased to 99.71% of molybdenum recovered from the molybdenum oxide concentrate compared to the case where no ammonium chloride was added.

In Examples 1 and 2, it was found that adding 10 g more than adding 5 g of ammonium chloride had a greater effect of inhibiting leaching of molybdenum in the molybdenum oxide concentrate (recovery rate of molybdenum oxide concentrate at 5 g was 99.86%). However, at 10 g it increases to 99.93%).

In Example 2 and Example 3, the leaching temperature was raised from room temperature to 70 ° C., and as a result, molybdenum leaching of molybdenum oxide concentrate was suppressed and copper was leached more.

In Examples 2, 4 and 5, it can be seen that as the leaching time increases, the molybdenum leaching of the molybdenum oxide concentrate is suppressed. In other words, with increasing reaction time, the elution of molybdenum in the leaching solution decreases, thereby increasing the recovery rate of molybdenum in the molybdenum oxide concentrate, and the content of copper in the concentrate decreases.

By washing in Examples 1 and 6, it is possible to minimize the chemicals remaining in the molybdenum oxide concentrate separated after leaching and to safely lower the grade of copper in the molybdenum oxide concentrate, and the loss of molybdenum in the test results It appeared to be insignificant.

Example 7 and Example 8 are to determine the dissolution rate of copper and other metals contained in the concentrate when leaching molybdenum oxide concentrate, and the leaching effect of metals such as copper, iron, lead, zinc and ammonium chloride You can see that it raises. In addition, as the leaching temperature increases, leaching of the metal and the like can be seen to increase.

As described above, those skilled in the art will understand that the present invention can be implemented in other specific forms without changing the technical spirit or essential features. Therefore, the above-described embodiments are to be understood as illustrative in all respects and not as restrictive. The scope of the present invention should be construed that all changes or modifications derived from the meaning and scope of the appended claims and their equivalents, rather than the detailed description, are included in the scope of the present invention.

The molybdenum oxide concentrate produced by the present invention can be used as a submaterial to make stainless steel, alloy steel and special steel. In addition, the molybdenum oxide concentrate can be used as a substitute for tungsten used in airplane parts, electrical materials, industrial motors and filaments.

Claims

A method for leaching impurities contained in a molybdenum oxide concentrate comprising leaching impurities of molybdenum oxide concentrate using a leaching solution containing ammonium chloride and hydrochloric acid.
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 leaching solution is a leaching method of impurities contained in the molybdenum oxide concentrate, characterized in that 5 to 20 parts by weight of ammonium 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.
The method of claim 1,

The 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,

Leaching is a method of leaching impurities contained in molybdenum oxide concentrate, characterized in that the temperature range of 20 ℃ to 90 ℃.
The method of claim 1,

A leaching method of impurities contained in molybdenum oxide concentrate, characterized in that leaching is carried out for 30 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 7, wherein

The method for 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 8,

The amount of the wash water is a leaching method of impurities contained in the molybdenum oxide concentrate, characterized in that 1/3 to 1 of the leaching solution.