CN1195082C - Process for recovering Mo from low-grade molybdenite by dump leaching - Google Patents
Process for recovering Mo from low-grade molybdenite by dump leaching Download PDFInfo
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- CN1195082C CN1195082C CNB021136998A CN02113699A CN1195082C CN 1195082 C CN1195082 C CN 1195082C CN B021136998 A CNB021136998 A CN B021136998A CN 02113699 A CN02113699 A CN 02113699A CN 1195082 C CN1195082 C CN 1195082C
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- molybdenum
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Abstract
The present invention relates to novel technology for recovering molybdenum from low-grade molybdenite through heap leaching. Sodium hypochlorite (NaClO) solution with low concentration is used for oxidizing leaching in an alkaline medium, and molybdenum products are prepared by the direct heap leaching of crushed crude ore, so that the high ore grinding cost in the traditional technology of floatation, roasting and leaching is avoided. Heap leaching, ion exchange and tail water regeneration in the technology form a communicated closed circulating system, and leach solution with a low molybdenum content is purified, enriched and crystallized through ion exchange to finally obtain ammonium molybdate products. Simultaneously, the present invention also provides an economical and practical tail water regenerating step. Due to sodium hypochlorite regeneration through the electro-oxidation of tail water, the raw material consumption and the cost can be reduced. Besides, closed solution circulation is formed, the transportation and the storage of sodium hypochlorite are reduced, and the discharge of waste solution is reduced. The ammonium molybdate product prepared by the technology has the advantages of stable quality, low cost, little environmental pollution and easy realization of industrialization.
Description
Technical field: the present invention relates to the treatment technology of molybdenum-bearing mineral matter, the technology of molybdenum product is produced in especially a kind of low grade molybdenite dump leaching.
Background technology: in the industrial production of molybdenum, present continuous exploitation along with molybdenum ore resource, can be fewer and feweri for the higher-grade molybdenum ore resource that utilizes, low-grade molybdenum ore is then stored up in a large number, and traditional technology flotation-roasting-extract technology is handled these ores can not obtain satisfied economic and social benefit.Require selected raw ore molybdenum grade to be higher than 0.08% as Jinduicheng Molybdenum Industry Corp, be lower than a large amount of ores of 0.08% and then store up, wasted a large amount of resources, also caused the serious environmental pollution as lean ore.Develop new Technology, to these enormous amount, bulky low-grade molybdenum ore economy, be used effectively, become molybdenum ore enterprise and be badly in need of the new problem that solves.The applicant has carried out bacterium leaching and sulfuric acid leaching research to the molybdenum grade at 0.06～0.08% Jin Dui city low grade molybdenite, and it is to carry out under sulfuric acid medium pH=1.5～2.0 conditions that bacterium is leached, and sulfuric acid leaches and also keeps same acidity.Because the physics-chem characteristic of low grade molybdenite, bacterium leaching and sulfuric acid leach all fails to obtain ideal results.Above-mentioned two leaching process all cause the metal ion of association to enter solution, and molybdenum in acidic solution easily and other metal ion in the solution (as Fe
3+, Ca
2+, Al
3+) generate insoluble complex compound and be deposited in the slag, through test as can be known, the molybdenum in the slag is difficult to propose once more.Therefore the concentration of molybdenum in leach liquor is very low, and the leaching yield that bacterium and sulfuric acid leach molybdenum is all very low, does not have practical value.
Summary of the invention: the present invention proposes a kind of technology of recovering Mo from low-grade molybdenite by dump leaching, at Jin Dui city low grade molybdenite association alkaline-earth metal and the high characteristics of transition metal, under alkaline medium, carry out oxidation with lower concentration clorox NaClO solution and leach processing, handle broken raw ore by direct leaching in dumps and produce the molybdenum product, avoided ore grinding expense expensive in traditional flotation-roasting-extract technology, dump leaching in this technology, ion-exchange, tail water is regenerated as a closed circulation system that connects, low molybdenum leach liquor is purified by ion-exchange, enrichment, the ammonium molybdate product is finally produced in crystallization.
The present invention also provides economical and practical tail water regeneration step simultaneously, tail water electrooxidation regeneration clorox can reduce raw material consumption, reduce cost, and the closed cycle of formation solution, reduce the transportation and the storage of clorox, reduce waste liquid and efflux, even do not discharge waste liquid, economic benefit and environmental benefit are obvious.Tail water after the electrooxidation returns dump leaching field continuation leaching molybdenum ore after directly returning or replenish a spot of fresh chlorine bleach liquor.
The chlorine bleach liquor's (being diluted to identical effective chlorine density) that chemical method that the chemical plant buys produces that coexists compares regeneration tail water, almost equal oxidation activity is arranged, the ability basically identical of low grade molybdenite is leached in its oxidation, but its cost is then than buying low 25～35%.
The present invention realizes by following technical measures: with the molybdenum grade in 0.03%～0.5% molybdenum glance ore reduction to-8mm granularity, build heap, under alkaline medium, carry out dump leaching at 1: 5 by liquid-solid ratio, the chlorine bleach liquor who adopts lower concentration is for soaking the ore deposit agent, soak ore deposit agent effective chlorine density at 5～30g/L, 5～40 ℃ of temperature, dump leaching is 50～80 days under pH=6～13 conditions, with the molybdenum in the strongly basic anion exchange resin absorption leach liquor, with eluent from absorption saturated resin on the wash-out molybdenum, elutriant is through enrichment, purify, crystallization obtains the ammonium molybdate product, liquid after the absorption of ion exchange resin, be that tail water is through electrolytic process, regeneration section concentration is the available chlorine of 2～20g/L, this regeneration tail water directly or add and return raw ore dump leaching field behind the part clorox and do to soak the ore deposit agent and continue to leach is controlled its effective chlorine density at 5～30g/L, and the whole process flow that molybdenum is reclaimed in dump leaching is a closed circulation system.
Continous way production is adopted in the electrooxidation regeneration of described tail water, promptly regenerated tail water does not flow in the electrolyzer with certain flow, after the electrooxidation, regenerated tail water flows out from electrolyzer with certain flow again, adjust the effective chlorine density of regeneration tail water in the pond by equalizing tank after, directly solution is done to soak ore deposit agent usefulness, the used solution of electrooxidation is that molybdenum ore leaches gained filtrate through the chlorine bleach liquor, liquid after the exchange behind the ion exchange resin absorption molybdenum, tail water Cl
-Content 30～70g/L, 20～60 ℃ of electrolysis temperatures, current density 300～3000mA/m
2, stoste pH=3～12, electrolysis time 5～60 minutes.Continuous electrolysis, per hour renewable 30～100L lower concentration chlorine bleach liquor.
Adopt NaOH solution, Na in the above-mentioned leaching process
2CO
3Solution is regulated alkalescence; The resin that ion exchange process adopts is two types of gel in the strongly basic anion exchange resin and macroporous types; Eluent adopts 0.5～4.0mol/LNaOH solution or 1.0～4.0mol/L ammoniacal liquor; The molybdenum product is mainly ammonium molybdate.
The industrial ammonium molybdate constant product quality of this prepared, cost is low, and is little to the pollution of environment, easily realizes industrialization.
Description of drawings: Fig. 1 is a process flow sheet of the present invention.
Embodiment:
Embodiment 1:
One, get representational low grade molybdenite 36kg, the chemical ingredients of molybdenum ore sees Table 1, table 2, table 3.
The spectroscopic analysis result of table 1 molybdenum ore
| Element | Al | Si | Mn | Mg | Fe | Ti | Mo | Ca | Cu | Na |
| Content % | 1.0 | ＞10.0 | 0.03 | 0.3-1.0 | 10.0 | 0.1 | 0.01 | 0.3 | 0.03 | 1.0 |
The chemical analysis results of main ingredient in table 2 molybdenum ore
| Element | Mo | S | Fe | CaO | MgO | SiO 2 | Al 2O 3 |
| Content % | 0.078 | 3.72 | 8.20 | 4.92 | 2.81 | 55.26 | 11.19 |
The thing phase composite of table 3 molybdenum ore (weight percent %)
| Mineral name | Pyrite (FeS 2) | Molybdenum glance (MoS 2) | Rhombohedral iron ore (Fe 2O 3) | Magnetite (Fe 3O 4) | Aluminosilicate mineral | Carbonate minerals | Quartzy (SiO 2) | Other mineral |
| Content % | 7.0 | 0.1 | 2.7 | 1.2 | 57.0 | 10.0 | 20 | 2.0 |
By material phase analysis, the metallic sulfide in the ore contains a small amount of molybdenum glance based on pyrite; Metal oxide is based on rhombohedral iron ore, a small amount of magnetite; Carbonate minerals is based on calcite; Aluminosilicate mineral mainly is feldspar, mica mineral; Oxide compound mainly is a quartz etc.If molybdenum ore owner molybdenum glance in the ore, the tight embedding cloth of these mineral and pyrite or wrapped up by pyrite.The maximum 0.06mm of grain size number, general granularity 0.02-0.005mm, minimum less than 0.005mm.Molybdenum glance chemical ingredients electron probe microanalysis result: Mo=58.37% Fe=2.40% S=39.16%.
Two, with 36 kilograms of ore reduction one-tenth-8mm granularities, in its organic glass column of packing into.By the acid-fast alkali-proof pump, the chlorine bleach liquor at 5～30g/L pumps in the post from Lower tank with effective chlorine density, keeps circulation to leach ore.Detected molybdenum concentration and effective chlorine density in the leach liquor every three days, detect the pH of leach liquor every day, make its pH maintain 3～12 scope.When molybdenum concentration is above 0.5g/L in the leach liquor, it is imported strongly basic anion exchange resin post carry out ion-exchange, the leach liquor that molybdenum concentration is lower than 0.5g/L returns it to leaching post continuation circulation leaching.When the immersion liquid effective chlorine density is lower than 5-30g/L, should replenishes an amount of clorox it is maintained in the above-mentioned scope.Room temperature leached 49 days, and the molybdenum leaching yield is 80%, and adsorption rate can reach more than 95%.As eluent, wash-out adsorbs the molybdenum on the saturated resin with 1.0～4.0mol/L ammoniacal liquor, and eluting rate is more than 85%.Elutriant obtains the ammonium molybdate product through concentrated, purification, crystallization, and molybdenum content is 54.3%, and the comprehensive recovery of product is 65%.The absorption saturated resin need carry out manipulation of regeneration so that recycle to resin behind wash-out.The regenerator of strongly basic anion exchange resin adopts 4% HCl, and regenerative process is reverse carrying out in ion exchange column.Liquid after the ion-exchange (tail water) imports electrolytic system, this tail water Cl
-Content 30～70g/L, 20～60 ℃ of electrolysis temperatures, current density 300～3000mA/m
2, stoste pH=3～12, electrolysis time 5～60 minutes.Continuous electrolysis, per hour renewable 30～100L lower concentration chlorine bleach liquor.This solution has produced the chlorine bleach liquor that effective chlorine density is approximately 2～20g/L after electrooxidation, and it is directly returned low grade molybdenite leach heap, dump leaching three days, the molybdenum leaching yield can reach 43.44%.
Embodiment 2:
One, get representational low grade molybdenite 1000kg, table 1, table 2, the table 3 of embodiment 1 seen in the chemical ingredients of molybdenum ore and content and thing phase composite.
Two, with 1000kg ore reduction one-tenth-8mm granularity, build heap, with the chlorine bleach liquor of lower concentration for soaking the ore deposit agent, effective chlorine density 5-30g/L, pH6～13,5～40 ℃ of temperature, liquid-solid ratio 1: 5.To soak the ore deposit agent with the pipeline sprinkling system and be sprayed at heap surface, ore deposit, and soak the ore deposit agent and permeate to the lower floor of ore deposit heap gradually by gravity.Through dump leaching in 70 days, the molybdenum leaching yield can reach more than 80%, the adsorption rate of strong basic type anion-exchange resin is 97%, with the eluent of 0.5～4.0mol/LNaOH solution as the absorption saturated resin, eluting rate is 87%, and elutriant obtains the ammonium molybdate product through concentrated, purification, crystallization, molybdenum content is 54.1%, and the comprehensive recovery of product is 69%.Tail water continuous electrolysis regeneration section clorox treatment step is with embodiment 1.
Claims (5)
1, a kind of technology of recovering Mo from low-grade molybdenite by dump leaching, be to the broken processing of molybdenum ore, leach, recovery contains the molybdenum leach liquor, obtain the molybdenum product through enrichment and purification, it is characterized in that: with the molybdenum grade in 0.03%～0.5% molybdenum glance ore reduction to-8mm granularity, build heap, under alkaline medium, carry out dump leaching at 1: 5 by liquid-solid ratio, the chlorine bleach liquor who adopts lower concentration is for soaking the ore deposit agent, soak ore deposit agent effective chlorine density at 5～30g/L, 5～40 ℃ of temperature, dump leaching is 49～70 days under pH=6～13 conditions, with the molybdenum in the strongly basic anion exchange resin absorption leach liquor, with eluent from absorption saturated resin on the wash-out molybdenum, elutriant is through enrichment, purify, crystallization obtains the ammonium molybdate product, liquid after the absorption of ion exchange resin, be that tail water is through electrolytic process, regeneration section concentration is the available chlorine of 2～20g/L, this regeneration tail water directly or add and return raw ore dump leaching field behind the part clorox and do to soak the ore deposit agent and continue to leach, control its effective chlorine density at 5～30g/L, the whole process flow that molybdenum is reclaimed in dump leaching is a closed circulation system.
2, technology according to claim 1, it is characterized in that: continous way production is adopted in the electrooxidation regeneration of tail water, promptly regenerated tail water does not flow in the electrolyzer with certain flow, after the electrooxidation, regenerated tail water flows out from electrolyzer with certain flow again, behind the effective chlorine density by regeneration tail water in the equalizing tank adjustment pond, directly solution being done to soak the ore deposit agent uses, the used solution of electrooxidation is that molybdenum ore leaches gained filtrate through the chlorine bleach liquor, liquid after the exchange behind the ion exchange resin absorption molybdenum, tail water Cl
-Content 30～70g/L, 20～60 ℃ of electrolysis temperatures, current density 300～3000mA/m
2, stoste pH=3～12, electrolysis time 5～60 minutes, continuous electrolysis, the chlorine bleach liquor of per hour renewable 30～100L available chlorine, 2～20g/L.
3, technology according to claim 1 is characterized in that: adopt NaOH solution, Na in the leaching process
2CO
3Solution is regulated alkalescence.
4, technology according to claim 1 is characterized in that: the resin that ion exchange process adopts is two types of gel in the strongly basic anion exchange resin and macroporous types.
5, technology according to claim 1 is characterized in that: eluent adopts 0.5～4.0mol/LNaOH solution or 1.0～4.0mol/L ammoniacal liquor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021136998A CN1195082C (en) | 2002-04-30 | 2002-04-30 | Process for recovering Mo from low-grade molybdenite by dump leaching |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021136998A CN1195082C (en) | 2002-04-30 | 2002-04-30 | Process for recovering Mo from low-grade molybdenite by dump leaching |
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| CN1386870A CN1386870A (en) | 2002-12-25 |
| CN1195082C true CN1195082C (en) | 2005-03-30 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101451187B (en) * | 2007-12-04 | 2010-09-01 | 灵宝市金源矿业有限责任公司 | Comprehensive recovery method of gold ore resource containing molybdenum multi-metal |
| US9057119B2 (en) | 2010-03-18 | 2015-06-16 | Metaleach Limited | Method of oxidative leaching of molybdenum—rhenium sulfide ores and/or concentrates |
| CN103555932B (en) * | 2013-11-15 | 2015-07-22 | 紫金矿业集团股份有限公司 | Method for roasting molybdenum concentrate |
| CN104726704A (en) * | 2013-12-18 | 2015-06-24 | 核工业北京化工冶金研究院 | Reinforced dump leaching method of low grade molybdenite |
| CN104762474B (en) * | 2015-05-06 | 2017-04-12 | 中南大学 | Method for preparing ammonium molybdate through molybdenite |
| CN107188261A (en) * | 2017-06-02 | 2017-09-22 | 北京中科康仑环境科技研究院有限公司 | A kind of recycling treatment process of molybdenum-containing acid wastewater |
| CN107694761B (en) * | 2017-10-20 | 2019-10-01 | 西南科技大学 | A kind of environmentally friendly jordisite object collecting agent, preparation method and application |
| CN113929143B (en) * | 2021-11-30 | 2022-09-13 | 昆明理工大学 | Method for extracting high-purity molybdenum oxide from low-grade molybdenite through microwave roasting separation |
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