CN107081220A - It is a kind of to improve the method for molybdenum oxide concentration effect in white tungsten flotation concentrate - Google Patents
It is a kind of to improve the method for molybdenum oxide concentration effect in white tungsten flotation concentrate Download PDFInfo
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- CN107081220A CN107081220A CN201710325108.1A CN201710325108A CN107081220A CN 107081220 A CN107081220 A CN 107081220A CN 201710325108 A CN201710325108 A CN 201710325108A CN 107081220 A CN107081220 A CN 107081220A
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- molybdenum
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- molybdenum oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/008—Organic compounds containing oxygen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/002—Inorganic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/018—Mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/007—Modifying reagents for adjusting pH or conductivity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/06—Depressants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
Abstract
The method that the present invention proposes molybdenum oxide concentration effect in a kind of white tungsten flotation concentrate of improvement, using molybdenum sulfide flotation tailing pulp as raw material, Scheelite Flotation ore deposit obtains being enriched with the white tungsten flotation concentrate of molybdenum oxide, including：Step one, molybdenum oxide modifying agent, regulator, selective depressant, collecting agent and potent dose of collecting agent are sequentially added into molybdenum sulfide flotation tailing pulp, normal temperature flotation is carried out, tungsten mixed crude concentrate slurry is obtained；Step 2, is concentrated to the product of step one；Step 3, pH regulators, reagent removal agent, selection inhibitor, collecting agent and potent dose of collecting agent are added into the product of step 2；Step 4, the white tungsten flotation concentrate that rear flotation obtains enrichment molybdenum oxide is diluted by the product of step 3；The present invention pointedly adds molybdenum oxide modifying agent in Tailings Slurry and molybdenum oxide surface property is modified, particularly molybdenum dioxide, molybdenum trioxide and calcium molybdate resource, greatly improves the content of molybdenum oxide in the scheelite of recovery.
Description
Technical field
The invention belongs to technical field of mineral processing, it is related to molybdenum oxide concentration effect in the white tungsten flotation concentrate of improvement, specifically
It is related to one kind and during recovery scheelite, improves the method that molybdenum recovery is aoxidized in white tungsten flotation concentrate from molybdenum sulfide flotation tailing.
Background technology
Molybdenum is a kind of important rare metal and strategic reserves resource, to whole national economy and human health, is all played
Extremely important effect.As Mo resource is exploited and using the continuous expansion of scale, the molybdenum ore simply easily selected is increasingly reduced,
Poor, thin, high oxidation rate molybdenum ore preparation proportion gradually increases, for the ore dressing of molybdenum, generally using hydrocarbon ils (kerosene and bavin
Oil) the floating technique of mill of making collecting agent reclaims molybdenite in ore.Because hydrocarbon oils collecting agent is only capable of by physisorption
In the good molybdenite particle surface of native floatability, the floatability of molybdenite is improved, the high efficiente callback of molybdenite is realized, but to ore deposit
Molybdenum oxide in stone causes the oxidation Mo resource in ore as resource of tailings is lost in without any collecting ability.
The recovery of molybdenum oxide belongs to global problem, and its difficulty selects reason to essentially consist in：1. molybdenum oxide is oxidized to ore deposit in table life
During, mineral lattice is by a certain degree of destruction, and the easily argillization in ore grinding influences its recovering effect；2. ore is usual
The oxysalt of a variety of cations of the same name is associated with, their property of swimming is close, in molybdenum oxide floatation process, makes it difficult to
Separated with the gangue mineral with cation of the same name, thus oxidation molybdenum concntrate product grade it is all relatively low, such as molybdenum calcium ore deposit be difficult with
The scheelite of association, calcite, fluorite, apatite etc. are separated in ore.At present, it is few for the beneficiation research of molybdenum oxide, grind
It is mainly molybdenum calcium ore deposit, ferrimolybdite and wulfenite to study carefully object, obtains its low-grade concentrate using flotation more, then using low-grade essence
Ore deposit carries out the Mo resource in the method recovery ore leached, and its cost is higher, and therefore, few enterprises can individually reclaim molybdenum oxide
Resource.
For Wolfram-molybdenum Deposits, its mineral processing circuit, which is used, first selects molybdenite, floating molybdic tailing to select the excellent of scheelite again
First flotation flowsheet：In white tungsten floatation process, obtain coarse-fine containing white tungsten and other calcium mineral frequently with fatty acid collecting agent
Ore deposit, then it is selected using the progress of Dinko Petrov method dialogue tungsten rough concentrate, obtain white tungsten fine ore.Because fatty acid collecting agent belongs to oxygen
Change ore deposit collecting agent, equally there is certain collecting ability to molybdenum oxide, so contain small amounts molybdenum in white tungsten fine ore, but by
In not reclaiming molybdenum oxide targetedly, still there is substantial amounts of oxidation Mo resource not recycled rationally in mine tailing, cause
The loss and waste of Mo resource.
At present, the research that white tungsten resource and oxidation Mo resource are reclaimed from Wolfram-molybdenum Deposits molybdenite flotation mine tailing is existing
Progress, Henan Luo Mu groups white tungsten resource of synthetical recovery from molybdenite flotation mine tailing has been carried out industrialized production, in floating molybdenum
WO in mine tailing3Grade is that in the case that 0.07~0.1%, molybdenum grade is 0.025% or so, collecting agent, one are made using oleate soap
Secondary roughing obtains WO3Grade is the tungsten rough concentrate that 1.6% or so, molybdenum grade is 0.16% or so, rough concentrate essence heating concentration,
Output WO3The rate of recovery 65% or so of content 25%~30%, the tungsten concentrate of the rate of recovery 30% of molybdenum content 2% or so, the technique
Mainly reclaim oxidation Mo resource in white tungsten resource, tungsten bulk concentrate do not reclaim targetedly therefore molybdenum the rate of recovery
It is very low.Zhengzhou Institute of Multipurpose Utilization of Mineral Resources, CAGS and Changsha Research Institute of Mining and Metallurgy Co., Ltd. disclose respectively
Processing technology for molybdenum and tungsten oxidized ore (CN101224441) and the ore dressing that white tungsten/oxidizing molybdenum ore is reclaimed from molybdenum sulfide flotation tailing
Method (CN102489407A), their identical point is：Use sized mixing with alkali, waterglass makees inhibitor, fatty acid soaps (emulsification or
It is modified) as scheelite and the collecting agent of molybdenum oxide, difference is the normal temperature flotation method that CN102489407A is used,
The heating floatation that CN101224441 is used.However, fatty acid soaps make collecting agent and can only reclaim scheelite in the two techniques
Molybdenum (tungsten) calcium ore deposit in (i.e. scheelite) and molybdenum oxide, to molybdine molybdite, the recovering effect extreme difference of wolfram ocher, causes this partial oxidation molybdenum and oxygen
Change the loss of tungsten resource, meanwhile, WO in the tungsten bulk concentrate that the two techniques are obtained3It is relatively low with molybdenum content, if directly
Tap into and handled into low scheelite middling production ammonium paratungstate technique (APT), production cost is higher, need to further handle ability
Use.
The content of the invention
In view of the deficienciess of the prior art, it is an object of the present invention to provide a kind of improve oxygen in white tungsten flotation concentrate
Change the method for molybdenum concentration effect, solve current molybdenum oxide and reclaim difficult, be lost in serious technical problem.
In order to solve the above-mentioned technical problem, the present invention, which is adopted the following technical scheme that, is achieved：
It is a kind of carry improve tungsten flotation concentrate in molybdenum oxide concentration effect method, this method using molybdenum sulfide flotation tailing pulp as
Raw material, Scheelite Flotation ore deposit obtains being enriched with the white tungsten flotation concentrate of molybdenum oxide；
Step includes：
Step one, sequentially added into molybdenum sulfide flotation tailing pulp molybdenum oxide modifying agent, regulator, selective depressant,
Collecting agent and potent dose of collecting agent, carry out normal temperature flotation, obtain tungsten mixed crude concentrate slurry；
Step 2, is concentrated to the product of step one；
Step 3, pH regulators, reagent removal agent, selective depressant, oleate soap and collecting are added into the product of step 2
Potent dose of agent；
Step 4, the white tungsten flotation concentrate that rear flotation obtains enrichment molybdenum oxide is diluted by the product of step 3；
The molybdenum oxide modifying agent includes Pb2+、Fe3+、Fe2+、Al3+、Ca2+、Mg2+And Ba2+In one or more elements；
The selective depressant includes modified water glass, phosphate, modified starch, dextrin, tannin, cellulose, winestone
One or more compositions in acid, citric acid, oxalic acid and phosphoramidic acid.
Molybdenum oxide, the tungsten included in the raw material is mainly deposited with calcium molybdate, molybdenum dioxide, molybdenum trioxide and wolframic acid calcium form
, and the one or more in quartz, calcite, fluorite and barite are included in the raw material.
Potent dose of the collecting agent include oxidation kerosene, oxidated diesel oil, sulfovinic acid soap and its ester, hydrocarbyl sulfonic soap and its
One or more compositions in ester, hydroximic acid, naphthalene and its derivative and alkyl bromination ammonium.
The collecting agent includes oleic acid and its derivative.
The product of step one carries out being concentrated into more than 60%.
Less than 20% is diluted in the step 4.
Molybdenum oxide modifying agent in molybdenum sulfide flotation tailing pulp per ton in the step one, regulator, selective depressant, catch
The addition for receiving agent and potent dose of collecting agent be respectively 100g~1000g, 500g~2000g, 200g~2000g, 100g~
500g and 50g~300g.
PH regulators in the step 3, reagent removal agent, selective depressant, the addition of collecting agent and potent dose of collecting agent
The accounting of step 2 product be respectively 100g/t~500g/t, 200g/t~800g/t, 3000g/t~8000g/t, 0~
100g/t and 0~50g/t.
The present invention compared with prior art, has the following technical effect that：
(1) present invention pointedly adds molybdenum oxide modifying agent in Tailings Slurry and molybdenum oxide surface property is modified,
Particularly molybdenum dioxide, molybdenum trioxide and calcium molybdate resource, collecting agent of the invention are total to using potent dose of collecting agent and oleate soap
Same-action, optionally adsorbs the recovery in modified oxidized molybdenum surface peening roughing section molybdenum oxide, with reference to rational flotation agent and
Floatation process, on the premise of white tungsten fine ore grade is not influenceed, the overall recovery of molybdenum can reach more than 75%, greatly improve recovery
Scheelite in molybdenum oxide content, solve current molybdenum oxide and reclaim difficult, be lost in serious problem.
(2) present invention adds the good calcic gangue mineral of selective depressant reduction floatability to selected bad shadow simultaneously
Ring, certain inhibitory action is played to gangue minerals such as fluorite, calcites by floating agent during heating reagent removal, meanwhile,
The white tungsten in part and molybdenum oxide is avoided to be lost in because of reagent removal with mine tailing by adding collecting agent during heating reagent removal.
Explanation is further explained in detail to the particular content of the present invention with reference to embodiments.
Embodiment
This method vulcanizes the molybdenum sulfide flotation tailing pulp after molybdenum ore as raw material using flotation, and therefrom Scheelite Flotation ore deposit, obtains richness
Collect the white tungsten flotation concentrate of molybdenum oxide.Wherein step one, molybdenum oxide modifying agent, tune are sequentially added into molybdenum sulfide flotation tailing pulp
Whole dose, selective depressant, collecting agent and potent dose of collecting agent, carry out normal temperature flotation, obtain tungsten mixed crude concentrate slurry；Oxidation
Molybdenum modifying agent occurs chemical reaction with molybdenum oxide mineral surfaces and produces the material easily acted on collecting agent.Regulator is in this step
Conventional selection, refers to this area ore dressing preparation, and the present invention selects sodium carbonate regulator.Wherein step 2, the production to step one
Thing carries out being concentrated into more than 60%, primarily to reduction energy consumption, saves production dosing.Wherein step 3, Xiang Bu
PH regulators, reagent removal agent, selective depressant, collecting agent and potent dose of collecting agent are added in rapid two product；PH regulators can
It is this area conventional selection with the best use of environment of regulating agent, the present invention selects sodium hydroxide, and reagent removal agent can remove arteries and veins
Stone mineral surfaces collecting agent, is this area conventional selection, and the present invention selects calcium ions and magnesium ions, and selective depressant can be optionally
Strengthen the inhibitory action to gangue mineral.Wherein step 4, is diluted rear flotation by the product of step 3 and obtains enrichment oxidation
The white tungsten flotation concentrate of molybdenum, the selected purpose of flotation is that target minreal and gangue mineral are separated, while pulp density is lower,
Separating effect is better.
Molybdenum oxide modifying agent in molybdenum sulfide flotation tailing pulp per ton in step one of the present invention, regulator, selective depressant,
The addition of collecting agent and potent dose of collecting agent be respectively 100g~1000g, 500g~2000g, 200g~2000g, 100g~
500g and 50g~300g；PH regulators in step 3, reagent removal agent, selective depressant, collecting agent and potent dose of collecting agent plus
It is respectively 100g/t~500g/t, 200g/t~800g/t, 3000g/t~8000g/t, 0 to enter amount in the accounting of step 2 product
~100g/t and 0~50g/t, only provides the specific implementation of the present invention with some value citing in the span of each raw material below
Example is, it is necessary to which explanation is that the invention is not limited in specific examples below, it should be understood that cover the span of the above, and
All equivalents done on the basis of technical scheme each fall within protection scope of the present invention.
Embodiment 1：
The method that the present embodiment provides molybdenum oxide concentration effect in a kind of white tungsten flotation concentrate of improvement, wherein, from Henan
Main tungsten mineral is scheelite in certain Wolfram-molybdenum Deposits molybdenite flotation mine tailing, mine tailing, and molybdenum ore thing is mainly molybdenum oxide, wherein three
Tungsten oxide content is 0.1%, and molybdenum content is 0.02% in molybdenum oxide, and mog is -200, content 65%.Specifically include as follows
Step：
Step one, lead ion molybdenum oxide modifying agent is sequentially added into the molybdenite flotation Tailings Slurry that concentration is 35%
200g/t, sodium carbonate regulator 1500g/t, modified water glass 1000g/t, citric acid 20g/t and modified starch 500g/t make arteries and veins
Stone inhibitor, oleate soap 300g/t makees collecting agent, and oxidation kerosene 150g/t, sulfovinic acid soap 100g/t make potent dose of collecting agent,
Selected through three coarse scans of one roughing, obtain tungsten mixed crude concentrate；
Step 2,65% is concentrated into by the product that step one is obtained；
Step 3, to step 2 product carry out heating reagent removal processing, be separately added into sodium hydroxide 400g/t make pH regulators,
Calcium ions and magnesium ions 500g/t makees reagent removal agent, modified water glass 5000g/t, citric acid 200g/t, modified starch 1500g/t, a small amount of oil
Sour potent dose of 20g/t of soap 20g/t and collecting agent, insulation slurry dilution to 18% concentration carries out triple cleaning and obtains final tungsten
Bulk concentrate, testing result is as follows, after testing, and wherein tungstic acid content is 30%, and overall recovery is 81%, and molybdenum content is
5.62%, overall recovery is 75.87%.
Comparative example 1：
This comparative example provides one kind using molybdenum sulfide flotation tailing pulp as raw material, the method for Scheelite Flotation ore deposit, different from implementing
Without addition molybdenum oxide modifying agent, selective depressant and potent dose of collecting agent in example 1, this comparative example step one, and
And white tungsten flotation concentrate is obtained through direct flotation after step one, testing result is as follows, as a result shows, tungstic acid content is
26.67%, overall recovery is 67.74%, and molybdenum content is 2.15%, and overall recovery is 27.30%.
Claims (8)
1. a kind of improve the method for molybdenum oxide concentration effect in white tungsten flotation concentrate, it is characterised in that methods described includes as follows
Step：
Step one, molybdenum oxide modifying agent, regulator, selective depressant, collecting are sequentially added into molybdenum sulfide flotation tailing pulp
Agent and potent dose of collecting agent, carry out normal temperature flotation, obtain tungsten mixed crude concentrate slurry；
Step 2, is concentrated to the product of step one；
Step 3, pH regulators, reagent removal agent, selective depressant, collecting agent and collecting agent is added into the product of step 2 strong
Imitate agent；
Step 4, the rear selected white tungsten flotation concentrate for obtaining enrichment molybdenum oxide is diluted by the product of step 3；
The molybdenum oxide modifying agent includes Pb2+、Fe3+、Fe2+、Al3+、Ca2+、Mg2+And Ba2+In one or more elements；
The selective depressant includes modified water glass, phosphate, modified starch, dextrin, tannin, cellulose, tartaric acid, lemon
One or more mixtures in lemon acid, oxalic acid and phosphoramidic acid.
2. method as claimed in claim 1, it is characterised in that the molybdenum oxide that is included in the molybdenum sulfide flotation tailing pulp, tungsten master
To exist with calcium molybdate, molybdenum dioxide, molybdenum trioxide and artificial schellite, wolfram ocher form, and quartz, Fang Xie are included in the raw material
One or more in stone, fluorite and barite.
3. method as claimed in claim 1, it is characterised in that potent dose of the collecting agent includes oxidation kerosene, oxidated diesel oil, hydrocarbon
One or more in base sulfur soap and its ester, hydrocarbyl sulfonic soap and its ester, hydroximic acid, naphthalene and its derivative and alkyl bromination ammonium
Composition.
4. method as claimed in claim 1, it is characterised in that the collecting agent includes oleic acid and its derivative.
5. method as claimed in claim 1, it is characterised in that the product of the step one carries out being concentrated into more than 60%.
6. method as claimed in claim 1, it is characterised in that be diluted to less than 20% in the step 4.
7. method as claimed in claim 1, it is characterised in that molybdenum oxide in molybdenum sulfide flotation tailing pulp per ton in the step one
Modifying agent, regulator, selective depressant, the addition of collecting agent and potent dose of collecting agent are respectively 100g~1000g, 500g
~2000g, 200g~2000g, 100g~500g and 50g~300g.
8. method as claimed in claim 1, it is characterised in that pH regulators, reagent removal agent, selective depression in the step 3
The addition of agent, collecting agent and potent dose of collecting agent is respectively 100g/t~500g/t, 200g/t in the accounting of step 2 product
~800g/t, 3000g/t~8000g/t, 0~100g/t and 0~50g/t.
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| CN201710325108.1A CN107081220B (en) | 2017-05-10 | 2017-05-10 | Method for improving enrichment effect of molybdenum oxide in scheelite flotation concentrate |
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| CN108993776A (en) * | 2018-06-22 | 2018-12-14 | 昆明理工大学 | A kind of Scheelite Flotation composite restrainer and its application method |
| CN109482362A (en) * | 2018-12-26 | 2019-03-19 | 高台县宏源矿业有限责任公司 | A kind of inhibitor and the method that calcite is separated from fluorite ore using the inhibitor |
| CN109465114A (en) * | 2019-01-09 | 2019-03-15 | 湖南有色金属研究院 | A kind of flotation separation method of barite and dolomite |
| CN111330743A (en) * | 2020-04-09 | 2020-06-26 | 北京矿冶科技集团有限公司 | Spodumene ore flotation collector, preparation method thereof and spodumene ore dressing process for clay mineralization |
| CN114749282A (en) * | 2022-05-31 | 2022-07-15 | 西安建筑科技大学 | Calcium molybdate sulfuration flotation method |
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