CN102205268A - Wet processing method of tungsten-containing molybdenum oxide rough concentrate - Google Patents
Wet processing method of tungsten-containing molybdenum oxide rough concentrate Download PDFInfo
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- CN102205268A CN102205268A CN2011101282571A CN201110128257A CN102205268A CN 102205268 A CN102205268 A CN 102205268A CN 2011101282571 A CN2011101282571 A CN 2011101282571A CN 201110128257 A CN201110128257 A CN 201110128257A CN 102205268 A CN102205268 A CN 102205268A
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- rough concentrate
- molybdenum
- molybdenum oxide
- tungstenic
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Abstract
The invention discloses a wet processing method of tungsten-containing molybdenum oxide rough concentrate, which sequentially comprises the following steps: (1) performing sodium carbonate leaching on the tungsten-containing molybdenum oxide rough concentrate; (2) filtering and separating; (3) adding inorganic acid into the filtrate to adjust the pH value to 3.5-6.5; (4) adding a precipitator into the solution with the adjusted pH value to carry out molybdenum precipitation and tungsten precipitation reaction; (5) and filtering, washing and drying the filtered precipitate to obtain a mixture of calcium molybdate and calcium tungstate. The invention has the advantages of high molybdenum precipitation rate and low molybdenum content in the precipitated solution, and does not need an ion exchange process.
Description
Technical field
A kind of wet treatment method of tungstenic molybdenum oxide rough concentrate relates to a kind of low-grade oxidizing molybdenum tungsten bulk concentrate Wet-process metallurgy method.
Background technology
Molybdenum ore has two kinds of sulfuration molybdenum ore and oxidizing molybdenum ores, and the enrichment of sulfuration molybdenum ore is a desulfurization with roasting technique behind the molybdenum concntrate, obtains the molybdenum oxide concentrate, is used further to produce molybdenum-iron or molybdenum chemical products afterwards; And oxidizing molybdenum ore is a kind of difficult ore dressing, be difficult to obtain qualified molybdenum oxide concentrate product, generally be to be rough concentrate by the ore dressing means with the oxidizing molybdenum ore enrichment earlier, the method by chemical industry is enriched to qualified molybdenum oxide concentrate then, is used further to molybdenum-iron smelting or the processing of molybdenum chemical products.
For low-grade tungstenic molybdenum oxide rough concentrate, because the molybdenum grade is low, impurity content height such as phosphorus, sulphur, fluorine can't be directly used in molybdenum-iron or the production of tungstenic ferro-molybdenum; Traditional molybdenum chemical process is the thorough tungsten in the Separation of Molybdenum again, is difficult to produce independent tungsten, molybdenum chemical products.Because low-grade tungstenic molybdenum oxide rough concentrate uses approach limited, therefore, this type rough concentrate selling price is low, and tungsten is without charge, and this brings difficulty for the development and use of tungstenic oxidizing molybdenum ore.
At present, low-grade oxidizing molybdenum concentrate to tungstenic, the normal method that adopts direct hydrochloric acid to leach is handled, to reach the effect of initial gross separation tungsten, but for the low-grade molybdenum concntrate of the high tungstenic of carbonate content is main gangue mineral (impure phosphorus, sulphur, fluorine height), the difficulty of this method is big, the production cost height.
Summary of the invention
This patent is a research object with the low-grade oxidizing molybdenum rough concentrate (containing a large amount of carbonate gangue mineral) of tungstenic, has proposed a kind of method that can fully utilize tungsten, and this method production cost is low, the rate of recovery is high, and product can be directly used in the tungsten ferroalloy smelting.
The objective of the invention is to be achieved through the following technical solutions.
A kind of wet treatment method of tungstenic molybdenum oxide rough concentrate is characterized in that the steps in sequence of its wet-treating process comprises:
(1) tungstenic molybdenum oxide rough concentrate being carried out sodium carbonate leaches;
(2) isolated by filtration;
(3) in the filtrate that filters to isolate, add inorganic acid and adjust pH to 3.5-6.5;
(4) add precipitating reagent in the solution of adjusting behind the pH, sink molybdenum, tungsten reacts;
(5) filter, with the sediment that leaches wash, drying obtains calcium molybdate and the mixture of artificial schellite.
The wet treatment method of a kind of tungstenic molybdenum oxide rough concentrate of the present invention is characterized in that inorganic acid in the step (3) can be any of sulfuric acid, hydrochloric acid, nitric acid.
The wet treatment method of a kind of tungstenic molybdenum oxide rough concentrate of the present invention is characterized in that the precipitating reagent in the step (4) can be the salt or the quick lime of calcic.
The wet treatment method of a kind of tungstenic molybdenum oxide rough concentrate of the present invention, the leaching process that it is characterized in that its step (1) is to carry out at airtight container, its extraction temperature is 130-200 ℃, extraction time 30-80min; Na
2CO
3Addition is 1-4 a times of theoretical amount, and liquid-solid mass ratio is 1-3.
The wet treatment method of a kind of tungstenic molybdenum oxide rough concentrate of the present invention is characterized in that the filter residue of the isolated by filtration process of step (2) is carried out water washing, washs the filtered fluid that 1-2 time wash water can add step (3); Also can return step (1) together and leach batching with 3-4 wash water.
The wet treatment method of a kind of tungstenic molybdenum oxide rough concentrate of the present invention, the precipitation dosage that it is characterized in that step (4) adding are 2-3 times of theoretical amount; Reaction temperature is 60-90 ℃, and the reaction time is 0.5-2.5h.
The wet treatment method of a kind of tungstenic molybdenum oxide rough concentrate of the present invention is characterized in that the filtration rear filtrate of step (5) returns step (3).
The wet treatment method of a kind of tungstenic molybdenum oxide rough concentrate of the present invention is characterized in that the drying of step (5) is carried out under 105 ℃.
The wet treatment method of a kind of tungstenic molybdenum oxide rough concentrate of the present invention, it is higher to have a molybdenum rate of deposition, and post precipitation liquid contains the lower advantage of molybdenum (about Mo0.01g/L), and no longer needs ion-exchange process to reclaim molybdenum in the liquid of heavy back.
Description of drawings
Fig. 1 is a process chart of the present invention.
The specific embodiment
A kind of wet treatment method of tungstenic molybdenum oxide rough concentrate, the step of its processing procedure comprises:
(1) tungstenic molybdenum oxide rough concentrate being carried out sodium carbonate leaches; Extraction temperature is 130-200 ℃, and the own pressure that extraction time 30-80min, leaching process utilize autoclave to produce is finished leaching, and pressure following temperature changes and changes, and the leaching pressure limit is 0-2MPa; Na
2CO
3Addition be by write chemical equation CaMoO4+Na2CO3=Na2MoO4+CaCO3 ↓;
The 1-4 of the theoretical value of CaWO4+Na2CO3=Na2WO4+CaCO3 ↓ calculate doubly counts; Liquid-solid mass ratio is 1-3;
(2) isolated by filtration;
(3) in the filtrate that filters to isolate, add inorganic acid and adjust pH to 3.5-6.5;
(4) adjust in the filtered fluid behind the pH and add precipitating reagent, sink molybdenum, tungsten reacts, and ion-reaction equation is: Na2MoO4+Ca
2+=CaMoO4 ↓+2Na
+, Na2WO4+ Ca
2+=CaWO4 ↓+2Na
+, reaction temperature 70-90 ℃, precipitation dosage is 2-3 times of theoretical amount, and the reaction time is 0.5-2.5h, and the pH value is 7-8;
(5) filter, the sediment that leaches is washed, carries out the mixture that drying obtains calcium molybdate and artificial schellite under 105 ℃ of temperature.
Embodiment 1
Raw material is for taking from mining industry Henan, Sheng source Sanmenxia Chemical Plant, molybdenum-tungsten oxide rough concentrate molybdenum, W content Mo5.27 %, WO
31.34%, the molybdenum-tungsten oxide raw ore is milled to-0.074mm accounts for 60%, and carries out flotation; Be used in combination hydroclone classification, vortex sieve, vibratory sieve and flow type grader the mineral grain that obtains carried out classification, greater than 0.031mm be coarse fraction, smaller or equal to 0.031mm is fine fraction.Fine fraction molybdenum oxide tungsten ore adding water and sodium carbonate are carried out the high pressure leaching, and extraction temperature is 130 ℃, extraction time 80min, Na
2CO
3Be 3 times of theoretical amount, liquid-solid ratio is 3; Carry out filtration washing then, filtrate and 1-2 the wash water adding inorganic acid (pH value 3.5) that obtains carried out preliminary treatment, 3-4 wash water returned high pressure leach batching; Add calcium oxide to the liquid that obtains after treatment, adjust 70 ℃ of reaction temperatures, precipitation dosage is 2 times of theoretical amount, and the pH value is 7-8, reaction time 1.5h; Calcium molybdate, artificial schellite that precipitation is obtained carry out filtration washing, with the filtration cakes torrefaction that obtains, obtain product Mo41.84 %, WO
39.38%, will sink that liquid part Returning process uses behind the molybdenum.
Embodiment 2
Raw material is for taking from the mining industry of golden port, molybdenum-tungsten oxide rough concentrate molybdenum, W content Mo5 %, WO
31.4%, the molybdenum-tungsten oxide raw ore is milled to-0.074mm accounts for 60%, and carries out flotation; Be used in combination hydroclone classification, vortex sieve, vibratory sieve and flow type grader the mineral grain that obtains carried out classification, greater than 0.031mm be coarse fraction, smaller or equal to 0.031mm is fine fraction.Fine fraction molybdenum oxide tungsten ore adding water and sodium carbonate are carried out the high pressure leaching, and extraction temperature is 200 ℃, extraction time 30min, Na
2CO
3Be 1 times of theoretical amount, liquid-solid ratio is 1.5; Carry out filtration washing then, filtrate and 1-2 the wash water adding inorganic acid (pH value 4) that obtains carried out preliminary treatment, 3-4 wash water returned high pressure leach batching; Add calcium oxide to the liquid that obtains after treatment, adjust 80 ℃ of reaction temperatures, precipitation dosage is 3 times of theoretical amount, and the pH value is 7-8, reaction time 0.5h; Calcium molybdate, artificial schellite that precipitation is obtained carry out filtration washing, with the filtration cakes torrefaction that obtains, obtain product Mo40.12 %, WO
310.14%, will sink that the liquid Returning process uses behind the molybdenum.
Embodiment 3
Raw material is iron resource factory in taking from, molybdenum-tungsten oxide rough concentrate molybdenum, W content Mo5.02 %, WO
31.0%, the molybdenum-tungsten oxide raw ore is milled to-0.074mm accounts for 60%, and carries out flotation; Be used in combination hydroclone classification, vortex sieve, vibratory sieve and flow type grader the mineral grain that obtains carried out classification, greater than 0.031mm be coarse fraction, smaller or equal to 0.031mm is fine fraction.Fine fraction molybdenum oxide tungsten ore adding water and sodium carbonate are carried out the high pressure leaching, and extraction temperature is 150 ℃, extraction time 60min, Na
2CO
3Be 2 times of theoretical amount, liquid-solid ratio is 2; Carry out filtration washing then, filtrate and 1-2 the wash water adding inorganic acid (pH value 5) that obtains carried out preliminary treatment, 3-4 wash water returned high pressure leach batching; Add calcium oxide to the liquid that obtains after treatment, adjust 90 ℃ of reaction temperatures, precipitation dosage is 2.45 times of theoretical amount, and the pH value is 7-8, reaction time 1h; Calcium molybdate, artificial schellite that precipitation is obtained carry out filtration washing, with the filtration cakes torrefaction that obtains, obtain product Mo40.16 %, WO
37.34%, will sink that the liquid Returning process uses behind the molybdenum.
Embodiment 4
Raw material selects oxidizing molybdenum ore for taking from Inner Mongol difficulty, molybdenum-tungsten oxide rough concentrate molybdenum, W content Mo4.99 %, WO
31.41%, the molybdenum-tungsten oxide raw ore is milled to-0.074mm accounts for 60%, and carries out flotation; Be used in combination hydroclone classification, vortex sieve, vibratory sieve and flow type grader the mineral grain that obtains carried out classification, greater than 0.031mm be coarse fraction, smaller or equal to 0.031mm is fine fraction.Fine fraction molybdenum oxide tungsten ore adding water and sodium carbonate are carried out the high pressure leaching, and extraction temperature is 160 ℃, extraction time 50min, Na
2CO
3Be 4 times of theoretical amount, liquid-solid ratio is 1; Carry out filtration washing then, filtrate and 1-2 the wash water adding nitric acid (pH value 6) that obtains is carried out preliminary treatment, 3-4 wash water returned high pressure leach batching; Add calcium oxide to the liquid that obtains after treatment, adjust 85 ℃ of reaction temperatures, precipitation dosage is 2.15 times of theoretical amount, and the pH value is 7-8, reaction time 1h; Calcium molybdate, artificial schellite that precipitation is obtained carry out filtration washing, with the filtration cakes torrefaction that obtains, obtain product Mo40.12 %, WO
310.21%, will sink that the liquid Returning process uses behind the molybdenum.
Embodiment 5
Raw material is for taking from the mine, Ejina Banner, molybdenum-tungsten oxide rough concentrate molybdenum, W content Mo5.44 %, WO
31.21%, the molybdenum-tungsten oxide raw ore is milled to-0.074mm accounts for 60%, and carries out flotation; Be used in combination hydroclone classification, vortex sieve, vibratory sieve and flow type grader the mineral grain that obtains carried out classification, greater than 0.031mm be coarse fraction, smaller or equal to 0.031mm is fine fraction.Fine fraction molybdenum oxide tungsten ore adding water and sodium carbonate are carried out the high pressure leaching, and extraction temperature is 170 ℃, extraction time 40min, Na
2CO
3Be 2.5 times of theoretical amount, liquid-solid ratio is 1.5; Carry out filtration washing then, the filtrate that obtains is added sulfuric acid (pH value 6.5) carry out preliminary treatment, 1-2 wash water and 3-4 wash water merging are returned high pressure leaching batching; Add calcium oxide to the liquid that obtains after treatment, adjust 75 ℃ of reaction temperatures, precipitation dosage is 2.5 times of theoretical amount, and the pH value is 7-8, reaction time 2.5h; Calcium molybdate, artificial schellite that precipitation is obtained carry out filtration washing, filtration cakes torrefaction, obtain product Mo43.52 %, WO
38.47%, will sink that the liquid Returning process uses behind the molybdenum.
Claims (8)
1. the wet treatment method of a tungstenic molybdenum oxide rough concentrate is characterized in that the steps in sequence of its wet-treating process comprises:
(1) tungstenic molybdenum oxide rough concentrate being carried out sodium carbonate leaches;
(2) isolated by filtration;
(3) in the filtrate that filters to isolate, add inorganic acid and adjust pH to 3.5-6.5;
(4) add precipitating reagent in the solution of adjusting behind the pH, sink molybdenum, tungsten reacts;
(5) filter, with the sediment that leaches wash, drying obtains calcium molybdate and the mixture of artificial schellite.
2. the wet treatment method of tungstenic molybdenum oxide rough concentrate according to claim 1 is characterized in that inorganic acid in the step (3) can be any of sulfuric acid, hydrochloric acid, nitric acid.
3. the wet treatment method of tungstenic molybdenum oxide rough concentrate according to claim 1 is characterized in that the precipitating reagent in the step (4) can be the salt or the quick lime of calcic.
4. the wet treatment method of tungstenic molybdenum oxide rough concentrate according to claim 1, the leaching process that it is characterized in that its step (1) is to carry out at airtight container, its extraction temperature is 130-200 ℃, extraction time 30-80min; Na
2CO
3Addition is 1-4 a times of theoretical amount, and liquid-solid mass ratio is 1-3.
5. the wet treatment method of tungstenic molybdenum oxide rough concentrate according to claim 1 is characterized in that the filter residue of the isolated by filtration process of step (2) is carried out water washing, washs the filtered fluid that 1-2 time wash water can add step (3); Also can return step (1) together and leach batching with 3-4 wash water.
6. the wet treatment method of tungstenic molybdenum oxide rough concentrate according to claim 1, the precipitation dosage that it is characterized in that step (3) adding are 2-3 times of theoretical amount; Reaction temperature is 60-90 ℃, and the reaction time is 0.5-2.5h.
7. the wet treatment method of tungstenic molybdenum oxide rough concentrate according to claim 1 is characterized in that the filtration rear filtrate of step (5) returns step (3).
8. the wet treatment method of tungstenic molybdenum oxide rough concentrate according to claim 1 is characterized in that the drying of step (5) is carried out under 105 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102912129A (en) * | 2012-11-14 | 2013-02-06 | 中湘钨业股份有限公司 | Method for recycling tungsten in liquids after tungsten smelting exchanges |
| CN105567973A (en) * | 2014-10-11 | 2016-05-11 | 江苏光明新材料有限公司 | Method for preparing ferro-nickel alloy and ferrotungsten-molybdenum alloy from waste material containing tungsten, molybdenum and nickel |
| CN106552712A (en) * | 2016-12-07 | 2017-04-05 | 广西大学 | A kind of method that Mo-bearing Iron Ores are reclaimed in the mine tailing from scheelite |
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| CN1177012A (en) * | 1997-06-23 | 1998-03-25 | 贵州天星钼镍冶金有限公司 | Process for separation molybdenum and nickel from black shale by sodium carbonate conversion treatment |
| RU2296802C1 (en) * | 2005-07-11 | 2007-04-10 | Государственное Учреждение Институт металлургии Уральского отделения Российской Академии Наук (ГУ ИМЕТ УрО РАН) | Method of extraction of molybdenum from molybdenum-containing cinder |
| CN101333598A (en) * | 2008-01-17 | 2008-12-31 | 郴州钻石钨制品有限责任公司 | Method for separating and extracting metallic tungsten and molybdenum from molybdenum removal slag generated by smelting tungsten |
| CN101792852A (en) * | 2009-11-17 | 2010-08-04 | 灵宝市金源矿业有限责任公司 | Processing for recovering low-grade molybdenum oxide concentrate through wet process |
-
2011
- 2011-05-18 CN CN2011101282571A patent/CN102205268A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1177012A (en) * | 1997-06-23 | 1998-03-25 | 贵州天星钼镍冶金有限公司 | Process for separation molybdenum and nickel from black shale by sodium carbonate conversion treatment |
| RU2296802C1 (en) * | 2005-07-11 | 2007-04-10 | Государственное Учреждение Институт металлургии Уральского отделения Российской Академии Наук (ГУ ИМЕТ УрО РАН) | Method of extraction of molybdenum from molybdenum-containing cinder |
| CN101333598A (en) * | 2008-01-17 | 2008-12-31 | 郴州钻石钨制品有限责任公司 | Method for separating and extracting metallic tungsten and molybdenum from molybdenum removal slag generated by smelting tungsten |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102912129A (en) * | 2012-11-14 | 2013-02-06 | 中湘钨业股份有限公司 | Method for recycling tungsten in liquids after tungsten smelting exchanges |
| CN105567973A (en) * | 2014-10-11 | 2016-05-11 | 江苏光明新材料有限公司 | Method for preparing ferro-nickel alloy and ferrotungsten-molybdenum alloy from waste material containing tungsten, molybdenum and nickel |
| CN106552712A (en) * | 2016-12-07 | 2017-04-05 | 广西大学 | A kind of method that Mo-bearing Iron Ores are reclaimed in the mine tailing from scheelite |
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Application publication date: 20111005 |