WO2011052993A2 - Method for leaching impurities contained in molybdenum oxide concentrates - Google Patents

Method for leaching impurities contained in molybdenum oxide concentrates Download PDF

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WO2011052993A2
WO2011052993A2 PCT/KR2010/007428 KR2010007428W WO2011052993A2 WO 2011052993 A2 WO2011052993 A2 WO 2011052993A2 KR 2010007428 W KR2010007428 W KR 2010007428W WO 2011052993 A2 WO2011052993 A2 WO 2011052993A2
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leaching
molybdenum
molybdenum oxide
weight
oxide concentrate
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PCT/KR2010/007428
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French (fr)
Korean (ko)
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WO2011052993A3 (en
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임경미
송진곤
허천회
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주식회사 광양합금철
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/34—Obtaining molybdenum
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • 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 distributed 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.
  • 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.
  • the leaching method of impurities contained in the molybdenum oxide concentrate according to the present invention aims to solve the following problems.
  • 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 method of leaching impurities contained in the molybdenum oxide concentrate according to the present invention preferably includes leaching impurities of molybdenum oxide concentrate using a third leaching solution containing ammonium chloride, sodium chloride, calcium chloride and hydrochloric acid.
  • the molybdenum oxide concentrate is preferably obtained by roasting ore of molybdenum.
  • 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.
  • 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.
  • 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.
  • 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.
  • the leaching temperature is preferably 20 ° C. to 90 ° C., more preferably 60 ° C. to 80 ° C.
  • the leaching time is preferably 30 minutes to 180 minutes.
  • 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.
  • the separation step after the separation step, it is preferable to further include the step of washing the separated molybdenum oxide concentrate with washing water.
  • the volume of the washing water is preferably 1/3 to 1 of the leaching liquid volume.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • ammonium chloride, sodium chloride or calcium chloride serves as a dissolution inhibiting agent to dissolve molybdenum.
  • sodium chloride and calcium chloride reduce the amount of ammonium chloride used.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the amount of other ammonium chloride used in the present invention is preferably 3 to 10 parts by weight.
  • 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.
  • 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.
  • the amount of hydrochloric acid according to the present invention is preferably 8 to 20 parts by weight.
  • the water content is preferably 50 to 300 parts by weight. Usually about 100 parts by weight is an appropriate amount.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the reaction between hydrochloric acid and metal oxides is exothermic, it does not significantly affect the reaction rate even if the temperature of the leaching liquid is not high.
  • 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.
  • the leaching temperature according to the present invention is preferably 20 to 90 °C. This is because, if the leaching temperature is less than 20 °C has a problem that the speed of the leaching reaction is slow, and if it exceeds 90 °C there is a problem that the cost used to heat the leaching liquid is excessive.
  • the temperature of the leachate is approximately 60 o
  • the leaching temperature according to the present invention is 60 ° C. It is more preferable that it is -80 degreeC.
  • 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.
  • 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.
  • 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 the 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.
  • 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 °C to 350 °C. Drying apparatus is not particularly limited, it is common to use a rotary drying furnace.
  • 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).
  • 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.
  • 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 1 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).
  • 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 1 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).
  • 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 1 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).
  • 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 1 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).
  • 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.
  • 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.
  • 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.
  • 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 2 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 quality 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.
  • 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.
  • 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 quality of the 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.
  • 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.
  • 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.
  • Example 1 Composition of materials used in the test Molybdenum oxide concentrate (g) Water (mL) Sodium chloride (g) Calcium chloride (g) Ammonium Chloride (g) Hydrochloric acid (mL) Wash solution (mL) Sulfuric acid (mL) Temperature ( oC )
  • 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 1 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, thus exhibiting 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.
  • 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.
  • 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 in Examples 3 and 4 reduced the dissolution inhibiting effect of molybdenum oxide. can see.
  • 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.
  • Example 7 when the amount of ammonium chloride used was reduced from 5 g to 3 g, the dissolution inhibiting effect of molybdenum oxide appears to be reduced as in Examples 3 and 4.
  • Example 8 when using the amount of 3 g of ammonium chloride and hydrochloric acid to 12 mL, molybdenum oxide is largely dissolved.
  • 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.

Abstract

The method for leaching impurities contained in molybdenum oxide concentrates according to the present invention comprises a step in which impurities in a molybdenum oxide concentrate are leached by the use of a leaching solution selected from the group consisting of a first leaching solution comprising ammonium chloride, sodium chloride and hydrochloric acid, a second leaching solution comprising ammonium chloride, calcium chloride and hydrochloric acid, and a third leaching solution comprising ammonium chloride, sodium chloride, calcium chloride and hydrochloric acid. The leaching method according to the present invention has the advantage that it dispenses with the need for or minimises processing carried out in order to recover molybdenum dissolved in the leaching solution, since the majority of the molybdenum oxide concentrate is present in solid form after the leaching has been completed. Also, because the amount of ammonium chloride used is reduced, the leaching method according to the present invention can be expected to have the advantage of improved water quality, since it has the effect of reducing the total amount of nitrogen in the waste water which is discharged.

Description

산화몰리브덴 정광에 함유된 불순물의 침출방법Leaching method of impurities contained in molybdenum oxide concentrate
본 발명은 산화몰리브덴 정광에 함유된 불순물의 침출방법에 관한 것이다, 구체적으로 배소된 산화몰리브덴 정광 중에 함유된 동, 철, 납 및 아연 등의 불순물을 침출액을 이용하여 선택적으로 침출시킴으로써 양질의 산화몰리브덴 정광을 생산할 수 있는 침출방법에 관한 것이다.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.
몰리브덴(molybdenum)은 고열성, 부식방지성 및 용접성이 강하며, 스테인레스강, 합금강 및 특수강을 만드는데 부재료로 사용된다. 또한 몰리브덴은 비행기부품, 전기재, 산업전동기 및 필라멘트 등에 사용되는 텅스텐의 대체품으로도 사용되고 있다.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.
전세계 몰리브덴의 가채광량(금속량기준)은 약 8,600천 톤 정도로 2005년도 기준 연간수요량인 약 180천 톤과 비교해 볼 때, 앞으로 약 50년 동안 사용이 가능하다. 몰리브덴의 전 세계의 가채광량의 약 88%는 중국, 미국, 칠레, 캐나다 4개국에 편재되어 있다. 전세계 몰리브덴 시장에 있어서 지난 10년간의 수요 증가율은 5.2%이고, 공급 증가율은 3.8%로서 수요 증가율이 공급 증가율보다 높아지고 있는 실정이며, 2002년부터는 공급 부족현상이 나타나기 시작하였다. 현재 세계 광산에서 몰리브덴 정광의 생산량은 증가하고 있으나, 가공을 위한 배소공장의 생산능력 부족으로 인하여 공급이 부족한 병목현상을 나타내고 있다. 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, 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.
몰리브덴은 원광석인 유화몰리브덴(Molybdenite)으로부터 생산되는데, 이러한 원광석은 대부분 다른 유화광물과 함께 산출된다. 몰리브덴을 제강시 첨가되는 부재료로 사용하기 위하여, 유화몰리브덴 정광을 부유선광(flotation) 등의 선광(選鑛; mineral processing)공정에 의해 정광(精鑛; concentrates)을 얻은 후 배소로(焙燒爐; roaster)에서 배소(焙燒;roasting)한다. 그 후에 침출(浸出;leaching processing) 공정에서 몰리브덴을 제외한 금속 불순물을 용해 분리한다.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.
배소한 산화몰리브덴 정광 중에 함유되어 있는 불순물인 동, 철, 납 및 아연 등의 금속 불순물을 침출해 내기 위한 종래의 침출액 시약으로는 염산, 질산, 황산, 수산화암모늄, 염화철, 시안화소다 및 가성소다 등의 많은 화학 약품들이 있었다. 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.
이러한 침출액 시약들은 대부분 불순물을 용해시키지만, 동시에 많은 양의 몰리브덴을 함께 용해시키기도 한다. 그러므로 침출액에 용해된 몰리브덴을 회수할 필요성이 제기되었고, 용매추출방법, 이온교환수지 방법, 활성탄에 의한 흡착방법 등이 회수 용도로 이용되었다. 하지만 이러한 종래의 방법은 몰리브덴을 회수한 후 탈착시키는 공정 등 많은 부수 공정을 필요로 하게 되며, 매 공정마다 몰리브덴의 손실이 발생하게 되는 문제점이 있다. 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.
이러한 문제점을 해결하기 위하여, 본 발명자들은 산화몰리브덴 정광의 침출 방법에 대하여 지속적인 연구를 진행하여 왔다. 선행연구로서, 염화암모늄 및 염산을 침출액으로서 함께 사용하면 산화몰리브덴 정광 중에 있는 금속 불순물은 대부분이 용해되나 몰리브덴은 용해되지 않고 대부분 고체 상태로 존재한다는 점을 착안하여 한국특허출원 제10-2009-0009382호(출원일: 2009.02.05) 가 진행되었다.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.
이 후, 염화나트륨과 염화암모늄 및 염산을 포함하는 침출액을 사용하거나 염화칼슘과 염화암모늄 및 염산을 포함하는 침출액을 사용하거나 염화나트륨, 염화칼슘, 염화암모늄 및 염산을 포함하는 침출액을 사용함으로써 더 좋은 효과를 얻게 되었다. 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. .
본 발명에 따른 산화몰리브덴 정광에 함유된 불순물의 침출방법은 다음과 같은 해결과제를 목적으로 한다.The leaching method of impurities contained in the molybdenum oxide concentrate according to the present invention aims to solve the following problems.
첫째, 침출액에 용해되는 몰리브덴을 최소화하여, 몰리브덴의 사후적 회수공정을 최소화하거나 불필요하게 하고자 한다.First, to minimize molybdenum dissolved in the leachate, it is intended to minimize or unnecessary the subsequent recovery process of molybdenum.
둘째, 염화암모늄 등의 화학약품의 사용량을 감소시키고자 한다.Second, to reduce the amount of chemicals such as ammonium chloride.
셋째, 상대적으로 저렴한 약품을 사용가능하도록 한다.Third, make relatively cheap drugs available.
넷째, 방류되는 폐수로 인한 환경오염을 최소화하고자 한다.Fourth, to minimize environmental pollution caused by discharged wastewater.
본 발명의 해결과제는 이상에서 언급된 것들에 한정되지 않으며, 언급되지 아니한 다른 해결과제들은 아래의 기재로부터 당업자에게 명확하게 이해되어 질 수 있을 것이다.The problem of the present invention is not limited to those mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.
본 발명에 따른 산화몰리브덴 정광에 함유된 불순물의 침출방법은 염화암모늄, 염화나트륨 및 염산이 포함된 제1 침출액을 사용하여 산화몰리브덴 정광의 불순물을 침출하는 단계를 포함하는 것이 바람직하다.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.
본 발명에 따른 산화몰리브덴 정광에 함유된 불순물의 침출방법은 염화암모늄, 염화칼슘 및 염산이 포함된 제2 침출액을 사용하여 산화몰리브덴 정광의 불순물을 침출하는 단계를 포함하는 것이 바람직하다.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.
본 발명에 따른 산화몰리브덴 정광에 함유된 불순물의 침출방법은 염화암모늄, 염화나트륨, 염화칼슘 및 염산이 포함된 제3 침출액을 사용하여 산화몰리브덴 정광의 불순물을 침출하는 단계를 포함하는 것이 바람직하다.The method of leaching impurities contained in the molybdenum oxide concentrate according to the present invention preferably includes leaching impurities of molybdenum oxide concentrate using a third leaching solution containing ammonium chloride, sodium chloride, calcium chloride and hydrochloric acid.
본 발명에 따른 산화몰리브덴 정광에 함유된 불순물의 침출방법에 있어서, 산화몰리브덴 정광은 몰리브덴의 원광석을 배소하여 얻은 것이 바람직하다.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.
본 발명에 따른 산화몰리브덴 정광에 함유된 불순물의 침출방법에 있어서, 제1 침출액은 산화몰리브덴 정광 100 중량부에 대하여, 염화암모늄 3 내지 10 중량부, 염화 나트륨 3 내지 10 중량부, 염산 8 내지 20 중량부 및 물 50 내지 300 중량부를 사용하는 것이 바람직하다.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.
본 발명에 따른 산화몰리브덴 정광에 함유된 불순물의 침출방법에 있어서, 제2 침출액은 산화몰리브덴 정광 100 중량부에 대하여, 염화암모늄 3 내지 10 중량부, 염화칼슘 3 내지 10 중량부, 염산 8 내지 20 중량부 및 물 50 내지 300 중량부를 사용하는 것이 바람직하다.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.
본 발명에 따른 산화몰리브덴 정광에 함유된 불순물의 침출방법에 있어서, 제3 침출액은 산화몰리브덴 정광 100 중량부에 대하여, 염화암모늄 3 내지 10 중량부, 염화 나트륨 3 내지 10 중량부, 염화칼슘 3 내지 10 중량부, 염산 8 내지 20 중량부 및 물 50 내지 300 중량부를 사용하는 것이 바람직하다.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.
본 발명에 따른 산화몰리브덴 정광에 함유된 불순물의 침출방법에 있어서, 산화몰리브덴 정광의 무게(g)와 침출액의 부피(mL)의 비율이 1:1 내지 1:2인 것이 바람직하다.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.
본 발명에 따른 산화몰리브덴 정광에 함유된 불순물의 침출방법에 있어서, 침출 온도는 20oC 내지 90℃인 것이 바람직하며, 60oC 내지 80℃인 것이 더욱 바람직하다.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.
본 발명에 따른 산화몰리브덴 정광에 함유된 불순물의 침출방법에 있어서, 침출 시간은 30분 내지 180분인 것이 바람직하다.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.
본 발명에 따른 산화몰리브덴 정광에 함유된 불순물의 침출방법에 있어서, 침출이 종료된 후, 침출액 및 산화몰리브덴 정광을 분리하는 단계를 추가로 포함하는 것이 바람직하다.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.
본 발명에 따른 산화몰리브덴 정광에 함유된 불순물의 침출방법에 있어서, 분리단계 후에는, 분리된 산화몰리브덴 정광을 세척수로 세척하는 단계를 추가로 포함하는 것이 바람직하다.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.
본 발명에 따른 산화몰리브덴 정광에 함유된 불순물의 침출방법에 있어서, 세척단계의 경우, 세척수의 부피는 침출액 부피의 1/3 내지 1인 것이 바람직하다.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.
본 발명에 따른 침출방법에 의하면, 침출이 종료된 후 산화몰리브덴 정광은 대부분이 고체상태로 존재하므로, 침출액 중 용해되어 있는 몰리브덴을 회수하기 위한 공정이 불필요하거나 최소화되는 효과가 있다.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.
본 발명에 따른 침출방법에 의하면, 염화암모늄의 사용량이 감소하므로 방류되는 폐수 중 총 질소량을 감소시키는 효과가 있으므로 수질개선의 효과를 기대할 수 있다.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.
본 발명에 따른 침출방법에 의하면, 화학약품의 사용량도 감소되고, 상대적으로 저렴한 약품을 사용가능하게 하므로 생산성을 향상시키고, 경제성을 확보하는 효과가 있다.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.
본 발명의 효과는 이상에서 언급된 것들에 한정되지 않으며, 언급되지 아니한 다른 효과들은 아래의 기재로부터 당업자에게 명확하게 이해되어 질 수 있을 것이다.The effects of the present invention are not limited to those mentioned above, and other effects that are not mentioned will be clearly understood by those skilled in the art from the following description.
도 1은 암모늄 이온과 산화몰리브덴 이온의 Eh-pH 도표를 나타낸다. 1 shows an Eh-pH diagram of ammonium ions and molybdenum oxide ions.
이하에서는 본 발명에 따른 침출방법에 관하여 상세하게 설명하고자 한다. Hereinafter will be described in detail with respect to the leaching method according to the present invention.
본 발명에 따른 침출방법은 산화몰리브덴 정광에 함유된 불순물 동(copper), 납(lead), 철(iron) 및 아연(zinc) 등을 보다 효과적으로 침출할 수 있는 방법을 제공한다. 본 발명에 따른 침출방법의 경우, 몰리브덴의 용해는 억제되므로 산화몰리브덴은 용해되지 않고 고체 상태로 존재 되는 특징이 있다. 한편, 본 발명에 따른 산화몰리브덴 정광(MoO3: Molybdenum Trioxide)은 유화 몰리브덴 정광(MoS2 : Molybdenite Concentrate)을 배소(roasting)하여 얻은 것을 의미한다. 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).
본 발명에 따른 침출액은 산화몰리브덴 정광 중의 금속 불순물을 침출하기 위해 사용하는 수용액이다. 물, 염화암모늄 및 염산 또는 물, 염화나트륨, 염화암모늄 및 염산 또는 물, 염화칼슘, 염화암모늄 및 염산 또는 물, 염화나트륨, 염화칼슘, 염화암모늄 및 염산을 포함한다. 이러한 침출액은 산화몰리브덴 정광을 충분히 적셔줄 수 있도록 하는 것이 바람직하다. 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.
본 발명에 따른 침출방법은 염화나트륨과 염화암모늄 및 염산을 포함하는 제1 침출액을 사용하거나, 염화칼슘과 염화암모늄 및 염산을 포함하는 제2 침출액을 사용하거나, 염화나트륨, 염화칼슘, 염화암모늄 및 염산을 포함하는 제3 침출액을 사용하여 진행할 수 있다.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.
여기서 염화암모늄이나 염화나트륨 또는 염화칼슘은 몰리브덴을 용해되지 않도록 하는 용해억제재의 역할을 한다. 또한 염화나트륨과 염화칼슘은 염화암모늄의 사용량을 절감시키는 효과를 나타낸다. 그리고 염산은 동, 철 아연 및 몰리브덴 등을 용해시키는 역할을 하게 된다.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.
본 발명에 따른 침출액에 포함되는 염화암모늄 및 염산의 함량은 산화몰리브덴 정광의 품위에 따라 달라지게 된다. 예를 들면 철을 많이 함유하는 경우, 또는 동의 품위가 높은 경우에는 염산의 사용량이 상대적으로 증가하게 될 것이다.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.
광석의 원광 중 동, 철, 연, 아연 등은 품위가 일정하지 않고 다양하며, 특히 광석의 산지에 따라 성질이 다른 측면이 있다. 이에 배소된 몰리브덴 옥사이드 광석을 먼저 염산으로 침출 시험을 한다. 그리고 몰리브덴의 용해량을 분석한 후, 용해된 몰리브덴을 복합염으로 형성시킬 수 있는 염화암모늄 량을 산출하여 첨가한다. 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.
시험결과에 따르면, 염화나트륨의 사용만으로는 몰리브덴의 용해억제 효과가 낮으며, 소정의 염화암모늄을 함께 사용하여야 몰리브덴의 용해억제 효과가 좋은 것으로 나타났다.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.
본 발명에 따른 침출액에서, 염산의 양은 침출하고자 하는 불순물의 화학 당량에 대응하는 양에 대하여 20 내지 30%정도를 더 사용하는 것이 바람직하다.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.
본 발명에 따른 침출액에서, 염화암모늄의 양은 염화암모늄을 사용하지 않고 염산만을 사용하여 침출 시험을 하였을 경우에 용해되는 몰리브덴의 양을 고려하여, 그에 대응하는 화학 당량에 해당하는 양을 첨가하는 것이 바람직하다. 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.
본 발명에 따른 제1 침출액에는 염화암모늄, 염화나트륨 및 염산과 물이 포함된다. 구체적으로 본 발명에 따른 제1 침출액은 산화몰리브덴 정광 100 중량부에 대하여, 염화암모늄 3 내지 10 중량부, 염화 나트륨 3 내지 10 중량부, 염산 8 내지 20 중량부 및 물 50 내지 300 중량부를 사용하는 것이 바람직하다.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.
본 발명에 따른 제1 침출액에서, 염화암모늄이 3 중량부 미만이면 암모늄 이온이 부족하여, 염산에 의해 용해된 몰리브덴 옥사이드 이온을 암모늄 몰리브덴 옥사이드의 복합염으로 충분히 만들 수 없게 된다. 따라서, 침출액 중에 몰리브덴의 품위가 높아지는 문제점이 있다. 염화암모늄이 10 중량부를 초과하면 암모늄 이온과 몰리브덴 옥사이드 이온이 복합염을 형성한 후에도 암모늄 이온이 남아있게 되므로 경제적이지 못한 문제점이 있다. 따라서 본 발명에 다른 염화암모늄의 사용량은 3 내지 10 중량부인 것이 바람직하다.In the first leachate according to the present invention, when ammonium chloride is less than 3 parts by weight, the ammonium ions are insufficient, so that the molybdenum oxide ions dissolved by hydrochloric acid cannot be sufficiently made into a 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.
본 발명에 따른 제1 침출액에서, 염화나트륨의 사용량은 염화암모늄의 사용량을 대체하는 효과를 얻기위한 것이다. 염화나트륨이 3 중량부 미만이면 몰리브덴의 용해량이 증가되는 문제점이 있다. 염화나트륨이 10 중량부를 초과하면 화학약품의 낭비가 되므로 경제적이지 못한 문제점이 있다. 본 발명에 따른 염화나트륨의 사용량은 실험에 의하여 적정량이 결정될 수 있으며, 3 내지 10 중량부인 것이 바람직하다. 통상적으로 대략 5 중량부 정도가 적정량이다.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.
본 발명에 따른 제1 침출액에서, 염산의 양은 침출하고자 하는 불순물의 화학 당량에 대응하는 양에 대하여 20 내지 30%정도를 더 사용하는 것이 가능하다. 통상적으로 리칭실험을 하여 동, 철, 연, 아연 등을 용해하여 고체 내에 허용되는 품위(Cu 0.5% 이하, Pb 0.05% 이하)가 되는 최소한의 양을 사용하는 것이 바람직하며, 염산은 8 내지 20 중량부를 사용하는 것이 더욱 바람직하다. 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.
염산이 8 중량부 미만이면 고체 중 불순물이 허용되는 품위보다 높게 될 우려가 있다. 염산이 20 중량부를 초과하면 많은 양의 몰리브덴을 용해하게 되므로 염화암모늄이나 염화나트륨을 많이 사용해야 하는 문제점이 있고, 화학약품을 많이 사용하게 되면 비용과 설비의 부식 및 마모를 초래하게 되는 문제점이 파생된다. 따라서 본 발명에 따른 염산의 사용량은 8 내지 20 중량부인 것이 바람직하다.If the hydrochloric acid is less than 8 parts by weight, the impurities in the solid may be higher than the acceptable quality. 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.
본 발명에 따른 제1 침출액에서, 물의 사용량이 50 중량부 미만이면 광석이 침출액에 충분히 적셔지지 않을 우려와, 기계에 과부하가 걸릴 우려가 있다. 물이 300 중량부를 초과하면 시설이 커야하고 화학약품이 많이 필요하므로 비경제적인 문제점이 있다. 따라서 물의 함량은 50 내지 300 중량부인 것이 바람직하다. 통상적으로는 대략 100 중량부가 적정량이다.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.
본 발명에 따른 제2 침출액과 제3 침출액에 있어서, 염화칼슘의 사용량은 염화암모늄의 사용량을 대체하는 효과를 얻기 위한 것이다. 염화칼슘이 3 중량부 미만이면 염화암모늄의 사용량이 증가되는 문제점이 있다. 염화칼슘이 10 중량부를 초과하면 화학약품의 낭비가 되므로 경제적이지 못한 문제점이 있다. 따라서 본 발명에 따른 염화칼슘의 사용량은 3 내지 10 중량부가 바람직하다. 통상적으로는 대략 5 중량부 정도가 적정량이다.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.
본 발명에 따른 침출방법에 있어서, 산화몰리브덴정광의 무게(g)와 침출액의 부피(mL)의 비율은 화학약품의 농도 및 침출액의 점도에 따라 달라지지만, 대략 1:1 내지 1:2인 것이 바람직하며, 대략 1:1인 것이 더욱 바람직하다.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.
상기 비율이 1:1 미만이면 침출액과 광석의 접촉이 부족하므로 침출이 원활하지 않고 기계에 과부화가 생길 수 있으며, 1:2를 초과하면 시설의 과잉투자 및 화학약품의 과대사용의 우려가 있기 때문이다.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.
이하에서는 화학 반응식을 제시하면서, 본 발명에 따른 침출방법에 대하여 더욱 상세히 설명하고자 한다.Hereinafter, the leaching method according to the present invention will be described in more detail while presenting a chemical reaction formula.
본 발명에 따른 침출액에 포함되어 있는 염산은 산화몰리브덴 정광과 반응하여 동, 철, 납 및 아연을 용해시킬 뿐만 아니라 하기 반응식 1에서 나타낸 바와 같이 산화몰리브덴을 산화몰리브덴 이온(MoO4 -2)으로 용해시킨다.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.
[반응식 1] Scheme 1
HCl + MoO3 + H2O -> MoO4 -2 + 3H+ + Cl- HCl + MoO 3 + H 2 O -> MoO 4 -2 + 3H + + Cl -
상기 산화몰리브덴 이온은 염화암모늄과 반응하여 고체 상태로 변화된다. 이러한 변화는 도 1의 암모늄 이온과 산화몰리브덴 이온의 Eh-pH 도표에서 이온화 거동을 보면 알 수 있다. 이러한 변화는 산화몰리브덴이 pH 6.0 이상에서는 MoO4 -2로 이온화 되어 있으나, pH 5.0 이하에서는 MoO3로서 고체 상태로 존재하는 것과 일치한다. 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.
즉 하기 반응식 2에 나타낸 바와 같이 염화암모늄을 첨가하면 낮은 pH, 바람직하게는 pH 5.0 이하에서는 산화몰리브덴이 결정수를 함유한 암모늄 몰리브덴 옥사이드의 복합염을 만들어 고체 상태로 존재하게 되므로 몰리브덴 용해가 억제되는 것이다. 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.
[반응식 2] Scheme 2
2NH4Cl + MoO4 -2 + 3H+ + Cl- -> (NH3)2ㆍMoO3ㆍH2O + 3HCl 2NH 4 Cl + MoO 4 -2 + 3H + + Cl - -> (NH 3) 2 and MoO 3 and H 2 O + 3HCl
반응식 2에 나타난 바와 같이 염화암모늄을 사용하면 몰리브덴 옥사이드 복합염 형성시 결정수가 포함되므로 산화몰리브덴 정광의 무게는 증가하게 되고 고체 상태로 유지된다.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.
본 발명에 따른 침출방법에 있어서, 염산과 금속산화물(Cu, Zn, Fe, Pb, Mo etc)과의 반응은 발열반응이므로, 침출액의 온도가 높지 않아도 반응속도에 큰 영향을 미치지 아니한다. 그러나 NH4 + ion 과 MoO4 -2 ion이 결합하여 복합염을 형성하는 때에는 침출액의 온도가 일정 정도 높아야 반응속도가 향상될 수 있다.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.
이에 본 발명에 따른 침출 온도는 20 내지 90℃인 것이 바람직하다. 이는 침출 온도가 20℃ 미만이면 침출 반응의 속도가 늦어질 문제점이 있으며, 90℃를 초과하면 침출액을 가열하는데 사용되는 비용이 과다해질 문제점이 있기 때문이다.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 ℃ has a problem that the speed of the leaching reaction is slow, and if it exceeds 90 ℃ there is a problem that the cost used to heat the leaching liquid is excessive.
또한, 침출액의 온도를 대략 60oC 에서 Mo가 거의 용해되지 않는 용해억제 측면과, 온도 상승이 반응속도에 미치는 영향을 고려할 때, 본 발명에 따른 침출온도는 60℃ 내지 80℃인 것이 더욱 바람직하다.In addition, the temperature of the leachate is approximately 60oConsidering the dissolution inhibiting aspect in which Mo is hardly dissolved at C and the effect of temperature rise on the reaction rate, the leaching temperature according to the present invention is 60 ° C. It is more preferable that it is -80 degreeC.
한편, 침출시간은 반응속도와 관계가 있으며, 반응속도는 입도 분포의 영향을 받는다. 즉 입자의 사이즈 분포(particle size distribution)가 거칠면(coarse) 반응시간이 많이 필요하고, 입자의 사이즈 분포가 미세(fine)하면 반응시간이 상대적으로 적게 소요될 수 있다. 또한 반응속도는 교반(agitation)의 정도에 따라서도 영향을 받는다. 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.
이러한 제반 사항을 고려하여 본 발명에 따른 침출시간은 30분 내지 180분인 것이 바람직하다. 이는 침출시간이 30분 미만이면 침출 반응이 제대로 일어나지 않는 문제점이 발생가능하며, 180분을 초과하면 불필요한 경비손실 및 과잉 기계 설비의 우려가 있기 때문이다. 그리고 실험 결과에 따르면, 침출반응의 측면과 과잉 기계설비의 측면을 고려할 때, 침출시간은 60분인 것이 보다 적절하다고 볼 수 있다.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.
침출방법에 있어서 침출액의 초기 pH는 충분히 낮아야 하며 통상 1.0 이하인 것이 바람직하며, 침출이 끝난 후에는 2.0 이하인 것이 바람직하다.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.
본 발명은 침출이 종료된 후, 침출액과 산화몰리브덴 정광을 분리하는 단계를 추가로 포함할 수 있다. 침출액과 산화몰리브덴 정광을 분리하는 방법은 특별히 한정되지 않고, 중력 여과, 가압 여과, 감압 여과 및 필터 프레스 등의 여과 분리 및 원심 분리 등의 일반적인 방법을 사용할 수 있다. 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.
본 발명에 따른 침출방법은 침출액으로부터 분리된 산화몰리브덴 정광을 세척수로 세척하는 단계를 추가로 포함할 수 있다. 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.
본 발명에 따른 세척 단계는 침출액으로부터 분리된 산화몰리브덴 정광에 물리적으로 잔류하는 불순물, 바람직하게는 잔류 화학성분을 포함하는 불순물을 제거하기 위하여 수행하는 단계이다. 세척 단계는 산화몰리브덴 정광 중에 잔존하는 화학약품을 최소화할 수 있으며, 생산된 산화몰리브덴 정광 중 동의 품위를 안전하게 낮출 수 있다. 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.
본 발명에 따른 세척수는 침출액을 여과하여 침출액과 고체를 분리한 후, 여과된 고체를 세척하는 물을 의미한다. 본 발명에 따른 세척액은 세척수로 세척하여 여과된 액을 의미한다. 세척액에는 동, 몰리브덴, 철, 아연 등 여러 금속 이온들이 포함될 수 있다.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.
세척수는 혼입된 잔류화학성분을 씻어내기 위하여 사용되며, 또한 녹아있는 동 성분을 제거하기 위하여 사용된다. 세척수를 많이 사용하여 액의 pH가 높아지면 몰리브덴이 용해되어 나올 수 있으므로 유의하여야 한다. 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.
세척수는 산화몰리브덴 정광의 용도나 용해성을 고려하여 선택되는 것이 바람직하며, 물을 사용하는 것이 좋다. Washing water is preferably selected in consideration of the use and solubility of the molybdenum oxide concentrate, it is preferable to use water.
본 발명에 따른 세척수의 부피는 침출액의 부피의 1/3 내지 1인 것이 바람직하며, 약 1/2인 것이 더욱 바람직하다.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.
세척수의 부피가 침출액의 부피의 1/3 미만이면 산화몰리브덴 정광에 잔류하는 불순물 및 잔류 화학성분을 모두 제거하는 것이 곤란하며, 1을 초과하면 세척액에 몰리브덴옥사이드가 용해될 우려가 있다. 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.
본 발명에 따른 세척단계가 종료된 후의 세척수의 pH는 3.0 이하인 것이 바람직하다. 세척단계까지 종료된 산화몰리브덴 정광은 300℃ 내지 350℃의 온도범위에서 하소과정을 거쳐서 건조한다. 건조장치는 특별히 한정되지 않으며, 회전건조로를 사용하는 것이 일반적이다.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.
한편, 침출액 중에 존재하는 유가금속인 동은 폐철에 의한 동치환 반응으로 회수할 수 있다. On the other hand, copper, a valuable metal present in the leachate, can be recovered by a copper substitution reaction by waste iron.
이하에서 실시예를 통하여 본 발명을 구체적으로 설명하기로 한다. 그러나 하기의 실시예는 오로지 본 발명을 구체적으로 설명하기 위한 것으로 이들 실시예에 의해 본 발명의 범위를 한정하는 것은 아니다.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.
[ 실시예 1 ]Example 1
배소한 산화몰리브덴 정광 100g을 물 100mL, 염화나트륨 5g, 염화암모늄 5g 및 염산 15mL를 사용하여 70℃에서 60분 동안 침출 후 침출액과 산화몰리브덴 정광을 여과분리 하였다. 침출액과 산화몰리브덴정광을 분리한 다음 다시 물 50mL로 세척하여 여과하여 세척액과 산화몰리브덴정광을 얻었다(표1 참조). 침출이 종료된 산화몰리브덴 정광은 건조기에서 건조 후 시료를 채취하여 ICP분석기[Perkin-Elmers, 미국]로 분석하였다. 침출액과 세척액도 시료를 채취하여 ICP분석기로 분석하였다. 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.
그 결과, 침출액의 부피는 75mL이고, 세척액의 부피는 49mL 이었다. 침출 후 분리된 산화몰리브덴 정광의 무게는 94.93g 이었다. 산화몰리브덴 정광의 품위는 침출 전 몰리브덴이 54.33%이고, 동이 2.80% 이었다. 침출이 종료된 후에는 몰리브덴이 55.23%이고, 동이 0.146%이었다. 침출액의 품위는 몰리브덴이 0.01g/L이고, 동이 23.25 g/L이었다. 세척액의 품위는 몰리브덴이 0.01g/L이고, 동이 18.69 g/L 이었다.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.
[ 실시예 2 ]Example 2
실시예 1과 동일한 방법으로 실시하되, 염화나트륨 12g, 염화암모늄 5g 및 염산 15mL을 하였다(표1 참조). 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).
그 결과, 침출액의 부피는 71mL 세척액의 부피는 51mL 이었다. 침출 후 분리된 산화몰리브덴 정광의 무게는 95.66g 이었다. 산화몰리브덴 정광의 품위는 침출전 몰리브덴이 54.86% 이고 동이 2.83% 이었다. 침출이 종료된 후에는 몰리브덴이 57.34%이고, 동이 0.174%이었다. 침출액의 품위는 몰리브덴이 0.135g/L이고, 동이 23.6g/L이었다. 세척액의 품위는 몰리브덴이 0.058g/L이고, 동이 19.37 g/L 이었다.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.
[ 실시예 3 ]Example 3
실시예 1과 동일한 방법으로 실시하되, 염화나트륨 5g 염화암모늄 3g 및 염산 15mL를 사용하였다(표1 참조). 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).
그 결과, 침출액의 부피는 73.5mL이고, 세척액의 부피는 47mL 이었다. 침출 후 분리된 산화몰리브덴 정광의 무게는 95.93g이었다. 산화몰리브덴 정광의 품위는 침출전 몰리브덴이 55.22%이고, 동이 2.88%이었다. 침출이 종료된 후에는 몰리브덴이 57.54%이고, 동이 0.193%이었다. 침출액의 품위는 몰리브덴이 0.19g/L이고, 동이 24.32g/L이었다. 세척액의 품위는 몰리브덴이 0.171g/L이고, 동이 19.31 g/L이었다.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.
[ 실시예 4 ]Example 4
실시예 1과 동일한 방법으로 실시하되, 염화나트륨 5g, 염화암모늄 5g 및 염산 15mL를 사용하여 침출하였다(표1 참조). 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).
그 결과, 침출액의 부피는 80mL이고, 세척액의 부피는 49.5mL 이었다. 침출 후 분리된 산화몰리브덴 정광의 무게는 94.93g이었다. 산화몰리브덴 정광의 품위는 침출전 몰리브덴이 54.14%이고, 동이 2.98%이었다. 침출이 종료된 후에는 몰리브덴이 57.44%이고, 동이 0.23%이었다. 침출액의 품위는 몰리브덴이 0.234g/L이고, 동이 25.28g/L이었다. 세척액의 품위는 몰리브덴이 0.235g/L이고, 동이 14.92 g/L 이었다.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.
[ 실시예 5 ]Example 5
실시예 1과 동일한 방법으로 실시하되, 염화칼슘 5g, 염화암모늄 5g 및 염산 15mL를 사용하여 침출하였다(표1 참조). 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).
그 결과, 침출액의 부피는 76mL이고, 세척액의 부피는 49mL 이었다. 침출 후 분리된 산화몰리브덴 정광의 무게는 95.52g이었다. 산화몰리브덴 정광의 품위는 침출전 몰리브덴이 54.24%이고, 동이 2.76%이었다. 침출이 종료된 후에는 몰리브덴이 56.78%이고, 동이 0.212%이었다. 침출액의 품위는 몰리브덴이 0.01g/L이고, 동이 23.36g/L이었다. 세척액의 품위는 몰리브덴이 0.01g/L이고, 동이 15.95 g/L 이었다.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.
[ 실시예 6 ]Example 6
실시예 1과 동일한 방법으로 하되, 염화칼슘 10g, 염화암모늄 5g 및 염산 15mL를 사용하여 침출하였다(표1 참조). 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).
그 결과, 침출액의 부피는 70mL이고, 세척액의 부피는 51.5mL 이었다. 침출 후 분리된 산화몰리브덴 정광의 무게는 96.66g이었다. 산화몰리브덴 정광의 품위는 침출전 몰리브덴이 55.20%이고, 동이 2.78%이었다. 침출이 종료된 후에는 몰리브덴이 57.10%이고, 동이 0.254%이었다. 침출액의 품위는 몰리브덴이 0.026g/L이고, 동이 23.24g/L이었다. 세척액의 품위는 몰리브덴이 0.01g/L이고, 동이 17.56g/L 이었다.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.
[ 실시예 7 ]Example 7
실시예 1과 동일한 방법으로 하되, 염화칼슘 5g, 염화암모늄 3g 및 염산 15mL를 사용하여 침출하였다(표1 참조). 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).
그 결과, 침출액의 부피는 77mL이고, 세척액의 부피는 50mL 이었다. 침출 후 분리된 산화몰리브덴 정광의 무게는 95.87g이었다. 산화몰리브덴 정광의 품위는 침출 전 몰리브덴이 55.17%이고, 동이 2.82%이었다. 침출이 종료된 후에는 몰리브덴이 57.52%이고, 동이 0.218%이었다. 침출액의 품위는 몰리브덴이 0.207g/L이고, 동이 23.64g/L이었다. 세척액의 품위는 몰리브덴이 0.165g/L이고, 동이 15.84g/L 이었다.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.
[ 실시예 8 ]Example 8
실시예 1과 동일한 방법으로 하되, 염화칼슘 5g, 염화암모늄 3g 및 염산 12mL를 사용하여 침출하였다(표1 참조). 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).
그 결과, 침출액의 부피는 71mL이고, 세척액의 부피는 50mL 이었다. 침출 후 분리된 산화몰리브덴 정광의 무게는 94.35g이었다. 산화몰리브덴 정광의 품위는 침출전 몰리브덴이 55.09%이고, 동이 2.82%이었다. 침출이 종료된 후에는 몰리브덴이 57.46%이고, 동이 0.20%이었다. 침출액의 품위는 몰리브덴이 7.696g/L이고, 동이 23.87g/L이었다. 세척액의 품위는 몰리브덴이 6.59g/L이고, 동이 18.82g/L 이었다.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.
[ 실시예 9 ]Example 9
실시예 1과 동일한 방법으로 하되, 염화나트륨 3g, 염화칼슘 3g, 염화암모늄 4g 및 염산 15mL를 사용하여 침출하였다(표1 참조). 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).
그 결과, 침출액의 부피는 75mL이고, 세척액의 부피는 50mL이었다. 침출 후 분리된 산화몰리브덴 정광의 무게는 93.55g이었다. 산화몰리브덴 정광의 품위는 침출 전 몰리브덴이 55.60%이고, 동이 3.03%이었다. 침출이 종료된 후에는 몰리브덴이 58.16%이고, 동이 0.22%이었다. 침출액의 품위는 몰리브덴이 0.256g/L이고, 동이 25.58g/L이었다. 세척액의 품위는 몰리브덴이 0.215g/L이고, 동이 17.97g/L 이었다.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.
[ 비교예 1 ]Comparative Example 1
실시예 1과 동일한 방법으로 하되, 염화암모늄 12g 및 염산 15mL를 사용하여 침출하였다(표1 참조). 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).
그 결과, 침출액의 부피는 72.5mL이고, 세척액의 부피는 50mL 이었다. 침출 후 분리된 산화몰리브덴 정광의 무게는 98.08g이었다. 산화몰리브덴 정광의 품위는 침출전 몰리브덴이 55.44%이고, 동이 2.72%이었다. 침출이 종료된 후에는 몰리브덴이 56.52%이고, 동이 0.44%이었다. 침출액의 품위는 몰리브덴이 0.01g/L이고, 동이 19.18g/L이었다. 세척액의 품위는 몰리브덴이 0.01g/L이고, 동이 12.23g/L 이었다.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.
[ 비교예 2 ]Comparative Example 2
실시예 1과 동일한 방법으로 하되, 염산 15mL를 사용하여 침출하였다(표1 참조). In the same manner as in Example 1, but leached using 15 mL of hydrochloric acid (see Table 1).
그 결과, 침출액의 부피는 81mL이고, 세척액의 부피는 50mL 이었다. 침출 후 분리된 산화몰리브덴 정광의 무게는 90.34g이었다. 산화몰리브덴 정광의 품위는 침출전 몰리브덴이 54.73%이고, 동이 2.89%이었다. 침출이 종료된 후에는 몰리브덴이 57.76%이고, 동이 0.258%이었다. 침출액의 품위는 몰리브덴이 22.25g/L이고, 동이 23.97g/L이었다. 세척액의 품위는 몰리브덴이 15.04g/L이고, 동이 14.23g/L 이었다.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.
[ 비교예 3 ]Comparative Example 3
실시예 1과 동일한 방법으로 하되, 황산 2mL을 첨가하고 침출반응은 상온에서 실시하였다(표1 참조).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).
그 결과, 침출액의 부피는 88mL이고, 세척액의 부피는 50mL 이었다. 침출 후 분리된 산화몰리브덴 정광의 무게는 86.27g이었다. 산화몰리브덴 정광의 품위는 침출전 몰리브덴이 55.49%이고, 동이 2.90%이었다. 침출이 종료된 후에는 몰리브덴이 56.93%이고, 동이 0.30%이었다. 침출액의 품위는 몰리브덴이 59.87g/L이고, 동이 25.36g/L이었다. 세척액의 품위는 몰리브덴이 22.14g/L이고, 동이 8.28g/L 이었다.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.
[ 비교예 4 ]Comparative Example 4
실시예 1과 동일한 방법으로 하되, 염화나트륨 12g과 염산 15mL를 사용하여 침출하였다(표1 참조). 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).
그 결과, 침출액의 부피는 77mL이고, 세척액의 부피는 51.5mL 이었다. 침출 후 분리된 산화몰리브덴 정광의 무게는 94.33g이었다. 산화몰리브덴 정광의 품위는 침출전 몰리브덴이 55.93%이고, 동이 2.82%이었다. 침출이 종료된 후에는 몰리브덴이 57.47%이고, 동이 0.17%이었다. 침출액의 품위는 몰리브덴이 6.13g/L이고, 동이 24.03g/L이었다. 세척액의 품위는 몰리브덴이 4.81g/L이고, 동이 15.71g/L 이었다.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 quality 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.
[ 비교예 5 ]Comparative Example 5
실시예 1과 동일한 방법으로 하되, 염화나트륨 15g과 염산 15mL를 사용하여 침출하였다(표1 참조). 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).
그 결과, 침출액의 부피는 82mL이고, 세척액의 부피는 50mL 이었다. 침출 후 분리된 산화몰리브덴 정광의 무게는 94.51g이었다. 산화몰리브덴 정광의 품위는 침출전 몰리브덴이 54.63%이고, 동이 2.92%이었다. 침출이 종료된 후에는 몰리브덴이 56.98%이고, 동이 0.196%이었다. 침출액의 품위는 몰리브덴이 6.53g/L이고, 동이 24.41g/L이었다. 세척액의 품위는 몰리브덴이 4.83g/L이고, 동이 14.73g/L 이었다.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.
[ 비교예 6 ]Comparative Example 6
실시예 1과 동일한 방법으로 하되, 염화칼슘 12g과 염산 15mL를 사용하여 침출하였다(표1 참조). 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).
그 결과, 침출액의 부피는 82.5mL이고, 세척액의 부피는 50mL 이었다. 침출 후 분리된 산화몰리브덴 정광의 무게는 94.33g이었다. 산화몰리브덴 정광의 품위는 침출전 몰리브덴이 55.33%이고, 동이 2.81%이었다. 침출이 종료된 후에는 몰리브덴이 57.43%이고, 동이 0.196%이었다. 침출액의 품위는 몰리브덴이 9.89g/L이고, 동이 23.38g/L이었다. 세척액의 품위는 몰리브덴이 6.71g/L이고, 동이 12.55g/L 이었다.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 quality of the 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.
[ 비교예 7 ]Comparative Example 7
실시예 1과 동일한 방법으로 하되, 염화칼슘 15g과 염산 15mL를 사용하여 침출하였다(표1 참조). 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).
그 결과, 침출액의 부피는 84.5mL이고, 세척액의 부피는 51mL 이었다. 침출 후 분리된 산화몰리브덴 정광의 무게는 93.1g이었다. 산화몰리브덴 정광의 품위는 침출전 몰리브덴이 54.92%이고, 동이 2.84%이었다. 침출이 종료된 후에는 몰리브덴이 57.82%이고, 동이 0.21%이었다. 침출액의 품위는 몰리브덴이 9.03g/L이고, 동이 23.73g/L이었다. 세척액의 품위는 몰리브덴이 6.45g/L이고, 동이 12.57g/L 이었다.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.
표 1 시험시 사용한 물질들의 조성
산화몰리브덴정광(g) 물(mL) 염화나트륨(g) 염화칼슘(g) 염화암모늄(g) 염산(mL) 세척액(mL) 황산(mL) 온도(oC)
실시예1 100 100 5 - 5 15 50 - 70
실시예2 100 100 12 - 5 15 50 - 70
실시예3 100 100 5 - 3 15 50 - 70
실시예4 100 100 5 - 4 15 50 - 70
실시예5 100 100 - 5 5 15 50 - 70
실시예6 100 100 - 10 5 15 50 - 70
실시예7 100 100 - 5 3 15 50 - 70
실시예8 100 100 - 5 3 12 50 - 70
실시예9 100 100 3 3 4 15 50 - 70
비교예1 100 100 - - 12 15 50 - 70
비교예2 100 100 - - - 15 50 - 70
비교예3 100 100 - - - - 50 2 상온
비교예4 100 100 12 - - 15 50 - 70
비교예5 100 100 15 15 50 70
비교예6 100 100 12 15 50 70
비교예7 100 100 15 15 50 70
Table 1 Composition of materials used in the test
Molybdenum oxide concentrate (g) Water (mL) Sodium chloride (g) Calcium chloride (g) Ammonium Chloride (g) Hydrochloric acid (mL) Wash solution (mL) Sulfuric acid (mL) Temperature ( oC )
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
여기서 상기 전 시험 중 침출시간은 60분이며, 상기 상온은 25℃를 의미한다. 상기 산화몰리브덴 정광은 [Codelco 광산의 유화몰리브덴 정광을 광양합금철의 배소로에서 배소한 정광, 광양합금철, 한국] 이며, 상기 염화나트륨은 염화나트륨 99.5% 이상, [WAKO, 일본] 이며, 상기 염화칼슘은 염화칼슘 95.0% 이상, [JUNSEI, 일본] 이며, 상기 염화암모늄은 염화암모늄 99.5% 이상, [JUNSEI, 일본]이며, 상기 염산은 염산 36%이고, 비중=1.18, [㈜동우화인켐, 한국]이며, 상기 황산은 황산 96%이고, 비중=1.84, [㈜동우화인켐, 한국] 이다.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 the 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].
표 2 본 발명의 실시예 및 비교예에 따른 회수율
침출액에서의회수율(%) 세척액에서의 회수율(%) 정광에서의 회수율(%)
몰리브덴 동 몰리브덴 동 몰리브덴 동
실시예1 0.00 62.32 0.00 32.73 100 4.95
실시예2 0.02 59.21 0.01 34.91 99.98 5.88
실시예3 0.03 62.06 0.01 31.51 99.96 6.43
실시예4 0.03 67.83 0.02 24.77 99.94 7.40
실시예5 0.00 64.34 0.00 28.32 100 7.34
실시예6 0.00 58.59 0.00 32.57 100 8.84
실시예7 0.03 64.52 0.01 28.07 99.96 7.41
실시예8 0.99 60.00 0.60 33.32 98.41 6.68
실시예9 0.03 63.38 0.02 29.68 99.95 6.94
비교예1 0.00 61.70 0.00 22.45 100 15.84
비교예2 3.29 67.27 1.37 24.65 95.33 8.08
비교예3 9.49 76.84 1.99 14.25 88.51 8.91
비교예4 0.86 65.62 0.45 28.69 98.69 5.69
비교예5 0.98 68.47 0.44 25.19 98.58 6.34
비교예6 1.48 68.69 0.61 22.34 97.92 8.97
비교예7 1.39 70.56 0.60 22.56 98.01 6.88
TABLE 2 Recovery rate according to the examples and comparative examples of the present invention
Recovery rate in leachate (%) % Recovery in Washing Liquid % Recovery from concentrate
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
비교예 1에 있어서, 염화암모늄 12g 및 염산 15mL를 사용하여, 산화몰리브덴 정광 중의 동의 침출이 85.15% 이며, 몰리브덴의 침출이 전혀 발생되지 않으므로 100% 의 억제효과를 나타낸다. 이를 실시예 1과 비교해볼 때 염화암모늄 12g 대신 염화나트륨 5g 과 염화암모늄 5g 을 사용했을때 더 좋은 결과를 보임을 알 수 있다. 이 경우, 화학약품 절감 효과와 염화암모늄 사용량 감소 효과로 인해, 수질 환경개선에도 도움을 주게 된다.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, thus exhibiting 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.
비교예 2에 있어서, 염화암모늄을 첨가하지 않고 염산만 사용하여 산화몰리브덴 정광을 침출한 경우, 동은 91.92%가 용출되므로 좋은 결과를 나타내었다. 그러나 몰리브덴은 3.66%가 침출액에 용해되므로 막대한 몰리브덴의 손실을 가져온다. In Comparative Example 2, when molybdenum oxide concentrate was leached using only hydrochloric acid without adding ammonium chloride, copper showed a good result because 91.92% was eluted. However, molybdenum dissolves in 3.66% of the leachate, resulting in a significant loss of molybdenum.
비교예 3에 있어서, 황산을 사용할 때도 동은 91.09%가 용출되므로 좋은 결과를 나타내었다. 그러나 몰리브덴은 11.48%가 침출액에 용해되므로 막대한 몰리브덴의 손실을 가져온다.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.
비교예 4에 있어서, 염화암모늄을 첨가하지 않고 염화나트륨 12g과 염산 15mL 를 사용하여 산화몰리브덴 정광을 침출한 경우, 동은 94.31%가 용출되므로 좋은 결과를 나타내었다. 그러나 몰리브덴은 1.31%가 침출액에 용해되므로 막대한 몰리브덴의 손실을 가져온다.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.
비교예 5에 있어서, 염화암모늄을 첨가하지 않고 염화나트륨 15g으로 증가시켜 사용하고, 염산 15mL 를 사용하여도 성적의 향상은 없었다.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.
비교예 6에 있어서, 염화암모늄을 첨가하지 않고 염화칼슘 12g과 염산 15mL 를 사용하여 산화몰리브덴 정광을 침출한 경우, 동은 91.03% 용출되므로 좋은 결과를 나타내었다. 그러나 몰리브덴은 2.09%가 침출액에 용해되므로 막대한 몰리브덴의 손실을 가져온다.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.
비교예 7에 있어서, 염화암모늄을 첨가하지 않고 염화칼슘을 15g으로 증가시켜 사용하고 염산 15mL를 사용하여도 성적의 향상은 없다. 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.
이상의 비교시험에서 나타난 결과를 보면, 염화암모늄을 사용하지 않고 염화나트륨이나 염화칼슘만을 사용하면 산화몰리브덴의 용해를 완전히 억제할 수 없으며 염화나트륨이나 염화칼슘을 염화암모늄과 같이 사용할 때 산화몰리브덴의 용해 상승 억제효과가 있음을 알 수 있다.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.
실시예 1에 있어서, 염화나트륨 5g과 염화암모늄을 5g첨가하거나, 실시예 5에서 염화칼슘 5g과 염화암모늄 5g을 첨가하면, 비교예 1의 염화암모늄 12g 첨가와 같은 성적을 나타내면서 화학약품의 사용을 감소시키는 효과가 있다.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.
실시예 2에 있어서, 염화나트륨을 12g으로 증가시켜 사용하는 것은 성적의 향상에 도움이 되지 않으며, 실시예 3과 실시예 4에서 염화암모늄의 사용량을 과다히 감소하면 산화몰리브덴의 용해억제작용이 감소 됨을 볼 수 있다.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 in Examples 3 and 4 reduced the dissolution inhibiting effect of molybdenum oxide. can see.
실시예 6에 있어서, 실시예 5의 염화칼슘 5g으로부터 염화칼슘 10g으로 증가시켜 사용할 때 성적의 변화는 별반 없으나 약품의 사용량이 과다하다.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.
실시예 7에 있어서, 염화암모늄 사용량을 5g에서 3g으로 감소시켜 사용하는 경우에는, 실시예 3 및 실시예 4에서와 마찬가지로 산화몰리브덴의 용해억제 효과가 감소하는 것으로 나타난다.In Example 7, when the amount of ammonium chloride used was reduced from 5 g to 3 g, the dissolution inhibiting effect of molybdenum oxide appears to be reduced as in Examples 3 and 4.
실시예 8에 있어서, 염화암모늄 3g과 염산의 사용량을 12mL로 감소시켜 사용하는 경우에는 산화몰리브덴이 많이 용해된다.In Example 8, when using the amount of 3 g of ammonium chloride and hydrochloric acid to 12 mL, molybdenum oxide is largely dissolved.
실시예 9에 있어서, 염화나트륨 3g과 염화칼슘 3g 및 염화암모늄 4g을 사용하여 침출하는 경우에도 실시예 3이나 실시예 4와 같은 좋은 결과를 나타낸다.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.
본 명세서에서 설명되는 실시예와 첨부된 도면은 본 발명에 포함되는 기술적 사상의 일부를 예시적으로 설명하는 것에 불과하다. 따라서, 본 명세서에 개시된 실시예들은 본 발명의 기술적 사상을 한정하기 위한 것이 아니라 설명하기 위한 것이므로, 이러한 실시예에 의하여 본 발명의 기술 사상의 범위가 한정되는 것은 아님은 자명하다. 본 발명의 명세서 및 도면에 포함된 기술적 사상의 범위 내에서 당업자가 용이하게 유추할 수 있는 변형 예와 구체적인 실시 예는 모두 본 발명의 권리범위에 포함되는 것으로 해석되어야 할 것이다.The embodiments described in the present specification and the accompanying drawings merely illustrate some of the technical ideas included in the present invention. Therefore, since the embodiments disclosed herein are not intended to limit the technical spirit of the present invention but to explain, it is obvious that the scope of the technical spirit of the present invention is not limited by these embodiments. Modifications and specific embodiments that can be easily inferred by those skilled in the art within the scope of the technical idea included in the specification and drawings of the present invention should be construed as being included in the scope of the present invention.

Claims (12)

  1. 산화몰리브덴에 함유된 불순물을 침출시키는 방법에 있어서,       In the method of leaching impurities contained in molybdenum oxide,
    염화암모늄, 염화나트륨 및 염산이 포함된 제1 침출액, 염화암모늄, 염화칼슘 및 염산이 포함된 제2 침출액 및 염화암모늄, 염화나트륨, 염화칼슘 및 염산이 포함된 제3 침출액으로 이루어진 군 중에서 선택되는 어느 하나의 침출액을 사용하여 산화몰리브덴 정광의 불순물을 침출하는 단계를 포함하는 것을 특징으로 하는 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 the impurities of molybdenum oxide concentrate using
    산화몰리브덴 정광에 함유된 불순물의 침출방법.Method for leaching impurities contained in molybdenum oxide concentrate.
  2. 제1항에 있어서,The method of claim 1,
    상기 산화몰리브덴 정광은 몰리브덴의 원광석을 배소하여 얻은 것을 특징으로 하는 산화몰리브덴 정광에 함유된 불순물의 침출방법.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.
  3. 제1항에 있어서,The method of claim 1,
    상기 제1 침출액은 산화몰리브덴 정광 100 중량부에 대하여, 염화암모늄 3 내지 10 중량부, 염화 나트륨 3 내지 10 중량부, 염산 8 내지 20 중량부 및 물 50 내지 300 중량부를 사용하는 것을 특징으로 하는 산화몰리브덴 정광에 함유된 불순물의 침출방법.The first leachate is characterized in that the use of 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. Method for leaching impurities contained in molybdenum concentrate.
  4. 제1항에 있어서,The method of claim 1,
    상기 제2 침출액은 산화몰리브덴 정광 100 중량부에 대하여, 염화암모늄 3 내지 10 중량부, 염화칼슘 3 내지 10 중량부, 염산 8 내지 20 중량부 및 물 50 내지 300 중량부를 사용하는 것을 특징으로 하는 산화몰리브덴 정광에 함유된 불순물의 침출방법.The second leaching solution is used molybdenum oxide, characterized in that 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 based on 100 parts by weight of molybdenum oxide concentrate. Method of leaching impurities contained in concentrate.
  5. 제1항에 있어서,The method of claim 1,
    상기 제3 침출액은 산화몰리브덴 정광 100 중량부에 대하여, 염화암모늄 3 내지 10 중량부, 염화 나트륨 3 내지 10 중량부, 염화칼슘 3 내지 10 중량부, 염산 8 내지 20 중량부 및 물 50 내지 300 중량부를 사용하는 것을 특징으로 하는 산화몰리브덴 정광에 함유된 불순물의 침출방법.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.
  6. 제1항에 있어서,The method of claim 1,
    상기 산화몰리브덴 정광의 무게(g)와 침출액의 부피(mL)의 비율이 1:1 내지 1:2인 것을 특징으로 하는 산화몰리브덴 정광에 함유된 불순물의 침출방법.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.
  7. 제1항에 있어서, The method of claim 1,
    침출 온도는 20oC 내지 90℃인 것을 특징으로 하는 산화몰리브덴 정광에 함유된 불순물의 침출방법.The leaching temperature is leached method of impurities contained in molybdenum oxide concentrate, it characterized in that a 20 o C to 90 ℃.
  8. 제7항에 있어서,The method of claim 7, wherein
    침출 온도는 60oC 내지 80℃인 것을 특징으로 하는 산화몰리브덴 정광에 함유된 불순물의 침출방법.The leaching temperature is 60 o C to 80 ℃ leaching method of impurities contained in the molybdenum oxide concentrate.
  9. 제1항에 있어서,The method of claim 1,
    침출 시간은 30분 내지 180분인 것을 특징으로 하는 산화몰리브덴 정광에 함유된 불순물의 침출방법.The leaching time is a leaching method of impurities contained in the molybdenum oxide concentrate, characterized in that 30 minutes to 180 minutes.
  10. 제1항에 있어서,The method of claim 1,
    침출이 종료된 후, 침출액 및 산화몰리브덴 정광을 분리하는 단계를 추가로 포함하는 것을 특징으로 하는 산화몰리브덴 정광에 함유된 불순물의 침출방법.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.
  11. 제10항에 있어서,The method of claim 10,
    상기 분리단계 후에는, 상기 분리된 산화몰리브덴 정광을 세척수로 세척하는 단계를 추가로 포함하는 것을 특징으로 하는 산화몰리브덴 정광에 함유된 불순물의 침출방법.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.
  12. 제10항에 있어서,The method of claim 10,
    상기 세척단계의 경우, 상기 세척수의 부피는 침출액 부피의 1/3 내지 1인 것을 특징으로 하는 산화몰리브덴 정광에 함유된 불순물의 침출방법.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.
PCT/KR2010/007428 2009-10-28 2010-10-27 Method for leaching impurities contained in molybdenum oxide concentrates WO2011052993A2 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4083921A (en) * 1977-01-03 1978-04-11 Kennecott Copper Corporation Purifying molybdenum flotation concentrates
KR20040019292A (en) * 2001-05-09 2004-03-05 하.체. 스타르크 게엠베하 Production of Pure Molybdenum Oxide from Low Grade Molybdenite Concentrates
KR20080064516A (en) * 2007-01-05 2008-07-09 서울샤프중공업 주식회사 Removal method and system for copper
US20080166280A1 (en) * 2006-11-16 2008-07-10 Albemarle Netherlands B.V. Purification Of Molybdenum Technical Oxide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4083921A (en) * 1977-01-03 1978-04-11 Kennecott Copper Corporation Purifying molybdenum flotation concentrates
KR20040019292A (en) * 2001-05-09 2004-03-05 하.체. 스타르크 게엠베하 Production of Pure Molybdenum Oxide from Low Grade Molybdenite Concentrates
US20080166280A1 (en) * 2006-11-16 2008-07-10 Albemarle Netherlands B.V. Purification Of Molybdenum Technical Oxide
KR20080064516A (en) * 2007-01-05 2008-07-09 서울샤프중공업 주식회사 Removal method and system for copper

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