CN110280395A - Low-sulfur copper-lead-zinc polymetallic ore sequential preferential flotation separation method - Google Patents
Low-sulfur copper-lead-zinc polymetallic ore sequential preferential flotation separation method Download PDFInfo
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- CN110280395A CN110280395A CN201910452989.2A CN201910452989A CN110280395A CN 110280395 A CN110280395 A CN 110280395A CN 201910452989 A CN201910452989 A CN 201910452989A CN 110280395 A CN110280395 A CN 110280395A
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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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- 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
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Abstract
The invention discloses a sequential preferential flotation separation method for low-sulfur copper-lead-zinc polymetallic ores. The technical scheme is that copper flotation is performed firstly, and lead flotation is performed secondly, in the copper preferential flotation operation, a combined inhibitor T-9 is used, and the valuable elements of copper, lead and zinc in the ore are effectively separated under the condition of PH 6-7; in the lead-first flotation operation, the inhibitor F-8 is used, so that the floating of zinc minerals is effectively inhibited. T-9 reduces the floating activity of lead and zinc minerals, effectively increases the floatability difference of copper and lead and zinc minerals, and has no toxicity, harm, green and pollution; the inhibitor F-8 has a good inhibiting effect on sphalerite, has high activity on galena and silver minerals, has a certain collecting effect on the galena, and is beneficial to reducing the mutual content of lead and zinc in the product. After the method is adopted, the target minerals of copper, lead and zinc are effectively separated, and the aim of comprehensively recycling mineral resources is fulfilled.
Description
Technical field
The invention belongs to non-ferrous metal ore technical fields, and in particular to low sulfur type copper, lead, zinc polymetal sulphide ore preferentially floats
Select separation method.
Background technique
With the quickening that mineral products processing industryization is in progress, limited mineral resources are developed on a large scale, improve mineral products money
The comprehensive utilization ratio and energy conservation and environmental protection in source have become current theme.
In Nonferrous Metals mine floatation process, the ore dressing of copper, lead, zinc polymetal sulphide ore mostly uses copper-lead bulk flotation-
Cu-Pb separation selects zinc technology, also has using copper-lead zinc successively techniques such as diffeential floatation, Part-bulk flotation.It is floating in copper-lead mixing
Choosing-Cu-Pb separation selects in zinc technology, and current most effective two methods are that cyanide presses down the floating lead of copper and potassium bichromate presses down lead and floats copper,
The former has stronger inhibiting effect to copper mineral by cyanide, and is nearly free from inhibiting effect to lead, therefore presses down copper and float lead effect very
It is good, but drawback is that cyanide has severe toxicity, can cause seriously to pollute to environment；The latter floats copper, advantage using potassium dichromate method suppression lead
It is that dosing is small, production operation is stablized, but the extremely difficult processing of dichromate ion, can also cause seriously to pollute to environment.It is right
The multi-metal sulfide of in close relations and embedding cloth relationship complexity in mineral intergrowth, some need increase grinding fineness to improve mineral
Liberation degree of minerals, just can guarantee the separating effect of mineral；In grinding process, it is living that part secondary copper ores can generate copper ion
Change zinc mineral, zinc sulphur is caused to be difficult to inhibit, brings difficulty to the separation of copper and zinc sulfur mineral.
Currently, in the floatation process of Cu-Pb seperation, using it is most be the mixed floating-Cu-Pb separation-tailing of copper-lead
Zinc technology is selected, this, which is mixed, selects technique or carry out Cu-Pb separation using potassium bichromate or cyanide, dirty although good separating effect
Environment is contaminated, not environmentally；Or some composite drugs are used, environmentally friendly but inferior separating effect, copper, lead mutually contain seriously.Therefore, for low
The complicated copper, lead, zinc polymetal sulphide ore stone of sulfur type develops a kind of environmentally protective beneficiation reagent and suitable tcrude ore property
The ore-dressing technique of feature realizes that copper, lead and zinc ores object efficiently separate, the valuable elements such as Recovering Copper, lead, zinc, not only favorably
It is horizontal in improving comprehensive utilization of resources, resource utilization is improved, can also increase the economic benefit of enterprise and preserve the ecological environment.
Summary of the invention
The object of the present invention is to provide a kind of flotation separation method of low sulfur type copper, lead, zinc polymetal sulphide ore, this method is kept away
Environmental pollution caused by heavy metal salt inhibitor is exempted from, it can be achieved that copper, lead, Zn-Ca series separation and synthetical recovery.Using the party
Method can get higher economic and technical norms.
Technical solution of the present invention: a kind of low sulfur type Cu-Pb seperation sequence diffeential floatation separation method, by first floating
Select copper, again flotation of lead sequence carry out, in copper flotation operation, add composite restrainer T-9, adjust ore pulp pH value be 6~
7, to reduce the activity of swimming of lead and zinc ores object, increase the floatability difference of copper and lead and zinc ores object；In plumbum floatation operation, addition
Inhibitor F-8 inhibits zinc mineral, advantageously reduces the lead in product, zinc mutually contains；Flotation realizes copper, lead and zinc ores object in order
Efficient flotation separation separation.
The composite restrainer T-9 have selective inhibitory, by sodium pyrosulfite, sodium thiosulfate, ferrous sulfate,
Aluminum sulfate and humic acid are mixed according to 2~3:3 of mass ratio~5:2:1:2 ratio.
The inhibitor F-8 is by dimethyldithiocarbamate, zinc sulfate, sodium carbonate according to mass ratio 3:1:1's
Ratio mixes.
Specific step is as follows:
Step 1: raw ore is levigate, and 0.074 millimeter of fineness or less granularity accounts for 70~75%(mass ratio), adjust pulp density 30%-
35%, composite restrainer T-9 is added in obtained ore pulp, T-9 additional amount is 600~1200 g tons of raw ores, stirs 3~5 points
Zhong Hou, addition esters sulfide mineral collector carry out copper diffeential floatation roughing operation, and flotation time is 3~8 minutes, and it is coarse-fine to obtain copper
Mine；Composite restrainer T-9 is added in obtained copper rough concentrate ore pulp, T-9 additional amount is 100~300 g tons of raw ores, stirring 3
~after five minutes, it is selected to carry out a copper, and copper selected flotation time is 3~6 minutes, obtains smart I concentrate of copper, and copper I concentrate of essence passes through
Selected output copper concentrate several times；
Step 2: after the completion of copper diffeential floatation operation, 800~1200 g tons of raw ores of lime, stirring 3 are added in obtained ore pulp
~after five minutes, and adding inhibitor F-8, F-8 additive amount is 500~800 g tons of raw ores, stirring 3~after five minutes, then add second
Sulphur nitrogen and xanthate collectors carry out plumbum floatation operation, and flotation time is 3~8 minutes, obtain lead rough concentrate；It is thick in obtained lead
It is added inhibitor F-8 in concentrate pulp, F-8 additional amount is 100~200 g tons of raw ores, stirring 3~after five minutes, it carries out primary
Lead is selected, and lead selected flotation time is 3~8 minutes, obtains smart I concentrate of lead, lead I concentrate of essence is by selected output lead essence several times
Mine.
Inhibitor of the composite restrainer T-9 as lead and zinc ores object plays the synergistic effect between different agents.It is wherein burnt sub-
Sodium sulphate and sodium thiosulfate are under mildly acidic conditions, inhibited to zincblende and pyrite；Sodium thiosulfate and sulphur
Sour ferrous iron can press down lead in faintly acid ore pulp and float copper, and main function mechanism is that sodium thiosulfate and acid out go out sulfur dioxide, other side
Lead ore generates inhibiting effect；Aluminum sulfate is inhibited to gangue mineral, and plays the role of dispersing sludge.Ferrous sulfate is logical
It is often the inhibitor of sulfide mineral, and chalcopyrite can be activated in practicing, in weak acid environment, on the one hand depositing because of air
It is oxidized to ferric sulfate, and ferric sulfate can remove the surface film oxide of copper sulfide mineral, it is made to restore fresh mineral table
Face, on the other hand, the xanthic acid ionic oxide formation double xanthate that the presence of high price iron can be such that mineral surfaces adsorb enhances vulcanization
The hydrophobicity on copper mineral surface, to improve its floatability.Humic acid is a kind of macromolecule organic monoacid, nontoxic, and is contained
There are a variety of functional groups such as carboxyl, phenolic hydroxyl group, alcoholic extract hydroxyl group, quinonyl, carboxyl, phenolic group are the chief active groups of humic acid, it can
The acid-base property for neutralizing ore pulp, adjusts the pH value of ore pulp.The addition of humic acid, the collaboration being more advantageous between playing different agents are made
With promoting the combination medicament to the inhibitory effect of lead and zinc ores object, increase the floatability difference of copper and lead and zinc ores object.
Dimethyldithiocarbamate in inhibitor F-8 is a kind of organic low molecular inhibitor, as a kind of tool
There is the floating agent of double action, it has good inhibiting effect to zincblende and troilite, and to galena and silver mineral
Activity is higher, and has certain collecting effect to galena.Zinc sulfate is as a kind of conventional zincblende inhibitor, with diformazan
Base dithiocarbamate, sodium carbonate are used cooperatively, better effect.
Beneficial effects of the present invention: using sequence controling differential flotation process for copper process, and copper diffeential floatation operation addition combination inhibits
Agent T-9, T-9 have selective inhibitory, and pharmaceutical agent combinations can play the synergistic effect between different agents, reduce lead and zinc ores
The activity of swimming of object effectively increases the floatability difference of copper and lead and zinc ores object, and its component is nontoxic, green non-pollution；?
The floating of zinc mineral can be effectively suppressed in lead diffeential floatation operation, inhibitor F-8, and the lead, the zinc that reduce in product are mutually contained, had
Good effect.The addition of inhibitor T-9, F-8 in diffeential floatation operation effectively realize copper, the efficient of lead and zinc ores object is divided
From having achieved the purpose that resource comprehensive utilization utilizes.The technology is for handling low sulfur type copper, lead, zinc polymetal sulphide ore stone effect
Significantly.
Specific embodiment
Embodiment 1
Copper, lead, zinc FLOTATION SEPARATION are carried out to certain low sulfur type copper, lead, zinc polymetal sulphide ore, which is 0.60%,
Lead is 0.62%, zinc 3.96%, sulphur 2.15%, and silver is 13.2 g tons.It is 75%-0.074 millimeters of (granularities that ore, which is milled to fineness,
0.074 millimeter below to account for after 75%) mass ratio reaches, and composite restrainer T-9, which is added, under conditions of pulp density is 33% is
900 g tons of raw ores, after five minutes, addition ethyl ammonia sulfate is as collecting agent progress copper diffeential floatation roughing operation, when flotation for stirring
Between obtain copper rough concentrate for 5 minutes；It is 200 g tons of raw ores that composite restrainer T-9 is added in obtained copper rough concentrate ore pulp,
After five minutes, it is selected to carry out a copper for stirring, and flotation time is 5 minutes, obtains smart I concentrate of copper, and copper I concentrate of essence is selected by 2 times
Output copper concentrate.The copper concentrate copper grade is 26.31%, copper recovery 91.63%, leaded 1.98%, contain zinc 4.36%.
After the completion of copper diffeential floatation operation, 1000 g tons of raw ores of lime are added in obtained ore pulp, are stirred after five minutes,
Addition inhibitor F-8 is 600 g tons of raw ores, and stirring after five minutes, then adds diethyldithiocarbamate and ethyl xanthogenate makees collecting agent to carry out lead excellent
First flotation operation, flotation time are 8 minutes, obtain lead rough concentrate；Inhibitor F-8 is added in obtained lead rough concentrate ore pulp is
200 g tons of raw ores, after five minutes, it is selected to carry out a lead for stirring, and flotation time is 6 minutes, obtains smart I concentrate of lead, I essence of lead essence
Mine passes through 2 selected output lead concentrates.The lead concentrate lead grade is 47.54%, and lead recovery 83.17% contains zinc 9.02%, contains
213.7 g tons of silver.(in gained dressing product, the measurement unit of noble metal gold, silver is usually g ton).
Reference examples 1: to the ore in embodiment 1, in copper diffeential floatation operation, using vulcanized sodium, sodium sulfite and sulfuric acid
Zinc carries out flotation as the inhibitor of lead minerals and zinc mineral and obtains copper concentrate, copper grade 23.51%, and copper recovery is
80.41%, leaded 5.18%, contain zinc 8.96%.In lead diffeential floatation operation, using zinc sulfate and sodium sulfite as zinc mineral
Inhibitor carries out flotation and obtains lead concentrate, and lead grade is 43.14%, and lead recovery 71.88% contains zinc 16.05%, argentiferous 160.7
G ton.
Reference examples 2: the suppression to the ore in embodiment 1, in copper diffeential floatation operation, using potassium bichromate as lead minerals
Preparation, sodium sulfite and zinc sulfate carry out flotation as the inhibitor of zinc mineral and obtain copper concentrate, copper grade 24.81%, and copper returns
Yield is 81.21%, leaded 4.12%, contain zinc 8.75%.In lead diffeential floatation operation, using dimethyldithiocarbamate
Flotation, which is carried out, as the inhibitor of zinc mineral with zinc sulfate obtains lead concentrate, lead grade is 46.14%, lead recovery 76.31%,
Containing zinc 12.05%, 202.50 g tons of argentiferous.
Find out from reference examples 1,2, the flotation effect of embodiment 1 is more preferable.
Embodiment 2
Copper, lead, zinc diffeential floatation separation are carried out to certain low sulfur type copper, lead, zinc polymetal sulphide ore, which is
0.59%, lead 4.28%, zinc 2.11%, sulphur 2.84%, silver is 31.98 g tons of raw ores.It is 72%- that ore, which is milled to fineness,
After 0.074 millimeter, it is 1200 g tons of raw ores that composite restrainer T-9, which is added, under conditions of pulp density is 35%, is stirred 5 minutes
Afterwards, addition sulphur nitrogen propionitrile ester carries out copper diffeential floatation roughing operation as collecting agent, and flotation time is coarse-fine to obtain copper within 7 minutes
Mine；It is 300 g tons of raw ores that composite restrainer T-9 is added in obtained copper rough concentrate ore pulp, and stirring after five minutes, carries out primary
Copper is selected, and flotation time is 5 minutes, obtains smart I concentrate of copper, and copper I concentrate of essence passes through 2 selected output copper concentrates.The copper concentrate
Copper grade is 24.51%, copper recovery 78.52%, leaded 9.85%, contain zinc 6.20%.
After the completion of copper diffeential floatation operation, 1200 g tons of raw ores of lime are added in obtained ore pulp, are stirred after five minutes,
Addition inhibitor F-8 is 800 g tons of raw ores, and stirring after five minutes, then adds diethyldithiocarbamate and makees collecting agent progress lead diffeential floatation work
Industry, flotation time are 5 minutes, obtain lead rough concentrate；It is 150 g tons that inhibitor F-8 is added in obtained lead rough concentrate ore pulp
Raw ore, after five minutes, it is selected to carry out a lead for stirring, and flotation time is 5 minutes, obtains smart I concentrate of lead, and lead I concentrate of essence passes through 3
Secondary selected output lead concentrate.The lead concentrate lead grade is 75.80%, and lead recovery 89.12% contains zinc 4.05%, argentiferous 398.10
G ton.
Reference examples 3: to the ore in embodiment 2, in copper diffeential floatation operation, using potassium bichromate, sodium pyrosulfite, sulphur
Sodium thiosulfate and zinc sulfate carry out flotation as the inhibitor of lead minerals and zinc mineral and obtain copper concentrate, copper grade 21.81%,
Copper recovery is 71.57%, leaded 14.12%, contain zinc 9.20%.In lead diffeential floatation operation, using dimethyl disulfide for amino first
Acid esters and zinc sulfate carry out flotation as the inhibitor of zinc mineral and obtain lead concentrate, and lead grade is 70.50%, and lead recovery is
83.91%, contain zinc 5.19%, 369.50 g tons of argentiferous.
Reference examples 4: to the ore in embodiment 2, in copper diffeential floatation operation, using vulcanized sodium, sodium sulfite and sulfuric acid
Zinc carries out flotation as the inhibitor of lead and zinc ores object and obtains copper concentrate, copper grade 20.16%, and copper recovery 68.40% contains
Lead 16.09% contains zinc 10.30%.In lead diffeential floatation operation, flotation is carried out as the inhibitor of zinc mineral using zinc sulfate and is obtained
Lead concentrate, lead grade be 66.80%, lead recovery 79.17%, contain zinc 7.16%, 302.60 g tons of argentiferous.
Find out from reference examples 3,4, the flotation effects such as lead recovery of embodiment 2 are better than reference examples.
Claims (4)
1. a kind of low sulfur type Cu-Pb seperation sequence diffeential floatation separation method, it is characterized in that: by first Floatation of Copper, again flotation
The sequence of lead carries out, and in copper flotation operation, adds composite restrainer T-9, and the pH value for adjusting ore pulp is 6~7, with reduce lead,
The activity of swimming of zinc mineral increases the floatability difference of copper and lead and zinc ores object；In plumbum floatation operation, inhibitor F-8 is added,
Inhibit zinc mineral, advantageously reduces the lead in product, zinc mutually contains；Flotation realizes the efficient flotation separation of copper, lead and zinc ores object in order
Separation.
2. a kind of low sulfur type Cu-Pb seperation sequence diffeential floatation separation method as described in claim 1, it is characterized in that:
The composite restrainer T-9 have selective inhibitory, by sodium pyrosulfite, sodium thiosulfate, ferrous sulfate, aluminum sulfate and
Humic acid is mixed according to 2~3:3 of mass ratio~5:2:1:2 ratio.
3. a kind of low sulfur type Cu-Pb seperation sequence diffeential floatation separation method as described in claim 1, it is characterized in that:
The inhibitor F-8 is mixed by dimethyldithiocarbamate, zinc sulfate, sodium carbonate according to the ratio of mass ratio 3:1:1
It forms.
4. a kind of low sulfur type Cu-Pb seperation sequence diffeential floatation separation method as described in claim 1, feature exist
In specific step is as follows:
Step 1: raw ore is levigate, and 0.074 millimeter of fineness or less granularity accounts for 70~75%, adjusts pulp density 30%-35%,
To ore pulp in be added composite restrainer T-9, T-9 additional amount be 600~1200 g tons of raw ores, stirring 3~after five minutes, addition
Esters sulfide mineral collector carries out copper diffeential floatation roughing operation, and flotation time is 3~8 minutes, obtains copper rough concentrate；It is obtaining
Copper rough concentrate ore pulp in be added composite restrainer T-9, T-9 additional amount be 100~300 g tons of raw ores, stir 3~5 minutes
Afterwards, it is selected to carry out a copper, copper selected flotation time is 3~6 minutes, obtains smart I concentrate of copper, copper I concentrate of essence is by several times
Selected output copper concentrate；
Step 2: after the completion of copper diffeential floatation operation, 800~1200 g tons of raw ores of lime, stirring 3 are added in obtained ore pulp
~after five minutes, and adding inhibitor F-8, F-8 additive amount is 500~800 g tons of raw ores, stirring 3~after five minutes, then add second
Sulphur nitrogen and xanthate collectors carry out plumbum floatation operation, and flotation time is 3~8 minutes, obtain lead rough concentrate；It is thick in obtained lead
It is added inhibitor F-8 in concentrate pulp, F-8 additional amount is 100~200 g tons of raw ores, stirring 3~after five minutes, it carries out primary
Lead is selected, and lead selected flotation time is 3~8 minutes, obtains smart I concentrate of lead, lead I concentrate of essence is by selected output lead essence several times
Mine.
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| CN110773328A (en) * | 2019-08-27 | 2020-02-11 | 湖南柿竹园有色金属有限责任公司 | Cyanide-free efficient combined sorting method for preferentially floating copper |
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| CN112619878A (en) * | 2020-11-10 | 2021-04-09 | 西北矿冶研究院 | Comprehensive recovery process for iron symbiotic nonferrous metal copper, lead and zinc |
| CN113908996A (en) * | 2021-08-18 | 2022-01-11 | 西北矿冶研究院 | Copper-molybdenum separation combined regulator and application method thereof |
| CN114505174A (en) * | 2022-01-17 | 2022-05-17 | 广东省科学院资源利用与稀土开发研究所 | Copper-lead separation flotation method for copper-lead ore |
| CN114505174B (en) * | 2022-01-17 | 2023-12-29 | 广东省科学院资源利用与稀土开发研究所 | Copper-lead separation flotation method for copper-lead ore |
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