CN106148732B - Method that is a kind of while handling molybdenite and bidery metal - Google Patents
Method that is a kind of while handling molybdenite and bidery metal Download PDFInfo
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- CN106148732B CN106148732B CN201510137991.2A CN201510137991A CN106148732B CN 106148732 B CN106148732 B CN 106148732B CN 201510137991 A CN201510137991 A CN 201510137991A CN 106148732 B CN106148732 B CN 106148732B
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- molybdenite
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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 provides method that is a kind of while handling molybdenite and bidery metal, bidery metal presses preset blending ratio mechanical mixture with molybdenite, through pyroreaction generation iron, the polynary sulfide mixed phase of copper, cobalt etc. with molybdenum, the gangue generation slag in the silicon and molybdenite in bidery metal removes.Extraction iron, copper, cobalt, the metal such as molybdenum are leached containing the polynary sulfide of molybdenum through wet oxidation again, the output in the form of sulphur of sulphur during leaching in original molybdenite.Using the method for the present invention make at high temperature two kinds of difficult materials of bidery metal and molybdenite react be transformed into it is a kind of easily leach polynary contain molybdenum sulphide, ore phase reconstruction is realized, is become difficult to be disposable and easy to operate, cost savings, it is easy to commercial Application.
Description
Technical field
The invention belongs to non-ferrous metallurgy technology field, the metallurgical skill of especially intractable bidery metal and molybdenite
A kind of art, and in particular to while the method that handles molybdenite and bidery metal.
Background technology
Bidery metal is a kind of intermediate products that cupric oxide cobalt concentrate etc. obtains through reduction melting, its main component be cobalt, copper,
Iron, also containing considerable amount of silicon, due to compact structure it is stable, it is extremely difficult it is broken, antiacid corrosion is strong, be a kind of typical difficult thing
Material.
Molybdenite is a kind of lamellar compound, is combined in layer with firm S-Mo-S ionic bonds, and between layers by micro-
Weak Van der Waals force maintains, easily cleavage.Nonpolar cleavage surface hydrophobicity is not strong, oxidizable so that molybdenite turns into one kind
Extremely intractable sulphide ore.
Two kinds of difficult materials are required for extreme leaching condition.As bidery metal needs to use chlorine under strongly acidic conditions
Or the strong oxidizer such as perchloric acid leaches；And molybdenite even reaches 0.77V/SHE Fe with oxidation-reduction potential3+/Fe2+Electricity is to all
It can not be oxidized.It is also required to carry out oxygen leaching in autoclave, or is also required to using chlorine, nitric acid, sodium hypochlorite etc.
Strong oxidizer.In addition, wet-leaching molybdenite sulphur almost all is changed into sulfate or low-concentration sulfuric acid, sulphur can not utilize also shape
Into noxious emission.
Molybdenum can form a series of ternary sulfides for being referred to as Chevrel phases, can be used as superconductor.It is this
Ternary sulfide is a kind of solid solution, and its composition can be written as MexMo6S8.Chevrel phases chemism is higher, holds very much
Sour molten or oxidation reaction easily occurs.
It is contemplated that molybdenite and the different difficult material of bidery metal two is set to react at high temperature, so as to pass through ore deposit
Phase reconstruction make two difficult mass transfers into it is a kind of it is higher it is chemically active easily leach raw material, and then extract and therein various have
Valency element.
The content of the invention
It is an object of the invention to provide method that is a kind of while handling molybdenite and bidery metal.White conjunction is made by ore phase reconstruction
Gold and molybdenite are converted into the polynary sulfide containing molybdenum, and the gangue reaction in molybdenite generates slag and separated with polynary testing sulphide.
And the polynary sulfide that is generated carries out wet-leaching, the oxidized oxygenatedchemicals for being transformed into sexavalence of molybdenum enter solution or stay in
Solid phase, further recovery.The metals such as iron, cobalt, copper are further reclaimed with cationic form into solution, and sulphur oxidation transformation is into element
Sulfur recovery.
The present invention is achieved by the steps of：
Method that is a kind of while handling molybdenite and bidery metal：Heated after molybdenite is mixed with bidery metal, make mixture
System reacts at high temperature, is transformed into containing the polynary testing sulphide of molybdenum, and the gangue generation slag in molybdenite separates with polynary testing sulphide,
The polynary sulfide generated is subjected to wet-leaching.
The molybdenum grade of handled molybdenite is 15~58% in the above method；Element mass fraction in bidery metal：Fe
10.5~34.5%, Cu 13.5~42.5%, Co 17.3~37.1%, Si 7.7~14.1%.
The particle diameter of handled bidery metal is less than 40mm in the above method.
Bidery metal and molybdenite mass ratio are (0.5~2) in the above method：1.
Handled 20~200 minutes at a temperature of 900~1500 DEG C after molybdenite and bidery metal mixing in the above method.
In the above method by the polynary sulfide generated it is broken after carry out wet-leaching, molybdenum is oxidized to be transformed into sexavalence
Oxygenatedchemicals enters solution or stayed in solid phase, and further recovery, iron, cobalt, copper are further returned with cationic form into solution
Receive, sulphur oxidation transformation is into elementary sulfur.
The polynary sulfide for handling to obtain in the above method is crushed to granularity less than 300 μm.
The polynary sulfide obtained in the above method adds mineral acid after crushing, then adds oxidant and carries out normal pressure acid
Leaching, or it is passed through ozone or oxygen progress oxygen pressure acidleach.Mineral acid includes sulfuric acid, one kind of hydrochloric acid or mixing.Oxidant includes
Nitric acid, sodium nitrate, ferric sulphate, ferric sesquichloride, hydrogen peroxide, persulfuric acid or its salt.
Invention advantage
1st, two kinds of difficult materials of bidery metal and molybdenite are made to react transformation at high temperature using the method for the present invention
Into it is a kind of easily leach it is polynary contain molybdenum sulphide, realize ore phase reconstruction, become difficult to be disposable；
2nd, the requirement to the sorting of copper-molybdenum mineral intergrowth is significantly not to be required to the associated metal vulcanization mineral content in molybdenite
Reduce；
3rd, the output in the form of elemental sulfur in leaching process of the sulphur in former molybdenite, it is easy to recovery and accumulating, is advantageous to
Solve the problems, such as the sulphur emissions in traditional molybdenite pyrogenic process and wet processing.
4th, the inventive method is easy to operate, cost savings, is easy to commercial Application.
Brief description of the drawings
Fig. 1 is the XRD that the high temperature of embodiment 1 reacts the product that ore phase reconstruction obtains；
Fig. 2 is the XRD that the high temperature of embodiment 2 reacts the product that ore phase reconstruction obtains；
Fig. 3 is the XRD that the high temperature of embodiment 3 reacts the product that ore phase reconstruction obtains.
Instantiation mode
In order to which the present invention is explained in greater detail, enumerates following examples and illustrate, but the present invention is not limited to these realities
Apply example.
Embodiment 1
By bidery metal powder, (granularity is≤150 μm and accounts for 99.6%, Fe 15%, Cu 14.5%, Co 37.1%, Si
11.1%) with molybdenite (containing Mo 57.92%, S 38.12%) in mass ratio 2:1 mechanical mixture, 1500 DEG C are heated to, insulation
Cooled down after reaction 20min.After the slag separation of upper strata, lower floor's material is levigate to account for 95% to particle diameter≤150 μm, and its XRD spectrum is shown in Fig. 1.
Configure 1.0molL-1Sulfuric acid solution, high-temperature reaction product is subjected to oxygen leaching, partial pressure of oxygen 0.8MPa, 120 DEG C of extraction temperature,
Extraction time 1.0h.After ore phase reconstruction containing the total oxygenation efficiency 98.67% of molybdenum sulphide (wherein 60.2% Mo enters solution,
39.8% enters solid phase), copper leaching rate 96.25%, cobalt leaching rate 95.46%, iron leaching rate 96.65%, chemical analysis show
Elementary sulfur conversion ratio 92.6%.
Embodiment 2
By bidery metal grain, (200 μm≤particle diameter≤1000 μm account for 98%, Fe 10.5%, Cu 24.6%, Co 23.7%, Si
8.4%) with molybdenite (containing Mo 48.23%, S 32.40%) in mass ratio 1.5:1 mechanical mixture, 1000 DEG C are heated to, insulation
Cooled down after reaction 120min.After the slag separation of upper strata, lower floor's material is levigate to account for 95% to particle diameter≤300 μm, and its XRD spectrum is shown in Fig. 2.
Configure 1.0molL-1Sulfuric acid, 1.0molL-1Salpeter solution, high-temperature reaction product is subjected to normal pressure leaching.Extraction temperature 80
DEG C, extraction time 1.5h.After ore phase reconstruction containing the total oxygenation efficiency 98.86% of molybdenum sulphide (wherein 44.6% Mo enters solution,
55.4% Mo enters solid phase), copper leaching rate 95.50%, cobalt leaching rate 95.64%, iron leaching rate 95.65%, chemical analysis
Show elementary sulfur conversion ratio 93.2%.
Embodiment 3
By bidery metal grain, (200 μm≤particle diameter≤1000 μm account for 98%, Fe 14.5%, Cu 22.5%, Co 34.7%, Si
14.1%) with molybdenite (containing Mo 15.86%, S 20.56%) in mass ratio 0.5:1 mechanical mixture, 900 DEG C are heated to, insulation
Cooled down after reaction 200min.After the slag separation of upper strata, lower floor's material is levigate to account for 95% to particle diameter≤300 μm, and its XRD spectrum is shown in Fig. 3.
Configure 1.0molL-1Sulfuric acid, 1.2molL-1Ammonium persulfate solution is leached high-temperature reaction product.Extraction temperature 80
DEG C, extraction time 2.0h.After ore phase reconstruction containing the total oxygenation efficiency 98.36% of molybdenum sulphide (wherein 34.5% Mo enters solution,
65.5% Mo enters solid phase), copper leaching rate 96.50%, cobalt leaching rate 95.64%, iron leaching rate 95.65%, chemical analysis
Show elementary sulfur conversion ratio 88.2%.
Embodiment 4
By bidery metal powder, (granularity is≤300 μm and accounts for 99.5%, Fe 15.4%, Cu 42.5%, Co 33.1%, Si
9.9% and molybdenite (containing Mo 32.25%, S 28.21%) in mass ratio 1:1 mechanical mixture is uniform, is heated to 1200 DEG C, protects
Temperature reaction 100min, cooling.After the separation of upper strata slag, lower floor's material is levigate to account for 95% to particle diameter≤300 μm.Configure 1.0molL-1
Sulfuric acid, 2.0molL-1Hydrogen peroxide solution, reaction product is leached, 50 DEG C of extraction temperature, extraction time 2.0h.Ore deposit is mutually overlapping
Total oxygenation efficiency 98.57% containing molybdenum sulphide (99.5% molybdenum fully enters solution) after structure, copper leaching rate 95.60%, cobalt leaching
Extracting rate 95.54%, iron leaching rate 95.86%, chemical analysis show elementary sulfur conversion ratio 84.1%.
Embodiment 5
By bidery metal grain, (200 μm≤particle diameter≤1000 μm account for 98%, Fe 10.5%, Cu 24.6%, Co 23.7%, Si
8.4%) with molybdenite (containing Mo 48.00%, S 32.00%) in mass ratio 1.5:1 mechanical mixture, 1000 DEG C are heated to, insulation
Cooled down after reaction 120min.After the separation of upper strata slag, lower floor's material is levigate to account for 95% to particle diameter≤300 μm, can by XRD analysis
To obtain result similar to Example 2.Configure 1.0molL-1Sulfuric acid, 1.2molL-1Sodium nitrate solution, by reaction product
Carry out normal pressure leaching.80 DEG C of extraction temperature, extraction time 1.5h.Total oxygenation efficiency 98.67% containing molybdenum sulphide after ore phase reconstruction
(wherein 22.7% Mo enters solution, and 77.3% Mo enters solid phase), copper leaching rate 99.20%, cobalt leaching rate 99.12%,
Iron leaching rate 99.34%, chemical analysis show elementary sulfur conversion ratio 93.6%.
Embodiment 6
By the bidery metal block (30mm≤He of lumpiness≤40mm, Fe 15.4%, Cu 42.5%, Co 33.1%, Si 9.9%
Molybdenite (containing Mo 32.00%, S 28.00%) in mass ratio 1:1 mechanical mixture is uniform, is heated to 1200 DEG C, insulation reaction
100min, cooling.After the separation of upper strata slag, lower floor's material is levigate to account for 95% to particle diameter≤150 μm.Configure 1.0molL-1Sulfuric acid,
2.0mol·L-1Ferric sulphate solution, reaction product is leached, 50 DEG C of extraction temperature, extraction time 2.0h.Ore phase reconstruction
(wherein 23.6% Mo enters solution, and 76.4% Mo enters solid phase) containing the total oxygenation efficiency 95.66% of molybdenum sulphide afterwards, copper leaching
Extracting rate 97.65%, cobalt leaching rate 98.64%, iron leaching rate 99.65%, chemical analysis show elementary sulfur conversion ratio 94.6%.
Embodiment 7
By bidery metal block (30mm≤lumpiness≤40mm, Fe 14.5%, Cu 22.5%, Co 34.7%, Si 14.1%)
With molybdenite (containing Mo 15.00%, S 20.00%) in mass ratio 0.5:1 mechanical mixture, 900 DEG C are heated to, insulation reaction
Cooled down after 200min.After the separation of upper strata slag, lower floor's material is levigate to account for 95% to particle diameter≤150 μm, by XRD analysis, can obtain
To result similar to Example 3.Configure 1.0molL-1Sulfuric acid, carry out ozone leaching.Ozone flow velocity 1.1Lmin-1, leaching
Go out 80 DEG C of temperature, extraction time 2.5h.80 DEG C of extraction temperature.Total (its of oxygenation efficiency 99.16% containing molybdenum sulphide after ore phase reconstruction
In 99.5% Mo enter solution), copper leaching rate 97.67%, cobalt leaching rate 97.68%, iron leaching rate 99.56%, chemistry point
Analysis shows elementary sulfur conversion ratio 73.9%.
Comparative example 1
Bidery metal (granularity is≤150 μm and accounts for 99.6%, Fe 15%, Cu 14.5%, Co 37.1%, Si 14.1%).
Configure 1.0molL-1Sulfuric acid solution, bidery metal is subjected to oxygen leaching, partial pressure of oxygen 0.8MPa, 120 DEG C of extraction temperature, during leaching
Between 1.0h, copper leaching rate 61.25%, cobalt leaching rate 56.46%, iron leaching rate 71.65%.
Comparative example 2
Molybdenite (Mo 46.5%).Configure 1.0molL-1Sulfuric acid solution oxygen leaching, partial pressure of oxygen 1.96MPa, leach temperature
120 DEG C, extraction time 2.5h of degree, molybdenite oxygenation efficiency 6.52%.
Claims (8)
1. method that is a kind of while handling molybdenite and bidery metal, it is characterised in that：900 after molybdenite and bidery metal are mixed
Handled 20~200 minutes at a temperature of~1500 DEG C；Be transformed into the polynary testing sulphide containing molybdenum, the gangue generation slag in molybdenite with
Polynary testing sulphide separation, mineral acid is added by the polynary sulfide generated after crushing, is then added oxidant and is carried out often
Acidleach is pressed, or is passed through ozone or oxygen progress oxygen pressure acidleach.
2. method that is according to claim 1 while handling molybdenite and bidery metal, it is characterised in that：Handled brightness molybdenum
The molybdenum grade of ore deposit is 15~58%；Element mass fraction in bidery metal：Fe 10.5~34.5%, Cu 13.5~42.5%, Co
17.3~37.1%, Si 7.7~14.1%.
3. method that is according to claim 1 while handling molybdenite and bidery metal, it is characterised in that：Handled white conjunction
The particle diameter of gold is less than 40mm.
4. method that is according to claim 1 while handling molybdenite and bidery metal, it is characterised in that：Bidery metal and brightness molybdenum
Ore deposit mass ratio is (0.5~2)：1.
5. the method for molybdenite and bidery metal is handled while described according to any one of claim 1-4, it is characterised in that：By institute
Wet-leaching is carried out after the polynary sulfide of generation is broken, the oxidized oxygenatedchemicals for being transformed into sexavalence of molybdenum enters solution or stayed
In solid phase, further recovery, iron, cobalt, copper are further reclaimed with cationic form into solution, in sulfide-sulphur of divalent aoxidizes
It is transformed into elementary sulfur.
6. method that is according to claim 5 while handling molybdenite and bidery metal, it is characterised in that：Processing obtains more
First sulfide is crushed to granularity less than 300 μm.
7. method that is according to claim 1 while handling molybdenite and bidery metal, it is characterised in that：Mineral acid includes sulphur
Acid, one kind of hydrochloric acid or mixing.
8. according to claim 1 carry out ore phase reconstruction processing to molybdenite to improve the method for its leaching activity, it is special
Sign is：Oxidant includes nitric acid, sodium nitrate, ferric sulphate, ferric sesquichloride, hydrogen peroxide, persulfuric acid or its salt.
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| CN102634675A (en) * | 2012-04-28 | 2012-08-15 | 中南大学 | Method for treating copper-molybdenum mixed ores |
| CN102643998A (en) * | 2012-04-28 | 2012-08-22 | 中南大学 | Method for processing molybdenite |
| CN103526013A (en) * | 2013-10-23 | 2014-01-22 | 北京矿冶研究总院 | Comprehensive recovery method of complex molybdenum sulfide ore |
| CN103866116A (en) * | 2014-03-27 | 2014-06-18 | 西北有色金属研究院 | Method for oxidizing molybdenum concentrate |
| CN103866142A (en) * | 2014-03-27 | 2014-06-18 | 西北有色金属研究院 | Method of recycling molybdenum and rhenium from molybdenum concentrate by hydrometallurgy |
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2015
- 2015-03-27 CN CN201510137991.2A patent/CN106148732B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534207A (en) * | 2010-12-10 | 2012-07-04 | 北京有色金属研究总院 | Method for decomposing molybdenite through introducing oxygen at high temperature and under normal pressure |
| CN102634675A (en) * | 2012-04-28 | 2012-08-15 | 中南大学 | Method for treating copper-molybdenum mixed ores |
| CN102643998A (en) * | 2012-04-28 | 2012-08-22 | 中南大学 | Method for processing molybdenite |
| CN103526013A (en) * | 2013-10-23 | 2014-01-22 | 北京矿冶研究总院 | Comprehensive recovery method of complex molybdenum sulfide ore |
| CN103866116A (en) * | 2014-03-27 | 2014-06-18 | 西北有色金属研究院 | Method for oxidizing molybdenum concentrate |
| CN103866142A (en) * | 2014-03-27 | 2014-06-18 | 西北有色金属研究院 | Method of recycling molybdenum and rhenium from molybdenum concentrate by hydrometallurgy |
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