CN101514403A - Method for volatilizing and enriching molybdenum from molybdenum tailings - Google Patents
Method for volatilizing and enriching molybdenum from molybdenum tailings Download PDFInfo
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- CN101514403A CN101514403A CNA2009100489125A CN200910048912A CN101514403A CN 101514403 A CN101514403 A CN 101514403A CN A2009100489125 A CNA2009100489125 A CN A2009100489125A CN 200910048912 A CN200910048912 A CN 200910048912A CN 101514403 A CN101514403 A CN 101514403A
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- molybdenum
- mine tailing
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Abstract
A method for volatilizing and enriching molybdenum from molybdenum tailings relates to a process for utilizing the molybdenum tailings for enriching and recovering the molybdenum. The molybdenum tailings are firstly ground, and the water content thereof is regulated to 30-40%WT to lead the molybdenum tailings to form slurry of the molybdenum tailings. Then, hydrofluoric acid is added in the slurry of the molybdenum tailings, hydrochloric acid is further added after the bubbles disappear and the reaction is complete; after that, the slurry of the molybdenum tailings is heated to 200-250 DEG C, a cover is used for thermal insulation for 30-50min to promote the formation of chloride of the molybdenum, then the cover is removed, and the drying is carried out at 65 DEG C. Finally, the thermal treatment of the molybdenum tailings after the pretreatment with the acid is carried out at 900 DEG C, thereby generating flue gas containing the molybdenum and silicon tetrafluoride and the residues of the thermal treatment, and the residues are used as road-building materials; the collected flue gas is condensed; when the temperature is lower than 250 DEG C, substances containing the molybdenum or molybdenum compounds are recovered; the silicon tetrafluoride in the flue gas is absorbed and hydrolyzed by using water, the filtration is carried out, and filtrate is fluorosilicic acid solution. The process of the invention is simple and easy to control, the products during the process can be recovered, the cost is low, the method has no environmental pollution, and the high temperature volatilization rate of the molybdenum achieves 70 percent-98.6 percent.
Description
Technical field
A kind of from the molybdenum mine tailing method of vaporization at high temperature molybdenum, relate to a kind of technology of utilizing molybdenum mine tailing enriching and recovering molybdenum, belong to the solid waste resource recovery technical field.
Technical background
At present, many storing up with the face of land based on tailing dam (storehouse) of depositing of 80% molybdenum mine tailing stacked, and takies a large amount of soils, contaminate environment, and can constitute the potential geologic hazard.And molybdenum is that a kind of mineral products amount is less, excellent property and broad-spectrum rare mineral, according to statistics, about 3,200,000 tons of molybdenum ore mountain, the whole nation annual molybdenum mine tailing discharge capacity, still contain 0.1～0.5% molybdenum among in these molybdenum mine tailings, as if though content is very low, metal molybdenum content is also considerable when the mine tailing discharge capacity is big especially, be worth hugely, be worth enriching and recovering.Therefore, no matter from protection molybdenum resource aspect, still from seeking aspects such as cheap molybdenum resource and environmental protection, extracting the recovery molybdenum from contain the molybdenum mine tailing becomes development trend gradually.And at present with SiO
2For the research of the molybdenum mine tailing resource utilization aspect of main thing phase generally is confined to conventional thought, promptly utilize mine tailing to make devitrified glass or multielement siliceous fertilizer, the molybdenum in the molybdenum mine tailing is carried out enriching and recovering relevant research report yet.
Summary of the invention
The purpose of this invention is to provide a kind of method of molybdenum in the molybdenum mine tailing being carried out volatilizing and enriching.It is simple to reclaim molybdenum technology with this method, and production cost is low, and the evaporation rate of molybdenum is higher, but and the waste residue recycling that produces in the technological process.
In order to achieve the above object, the present invention is to SiO
2Research and analyse discovery for the molybdenum mine tailing of main thing phase, the most of Mo in the molybdenum mine tailing can exist with the form that combines with Si.The existence of Mo-Si compound can reduce the evaporation rate of Mo in the heat treatment process, and molybdenum can be oxidized to MoO when being higher than 350 ℃
3, be higher than 500 ℃ and just can distil; And the Mo-Si oxidation-resistance strengthens, as MoSi
2Fusing point height (2030 ℃) has excellent oxidation-resistance property, the thermal stability height.So, by the molybdenum mine tailing is heat-treated, use for reference heavy metal evaporable research idea in the high-temperature process, the chemical conversion additive of research and development molybdenum mine tailing, destroy the constraint of mineral lattice to molybdenum, make the molybdenum in the ore deposit be converted into the compound that hangs down vapour point,, the molybdenum in the molybdenum mine tailing is reclaimed to realize the volatilizing and enriching under the hot conditions.The scheme that adopts is: add hydrofluoric acid and hydrochloric acid successively in (1) molybdenum mine tailing slurries; (2) carry out heat pre-treatment after adding acid; (3) pretreated molybdenum mine tailing carries out high-temperature heat treatment, makes molybdenum move in gas phase under hot conditions, and the molybdenum in the flue gas is reclaimed.
The molybdenum mine tailing of indication of the present invention is mainly taken from Huludao City, and main thing is SiO mutually
2, molybdenum content is 0.2～0.5%, and most of Mo exists with the form that combines with Si in the mine tailing, and the high-temperature oxidation resistance of molybdenum is stronger in the mine tailing, is difficult for toward gas-migration in heat treatment process.
Before carrying out pre-treatment and high-temperature heat treatment, ore grinding is a necessary step, can make the useful component molybdenum in the mine tailing reach monomer separation, can the molybdenum mine tailing is levigate to 0.08～0.1mm.Regulate mine tailing water ratio to 30%～40% behind the ore grinding, make it form mine tailing mud, have certain rheological property, can be better and acid be in contact with one another reaction.
After this, add HF in molybdenum mine tailing slurries, purpose is silica removal and destroys the constraint of mineral lattice to Mo.After question response is complete, add HCl again, add a cover in 200～250 ℃ immediately and heat 30～50min, generate, change the form that exists of Mo with the muriate that promotes molybdenum.Heat treated finishes the back except that lid, and 65 ℃ dry down.
In the process of HCl-HF pre-treatment molybdenum mine tailing, heating can be strengthened reacting to each other of Mo in the molybdenum mine tailing and HCl, promotes the muriatic generation of Mo, in the nitration mixture heat pre-treatment process there is contingent reaction:
4HF+SiO
2→SiF
4↑+2H
2O
HF+Si→H
2SiF
4
The easier generation of chlorination attitude form of Mo under heating condition, therefore Mo is easier in high-temperature heat treatment process moves in gas phase.
Mine tailing after the HF-HCl heat pre-treatment is heat-treated under 900 ℃ of conditions, flue gas is carried out condensation reclaim, and the evaporation rate of 900 ℃ of following molybdenums can reach 70%-98.6%.
Concrete steps are as follows:
At first, the molybdenum mine tailing is ground into 0.08-0.1mm, adds water then and stir, obtaining water ratio is the molybdenum mine tailing mud of 30%～40%WT; Then, in molybdenum mine tailing mud, add hydrofluoric acid, vigorous reaction take place produce a large amount of bubbles, treat that bubble collapse reacts completely after, add hydrochloric acid again; Be heated to 200～250 ℃ immediately and add a cover insulation and remove lid behind 30～50min, impel the muriate of molybdenum to generate, dry down at 65 ℃; At last, heat-treat under 900 ℃ of the pretreated molybdenum mine tailings of acid, molybdenum is moved in gas phase, the vaporization at high temperature rate of molybdenum reaches 70%-98.6%, obtain containing the flue gas and the thermal treatment residue of molybdenum and silicon tetrafluoride, residue is as road-making material, and flue gas condensing to 250 ℃ or be lower than 250 ℃ obtains containing the material of molybdenum or molybdenum compound, remaining flue gas water absorbs and hydrolysis, filter, filtrate is silicate fluoride solution, and filter residue is as road-making material.
The add-on of above-mentioned hydrofluoric acid adds 0.25ml～1ml HF metering by every g butt molybdenum mine tailing, and the mass percentage concentration concentration of this HF is 40%WT.
The add-on of above-mentioned hydrochloric acid is 0.25ml～1ml HCl/g butt molybdenum mine tailing, and HCl concentration is 36%WT.
Major advantage of the present invention is:
1. the present invention destroys with SiO by hydrofluoric acid-hydrochloric acid heat pre-treatment
2Be the constraint of the mineral lattice in the molybdenum mine tailing of main thing phase to molybdenum, or (most of Mo can exist with the form that combines with Si to make molybdenum in the ore deposit be converted into the compound of low vapour point, high-temperature stability is better), the volatilizing and enriching rate that realizes molybdenum under the hot conditions is higher, therefore, has important economic value.
2. because the present invention has found the method that the volatilization of the molybdenum in the molybdenum mine tailing is utilized, though make the low mine tailing discharge capacity of molybdenum content huge, the also appreciable molybdenum mine tailing of metal molybdenum content obtains utilizing, and therefore has environmental benefit.
3. the silicon tetrafluoride gas used water that produces in the technological process of the present invention absorbs and hydrolysis, filters and make silicate fluoride solution; And the final residue after the thermal treatment of molybdenum mine tailing can be used as utilizations again such as road-making material.The present invention has solved the molybdenum mine tailing and has piled up dust pollution and the rubble flow hidden danger that is caused from the source, and the technological process product is recyclable, has reduced production cost.
Embodiment
Embodiment 1
Adopt Huludao City's molybdenum mine tailing, the main thing of mine tailing is SiO mutually
2, molybdenum content is 0.19%, with the mine tailing ball milling to particle diameter in 0.08～0.1mm scope, add water and stir, make the molybdenum mine tailing form water ratio be 30%～40%WT have certain rheological properties can molybdenum mine tailing mud so as better and acid be in contact with one another reaction.Add 0.25mlHF (hydrofluoric acid) metering by every g butt molybdenum mine tailing then, the concentration of this HF is 40%WT, wait the reaction bubble collapse after, add HCl (hydrochloric acid), HCl concentration is 36%WT, the add-on of hydrochloric acid is a 0.25ml HCl/g butt molybdenum mine tailing.Add acid back and add a cover heating 40min under 250 ℃, lid is removed in the heat treated back that finishes, and is dried to till quality change＜5% under 65 ℃.Molybdenum mine tailing after the HF-HCl heat pre-treatment, under 900 ℃ of conditions, heat-treat, molybdenum is moved in gas phase, obtain containing the flue gas of molybdenum and silicon tetrafluoride, the vaporization at high temperature rate of molybdenum reaches 85.7%, collects thermal treatment and contains molybdenum and silicon tetrafluoride flue gas, and it is condensed to below 250 ℃, obtain containing the material of molybdenum or molybdenum compound, reclaim stand-by; Remaining thermal treatment flue gas water absorbs and hydrolysis, filters, and makes silicate fluoride solution; The residue that heat treatment process stays is as road-making material.
Embodiment 2
Except the add-on of hydrochloric acid is that all the other are identical with embodiment 1 the 1ml HCl/g butt molybdenum mine tailing, the vaporization at high temperature rate of 900 ℃ of following molybdenums can reach 98.6%.
Embodiment 3
Except the add-on of hydrofluoric acid is a 0.625ml/g butt molybdenum mine tailing, the add-on of hydrochloric acid is that all the other are identical with embodiment 1 outside the 0.625ml/g butt molybdenum mine tailing, and the vaporization at high temperature rate of 900 ℃ of following molybdenums can reach 85.8%.
Embodiment 4
Except the add-on of hydrofluoric acid is a 1ml/g butt molybdenum mine tailing, the add-on of hydrochloric acid is that all the other are identical with embodiment 1 outside the 0.25ml HCl/g butt molybdenum mine tailing, and the vaporization at high temperature rate of 900 ℃ of following molybdenums can reach 70.8%.
Claims (1)
1. the method for a volatilizing and enriching molybdenum from the molybdenum mine tailing is characterized in that: at first, the molybdenum mine tailing is ground into 0.08-0.1mm, regulates its water ratio to 30%～40%, make it form molybdenum mine tailing mud; Then, in molybdenum mine tailing mud, add hydrofluoric acid, vigorous reaction take place produce a large amount of bubbles, treat that bubble collapse reacts completely after, add hydrochloric acid again; Be heated to 200～250 ℃ immediately and add a cover the muriate generation that insulation 30～50min impels molybdenum, remove lid then, under 65 ℃, be dried to quality change＜5%; At last, with the pretreated molybdenum mine tailing of acid 900 ℃ of following thermal treatments, molybdenum is moved in gas phase, the vaporization at high temperature rate of molybdenum reaches 70%～98.6%, obtain containing the flue gas and the thermal treatment residue of molybdenum and silicon tetrafluoride, the thermal treatment residue is as road-making material, condenses to 250 ℃ or be lower than 250 ℃ after flue gas is collected, obtain containing the material of molybdenum or molybdenum compound, reclaim; Remaining flue gas water absorbs and hydrolysis, filters, and filtrate is silicate fluoride solution;
The add-on of above-mentioned hydrofluoric acid adds 0.25ml～1ml HF metering by every g butt molybdenum mine tailing, and the mass percentage concentration of this HF is 40%WT;
The add-on of above-mentioned hydrochloric acid is 0.25ml～1ml HCl/g butt molybdenum mine tailing, and HCl concentration is 36%WT.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100489125A CN101514403B (en) | 2009-04-07 | 2009-04-07 | Method for volatilizing and enriching molybdenum from molybdenum tailings |
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|---|---|---|---|
| CN2009100489125A CN101514403B (en) | 2009-04-07 | 2009-04-07 | Method for volatilizing and enriching molybdenum from molybdenum tailings |
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|---|---|
| CN101514403A true CN101514403A (en) | 2009-08-26 |
| CN101514403B CN101514403B (en) | 2010-09-22 |
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| CN2009100489125A Expired - Fee Related CN101514403B (en) | 2009-04-07 | 2009-04-07 | Method for volatilizing and enriching molybdenum from molybdenum tailings |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111349782A (en) * | 2020-04-15 | 2020-06-30 | 中核沽源铀业有限责任公司 | Method for improving filtering efficiency of complex molybdenum ore direct leaching ore pulp |
-
2009
- 2009-04-07 CN CN2009100489125A patent/CN101514403B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111349782A (en) * | 2020-04-15 | 2020-06-30 | 中核沽源铀业有限责任公司 | Method for improving filtering efficiency of complex molybdenum ore direct leaching ore pulp |
| CN111349782B (en) * | 2020-04-15 | 2022-04-22 | 中核沽源铀业有限责任公司 | Method for improving filtering efficiency of complex molybdenum ore direct leaching ore pulp |
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| CN101514403B (en) | 2010-09-22 |
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Granted publication date: 20100922 Termination date: 20130407 |