AU2021101479A4 - Interface Regulation Method for Flotation Separation of Copper-molybdenum Mixed Concentrate - Google Patents
Interface Regulation Method for Flotation Separation of Copper-molybdenum Mixed Concentrate Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
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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
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B13/00—Control arrangements specially adapted for wet-separating apparatus or for dressing plant, using physical effects
- B03B13/005—Methods or arrangements for controlling the physical properties of heavy media, e.g. density, concentration or viscosity
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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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
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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
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- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses an interface regulation method for flotation separation of
a copper-molybdenum mixed concentrate. The method comprises the following steps:
1) adding 7-10 kg/t of a mixed electric potential regulator containing sodium sulfide
and sodium dithionite, regulating mineral slurry electric potential to be -200 mV to -300
mV, and performing size mixing for 3 minutes; 2) adding 30-50 g/t of
polydimethylsiloxane, and stirring for 3 minutes; 3) adding 4-5 kg/t of a hydrophilic
inhibitor containing a thiourea functional group, stirring for 3 minutes, changing a
copper mineral surface from being hydrophobic to being hydrophilic, decreasing a
contact angle of chalcopyrite from 70 degrees to 10 degrees, maintaining the contact
angle of molybdenite at 85 degrees; and 4) adding 40-60 g/t of polymer compound
sodium polyacrylate to form an insulation layer on the surface of the chalcopyrite for
eliminating electron transfer effect between copper minerals and the molybdenite,
maintaining electrochemical difference between the chalcopyrite and the molybdenite,
and promoting the separation action. Effective separation of the copper-molybdenum
mixed concentrate is realized by mineral slurry electric potential regulation, foam
viscosity regulation, mineral surface hydrophilic regulation, and galvanic action
regulation among mineral particles.
Description
Interface Regulation Method for Flotation Separation of
Copper-molybdenum Mixed Concentrate
The invention relates to an interface regulation method for flotation
separation of copper-molybdenum mixed concentrate, which has a particularly
good effect on copper-molybdenum mixed concentrate with complex copper
mineral composition, low molybdenum content and high separation difficulty.
The traditional copper-molybdenum flotation separation is generally
divided into the copper-inhibiting molybdenum-floating method, and the
molybdenum-inhibiting copper-floating method, where copper content in
copper concentrate is about 0.2-1% while copper content is between 25-30%,
and therefore, copper is generally inhibited and molybdenum is generally
floated during production according to the principle of inhibiting the
high-content component and floating the low-content component. The
reagents for inhibiting copper and floating molybdenum include sodium sulfide,
potassium permanganate, sodium cyanide, phosphorus-Nokes, an organic
inhibitor containing sulfhydryl and pseudoacetylthiourea, where sodium sulfide
is the most common one, and other inhibitors are relatively poor in adaption
and effect. At present, sodium sulfide is mainly used in the separation and
production of copper-molybdenum mixed concentrate. However, a large
amount of gas needs to charge in the flotation process as sodium sulfide is a
reducing agent, and a large amount of sodium sulfide is consumed, which result in a large amount of sodium sulfide and a poor effect. Production is relatively troublesome due to the fact that a special nitrogen-making workshop is needed even through nitrogen gas can be filled to reduce consumption of sodium sulfide in inflated oxidation. The oxidant potassium permanganate is effective for some secondary copper minerals, but has no effect on most of the copper-molybdenum mixed concentrate. There is no successful report in the industry at present as sulfhydryl-like organic inhibition may fail in production, is strong in smell, and is great in impact on plant selecting environment.
Reagents with good effect such as cyanide and phosphorus-Nokes have been
eliminated in China as a result of relatively strong toxicity. Due to the complex
copper mineral composition, low molybdenum grade and collectors on the
surface of the copper-molybdenum mixed concentrate, the traditional
separation method is difficult to achieve the desired effect, and therefore, it is
necessary to develop a new copper-molybdenum mixed concentrate
separation method.
According to the characteristics and the properties of the
copper-molybdenum mixed concentrate, the invention discloses an interface
regulation method for flotation separation of copper-molybdenum mixed
concentrate, which can achieve efficient separation of complex low-grade
copper-molybdenum mixed concentrate containing 0.1-0.2% of molybdenum,
and copper minerals mainly including chalcopyrite, copper blue, and
chalcocite.
According to the technical scheme adopted by the invention, an interface
regulation method for flotation separation of copper-molybdenum mixed
concentrate includes solid-liquid mineral slurry potential regulation, gas-liquid
interface tension regulation, solid-liquid interface hydrophilic regulation and
solid-solid interface galvanic interaction regulation, where the specific
operation steps are as follows:
1) solid-liquid mineral slurry potential regulation: adsorption of collectors
on the surfaces of chalcopyrite and molybdenum is an electrochemical
process, and their desorption effects are also controlled by the mineral slurry
potential; 7-10 kg/t of the mixed potential regulator containing sodium sulfide
and sodium dithionite is added for regulating the mineral slurry potential to
-200mV to -300mV; and size mixing is performed for 3 minutes while a
collector film, in a metastable state, on the surface of the chalcopyrite is prone
to desorption, thereby facilitating competitive adsorption of the inhibitor.
2) gas-liquid interface tension control: the quality of floated concentrate is
related to foam stability. The quality of molybdenum concentrate is affected by
relatively high alkalinity of copper-molybdenum mixed concentrate during
separation, great viscosity of the flotation foam, poor fluidity of foam and
relatively strong foam inclusion carrying effect, and thus, molybdenum
concentrate with molybdenum content higher than 45% only can be obtained
by multi-time selection; water glass can be added to inhibit gangue minerals
for reducing inclusion effect, but it will affect copper concentrate filtration,
thereby affecting production of the main process. 30-50 g/t of
polydimethylsiloxane is added and stirring is performed for 3 minutes, so that
viscosity of the mineral slurry and bubble tension can be reduced, merge of the bubbles can be promoted, and carrying effect, on the copper minerals and gangues, of the bubbles is greatly reduced.
3) Solid-liquid interface hydrophilic regulation: based on the previous
regulation, 4-5 kg/t of pseudoacetylthiourea hydrophilic inhibitor containing a
thiourea functional group is added and stirring is performed for 3 minutes, so
that the copper mineral surface is changed to be hydrophobic from be
hydrophilic, the contact angle of chalcopyrite is decreased from 70 degrees to
degrees, the contact angle of molybdenite is maintained at 85 degrees.
and 4) solid-solid interface galvanic interaction regulation: The sulfide
minerals are semiconductor minerals, where the forbidden band of the
chalcopyrite is 0.4eV, and the forbidden band of the molybdenum ore is 2.0eV,
so that contact between the two can produce galvanic effect, resulting in the
Fermi energy level of the two to be close to each other; and the two are not
liable to separate as a result of reduced difference in electrochemical
properties; by adding 40-60 g/t of polymer compound sodium polyacrylate, an
insulation layer is formed on the surface of the chalcopyrite to eliminate
electron transfer effect between copper minerals and the molybdenite,
maintain electrochemical difference between the chalcopyrite and the
molybdenite, and promote the separation action.
The specific operation steps and the control technological conditions of
the interface regulation method for flotation separation of copper-molybdenum
mixed concentrate are as follows:
The copper minerals in the copper-molybdenum mixed concentrate of
mineral raw materials are chalcopyrite with copper content of 27%, the
molybdenum minerals are molybdenite with the molybdenum content of
0.1-0.2%; 7-10kg/t of sodium sulfide and sodium dithionite are added to
regulate the pH value of the mineral slurry to be 11-12 and the mineral slurry
potential to be -220mV to -300mV; size mixing is performed for 3 minutes;
-50 g/t of polydimethylsiloxane is added to regulate gas-liquid interfacial
tension, and stirring is performed for 2 minutes; 4-5kg/t of
pseudoacetylthiourea is added to regulate mineral hydrophilicity, and stirring is
performed for 3 minutes; and 40-60g/t of sodium polyacrylate is finally added,
and stirring is performed for 3 minutes, so that indexes of molybdenum
concentrate with molybdenum grade of 45.66% and a flotation recovery rate
being 85.36% can be obtained by once-roughing, four-time-refining and
twice-scavenging.
Unless otherwise specified, the percentages in the invention are all mass
percentages, based on 100% in total.
Regarding the unit of "liquid-solid ratio", the liquid-solid ratio is a term used
in the hydrometallurgical industry. In common textbooks, the
"volume-to-weight ratio of leaching solution to the amount of material" is
mentioned, and the unit of volume-to-weight ratio is ml/g, L/ Kg orm 3 /t.
The solid-solid interface refers to the interface among mineral particles.
The solid-liquid interface refers to the interface between the mineral
surface and water.
The gas-liquid interface refers to the interface between air and water in a
bubble.
The solid-liquid mineral slurry refers to a material in which mineral
particles are mixed with water. The mineral slurry contains both minerals and
water.
The invention has the following outstanding advantages that:
According to the properties and the characteristics of copper-molybdenum
mixed concentrate, mineral slurry, the solid-liquid interface, the gas-liquid
interface and the solid-solid interface are regulated to realize mineral slurry
potential regulation for flotation and separation of copper-molybdenum mixed
concentrate, gas-liquid interface tension regulation, mineral surface solid-liquid
interface hydrophilic regulation, and solid-solid interface galvanic interaction
regulation among mineral particles, thereby realizing effective separation of
the copper-molybdenum mixed concentrate.
The technical solution of the invention is further described below by way of
the following embodiments.
Embodiment 1
The embodiment was an example of the interface regulation method for
flotation and separation of copper-molybdenum mixed concentrate, where the
mineral raw materials and components were as follows: the copper minerals
were mainly chalcopyrite with copper content of 27%, the molybdenum
minerals were molybdenite with molybdenum content of 0.20%, 90% of
materials had material fineness of 0.074 microns, and concentration was 25%.
The specific operation steps were as follows:
1) solid-liquid mineral slurry potential regulation: 4 kg/t of sodium sulfide
and 3 kg/t of sodium hydrosulfite were added, and stirring was performed for 3
minutes, where the pH value of the mineral slurry was 11.5, and the mineral
slurry potential was -200 mV;
2) gas-liquid interface tension regulation: 30 g/t of polydimethylsiloxane
was added to regulate gas-liquid interface tension, and stirring was performed
for 2 minutes;
3) solid-liquid interface hydrophilic regulation: 4.0 g/t of
pseudoacetylthiourea was added to regulate mineral hydrophilicity, and stirring
was performed for 3 minutes;
and 4) solid-solid interface galvanic interaction regulation: 40g/t of sodium
polyacrylate was finally added, and stirring was performed for 3 minutes.
Indexes of molybdenum concentrate with molybdenum grade of 45.56%
and a flotation recovery rate being 85.36% could be obtained by
once-roughing, four-time-refining and twice-scavenging.
Embodiment 2
The embodiment was another example of the interface regulation method
for flotation and separation of copper-molybdenum mixed concentrate, where
the mineral raw materials and components were as follows: the copper
minerals were mainly chalcopyrite and copper blue with copper content of
27%, molybdenum minerals were molybdenite with molybdenum content of
0.12%, 90% of materials had material fineness of 0.074 microns, and
concentration was 25%. The specific operation steps were as follows:
1) solid-liquid mineral slurry potential regulation: 6 kg/t of sodium sulfide
and 4 kg/t of sodium hydrosulfite were added, and stirring was performed for 4
minutes, where the pH value of the mineral slurry was 12, and the mineral
slurry potential was -300 mV;
2) gas-liquid interface tension regulation: 40 g/t of polydimethylsiloxane
was added to regulate gas-liquid interface tension, and stirring was performed
for 3 minutes;
3) solid-liquid interface hydrophilic regulation: 4.5 g/t of
pseudoacetylthiourea was added to regulate mineral hydrophilicity, and stirring
was performed for 3 minutes;
and 4) solid-solid interface galvanic interaction regulation: 50g/t of sodium
polyacrylate was finally added, and stirring was performed for 3 minutes.
Indexes of molybdenum concentrate with molybdenum grade of 45.12%
and a flotation recovery rate being 84.21% could be obtained by
once-roughing, four-time-refining and twice-scavenging.
Embodiment 3
The embodiment was another example of the interface regulation method
for flotation and separation of copper-molybdenum mixed concentrate, where
the mineral raw materials and components were as follows: the copper mineral
were mainly chalcopyrite with copper content of 27%, molybdenum minerals
were molybdenite with molybdenum content of 0.15%, 90% of materials had
material fineness of 0.074 microns, and concentration was 25%. The specific
operation steps were as follows:
1) solid-liquid mineral slurry potential regulation: 8 kg/t of sodium sulfide
and 3 kg/t of sodium hydrosulfite were added, and stirring was performed for 3
minutes, where the pH value of the mineral slurry was 12.5, and the mineral
slurry potential was -250 mV;
2) gas-liquid interface tension regulation: 50 g/t of polydimethylsiloxane
was added to regulate gas-liquid interface tension, and stirring was performed
for 3 minutes;
3) solid-liquid interface hydrophilic regulation: 5.0 kg/t of
pseudoacetylthiourea was added to regulate mineral hydrophilicity, and stirring
was performed for 5 minutes;
and 4) solid-solid interface galvanic interaction regulation: 60g/t of sodium
polyacrylate was finally added, and stirring was performed for 4 minutes.
Indexes of molybdenum concentrate with molybdenum grade of 45.75%
and a flotation recovery rate being 83.82% could be obtained by
once-roughing, four-time-refining and twice-scavenging.
Embodiment 4
The embodiment was another example of the interface regulation method
for flotation and separation of copper-molybdenum mixed concentrate, where
the mineral raw materials and components were as follows:
copper-molybdenum mixed concentrate from certain copper mine in Inner
Mongolia, where the copper minerals were mainly chalcopyrite with copper
content of 27.15%, molybdenum minerals were molybdenite with molybdenum
content of 0.22%; the use of traditional sodium sulfide could not achieve
copper-molybdenum mixed concentrate separation, molybdenum concentrate
grade was only 30%, and the recovery rate was only 45%.
With the adoption of the interface regulation method provided by the
invention, concentration of mineral slurry was regulated to be 30%, 7kg/t of
sodium sulfide and sodium dithionite were added to regulate the pH value of
the mineral slurry to be 11.5 and the mineral slurry potential to be -250mV; size mixing was performed for 3 minutes; 30 g/t of polydimethylsiloxane was added to regulate gas-liquid interfacial tension, and stirring was performed for 2 minutes; 5.5kg of pseudoacetylthiourea was added to regulate mineral hydrophilicity, and stirring was performed for 3 minutes; and 45g/t of sodium polyacrylate was finally added, and stirring was performed for 3 minutes, so that indexes of molybdenum concentrate with molybdenum grade of 45.66% and a flotation recovery rate being 85% could be obtained by once-roughing, four-time-refining and twice-scavenging.
Claims (1)
1. An interface regulation method for flotation separation of
copper-molybdenum mixed concentrate, characterized by comprising
solid-liquid mineral slurry potential regulation, gas-liquid interface tension
regulation, solid-liquid interface hydrophilic regulation and solid-solid interface
galvanic interaction regulation, wherein the specific operation steps are as
follows
1) solid-liquid mineral slurry electric potential regulation: adding 7-10 kg/t
of the mixed electric potential regulator containing sodium sulfide and sodium
dithionite, regulating mineral slurry electric potential to be -200 mV to -300 mV,
regulating the pH value of the mineral slurry to be 11-12, and performing size
mixing for 3 minutes;
2) gas-liquid interface tension regulation: adding 30-50 g/t of
polydimethylsiloxane, and stirring for 3 minutes, thereby reducing viscosity of
the mineral slurry and bubble tension and reducing carrying effect, on the
copper minerals and gangues, of the bubbles;
3) solid-liquid interface hydrophilic regulation: based on the previous
regulation, adding 4-5 kg/t of the hydrophilic inhibitor containing a thiourea
functional group, stirring for 3 minutes, changing the copper mineral surface
from being hydrophobic to being hydrophilic, decreasing a contact angle of
chalcopyrite from 70 degrees to 10 degrees, maintaining the contact angle of
molybdenite at 85 degrees;
and 4) solid-solid interface galvanic interaction regulation: adding 40-60
g/t of polymer compound sodium polyacrylate to form an insulation layer on the
surface of the chalcopyrite for eliminating electron transfer effect between copper minerals and the molybdenite, maintaining electrochemical difference between the chalcopyrite and the molybdenite, and promoting the separation action.
2. The interface regulation method for flotation separation of
copper-molybdenum mixed concentrate according to claim 1, wherein the
copper minerals in the copper-molybdenum mixed concentrate of mineral raw
materials are chalcopyrite with copper content of 27.15%, the molybdenum
minerals are molybdenite with the molybdenum content of 0.1-0.2%; and the
specific operation steps and control technical conditions are as follows:
7-10kg/t of sodium sulfide and sodium dithionite are added to regulate the
pH value of the mineral slurry to be 11-12 and the mineral slurry potential to be
-220mV to -300mV; size mixing is performed for 3 minutes; 30-50 g/t of
polydimethylsiloxane is added to regulate gas-liquid interfacial tension, stirring
is performed for 2 minutes; 4-5kg/t of pseudoacetylthiourea is added to
regulate mineral hydrophilicity, and stirring is performed for 3 minutes; and
-60g/t of sodium polyacrylate is finally added, and stirring is performed for 3
minutes, so that indexes of molybdenum concentrate with molybdenum grade
of 45.66% and a flotation recovery rate being 85.36% can be obtained by
once-roughing, four-time-refining and twice-scavenging.
3. The interface regulation method for flotation separation of
copper-molybdenum mixed concentrate according to claim 1, wherein the
mineral raw materials and the components are as follows: copper minerals are
mainly chalcopyrite with copper content of 27%, molybdenum minerals are
molybdenite with molybdenum content of 0.20%, 90% of materials have material fineness of 0.074 microns, and concentration is 25%; and the specific operation steps and control technical conditions are as follows:
1) solid-liquid mineral slurry potential regulation: 4 kg/t of sodium sulfide
and 3 kg/t of sodium hydrosulfite are added, and stirring is performed for 3
minutes, wherein the pH value of the mineral slurry is 11.5, and the mineral
slurry potential is -200 mV;
2) gas-liquid interface tension regulation: 30 g/t of polydimethylsiloxane is
added to regulate gas-liquid interface tension, and stirring is performed for 2
minutes;
3) solid-liquid interface hydrophilic regulation: 4.0 kg/t of
pseudoacetylthiourea is added to regulate mineral hydrophilicity, and stirring is
performed for 3 minutes;
and 4) solid-solid interface galvanic interaction regulation: 40g/t of sodium
polyacrylate is finally added, and stirring is performed for 3 minutes;
and indexes of molybdenum concentrate with molybdenum grade of
45.56% and a flotation recovery rate being 85.36% are obtained by
once-roughing, four-time-refining and twice-scavenging.
4. The interface regulation method for flotation separation of
copper-molybdenum mixed concentrate according to claim 1, wherein the
mineral raw materials and the components are as follows: the copper minerals
are mainly chalcopyrite and copper blue with copper content of 27%,
molybdenum minerals are mainly molybdenite with molybdenum content of
0.12%, 90% of materials have material fineness of 0.074 microns, and
concentration is 25%; the specific operation steps and control technical
conditions are as follows:
1) solid-liquid mineral slurry potential regulation: 6 kg/t of sodium sulfide
and 4 kg/t of sodium hydrosulfite are added, and stirring is performed for 4
minutes, wherein the pH value of the mineral slurry is 12, and the mineral
slurry potential is -300 mV;
2) gas-liquid interface tension regulation: 40g/t of polydimethylsiloxane is
added to regulate gas-liquid interface tension, and stirring is performed for 3
minutes;
3) solid-liquid interface hydrophilic regulation: 4.5 kg/t of
pseudoacetylthiourea is added to regulate mineral hydrophilicity, and stirring is
performed for 3 minutes;
and 4) solid-solid interface galvanic interaction regulation: 50g/t of sodium
polyacrylate is finally added, and stirring is performed for 3 minutes;
and indexes of molybdenum concentrate with molybdenum grade of
45.12% and a flotation recovery rate being 84.21% are obtained by
once-roughing, four-time-refining and twice-scavenging.
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| AU2021101479A AU2021101479A4 (en) | 2021-03-23 | 2021-03-23 | Interface Regulation Method for Flotation Separation of Copper-molybdenum Mixed Concentrate |
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