CN101328540B - Method for reclaiming sodium molybdate solution from molybdenum-containing leached residue - Google Patents
Method for reclaiming sodium molybdate solution from molybdenum-containing leached residue Download PDFInfo
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- CN101328540B CN101328540B CN2008100457172A CN200810045717A CN101328540B CN 101328540 B CN101328540 B CN 101328540B CN 2008100457172 A CN2008100457172 A CN 2008100457172A CN 200810045717 A CN200810045717 A CN 200810045717A CN 101328540 B CN101328540 B CN 101328540B
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- molybdenum
- sodium molybdate
- molybdate solution
- liquid separation
- slip
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- 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 belongs to a method for reclaiming sodium molybdate liquid from leaching dregs generated in the molybdenum smelting process. The method comprises the following steps: molybdenum containing leaching dregs is mixed with pyrolusite powder, water and phosphoric acid and the mixed pulp is adjusted; under the condition of controlling the acidity-basicity of the pulp, the pulp is subjected to a boiling reaction and then the solid-liquid separation and the washing to obtain the sodium molybdate liquid. In the invention, the pyrolusite powder is used as an oxidant and the phosphoric acid is used as a decomposition agent of insoluble molybdenate, and the reaction is performed at the boiling temperature and in the normal pressure, the method has the characteristics of simple reclaiming method, high efficiency, no exhaust gas emission and low cost, and can reclaim more than 90 percent of the molybdenum in the leaching dregs in the mode of the sodium molybdate liquid; moreover, the method overcomes the defects of high energy consumption and high reagent consumption, or highly priced auxiliary materials and the existence of chlorine in the reclaiming liquid which is harmful to the subsequent production, or serious corrosion, etc. in the prior technology.
Description
Technical field
The invention belongs to a kind of method that from the leached mud that the molybdenum smelting process produces, reclaims sodium molybdate solution.Particularly a kind of pyrolusite powder (manganese sand) and phosphoric acid of utilizing is with the method for the molybdenum in the leached mud with the form recovery of sodium molybdate solution; Adopt this method can the molybdenum more than 90% in the leached mud be recycled.
Background technology
The hydrometallurgy of molybdenum mainly is divided into ammonia leaching process and alkaline leaching both at home and abroad, but no matter adopts which kind of process method, all that output is a large amount of molybdenum-containing leached residues.The main existence form of molybdenum is the molybdenum dioxide that roasting process takes off the halfway moly-sulfide of S, oxygen debtization generation in the slag; And insoluble molybdate such as lead molybdate, calcium molybdate etc.
In the leached mud there be the main recovery method of molybdenum: the yellow soda ash sintering process; This method is the sulphur that utilizes in the airborne oxygen oxidation sludge; Soda decomposes molybdate and oxide compound down at 700～750 ℃ and generates Sodium orthomolybdate, and this method leaching yield is high, but energy consumption is high, reagent consumption is big; Soda ash directly leaches, and this method is to utilize soda ash to leach down directly at 90～95 ℃, can leached mud in CaMoO
4, Fe (MoO
4)
3The molybdenum that form exists; Acid decomposition, this method are to utilize 20%～30% hydrochloric acid to decompose leached mud, and there is the volatility of hydrochloric acid in this method and corrodes comparatively serious; And need molybdenum (" molybdenum metallurgy ", press of Central South University, Xiang Tiegen in the recovered acid salt decomposed solution; 2002, P132～136); Also can decompose indissoluble molybdate (" utilizing ammonia leaching residue manufacture Sodium orthomolybdate ", China molybdenum industry, 2003.4, P32～35) with hydrochlorate earlier before, above method mainly reclaims the molybdenum that exists with insoluble molybdate form, to MoS
2And MoO
2Effect is little.Hypochlorite decomposition method, or hypochlorite and soda associating lixiviation process, these class methods are to MoS
2And MoO
2Leaching effect is better, but the auxiliary material hypochlorite is more expensive, and brings certain chlorine root into, and subsequent processing device is caused corrosion (" the hypochlorite decomposition technique of molybdenum-containing waste slag ", China molybdenum industry, 2002.10, P20～23) easily.
Summary of the invention
The objective of the invention is defective, study a kind of method that from molybdenum-containing leached residue, reclaims sodium molybdate solution to the background technology existence.Easy, efficient to realize recovery method, atmospheric operation under boiling temperature effectively improves the recovery of molybdenum, reduces purposes such as cost recovery and non-exhaust emission.
Solution of the present invention is at first the wash water after the molybdenum-containing leached residue material that produces in the molybdenum smelting process and pyrolusite powder (manganese sand), water or the solid-liquid separation and phosphoric acid to be mixed to size mixing; Boiling reaction under the condition of control slip potential of hydrogen; Carry out then solid-liquid separation, the washing promptly get sodium molybdate solution, thereby realize its goal of the invention.Therefore, the inventive method comprises:
A. prepare burden, size mixing: will (molybdenum smelt in produce) molybdenum-containing leached residue material and pyrolusite powder and the water or the wash water after C step solid-liquid separation that account for this dried slag charge weight 15～100wt% add in the lump in the reactive tank, mix and stir that to be made into density be 1.2～1.5g/cm
3Slurry, do to leach the ratio that slag charge adds 10～50ml in every kg then, adding concentration is the phosphoric acid of 85wt%, the back gained slip that stirs is for use, the manganese dioxede in powder amount of adding is with contained MoO
2The weight meter;
B. reacting by heating:, add sodium hydroxide or its solution simultaneously the pH value of slip is controlled in 8～11 scopes boiling reaction 1.5～3.5 hours with A operation gained slip stirring heating;
C. solid-liquid separation: gained material after the B operation reacting by heating is sent into filter carry out solid-liquid separation, filtrating is sodium molybdate solution; Filter residue adopts the pure water washing of 1～3 times of amount of filtrate volume again, its washings or incorporate filtrating into as the sodium molybdate solution product, or return the A operation and be used to allocate slip.
In batching, the wash water after phosphoric acid and water or the solid-liquid separation is added simultaneously in the operation of sizing mixing and then the density of slip is transferred to 1.2～1.5g/cm
3And said B operation reacting by heating gained material is carried out solid-liquid separation, be that press filtration or centrifuging separate.
The present invention adopts pyrolusite powder as oxygenant; Phosphoric acid is as the decomposition agent of insoluble molybdate; Under boiling temperature and normal pressure, react; Recovery method is easy, efficient is high and have, and non-exhaust emission can be recycled the molybdenum more than 90% in the leached mud and characteristics such as cost recovery is low with the form of sodium molybdate solution.
Embodiment
Embodiment 1:A. batching, size mixing: the Luanchuan calcining that at first 163kg is contained molybdenum 19.91wt% leaches dried slag and MnO
2Content is that the pyrolusite powder 125kg of 60wt% sends in the reactive tank, adds 1.8m then
3After (1800kg) water mixes, add concentration and be 85% phosphoric acid 22.2kg and stir, the gained slip is for use;
B. reacting by heating: with A operation gained slip heated and stirred, slowly add sodium hydroxide solution simultaneously, with the pH value of slip be controlled at about 9, boiling reaction 2.0 hours;
C. solid-liquid separation: will send into plate-and-frame filter press through the material after the B operation reacting by heating and filter, molybdenum concentration be the sodium molybdate solution 1.6m that 14.88g/ rises
3And then employing 2.0m
3Pure water washing filter residue, getting molybdenum concentration is the sodium molybdate solution 2m that 3.2g/ rises
3(wash water), this wash water and aforementioned filtrating merge to such an extent that molybdenum concentration is the sodium molybdate solution that 7.50g/ rises; This solution can be used as the liquid stock of subsequent production and uses.
Present embodiment tailings dry weight 240kg, wherein contain molybdenum 0.93%, the recovery of molybdenum is 93.12%.
Embodiment 2: the Luonan calcining that will contain molybdenum 15.0wt% leaches dried slag 250.3kg and 100kg contains MnO
2The pyrolusite powder of 60wt% places in the reactive tank, adds the residue washing liquid 2.0m contain after the solid-liquid separation that molybdenum 3.5g/ rises again
3Reaching concentration is 85% phosphatase 11 6.8kg, mixes, and the gained slip is for use;
Above-mentioned gained slip is heated under agitation condition; The pH value of feed liquid is controlled in 9.5～10 the scope through adding sodium hydroxide solution simultaneously; After the boiling reaction 3.0 hours, send into plate-and-frame filter press and filter, promptly getting molybdenum concentration is the sodium molybdate solution 1.8m that 20.16g/ rises
3Filter residue is used 2m
3The pure water washing, getting molybdenum concentration is that 3.5g/ rises sodium molybdate solution (washings) 2m
3, this washcoated liquid returns in order to the modulation slip.
The recovery of present embodiment molybdenum reaches 96.63%, tailings dry weight 258.0kg, wherein contains molybdenum only 0.49%.
Embodiment 3: the big Black Hills calcining that at first will contain molybdenum 14.61wt% leaches dried slag 173.7kg, MnO
2Content is pyrolusite powder 66kg, the water 1.5m of 60wt%
3And concentration is that 85% phosphatase 11 5.0kg places in the reactive tank; After mixing; Slow adding sodium hydroxide solution is controlled at the pH value of feed liquid in 9～10 scopes under the stirring heating condition, and boiling reaction is after 1.5 hours, and getting molybdenum concentration through press filtration is the sodium molybdate solution 1.3m that 13.83g/ rises
3Filter residue is through 2.0m
3The pure water washing, getting molybdenum concentration is the sodium molybdate solution 2m that 3.0g/ rises
3, getting volume after two groups of solution mix is 3.3m
3, molybdenum concentration is the sodium molybdate solution that 7.17g/ rises.The liquid stock that this solution can be used as subsequent production uses.
The recovery of present embodiment molybdenum is 94.49%, and tailings dry weight 155.2kg wherein contains molybdenum 0.9%.
Claims (3)
1. from molybdenum-containing leached residue, reclaim the method for sodium molybdate solution, its method comprises:
A. prepare burden, size mixing: molybdenum-containing leached residue material and pyrolusite powder and the water or the wash water after C step solid-liquid separation that account for this dried slag charge weight 15～100wt% are added in the reactive tank in the lump, mix and stir that to be made into density be 1.2～1.5g/cm
3Slurry, do to leach the ratio that slag charge adds 10～50ml in every kg then, adding concentration is the phosphoric acid of 85wt%, the back gained slip that stirs is for use; The amount that adds pyrolusite powder is with contained MoO
2The weight meter;
B. reacting by heating:, add sodium hydroxide simultaneously the pH value of slip is controlled in 8～11 scopes boiling reaction 1.5～3.5 hours with A operation gained slip stirring heating;
C. solid-liquid separation: gained material after the B operation reacting by heating is sent into filter carry out solid-liquid separation, filtrating is sodium molybdate solution; Filter residue adopts the pure water washing of 1～3 times of amount of filtrate volume again, its washings or incorporate filtrating into as the sodium molybdate solution product, or return the A operation and be used to allocate slip.
2. by the said method that from molybdenum-containing leached residue, reclaims sodium molybdate solution of claim 1, it is characterized in that in batching, the operation of sizing mixing, the wash water after phosphoric acid and water or the solid-liquid separation being added simultaneously and then the density of slip being transferred to 1.2～1.5g/cm
3
3. by the said method that from molybdenum-containing leached residue, reclaims sodium molybdate solution of claim 1, it is characterized in that saidly B operation reacting by heating gained material is sent into filter carrying out solid-liquid separation, be that press filtration or centrifuging separate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100457172A CN101328540B (en) | 2008-08-01 | 2008-08-01 | Method for reclaiming sodium molybdate solution from molybdenum-containing leached residue |
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|---|---|---|---|
| CN2008100457172A CN101328540B (en) | 2008-08-01 | 2008-08-01 | Method for reclaiming sodium molybdate solution from molybdenum-containing leached residue |
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| Publication Number | Publication Date |
|---|---|
| CN101328540A CN101328540A (en) | 2008-12-24 |
| CN101328540B true CN101328540B (en) | 2012-05-23 |
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|---|---|---|---|
| CN2008100457172A Expired - Fee Related CN101328540B (en) | 2008-08-01 | 2008-08-01 | Method for reclaiming sodium molybdate solution from molybdenum-containing leached residue |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101780979B (en) * | 2009-01-15 | 2012-08-29 | 自贡硬质合金有限责任公司 | Method for recycling ammonium molybdate solution from molybdenum contained ammonia leaching residues |
| CN105950876B (en) * | 2016-05-09 | 2017-08-29 | 信丰华锐钨钼新材料有限公司 | A kind of method of ammonium molybdate solution magnesium chloride purification slag high-efficiency comprehensive utilization |
| CN108715944B (en) * | 2018-05-03 | 2020-02-18 | 中南大学 | One-step alkali leaching method for molybdenum calcine |
| CN108913916A (en) * | 2018-07-27 | 2018-11-30 | 成都虹波钼业有限责任公司 | A kind of method of molybdenum in normal pressure leaching calcium molybdate |
| CN109468468B (en) * | 2018-11-29 | 2021-04-13 | 中南大学 | Method for comprehensively utilizing and treating molybdenum-copper slag |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3896210A (en) * | 1972-12-19 | 1975-07-22 | Kennecott Copper Corp | Method for recovering molybdenum from particulate silicate slags |
| CN1455008A (en) * | 2003-05-16 | 2003-11-12 | 自贡硬质合金有限责任公司 | Method of producing sodium tungstate solution using scheelite powder as raw material |
| CN101049968A (en) * | 2007-05-15 | 2007-10-10 | 中南大学 | Method for associated producing ammonium molybdate and manganese sulfate by roasting molybdenite and pyrolusite |
-
2008
- 2008-08-01 CN CN2008100457172A patent/CN101328540B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3896210A (en) * | 1972-12-19 | 1975-07-22 | Kennecott Copper Corp | Method for recovering molybdenum from particulate silicate slags |
| CN1455008A (en) * | 2003-05-16 | 2003-11-12 | 自贡硬质合金有限责任公司 | Method of producing sodium tungstate solution using scheelite powder as raw material |
| CN101049968A (en) * | 2007-05-15 | 2007-10-10 | 中南大学 | Method for associated producing ammonium molybdate and manganese sulfate by roasting molybdenite and pyrolusite |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2003-183745A 2003.07.03 |
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Granted publication date: 20120523 Termination date: 20160801 |