CN113249594B - Method for efficiently recovering molybdenum and rhenium from ion adsorption type molybdenum-rhenium ore - Google Patents

Method for efficiently recovering molybdenum and rhenium from ion adsorption type molybdenum-rhenium ore Download PDF

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CN113249594B
CN113249594B CN202011545662.9A CN202011545662A CN113249594B CN 113249594 B CN113249594 B CN 113249594B CN 202011545662 A CN202011545662 A CN 202011545662A CN 113249594 B CN113249594 B CN 113249594B
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rhenium
molybdenum
ore
ion adsorption
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CN113249594A (en
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赵鸿
张博
李超
黄凡
柳林
王均
赵九江
周利敏
李欣尉
屈文俊
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National Geological Experimental Testing Center china Geological Survey
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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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • 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
    • C22B3/065—Nitric 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
    • 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
    • C22B3/08—Sulfuric acid, other sulfurated 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
    • 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
    • C22B61/00—Obtaining metals not elsewhere provided for in this subclass
    • 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

Abstract

The invention relates to a method for efficiently recovering molybdenum and rhenium from ion adsorption type molybdenum-rhenium ore, belonging to the field of comprehensive utilization of mineral resources. The method of the invention comprises the following steps: (1) crushing the ion adsorption type molybdenum-rhenium ore to a particle size range of 0.15-1 mm; (2) uniformly mixing the ion adsorption type molybdenum-rhenium ore crushed in the step (1) with an additive, and roasting at a low temperature to obtain a roasted sample; (3) and (3) crushing the roasted sample obtained in the step (2) to a particle size range of 0.025-0.15 mm, leaching the roasted sample by adopting an acidic solution, and carrying out solid-liquid separation to obtain a leaching solution. According to the invention, through low-temperature roasting, the roasting temperature is controlled to be 150-250 ℃, so that the loss of molybdenum and rhenium in the roasting process is avoided; meanwhile, the roasting temperature is obviously reduced, and the effects of saving energy and reducing consumption are achieved; the activation of the ion adsorption type molybdenum-rhenium ore is realized through low-temperature roasting, so that the recovery rates of molybdenum and rhenium are improved, the recovery rate of rhenium in the method reaches over 90 percent, and the recovery rate of molybdenum reaches over 95 percent.

Description

Method for efficiently recovering molybdenum and rhenium from ion adsorption type molybdenum-rhenium ore
Technical Field
The invention relates to a method for efficiently recovering molybdenum and rhenium from ion adsorption type molybdenum-rhenium ore, belonging to the field of comprehensive utilization of mineral resources.
Background
Molybdenum and rhenium are important strategic resources, and molybdenum has the characteristics of high melting point, high strength, corrosion resistance and the like, so that the molybdenum is widely applied to the fields of steel industry, nonferrous metallurgy, petrochemical industry and the like, wherein the molybdenum consumed by the steel industry accounts for about 70-80% of the total consumption of the molybdenum, and is used for manufacturing various structural alloy steels, stainless steels, tool steels and high-speed steels; rhenium has excellent creep resistance and catalytic performance and is widely applied to the fields of aerospace, petrochemical industry and the like, wherein about 80 percent of rhenium is used for manufacturing single crystal blades of aero-engines, and about 20 percent of rhenium is used for producing petroleum hydrogenation catalysts.
The content of molybdenum in nature is very low, and the abundance of molybdenum in the earth crust is 1.1 multiplied by 10 -6 More than 20 known molybdenum ores, wherein the ore with the largest reserve and the most industrial value is molybdenite, which accounts for about 98 percent of the exploitation amount of molybdenum at home and abroad; rhenium has no independent mineral in nature, and the abundance of rhenium in the crust is only 0.7X 10 -9 Predominantly present in the form of isomorphs in the porphyry molybdenite, which is usually recovered as a by-product in the molybdenum concentrate smelting process. Molybdenum grade in molybdenum-rhenium ore found in Wuliqing of Guizhou is 0.1% -0.4%, rhenium grade is 20-40 g/t, and the molybdenum-rhenium ore reaches industrial grade, but detailed mineral structure research on the ore shows that no obvious molybdenum-containing mineral exists in the ore, the main phase structure of the mineral is quartz and clay mineral, and positive correlation exists between the distribution of rhenium and molybdenum and the clay mineral. Finally, the molybdenum-rhenium ore of Wulicheng plateau in Guizhou is proved that a small amount of rhenium is enriched from seawater in the deposition process of mudstone, the geological action occurs in the later period, the molybdenite existing on the periphery is melted by hydrothermal solution and decomposed into molybdenum and rhenium ions which are absorbed and enriched by clay minerals in the mudstone, and the novel ion-absorption type molybdenum-rhenium ore is formed.
Molybdenum and rhenium are extracted from rhenium-containing molybdenum concentrate, molybdenum sulfide and rhenium sulfide in minerals are oxidized into high-valence molybdenum oxide and rhenium oxide, and then the high-valence molybdenum oxide and rhenium oxide are prepared into ammonium molybdate and ammonium rhenate through leaching, impurity removal, extraction and other processes, and the rhenium-containing molybdenum concentrate is mainly oxidized by an oxidizing roasting method and a pressure oxidation method, wherein the main advantages and disadvantages are shown in table 1.
Table 1 main oxidation process of rhenium-containing molybdenum concentrate
Figure GDA0003155263800000021
The oxidation roasting method oxidizes molybdenum sulfide in molybdenum concentrate into molybdenum oxide calcine through oxidation roasting, the used oxidant is usually air or oxygen-enriched air, the oxidation roasting method has the characteristics of low cost, high production efficiency and the like, and the oxidation roasting method is a main molybdenum concentrate oxidation process in the world at present, and more than 80% of molybdenum oxide calcine is produced by the oxidation roasting process. The equipment used in the oxidation roasting method mainly comprises a multi-hearth furnace and a rotary kiln, the roasting temperature is generally controlled at 500-650 ℃, but molybdenum and rhenium in the ion adsorption type rare earth ore mainly exist in clay minerals in an ion adsorption mode, and Re 2 O 7 Sublimation at 273 ℃ MoO 3 Obviously sublime at 650 ℃, if the process is adopted to treat the ion adsorption type molybdenum-rhenium ore, the recovery rate of molybdenum and rhenium cannot be ensured, a spraying device is required to be arranged at the rear end to recover the volatilized molybdenum and rhenium, and the process is complex; on the other hand, the oxidizing-roasting method mainly provides heat through the oxidation reaction of sulfur in molybdenite, but the ion-adsorption-type molybdenum-rhenium ore has a very low sulfur content, and is difficult to generate enough heat to maintain the oxidation reaction, and the oxidizing-roasting method is not suitable for treating the ion-adsorption-type molybdenum-rhenium ore because it requires an external heat source to supplement the heat, which is high in cost.
The pressure oxidation method is mainly characterized in that under the conditions of high temperature and high pressure, molybdenum sulfide and rhenium sulfide are oxidized into molybdenum oxide and rhenium oxide by using a proper oxidant in a solution, then impurities are removed, extraction and precipitation are carried out for recovery, the temperature is usually controlled to be 200-300 ℃ in the production process, and the pressure is usually controlled to be 1-5 MPa. For the ion adsorption type molybdenum-rhenium ore, molybdenum and rhenium exist in an ion adsorption form, and the pressure oxidation method can ensure higher recovery rates of molybdenum and rhenium, but the process is carried out under the conditions of high temperature and high pressure, has higher requirements on the safety of production, simultaneously, the used reagent has stronger corrosivity, needs to be produced in special high-temperature-resistant, high-pressure-resistant and corrosion-resistant equipment, and has higher production cost, so the pressure oxidation method is not suitable for treating the ion adsorption type molybdenum-rhenium ore.
In conclusion, as a novel molybdenum-rhenium ore, a treatment method with reasonable technical economy is not available at present. Therefore, the development of a high-efficiency clean recovery process of molybdenum and rhenium for the ion adsorption type molybdenum-rhenium ore is urgent.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a low-temperature roasting method to realize the high-efficiency recovery of molybdenum and rhenium in the ion adsorption type molybdenum-rhenium ore.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for efficiently recovering molybdenum and rhenium from ion adsorption type molybdenum-rhenium ore, comprising the following steps:
(1) crushing the ion adsorption type molybdenum-rhenium ore to a particle size range of 0.15-1 mm;
(2) uniformly mixing the ion adsorption type molybdenum-rhenium ore crushed in the step (1) with an additive, and roasting at a low temperature to obtain a roasted sample;
(3) and (3) crushing the roasted sample obtained in the step (2) to a particle size range of 0.025-0.15 mm, leaching the roasted sample by adopting an acidic solution, and carrying out solid-liquid separation to obtain a leaching solution.
The ion adsorption type molybdenum-rhenium ore is a novel molybdenum-rhenium ore, and 60-80% of the mineral composition is quartz, 8-20% of the mineral composition is pyrite, and 10-20% of the mineral composition is clay mineral. The technical scheme of the invention is characterized in that by utilizing the characteristic, the ion adsorption type molybdenum-rhenium ore and alkali are uniformly mixed and then are roasted at low temperature, silicon in the clay mineral reacts with the alkali to generate silicate in the roasting process, so that the structure of the clay mineral is distorted and unstable, and molybdenum and rhenium are easy to dissolve in an acid solution in the leaching process, so that the recovery rate of the molybdenum and rhenium is improved.
In a preferred embodiment of the method of the present invention, in the step (2), the additive is at least one of sodium hydroxide, potassium hydroxide and magnesium hydroxide.
In a preferred embodiment of the method of the present invention, in the step (2), the weight ratio of the additive to the crushed ion-adsorbing molybdenum-rhenium ore is (0.5-2): 1.
In a preferred embodiment of the method of the present invention, in the step (2), the calcination temperature is 150 to 250 ℃.
In a preferred embodiment of the method of the present invention, in the step (2), the calcination time is 0.5 to 3 hours.
In a preferred embodiment of the method of the present invention, in the step (3), the acidic solution is at least one of a sulfuric acid solution, a hydrochloric acid solution, and a nitric acid solution.
In a preferred embodiment of the method of the present invention, in the step (3), the concentration of the acid in the acidic solution is 0.5 to 2.5 mol/L.
In a preferred embodiment of the method of the present invention, in the step (3), the liquid-solid ratio of the acidic solution to the roasted sample is 1 to 10L:1 kg.
As a preferable embodiment of the method of the invention, in the step (3), the leaching temperature is 30-90 ℃ and the leaching time is 0.5-2 h.
As a preferred embodiment of the method, in the step (3), a high turbulence stirring paddle is adopted in the leaching process, the ratio of the diameter of the stirring paddle to the diameter of the reaction kettle is 0.5-0.8, and the rotating speed is 50-200 rpm.
Compared with the prior art, the invention has the beneficial effects that:
(1) the roasting temperature of the molybdenum-rhenium ore is controlled to be 150-250 ℃, while the roasting temperature of the traditional molybdenum concentrate is generally controlled to be 500-650 ℃, and Re is controlled 2 O 7 Sublimation at 273 ℃ MoO 3 Obviously sublimes at 650 ℃, not only achieves the effects of energy saving and consumption reduction, but also can avoid the loss of molybdenum and rhenium in the roasting process through the reduction of the roasting temperature;
(2) the specific surface area of the ore is increased by controlling the crushing granularity of the molybdenum-rhenium ore, so that molybdenum and rhenium in the ore are fully exposed, heat transfer in the roasting process is facilitated, and the leaching rate of the molybdenum and rhenium can be improved;
(3) the high turbulence stirring paddle is adopted in the leaching process, so that the ore and the leaching agent are fully reacted at a lower rotating speed, the energy consumption is reduced, and the high-efficiency leaching of molybdenum and rhenium is realized;
(4) the activation of the ion adsorption type molybdenum-rhenium ore is realized through low-temperature roasting, so that the recovery rates of molybdenum and rhenium are improved, the recovery rate of rhenium in the method reaches over 90 percent, and the recovery rate of molybdenum reaches over 95 percent.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention. Unless otherwise specified, the reagents and materials used in the present invention are commercially available products or products obtained by a known method.
The used raw material is ion adsorption type molybdenum-rhenium ore produced in certain places in Guizhou, wherein the molybdenum content is 980g/t, and the rhenium content is 28 g/t.
Example 1
A method for efficiently recovering molybdenum and rhenium from ion adsorption type molybdenum-rhenium ore comprises the following steps:
(1) grinding the ion adsorption type molybdenum-rhenium ore in a vibration mill until the granularity is less than 0.3 mm.
(2) And (3) uniformly mixing 200g of crushed ion adsorption type molybdenum-rhenium ore and 200g of sodium hydroxide, and adding the mixture into a muffle furnace for roasting at the roasting temperature of 200 ℃ for 2h to obtain a roasted sample.
(3) Grinding a roasted sample to the particle size of 0.075mm, adding the ground sample into a reaction kettle, simultaneously adding 1L of sulfuric acid solution with the concentration of 1mol/L, leaching for 1h at 60 ℃, wherein the ratio of the high-turbulence stirring paddle to the diameter is 0.6, the rotating speed is 100rpm, after the reaction is finished, carrying out vacuum filtration for solid-liquid separation, and obtaining a leaching solution with the rhenium concentration of 5.21mg/L and the molybdenum concentration of 192.16mg/L, wherein the recovery rate of rhenium is 93.11%, and the recovery rate of molybdenum is 98.04%.
In the embodiment, the loss of molybdenum and rhenium in the roasting process is avoided through low-temperature roasting, meanwhile, the molybdenum and rhenium occurrence minerals react with the additive, so that the structures of the molybdenum and rhenium occurrence minerals are remarkably changed, and the molybdenum and rhenium are easier to enter the solution in the leaching process, thereby improving the recovery rate of the molybdenum and rhenium.
Example 2
A method for efficiently recovering molybdenum and rhenium from ion adsorption type molybdenum-rhenium ore comprises the following steps:
(1) grinding the ion adsorption type molybdenum-rhenium ore in a vibration mill until the granularity is less than 0.3 mm.
(2) And (3) uniformly mixing 200g of crushed ion adsorption type molybdenum-rhenium ore and 200g of potassium hydroxide, and adding the mixture into a muffle furnace for roasting at the roasting temperature of 200 ℃ for 2h to obtain a roasted sample.
(3) Grinding a roasted sample to the particle size of 0.075mm, adding the ground sample into a reaction kettle, simultaneously adding 1L of sulfuric acid solution with the concentration of 1mol/L, leaching for 1h at 60 ℃, wherein the ratio of the high-turbulence stirring paddle to the diameter is 0.6, the rotating speed is 100rpm, after the reaction is finished, carrying out vacuum filtration for solid-liquid separation, and obtaining a leaching solution with the rhenium concentration of 5.12mg/L and the molybdenum concentration of 189.08mg/L, wherein the recovery rate of rhenium is 91.36%, and the recovery rate of molybdenum is 96.47%.
Example 3
A method for efficiently recovering molybdenum and rhenium from ion adsorption type molybdenum-rhenium ore comprises the following steps:
(1) grinding the ion adsorption type molybdenum-rhenium ore in a vibration mill until the granularity is less than 0.3 mm.
(2) And (3) uniformly mixing 200g of crushed ion adsorption type molybdenum-rhenium ore and 400g of sodium hydroxide, and adding the mixture into a muffle furnace for roasting at the roasting temperature of 200 ℃ for 2h to obtain a roasted sample.
(3) Grinding a roasted sample to the particle size of 0.075mm, adding the ground sample into a reaction kettle, simultaneously adding 1L of sulfuric acid solution with the concentration of 1mol/L, leaching for 1h at 60 ℃, wherein the ratio of the high-turbulence stirring paddle to the diameter is 0.6, the rotating speed is 100rpm, after the reaction is finished, carrying out vacuum filtration for solid-liquid separation, and obtaining a leaching solution with the rhenium concentration of 5.31mg/L and the molybdenum concentration of 194.33mg/L, wherein the recovery rate of rhenium is 94.77% and the recovery rate of molybdenum is 99.15%.
Example 4
A method for efficiently recovering molybdenum and rhenium from ion adsorption type molybdenum-rhenium ore comprises the following steps:
(1) grinding the ion adsorption type molybdenum-rhenium ore in a vibration mill until the granularity is less than 0.3 mm.
(2) And (3) uniformly mixing 200g of crushed ion adsorption type molybdenum-rhenium ore and 200g of sodium hydroxide, and adding the mixture into a muffle furnace for roasting at the roasting temperature of 250 ℃ for 2h to obtain a roasted sample.
(3) Grinding a roasted sample to the granularity of 0.075mm, adding the ground roasted sample into a reaction kettle, simultaneously adding 1L of sulfuric acid solution with the concentration of 1mol/L, leaching for 1h at 60 ℃, wherein the ratio of the high turbulence stirring paddle to the diameter is 0.6, the rotating speed is 100rpm, after the reaction is finished, carrying out vacuum filtration to carry out solid-liquid separation, wherein the rhenium concentration in the obtained leaching solution is 5.22mg/L, the molybdenum concentration is 193.33mg/L, the recovery rate of rhenium is 93.24%, and the recovery rate of molybdenum is 98.64%.
Example 5
A method for efficiently recovering molybdenum and rhenium from ion adsorption type molybdenum-rhenium ore comprises the following steps:
(1) grinding the ion adsorption type molybdenum-rhenium ore in a vibration mill until the granularity is less than 0.3 mm.
(2) And (3) uniformly mixing 200g of crushed ion adsorption type molybdenum-rhenium ore and 200g of sodium hydroxide, and adding the mixture into a muffle furnace for roasting at the roasting temperature of 200 ℃ for 2h to obtain a roasted sample.
(3) Grinding a roasted sample to the particle size of 0.075mm, adding the ground sample into a reaction kettle, simultaneously adding 1L of sulfuric acid solution with the concentration of 2mol/L, leaching for 1h at 60 ℃, wherein the ratio of the high-turbulence stirring paddle to the diameter is 0.6, the rotating speed is 100rpm, after the reaction is finished, carrying out vacuum filtration for solid-liquid separation, and obtaining a leaching solution with the rhenium concentration of 5.37mg/L and the molybdenum concentration of 195.24mg/L, wherein the recovery rate of rhenium is 95.87%, and the recovery rate of molybdenum is 99.61%.
Example 6
A method for efficiently recovering molybdenum and rhenium from ion adsorption type molybdenum-rhenium ore comprises the following steps:
(1) grinding the ion adsorption type molybdenum-rhenium ore in a vibration mill until the granularity is less than 0.3 mm.
(2) And (3) uniformly mixing 200g of crushed ion adsorption type molybdenum-rhenium ore and 200g of sodium hydroxide, and adding the mixture into a muffle furnace for roasting at the roasting temperature of 200 ℃ for 2h to obtain a roasted sample.
(3) Grinding a roasted sample to the particle size of 0.075mm, adding the ground sample into a reaction kettle, simultaneously adding 2L of sulfuric acid solution with the concentration of 1mol/L, leaching for 1h at 60 ℃, wherein the ratio of the high-turbulence stirring paddle to the diameter is 0.6, the rotating speed is 100rpm, after the reaction is finished, carrying out vacuum filtration for solid-liquid separation, and obtaining a leaching solution with the rhenium concentration of 2.63mg/L and the molybdenum concentration of 96.61mg/L, wherein the recovery rate of rhenium is 94.08% and the recovery rate of molybdenum is 98.58%.
Example 7
A method for efficiently recovering molybdenum and rhenium from ion adsorption type molybdenum-rhenium ore comprises the following steps:
(1) grinding the ion adsorption type molybdenum-rhenium ore in a vibration mill until the granularity is less than 0.15 mm.
(2) And (3) uniformly mixing 400g of crushed ion adsorption type molybdenum-rhenium ore and 200g of sodium hydroxide, and adding the mixture into a muffle furnace for roasting at the roasting temperature of 250 ℃ for 3 hours to obtain a roasted sample.
(3) Grinding a roasted sample to the particle size of 0.025mm, adding the ground sample into a reaction kettle, simultaneously adding 0.6L hydrochloric acid solution with the concentration of 0.5mol/L, leaching for 2h at 30 ℃, wherein the ratio of the high turbulence stirring paddle to the paddle is 0.8, the rotating speed is 200rpm, after the reaction is finished, carrying out vacuum filtration for solid-liquid separation to obtain a leaching solution, wherein the rhenium concentration is 17.19mg/L, the molybdenum concentration is 626.15mg/L, the recovery rate of rhenium is 92.07%, and the recovery rate of molybdenum is 95.84%.
Example 8
A method for efficiently recovering molybdenum and rhenium from ion adsorption type molybdenum-rhenium ore comprises the following steps:
(1) grinding the ion adsorption type molybdenum-rhenium ore in a vibration mill until the granularity is less than 1 mm.
(2) And (3) uniformly mixing 200g of crushed ion adsorption type molybdenum-rhenium ore and 200g of sodium hydroxide, and adding the mixture into a muffle furnace for roasting at the roasting temperature of 150 ℃ for 0.5h to obtain a roasted sample.
(3) Grinding a roasted sample to the particle size of 0.15mm, adding the ground sample into a reaction kettle, simultaneously adding 4L of nitric acid solution with the concentration of 2.5mol/L, leaching for 0.5h at 90 ℃, wherein the ratio of the high turbulence stirring paddle to the diameter is 0.5, the rotating speed is 50rpm, after the reaction is finished, carrying out vacuum filtration for solid-liquid separation to obtain a leaching solution, wherein the rhenium concentration is 1.30mg/L, the molybdenum concentration is 47.37mg/L, the recovery rate of rhenium is 93.15%, and the recovery rate of molybdenum is 96.67%.
Comparative example 1
A method of recovering molybdenum rhenium comprising the steps of:
(1) and grinding the molybdenum-rhenium ore in a vibration mill until the granularity is less than 0.075 mm.
(2) 200g of crushed ion adsorption type molybdenum-rhenium ore is added into a muffle furnace to be roasted, the roasting temperature is 600 ℃, and the roasting time is 2 hours.
(3) Adding the roasted molybdenum-rhenium ore into a reaction kettle, simultaneously adding 1L of sulfuric acid solution with the concentration of 1mol/L, stirring and leaching for 1h at 60 ℃, after the reaction is finished, carrying out vacuum filtration for solid-liquid separation, wherein the rhenium concentration in the obtained leaching solution is 0.69mg/L, the molybdenum concentration is 95.92mg/L, the recovery rate of rhenium is 12.35%, and the recovery rate of molybdenum is 48.94%.
In this comparative example, the recovery rates of molybdenum and rhenium were low in the molybdenum-rhenium ore, mainly because most of the rhenium and a small part of the molybdenum were Re-respectively under the high-temperature calcination condition 2 O 7 And MoO 3 The form(s) volatilize, resulting in lower molybdenum and rhenium concentrations in the leachate.
Comparative example 2
A method of recovering molybdenum rhenium comprising the steps of:
(1) and grinding the molybdenum-rhenium ore in a vibration mill until the granularity is less than 0.075 mm.
(2) 200g of crushed ion adsorption type molybdenum-rhenium ore is added into a muffle furnace to be roasted, the roasting temperature is 200 ℃, and the roasting time is 2 hours.
(3) Adding the roasted molybdenum-rhenium ore into a reaction kettle, simultaneously adding 1L of sulfuric acid solution with the concentration of 1mol/L, stirring and leaching for 1h at 60 ℃, after the reaction is finished, carrying out vacuum filtration for solid-liquid separation, wherein the rhenium concentration in the obtained leaching solution is 3.18mg/L, the molybdenum concentration is 144.47mg/L, the recovery rate of rhenium is 56.87%, and the recovery rate of molybdenum is 73.71%.
In this comparative example, although the recovery rates of molybdenum and rhenium in the molybdenum-rhenium ore are improved compared with those under the high-temperature roasting condition, the recovery rates are still lower, mainly because the low-temperature roasting can avoid volatilization of molybdenum and rhenium, and simultaneously, the low-valence molybdenum and rhenium are converted into high-valence molybdenum and rhenium which are easily dissolved in the solution, but the existing clay mineral structure is not obviously changed, so that the concentrations of molybdenum and rhenium in the leaching solution are still lower.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (5)

1. A method for efficiently recovering molybdenum and rhenium from ion adsorption type molybdenum-rhenium ore, which is characterized by comprising the following steps:
(1) crushing the ion adsorption type molybdenum-rhenium ore to a particle size range of 0.15-1 mm;
(2) uniformly mixing the ion adsorption type molybdenum-rhenium ore crushed in the step (1) with an additive, and roasting at a low temperature to obtain a roasted sample, wherein the roasting temperature is 150-250 ℃;
(3) crushing the roasted sample obtained in the step (2) to a particle size range of 0.025-0.15 mm, leaching the roasted sample by adopting an acidic solution, and performing solid-liquid separation to obtain a leaching solution;
in the step (2), the weight ratio of the additive to the crushed ion adsorption type molybdenum-rhenium ore is (0.5-2) to 1;
in the step (2), the roasting time is 0.5-3 h;
the acid solution is at least one of sulfuric acid solution, hydrochloric acid solution and nitric acid solution;
in the step (3), a high turbulence stirring paddle is adopted in the leaching process, the ratio of the diameter of the stirring paddle to the diameter of the reaction kettle is 0.5-0.8, and the rotating speed is 50-200 rpm.
2. The method of claim 1, wherein in step (2), the additive is at least one of sodium hydroxide, potassium hydroxide and magnesium hydroxide.
3. The method according to claim 1, wherein in the step (3), the concentration of the acid in the acidic solution is 0.5 to 2.5 mol/L.
4. The method according to claim 1, wherein in the step (3), the liquid-solid ratio of the acidic solution to the roasted sample is 1-10L: 1 kg.
5. The method according to claim 1, wherein in the step (3), the leaching temperature is 30-90 ℃ and the leaching time is 0.5-2 h.
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