CN101920997A - Method for purifying molybdenum disulfide by leaching molybdenum concentrate with chlorate - Google Patents
Method for purifying molybdenum disulfide by leaching molybdenum concentrate with chlorate Download PDFInfo
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- CN101920997A CN101920997A CN2009100872625A CN200910087262A CN101920997A CN 101920997 A CN101920997 A CN 101920997A CN 2009100872625 A CN2009100872625 A CN 2009100872625A CN 200910087262 A CN200910087262 A CN 200910087262A CN 101920997 A CN101920997 A CN 101920997A
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Abstract
The invention relates to a method for purifying molybdenum disulfide by leaching molybdenum concentrate with chlorate, belonging to the field of wet-process metallurgy. The method comprises the steps of: removing metal sulfide impurities in the molybdenum concentrate used as raw material by heating a leaching solution, wherein the leaching solution is a mixed solution of ferric chloride and chlorate assistants (CuCl2, FeCl2, CaCl2, MgCl2, NaCl and the like), as well as water and a small quantity of hydrochloric acid; then adding a hydrofluoric acid solution to react with silica impurities in the molybdenum concentrate; and finally, dissolving with an organic solvent for recycling sulfur generated in the reaction, cleaning, drying and filtering to obtain the high-purity molybdenum disulfide. The method has simple preparation process; the leaching solution can be recycled after simply processed; and by-proucts of the sulfur and the like generated in the preparation process can be recycled to ensure that the resources are fully utilized and the waste emission is reduced, and finally, the molybdenum disulfide with purity of above 98 percent can be prepared.
Description
Technical field
The invention belongs to the hydrometallurgy field, particularly a kind of method of utilizing chlorate concentrated molybdenum ore to be leached purifying and preparing high-purity molybdenumdisulphide.
Background technology
Highly purified molybdenumdisulphide has good lubricating property, can be used as the lubricant or the slip additive of aspects such as automobile, industrial machine and space flight.According to United States Geological Survey's statistics in 2007, the molybdenum in China resource reserve ranks first in the world.But, the molybdenum product that China produces is mainly low value-added products such as concentrated molybdenum ore, molybdenum-iron, and highly purified molybdenumdisulphide output is lower, the product foreign matter content is higher, and produces a large amount of materials such as acid mist in producing, not only bring pollution, and caused the waste of resource to environment.
The method of suitability for industrialized production molybdenumdisulphide mainly is divided into two kinds both at home and abroad: natural method and synthesis method.Natural method is a kind of method of directly molybdenum glance being purified, and compositional rule is to be main raw material with sulphur source and molybdenum source, prepares the method for molybdenumdisulphide through series reaction.Wherein natural method cost is lower and can keep the natural crystal formation of molybdenumdisulphide to make it have better lubricant effect, and therefore natural method is the main method of preparation molybdenum disulfide lubricant.
Major impurity in the concentrated molybdenum ore is metallic sulfide (CuS, FeS
2And CuFeS
2Deng) and material such as silicon-dioxide, natural method is about to that these impurity in the concentrated molybdenum ore are removed one by one and the method that keeps molybdenumdisulphide.The natural method of preparation high purity molybdenumdisulphide mainly comprises following several:
(1) strengthening ore dressing acid leaching process: Lin Hecheng has reported by further flotation obtains the molybdenumdisulphide of higher degree to concentrated molybdenum ore in that " hydrometallurgy " 1998 the 2nd is interim, remove some detrimental impurity with acidleach again, finally obtain the method for molybdenumdisulphide product.This technology is simple, and cost is lower, and product purity is higher, but multiple flotation meeting produces a large amount of low-purity mine tailings, causes a large amount of waste of concentrated molybdenum ore.
(2) vacuum (or filling nitrogen) roasting; acidleach impurity removal process: Song Jun the people such as protects in " China molybdenum industry " the 21st volume the 2nd, 3 interim high-temperature roasting technologies of having reported that concentrated molybdenum ore carries out under vacuum or nitrogen protection in 1997; make pyrite be converted into pyrrhotite by roasting; use removal of impurities such as hydrochloric acid, hydrofluoric acid again, finally obtain purity and be the molybdenumdisulphide more than 98%.This method technology is simple, and cost is low, but high-temperature roasting may make the molybdenumdisulphide crystal formation change, and influences the lubricity of product.
(3) nitric acid oxidation, acidleach impurity removal process: Li Dacheng utilizes the strong oxidizing property of nitric acid that pyrite is converted into pyrrhotite in " China molybdenum industry " the 32nd volume the 3rd interim some enterprise that mentions in 2008, and other impurity is removed in acidleach again.This technology can effectively be removed indissoluble impurity such as chalcopyrite, pyrite, but a part of molybdenumdisulphide can be oxidized to molybdic oxide simultaneously, makes to contain the molybdic oxide impurity of high level in the product, thereby influences quality product.
(4) mixing acid lixiviation process: people such as Li Zhe have reported the method that the mixing acid that utilizes hydrofluoric acid and hydrochloric acid or silicofluoric acid to constitute is purified to concentrated molybdenum ore in " China molybdenum industry " 2007 the 31st the 3rd phases of volume.Be main leaching agent wherein, dissolve most of mineral substance, improve the solubleness of the indissoluble fluorochemical that generates by adding hydrochloric acid or silicofluoric acid with hydrofluoric acid.This technique process is few, and cost is low, the yield height, but quality product is lower, and operational condition is abominable, and this technology also can form high acid mist contaminate environment, so less aborning employing.
(5) cyaniding lixiviation process: Gan Jingchao has reported the copper molybdenum separating technology in U.S. Ke Podun copper dressing-works in " external metallic ore ore dressing " the 4th phase of calendar year 2001, has wherein used the cyaniding leaching-out technique.Prussiate can generate the copper complexing ion of solubility with the cupric ion reaction on cupric sulfide surface, thereby makes the sulfide dissolving of copper.This method only is applicable to the most of secondary copper mineral of high-quality concentrated molybdenum ore, and because of prussiate toxicity is too big, causes this technology to be difficult to promote.
(6) chlorination is leached: Yang Jiuliu leaches at 2000 the 5th interim villaumites of molybdenumdisulphide of mentioning of " non-ferrous metal " (ore dressing part), and this technology removal of impurities is more thorough, but medicine consumption and energy consumption height also are not widely used.
The present invention is a starting point from technological improvement and two aspects of process integration, original concentrated molybdenum ore chlorination extract technology is improved: improved the activity of protium in the oxidisability of leaching liquid and the leaching liquid by the method that adds oxidation promoter, thereby improved rate of oxidation greatly; By process integration, mother liquor is fully utilized, thereby reaches the effect of energy-saving and emission-reduction.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing the leaching molybdenum concentrate with chlorate purifying molybdenum disulfide, is molybdenumdisulphide more than 98% to obtain purity.
The present invention is to be raw material with the concentrated molybdenum ore, with iron(ic) chloride and chlorate auxiliary agent (CuCl
2, FeCl
2, CaCl
2, MgCl
2, NaCl etc.) and the mixing solutions of water and small amount of hydrochloric acid be leaching liquid, remove metallic sulfide impurity (CuS, FeS in the concentrated molybdenum ore by the heating leaching liquid
2And CuFeS
2Deng), add the silicon-dioxide impurity reaction in hydrofluoric acid solution and the concentrated molybdenum ore then, use organic reagent (CS at last
2Or kerosene etc.) dissolve and reclaim the elemental sulfur that produces in the reaction process, through cleaning, drying, make highly purified molybdenumdisulphide.Method preparation technology of the present invention is simple, leaching liquid can recycle after simple process, and the by products such as elemental sulfur that produce in the preparation process also can reclaim, and resource can be fully utilized, reduce waste discharge, finally can make purity and be the molybdenumdisulphide product more than 98%.
The method of leaching molybdenum concentrate with chlorate purifying molybdenum disulfide of utilizing of the present invention may further comprise the steps:
A. iron(ic) chloride, chlorate auxiliary agent and water are mixed obtaining mixed aqueous solution, the pH value that adds hydrochloric acid adjusting mixed aqueous solution is to obtain leaching liquid between 0～1; Then concentrated molybdenum ore being joined in this leaching liquid and this leaching liquid is heated to preferred temperature is 90～120 ℃, stirs, and metallic sulfide impurity (CuS, FeS are removed in leaching
2And CuFeS
2Deng), filter the concentrated molybdenum ore solid after the recycling;
B. the concentrated molybdenum ore that will obtain after will handling through step a leaching is put into hydrofluoric acid solution and is reacted, and stirs, thereby removes silicon-dioxide impurity, filters the concentrated molybdenum ore solid behind the recovery silica removal;
C. the concentrated molybdenum ore solid behind the silica removal that obtains through step b with organic reagent leaching filters, and the sulphur simple substance in the concentrated molybdenum ore is reclaimed by the organic reagent dissolving, and it is molybdenumdisulphide product more than 98% that remaining solid is purity.
Described chlorate auxiliary agent is selected from CuCl
2, FeCl
2, CaCl
2, MgCl
2, at least a in the group that NaCl etc. formed.
Preferably the concentration of iron(ic) chloride is 100～300g/L in the leaching liquid of step a, and the concentration of chlorate auxiliary agent is 10～300g/L; Preferred leaching solid-to-liquid ratio is 1: 2.5～1: 10; Preferred stirring velocity is 200～500rpm, and preferred leaching time is 4～10 hours.
Preferably in the filtration process of step a, also comprise and cleaning: promptly with 30～80 ℃ the concentrated molybdenum ore solid of hot water injection after the leaching processing 2～3 times, to remove the muriate of concentrated molybdenum ore surface adsorption reclaiming the concentrated molybdenum ore solid.
Among the preferred steps b in the hydrofluoric acid solution molar weight of institute's hydrofluoric acid containing be theoretical 2～3 times of consuming molar weight of silicon-dioxide, temperature of reaction is controlled at 60～90 ℃, the reaction times is 1～5 hour.
Preferably in the filtration process of step b, also comprise and cleaning: be the concentrated molybdenum ore solid that 0.5%～2% sodium hydroxide or potassium hydroxide solution cleaning are reclaimed promptly, remove the hydrofluoric acid of concentrated molybdenum ore surface adsorption with mass concentration to reclaiming the concentrated molybdenum ore solid.
The used organic reagent of preferred steps c is dithiocarbonic anhydride (CS
2) or kerosene: use the concentrated molybdenum ore solid temperature behind the silica removal that dithiocarbonic anhydride leaching step b obtains to be room temperature, the time is 1～3 hour; Filter, wash the dithiocarbonic anhydride that loads on the gained molybdenumdisulphide product, oven dry with ethanol; Behind the dithiocarbonic anhydride dissolve sulfur simple substance, heated volatile, the dithiocarbonic anhydride steam that reclaims dissolved sulphur simple substance solid simultaneously and volatilize; The temperature of the concentrated molybdenum ore that use kerosene leaching step b obtains is 30～50 ℃, and the time is 2～5 hours, lowers the temperature behind the kerosene dissolve sulfur simple substance, filters, and obtains the molybdenumdisulphide product, reclaims dissolved sulphur simple substance solid and kerosene liquid simultaneously.
Iron(ic) chloride has very strong oxidisability in the aqueous solution, and the temperature of its oxidisability and solution and pH value scope have much relations, except controlling its oxidisability by attemperation and control pH value scope, can also add other chlorate (CuCl except that it
2, FeCl
2, CaCl
2, MgCl
2, NaCl etc.) and as auxiliary agent.The adding of chlorate auxiliary agent can improve the boiling point of solution on the one hand, thereby improves the controlled range of temperature of reaction; Can improve hydrogen ion activity on the other hand, thereby increase the activity of leaching liquid.
Advantage of the present invention is: utilize to add the leaching liquid of small amount of hydrochloric acid as metallic sulfide impurity in the mixed aqueous solution of iron(ic) chloride and chlorate auxiliary agent, make it form synergistic effect, improved the leaching effect of iron(ic) chloride to concentrated molybdenum ore greatly.
In addition, the present invention also has the following advantages:
(1) the present invention is applicable to the various concentrated molybdenum ores that contain different impurities, because iron(ic) chloride has extremely strong oxidisability, oxidable most metallic sulfide impurity in the environment that contains chlorate auxiliary agent and small amount of hydrochloric acid of the present invention;
(2) the present invention makes the element sulphur in the metallic sulfide be converted into elemental sulfur rather than sulfurous gas, has not only reduced pollution, and has reclaimed the elemental sulfur by product;
(3) whole process flow of the present invention from bringing up to below 80% more than 98%, improved value-added content of product greatly, and technical process is simple with the purity of concentrated molybdenum ore, and resource can be fully recycled, and is convenient to operation, is suitable for scale operation.
Description of drawings
Fig. 1. concentrated molybdenum ore leaching schematic flow sheet of the present invention.
Embodiment
Advance below in conjunction with embodiment and accompanying drawing that the present invention is further illustrated, but it is not a limitation of the present invention.
Embodiment 1
Each main ingredient content of used concentrated molybdenum ore is as follows:
| The element kind | Mo | S | Fe | Cu | Si | Mg | Al | Ca | K | Cl |
| Mass content (%) | 50.1 | 37.0 | 4.28 | 2.72 | 1.97 | 0.34 | 0.92 | 1.78 | 0.34 | 0.41 |
See also Fig. 1.At first configuration contains iron(ic) chloride 300g/L, the aqueous solution 300ml of iron protochloride 100g/L, and the adding small amount of hydrochloric acid is adjusted to 0 with pH value of aqueous solution and obtains leaching liquid.The 30g concentrated molybdenum ore is joined leaching (solid-to-liquid ratio is 1: 10) in this leaching liquid, and heating makes temperature remain on 110 ℃, and the rotating speed of stirring rake remains on 300rpm.Leach 10 hours to remove metallic sulfide impurity (CuS, FeS
2And CuFeS
2Deng), cold filtration then is with the concentrated molybdenum ore solid of 30 ℃ hot water injections after leaching is handled 2～3 times, to remove the muriate of concentrated molybdenum ore surface adsorption.The concentrated molybdenum ore that will obtain after then will handling through leaching joins in the hydrofluoric acid solution of 200ml, and wherein, the molar weight of institute's hydrofluoric acid containing is theoretical 2 times of consuming molar weight of silicon-dioxide in the hydrofluoric acid solution; Heating makes solution remain on 80 ℃ when stirring, and the reaction times is 5 hours.Filter, reclaim the concentrated molybdenum ore solid and be the concentrated molybdenum ore solid that 0.5% potassium hydroxide solution flushing is reclaimed, remove the hydrofluoric acid of concentrated molybdenum ore surface adsorption, dry, obtain the concentrated molybdenum ore solid behind the silica removal with mass concentration.The concentrated molybdenum ore solid that obtains is put into 30 ℃ kerosene, stirs and lower the temperature after making kerosene dissolve sulfur simple substance in 5 hours, filter, oven dry, make on the gained molybdenumdisulphide product the kerosene volatilization fully, can obtain purity and be the molybdenumdisulphide product more than 98%.Kerosene can be recycled, and when sulphur content reached some amount in the kerosene, can lower the temperature separated out element sulphur.
Embodiment 2 (used concentrated molybdenum ore is identical with embodiment 1)
See also Fig. 1.At first configuration contains iron(ic) chloride 100g/L, calcium chloride 300g/L, and the aqueous solution 75ml of cupric chloride 10g/L, the adding small amount of hydrochloric acid is adjusted to 1 with pH value of aqueous solution and obtains leaching liquid.The 30g concentrated molybdenum ore is joined leaching (solid-to-liquid ratio is 1: 2.5) in this leaching liquid, and heating makes temperature remain on 90 ℃, and the rotating speed of stirring rake remains on 200rpm.Leach 4 hours to remove metallic sulfide impurity (CuS, FeS
2And CuFeS
2Deng), cold filtration then is with the concentrated molybdenum ore solid of 60 ℃ hot water injections after leaching is handled 2～3 times, to remove the muriate of concentrated molybdenum ore surface adsorption.The concentrated molybdenum ore that will obtain after then will handling through leaching joins in the hydrofluoric acid solution of 300ml, and wherein, the molar weight of institute's hydrofluoric acid containing is theoretical 3 times of consuming molar weight of silicon-dioxide in the hydrofluoric acid solution; Heating makes solution remain on 90 ℃ when stirring, and the reaction times is 1 hour.Filter, reclaim the concentrated molybdenum ore solid and be the concentrated molybdenum ore solid that 2% sodium hydroxide solution flushing is reclaimed, remove the hydrofluoric acid of concentrated molybdenum ore surface adsorption, dry, obtain the concentrated molybdenum ore solid behind the silica removal with mass concentration.The dithiocarbonic anhydride that the concentrated molybdenum ore solid that obtains is put under the room temperature (25 ℃) washs, and stirs 1 hour after-filtration, washes the dithiocarbonic anhydride that loads on the gained molybdenumdisulphide product with ethanol, and oven dry can obtain purity and be the molybdenumdisulphide product more than 98%.Dithiocarbonic anhydride can be recycled, when wherein sulphur simple substance content more for a long time, can heat and make the dithiocarbonic anhydride volatilization fully, sulphur simple substance solid and the dithiocarbonic anhydride steam that volatilizes are reclaimed simultaneously.
Embodiment 3 (used concentrated molybdenum ore is identical with embodiment 1)
See also Fig. 1.At first configuration contains iron(ic) chloride 100g/L, iron protochloride 300g/L, and the aqueous solution 150ml of cupric chloride 10g/L, the adding small amount of hydrochloric acid is adjusted to 0 with pH value of aqueous solution and obtains leaching liquid.The 30g concentrated molybdenum ore is joined leaching (solid-to-liquid ratio is 1: 5) in this leaching liquid, and heating makes temperature remain on 120 ℃, and the rotating speed of stirring rake remains on 500rpm.Leach 6 hours to remove metallic sulfide impurity (CuS, FeS
2And CuFeS
2Deng), cold filtration then is with the concentrated molybdenum ore solid of 80 ℃ hot water injections after leaching is handled 2～3 times, to remove the muriate of concentrated molybdenum ore surface adsorption.The concentrated molybdenum ore that will obtain after then will handling through leaching joins in the hydrofluoric acid solution of 250ml, and wherein, the molar weight of institute's hydrofluoric acid containing is theoretical 2.5 times of consuming molar weight of silicon-dioxide in the hydrofluoric acid solution; Heating makes solution remain on 60 ℃ when stirring, and the reaction times is 5 hours.Filter, reclaim the concentrated molybdenum ore solid and be the concentrated molybdenum ore solid that 1% sodium hydroxide solution flushing is reclaimed, remove the hydrofluoric acid of concentrated molybdenum ore surface adsorption, dry, obtain the concentrated molybdenum ore solid behind the silica removal with mass concentration.The concentrated molybdenum ore solid that obtains is put into 50 ℃ kerosene, stirs and lower the temperature after making kerosene dissolve sulfur simple substance in 2 hours, filter, oven dry, make on the gained molybdenumdisulphide product the kerosene volatilization fully, can obtain purity and be the molybdenumdisulphide product more than 98%.Kerosene can be recycled, and when sulphur content reached some amount in the kerosene, can lower the temperature separated out element sulphur.
Claims (9)
1. a method of utilizing the leaching molybdenum concentrate with chlorate purifying molybdenum disulfide is characterized in that, this method may further comprise the steps:
A. iron(ic) chloride, chlorate auxiliary agent and water are mixed obtaining mixed aqueous solution, the pH value that adds hydrochloric acid adjusting mixed aqueous solution is to obtain leaching liquid between 0～1; Then concentrated molybdenum ore being joined in this leaching liquid and this leaching liquid is heated to temperature is 90～120 ℃, stirs, and metallic sulfide impurity is removed in leaching, filters the concentrated molybdenum ore solid after the recycling;
B. the concentrated molybdenum ore that will obtain after will handling through step a leaching is put into hydrofluoric acid solution and is reacted, and stirs, and removes silicon-dioxide impurity, filters the concentrated molybdenum ore solid behind the recovery silica removal;
C. the concentrated molybdenum ore solid behind the silica removal that obtains through step b with organic reagent leaching filters, and the solid that obtains is the molybdenumdisulphide product.
Described chlorate auxiliary agent is selected from CuCl
2, FeCl
2, CaCl
2, MgCl
2, at least a in the group that NaCl formed;
Described organic reagent is dithiocarbonic anhydride or kerosene.
2. method according to claim 1 is characterized in that: the concentration of iron(ic) chloride is 100～300g/L in the described leaching liquid of step a, and the concentration of chlorate auxiliary agent is 10～300g/L; The leaching solid-to-liquid ratio is 1: 2.5～1: 10; Leaching time is 4～10 hours.
3. method according to claim 1 is characterized in that: the described stirring velocity of step a is 200～500rpm.
4. method according to claim 1, it is characterized in that: in the filtration process of step a, also comprise and cleaning reclaiming the concentrated molybdenum ore solid, described cleaning is the concentrated molybdenum ore solid of hot water injection after leaching is handled with 30～80 ℃, to remove the muriate of concentrated molybdenum ore surface adsorption.
5. method according to claim 1 is characterized in that: the temperature of reaction that the concentrated molybdenum ore that step b is described to be obtained after will handling through step a leaching is put into hydrofluoric acid solution is 60～90 ℃, and the reaction times is 1～5 hour.
6. method according to claim 1 or 5, it is characterized in that: the molar weight of institute's hydrofluoric acid containing is theoretical 2～3 times of consuming molar weight of silicon-dioxide in the described hydrofluoric acid solution.
7. method according to claim 1, it is characterized in that: in the filtration process of step b, also comprise and cleaning reclaiming the concentrated molybdenum ore solid, described cleaning is to be that 0.5%～2% sodium hydroxide or potassium hydroxide solution clean the concentrated molybdenum ore solid that is reclaimed with mass concentration, removes the hydrofluoric acid of concentrated molybdenum ore surface adsorption.
8. method according to claim 1 is characterized in that: step c is described to use the concentrated molybdenum ore solid temperature behind the silica removal that dithiocarbonic anhydride leaching step b obtains to be room temperature, and the time is 1～3 hour; Filter, wash the dithiocarbonic anhydride that loads on the gained molybdenumdisulphide product, oven dry with ethanol; Behind the dithiocarbonic anhydride dissolve sulfur simple substance, heated volatile, the dithiocarbonic anhydride steam that reclaims dissolved sulphur simple substance solid simultaneously and volatilize; The temperature of the concentrated molybdenum ore that use kerosene leaching step b obtains is 30～50 ℃, and the time is 2～5 hours, lowers the temperature behind the kerosene dissolve sulfur simple substance, filters, and obtains the molybdenumdisulphide product, reclaims dissolved sulphur simple substance solid and kerosene liquid simultaneously.
9. according to claim 1 or 8 described methods, it is characterized in that: the purity of described molybdenumdisulphide product is more than 98%.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102277481A (en) * | 2011-07-27 | 2011-12-14 | 西部鑫兴金属材料有限公司 | Method for reducing lead and protecting rhenium for high-lead rhenium and molybdenum containing concentrate |
| CN103342365A (en) * | 2013-06-24 | 2013-10-09 | 嵩县开拓者钼业有限公司 | Silicon-containing mineral processing method |
| CN104445410A (en) * | 2014-11-14 | 2015-03-25 | 金堆城钼业股份有限公司 | Method for washing commercial molybdenum oxide |
| CN107055616A (en) * | 2017-06-17 | 2017-08-18 | 金堆城钼业股份有限公司 | A kind of drop general labourer's skill of molybdenum disulfide |
| CN108043587A (en) * | 2017-10-20 | 2018-05-18 | 福建省双旗山矿业有限责任公司 | Extraction process containing ferrous sulfide in golden cyaniding tailing |
| CN108977656A (en) * | 2018-08-24 | 2018-12-11 | 淄博淦达环保科技有限公司 | A kind of lixiviation process preparation process of Zinc in Zinc Concentrates and sulphur |
| CN114164349A (en) * | 2022-02-11 | 2022-03-11 | 矿冶科技集团有限公司 | Method for removing impurities from molybdenum ore with high copper content and performing closed circulation on solution |
-
2009
- 2009-06-15 CN CN2009100872625A patent/CN101920997A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102277481A (en) * | 2011-07-27 | 2011-12-14 | 西部鑫兴金属材料有限公司 | Method for reducing lead and protecting rhenium for high-lead rhenium and molybdenum containing concentrate |
| CN103342365A (en) * | 2013-06-24 | 2013-10-09 | 嵩县开拓者钼业有限公司 | Silicon-containing mineral processing method |
| CN104445410A (en) * | 2014-11-14 | 2015-03-25 | 金堆城钼业股份有限公司 | Method for washing commercial molybdenum oxide |
| CN107055616A (en) * | 2017-06-17 | 2017-08-18 | 金堆城钼业股份有限公司 | A kind of drop general labourer's skill of molybdenum disulfide |
| CN108043587A (en) * | 2017-10-20 | 2018-05-18 | 福建省双旗山矿业有限责任公司 | Extraction process containing ferrous sulfide in golden cyaniding tailing |
| CN108977656A (en) * | 2018-08-24 | 2018-12-11 | 淄博淦达环保科技有限公司 | A kind of lixiviation process preparation process of Zinc in Zinc Concentrates and sulphur |
| CN114164349A (en) * | 2022-02-11 | 2022-03-11 | 矿冶科技集团有限公司 | Method for removing impurities from molybdenum ore with high copper content and performing closed circulation on solution |
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