CN1033465A - The treatment process of mineral materials containing copper oxide - Google Patents
The treatment process of mineral materials containing copper oxide Download PDFInfo
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- CN1033465A CN1033465A CN87107247A CN87107247A CN1033465A CN 1033465 A CN1033465 A CN 1033465A CN 87107247 A CN87107247 A CN 87107247A CN 87107247 A CN87107247 A CN 87107247A CN 1033465 A CN1033465 A CN 1033465A
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- ore
- copper
- copper oxide
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- flotation
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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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Abstract
The invention belongs to the processing of mineral materials containing copper oxide.To refractory copper oxide ore, can not need take to strengthen the sulfurized measure with direct flotation or conventional sulfide flotation enrichment.The invention provides a kind of simple and effective vulcanization process, promptly when copper oxide ore vulcanizes, make vulcanizing agent with elementary sulfur, add sulphur solvent and phase-transfer catalyst, as quaternary ammonium or season phosphine compound, or polyoxyethylene glycol and ethers thereof are transferred in the organic phase aqueous phase hydroxide ion, promote the disproportionation of sulphur, thereby the cupric oxide in the ore pulp is vulcanized.
Curing temperature of the present invention greatly reduces than hydro-thermal sulfuration method, simplified control, and the activity duration shortens, and cost reduces.Handle the Yunnan refractory oxidized copper ore, ore can be contained copper grade and bring up to 12.6% by 0.6%, the rate of recovery of copper reaches 81.5%.Handle Hubei skarn type difficulty and select copper iron ore, can obtain the copper ore concentrates of cupric 22.9% from the raw ore of cupric 1.65%, copper recovery reaches 87.6%.
Description
Invention belongs to the processing of mineral materials containing copper oxide.
Containing the lower ore of copper grade needs through beneficiation enrichment before smelting.Some ore that contains copper oxide mineral is with direct flotation or conventional sulfide flotation method enrichment the time, and copper oxide mineral wherein is lost in the mine tailing more.So-called copper oxide mineral is meant the oxygenatedchemicals of copper, as oxide compound, carbonate, silicate, vitriol and the oxyhydroxide etc. of copper.To this class refractory oxidized copper ore, need take measures before flotation, to strengthen sulfuration.The pressurized water heat curing system is exactly one of this vulcanization process [Ke Jiajun, Zhang Daoquan, non-ferrous metal (ore dressing part) 1980, No3,6-8].Ore pulp and sulphur powder heat in autoclave that (usually in 140-180 ℃ of scope) makes the sulphur disproportionation more than the elementary sulfur fusing point, utilize its disproportionation products that copper oxide mineral is vulcanized, and reclaim with flotation process again.Because the pressurized water heat curing system requires to carry out more than the fusing point of elementary sulfur, not only needs to consume a large amount of heat energy, and needs to use autoclave, cause the difficulty of operation, and the dispersion of sulphur is often bad, the ore pulp heating is uneven.For above-mentioned reasons, can reach satisfied result, fail industrialization so far though the pressurized water heat curing system is handled refractory oxidized copper ore in small-scale test.
The objective of the invention is to provide a kind of simple and effective novel method, handle the material that contains copper oxide mineral that is unsuitable for direct flotation and conventional sulfide flotation.
Method provided by the invention is the material water furnishing ore pulp that requires granularity with being milled to, and adds sulphur, sulphur solvent, and phase-transfer catalyst carries out the phase-transfer catalysis sulfuration of copper oxide mineral, reclaims with physical method for separation then.
Phase-transfer catalysis (PTC) is a kind of up-and-coming heterogeneous catalysis technology in the organic synthesis.Be in two kinds of reactants of not miscible organic phase and water respectively, be difficult to reaction owing to not contacting mutually.The negatively charged ion that phase-transfer catalyst then can participate in aqueous phase reaction is transferred to and is made it in the organic phase to be easy to react.Its major advantage is the reaction conditions gentleness, and tangible catalytic effect is arranged.The present invention utilizes phase-transfer catalyst that the hydroxide ion of aqueous phase is transferred in the organic phase, can make the elementary sulfur that is dissolved in wherein under the temperature far below fusing point disproportionation take place, and disproportionation products then makes the copper oxide mineral sulfuration in the ore pulp.Total reaction formula can be expressed as follows:
Mineral after the sulfuration can reclaim with conventional flotation process.
The phase-transfer catalyst that the present invention uses can be various quaternary ammoniums or season phosphine compound, or polyoxyethylene glycol and ethers thereof etc.Quaternary ammonium compound is better than the season phosphine compound, because the latter has toxicity.Best with the tricaprylmethylammonium compound in the quaternary ammonium compound, it is a most cheap present quaternary ammonium compound, and its phase-transfer catalysis ability is also the strongest.Its optimum amount is the 0.1-1 kilogram.
The sulphur solvent that the present invention uses has zellon, tetracol phenixin, toluene, dimethylbenzene, stone Nao oil, kerosene and diesel oil etc., and is most economical with kerosene and diesel oil.Optimum amount is in 0.5-5 liter/ton ore scope.Sulphur and sulphur solvent can add at ore grinding to any point that vulcanizes between steel basin, help contacting and dispersion between sulphur and its solvent most to add grinding operation.
Phase-transfer catalysis sulfurized temperature can be in any temperature more than 40 ℃.
Ore pulp physical method for separation after the sulfuration reclaims valuable component wherein.Most economical method is a froth-flotation method.Can add or not add collecting agent and pore forming material less as if using quaternary ammonium compound, roughly selecting during flotation during sulfuration with whipability and collecting.
Compare with the pressurized water heat curing system, the present invention has the following advantages:
1. reduce curing temperature, simplified operational condition.The pressurized water heat curing system requires temperature (as 140-180 ℃) more than the fusing point of sulphur, needs to use autoclave.When handling Dongchuan Mining Administration's soup pellet ore with it, require 180 ℃ of curing temperatures, this moment, the autoclave internal pressure reached 1MPa.Need be cooled to about 60 ℃ after the sulfuration and just can open the still discharging.Curing temperature 50-90 of the present invention ℃, can under normal pressure, operate, can directly send flotation operation after the ore pulp sulfuration.
2. shortened the activity duration.The pressurized water heat curing system is handled the red cupric oxide ore of soup and need be vulcanized more than 4 hours, also has the preceding temperature fall time of charging, discharging and discharging of autoclave in addition.The present invention only need vulcanize 2-3 hour, charging and discharging is also very easy saves time.
3. reduced the facility investment expense.The pressurized water heat curing system is equipped with autoclave need increase the facility investment expense.The present invention can use common steel basin, has saved investment greatly.
Specifically finish example
Example 1
Handled Yunnan mine disaster copper oxide ore stone with method of the present invention.This ore contains that copper grade is about about 0.6%, and oxidation ratio reaches 70-86%, wherein so-calledly accounts for 30-50% in conjunction with cupric oxide.The rate of recovery of conventional sulfide flotation fluctuates between 45-67% because of the difference of combination rate, and concentrate grade also is no more than 10%Cu.Handle this ore with method of the present invention, to be milled to after-200 purpose ores are sized mixing more than 65%, handle (pharmaceutical quantities is with the consumption of ore per ton) in best phase-transfer catalysis cure conditions: sulphur 2-5 kilogram, kerosene 0.5-5 liter, tricaprylmethylammonium compound (TOMAH) 0.3-0.6 kilogram, temperature 50-80 ℃, curing time 1-3 hour.Reclaim with pneumatic flotation then, obtain containing the copper ore concentrates of copper grade 12.6%, copper recovery reaches 81.5%.
Example 2
Handle Hubei skarn type difficulty with method of the present invention and selected copper iron ore.Ore contains copper grade 1.65%, iron content 47.2%, and oxidation ratio 78%, combination rate is about 15%.Under the top condition of example 1, obtain containing the copper ore concentrates of copper grade 22.9%, copper recovery reaches 87.6%.
Example 3
Handled Guangdong deep oxidation refractory copper ore with method of the present invention.Ore contains copper grade 1.78%, oxidation ratio 80%, and combination rate 17%, raw ore is by thin mud severe contamination.Under the top condition of example 1, obtain containing the copper ore concentrates of copper grade 20.5%, copper recovery 83.7%.
Example 4
With the TOMAH in the polyoxyethylene glycol replacement example 1, optimum amount is that 0.5-1kg(is to ore per ton), all the other conditions are identical, handle ore of the same race, obtain containing the copper ore concentrates of copper grade 14.8%, and copper recovery reaches 76.8%.
Claims (4)
1, a kind of reinforcement vulcanization process that is used for before the mineral materials containing copper oxide flotation, its characteristic are that elementary sulfur and its organic solvent and phase-transfer catalyst unite use, can make the copper oxide mineral in the material be converted into sulfide mineral, reclaim with flotation process then.
2, the method for claim 1, its characteristic be used phase-transfer catalyst be quaternary ammonium or season phosphine compound, or polyoxyethylene glycol and ether compound thereof, wherein best with the tricaprylmethylammonium compound effect, its optimum amount is ore 0.1-1kg per ton.
3, as claim 1,2 described methods, its characteristic is that used sulphur organic solvent is kerosene, diesel oil, stone Nao oil, zellon, tetracol phenixin, toluene and dimethylbenzene.
4, as claim 1,2 described methods, the curing temperature that its characteristic is to be adopted is more than 40 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87107247A CN1012355B (en) | 1987-12-05 | 1987-12-05 | Processing method for mineral materials containing copper oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87107247A CN1012355B (en) | 1987-12-05 | 1987-12-05 | Processing method for mineral materials containing copper oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1033465A true CN1033465A (en) | 1989-06-21 |
| CN1012355B CN1012355B (en) | 1991-04-17 |
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ID=4816024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87107247A Expired CN1012355B (en) | 1987-12-05 | 1987-12-05 | Processing method for mineral materials containing copper oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1012355B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101190426B (en) * | 2006-11-24 | 2010-04-14 | 中南大学 | Vulcanization-oxidization mixing copper ore floatation method |
| CN101824543A (en) * | 2010-05-27 | 2010-09-08 | 中南大学 | Method for sulfidizing heavy metal waste and recovering valuable metals in heavy metal waste |
| CN103191833A (en) * | 2013-04-23 | 2013-07-10 | 昆明理工大学 | Cuprite vulcanizing strengthening method in mixed copper ore floatation |
-
1987
- 1987-12-05 CN CN87107247A patent/CN1012355B/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101190426B (en) * | 2006-11-24 | 2010-04-14 | 中南大学 | Vulcanization-oxidization mixing copper ore floatation method |
| CN101824543A (en) * | 2010-05-27 | 2010-09-08 | 中南大学 | Method for sulfidizing heavy metal waste and recovering valuable metals in heavy metal waste |
| CN101824543B (en) * | 2010-05-27 | 2011-07-06 | 中南大学 | Method for sulfidizing heavy metal waste and recovering valuable metals in heavy metal waste |
| CN103191833A (en) * | 2013-04-23 | 2013-07-10 | 昆明理工大学 | Cuprite vulcanizing strengthening method in mixed copper ore floatation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1012355B (en) | 1991-04-17 |
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