CN107141241A - Copper-sulphide ores flotation collector and its preparation method and application - Google Patents
Copper-sulphide ores flotation collector and its preparation method and application Download PDFInfo
- Publication number
- CN107141241A CN107141241A CN201710546519.3A CN201710546519A CN107141241A CN 107141241 A CN107141241 A CN 107141241A CN 201710546519 A CN201710546519 A CN 201710546519A CN 107141241 A CN107141241 A CN 107141241A
- Authority
- CN
- China
- Prior art keywords
- copper
- formula
- sulphide ores
- collecting agent
- flotation collector
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 0 CCCNC(N*)=* Chemical compound CCCNC(N*)=* 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
- C07C329/12—Dithiocarbonic acids; Derivatives thereof
- C07C329/14—Esters of dithiocarbonic acids
- C07C329/16—Esters of dithiocarbonic acids having sulfur atoms of dithiocarbonic groups bound to acyclic carbon atoms
-
- 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
- B03D1/012—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/02—Monothiocarbamic acids; Derivatives thereof
- C07C333/04—Monothiocarbamic acids; Derivatives thereof having nitrogen atoms of thiocarbamic groups bound to hydrogen atoms or to acyclic carbon atoms
-
- 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
-
- 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 present invention provides a kind of copper-sulphide ores flotation collector and its preparation method and application, wherein shown in the concrete structure formula of the collecting agent such as formula (I),Formula (I)；R1For aryl alkyl.Preparation method is as follows：Occur substitution reaction with sodium chloroacetate and xanthogen sodium, produce intermediate xanthogen sodium acetate；It is eventually adding organic amine and occurs aminolysis reaction with xanthogen sodium acetate, produces target product.And application of the copper-sulphide ores flotation collector in floating cupric sulfide mineral and recovery copper-sulphide ores.The collecting agent of the present invention can realize the separation of copper-sulphide ores and pyrite under the conditions of low alkalinity, can effectively reclaim copper mine.
Description
Technical field
The invention belongs to metallurgical technology field, and in particular to a kind of copper-sulphide ores flotation collector and preparation method thereof and should
With.
Background technology
Copper sulfide deposit be typically generally main valuable mineral oil yellow copper mine in metal intergrowth mineral bed, ore, pyrite,
Magnetic iron ore, tetrahedrite, tennantite, vitreous copper, bornite, covellite etc., are associated with the beneficial minerals such as molybdenite, gold, silver,
The rare and dispersed elements such as indium, gallium, germanium, cadmium, rhenium, thallium, and the element, the height that these accompanying element economic values have such as cobalt, bismuth, sulphur
In several times even tens times of main metal, these elements are comprehensively utilized, are a vital measures for improving mine economic profit.
In Flotation of copper and sulphur separation practice, thiourethane is to apply a more class highly selective collector, and it is in alkalescent
Under the conditions of it is weak to the collecting ability of pyrite, it is strong to the collecting ability of chalcopyrite, so as to show more more preferable than xanthate and black powder
Selectivity.Therefore, focus always of concern in recent years, has synthesized substantial amounts of thiourethane class collecting agent (such as Z- in succession
200th, ECTC, PAC etc.), and applied to industrial practice, and achieve certain effect, but the shallow crust structures in actual production
Every factor still suffers from deficiency, and such as pH is too high, reaction temperature is excessively high, therefore the research and development of shallow crust structures collecting agent are still adding
By force, a kind of collecting agent that can effectively solve the various defects of current separation process is developed still to be very important.
The content of the invention
In view of the shortcomings of the prior art, the present invention is intended to provide a kind of copper-sulphide ores flotation collector and preparation method thereof and
Using the flotation for the collecting agent that the present invention is provided is completed under the conditions of low alkali, can effectively be realized separation chalcopyrite and pyrite, be caught
Receiving agent has preferable flotation activity to copper-sulphide ores.
On the one hand, the present invention provides a kind of copper-sulphide ores flotation collector, and its concrete structure formula is：
R1For aryl alkyl.
Further, the R1For C6-12Aryl C1-6Alkyl.
Further, the R1For phenyl C1-4Alkyl.
Further, R1For phenyl methyl, phenylethyl, phenyl propyl, propyloxy phenyl base, phenyl normal-butyl, phenyl uncle
Butyl or phenyl isobutyl base.
Further, copper-sulphide ores flotation collector of the present invention, its concrete structure formula is：
On the one hand, the present invention provides a kind of preparation method of copper-sulphide ores flotation collector, and it is comprised the following steps that：
Occur substitution reaction with sodium chloroacetate (formula (III)) and xanthogen sodium (formula (II)), produce intermediate propyl group
Xanthic acid sodium acetate (formula (IV))；It is eventually adding organic amine (formula (V)) and occurs aminolysis with xanthogen sodium acetate (formula (IV))
Reaction, produces target product (formula (I)).
Further, the condition that the substitution reaction occurs is pH=8.0, in stirring reaction at 30 DEG C.
Further, the mol ratio of the sodium chloroacetate (formula (III)) and xanthogen sodium (formula (II)) is 1:1.
Further, the condition that the aminolysis reaction occurs is added for organic amine using dropwise addition mode, at 30~35 DEG C
Reaction.
Further, the organic amine (formula (V)) and sodium chloroacetate (formula (III)) mole is 1:1.
On the one hand, the present invention provides a kind of application of copper-sulphide ores flotation collector, described copper-sulphide ores flotation collecting
Application of the agent in floating cupric sulfide mineral and recovery copper-sulphide ores.
Further, the present invention provides the application of copper-sulphide ores flotation collector of the present invention, and the collecting agent is carried out
Copper-sulphide ores flotation is comprised the following steps that：
Lime is first added into ore deposit, the pH value of ore pulp is adjusted in 5.6~11, regulator is added after stirring, add collecting
Agent flotation, collecting agent concentration is 5~10mg/L, and flotation obtains froth pulp.
Further, the present invention provides the application of copper-sulphide ores flotation collector of the present invention, the collecting agent concentration
For 10mg/L, the slurry pH is 9.0.
Further, the present invention provides the application of copper-sulphide ores flotation collector of the present invention, and the regulator is hydrogen
Sodium oxide molybdena, stirs 2min before adding regulator, it is 1min to add mixing time after regulator, adds collecting agent stirring 2min,
Flotation time is 3min.
The invention has the advantages that：
The new thiourethane collecting agent molecular structure that the present invention is built, by optimizing the synthesis technique of thiourethane, research
Show, when reacting solution pH value is 8, reaction temperature is 30 DEG C, and the first step substitution reaction time is 2 hours, when second step reacts
Between be 3 hours, compared to preparation method disclosed in existing literature, the yield and purity of thiourethane product are significantly improved, reaction condition
Also it is gentle.The new thiourethane that the present invention is provided has preferable flotation activity to sulphide ore.The copper-sulphide ores flotation collecting of offer
The optimal flotation conditions of agent are that collecting agent concentration is 10mg/L, and slurry pH is 9.0, and collecting agent can effectively realize copper sulfide
The separation of ore deposit and pyrite, it is good with selectivity, it is effective under the conditions of low alkali to solve to reclaim returning for copper using collecting agent at present
The problem of yield is not high.
In the collecting agent preparation process that the present invention is provided, monoxone and sodium carbonate reaction system before instead of with sodium chloroacetate
After sodium chloroacetate, reaction condition optimization, the purity and yield of product are significantly improved.
The collecting agent of the present invention can realize the separation of copper-sulphide ores and pyrite under the conditions of low alkalinity, can effectively reclaim copper
Ore deposit.The preparation method for the collecting agent that the present invention is provided, reaction condition is simple, and technique is simple, and accessory substance is few, environment-friendly, purity
Height, resulting yield is high, is adapted to industrial production.
Brief description of the drawings
Accompanying drawing is used for providing a further understanding of the present invention, and constitutes a part for specification, the reality with the present invention
Applying example is used to explain the present invention together, is not construed as limiting the invention.Chalcopyrite in figure:Chalcopyrite；pyrite:
Pyrite；The recovery rate of recovery；Dosage consumptions.
The HPLC spectrograms of Fig. 1 O- propyl group-N- benzyl thiocarbamates；
The nuclear magnetic spectrum of Fig. 2 O- propyl group-N- benzyl thiocarbamates；
Fig. 3 ore floatation flows；
Fig. 4 O- propyl group-N- benzyl thiourethane consumptions and the relation of collecting performance；
The relation of Fig. 5 O- propyl group-N- benzyl thiocarbamate flotation performances and pH.
Embodiment
To make those skilled in the art more fully understand technical scheme, below in conjunction with the accompanying drawings and specific embodiment party
The invention will be further described for formula.
Embodiment 1：The synthesis of O- propyl group-N- benzyl thiocarbamates
15.80g (0.10mol) n-propyl xanthan is added into the 250ml three neck round bottom flask for fill 100.0mL distilled water
Sour sodium, and 11.60g (0.10mol) sodium chloroacetate, are added dropwise 4mol/L NaOH solution regulation reaction solution pH=8.0, at 30 DEG C
Stirring 2 hours.10.70g (0.10mol) benzylamine is slowly added dropwise while stirring, in reaction 3 hours at 35 DEG C., will after reaction terminates
Turbid solution stratification, the oily liquids on upper strata is target product, isolated 16.09g products, yield 76.99%, with height
The content that effect liquid phase chromatogram (HPLC) determines product is 90.95%, specific as shown in Figure 1.As can be seen from Figure 2, nuclear magnetic data is as follows
：1H NMR(400MHz,CDCl3):δ0.90-0.97(m,3H,CH3CH2),1.68-1.75(m,2H,CH2CH3),4.37-4.44
(m,3H,CH2O,CH2Ph),4.72-4.73(m,1H,CH2Ph),6.57(br,1H,NHCH2),7.22-7.35(m,5H,PhH)。
The flotation performance research of the thiourethane collecting agent of embodiment 2
Specific floatation process is as shown in figure 3, under the conditions of nature pH, regulator (such as sodium hydroxide) is added after stirring 2min
1min, adds collecting agent stirring 2min, flotation 2min, collecting agent concentration is 5~10mg/L, and flotation obtains froth pulp.
Collecting agent shown in the embodiment of the present invention 1 has preferable flotation activity to chalcopyrite and pyrite, and to brass
The collecting ability of ore deposit is better than pyrite；With the increase of collector dosage, collecting agent to chalcopyrite, pyrite the rate of recovery gradually
Enhancing.Most of collecting agents are after drug concentration increases to 10mg/L, and the rate of recovery to chalcopyrite, pyrite increases not clear
It is aobvious, and the selectivity of this concentration is also preferable.Concrete condition please check Fig. 4~5.
Influence of the slurry pH of embodiment 3 to chalcopyrite and flotation of pyrite
Specific floatation process is as shown in figure 3, the pH value for adjusting ore pulp with lime adds between 5.6~11 after stirring 2min
Enter regulator (such as sodium hydroxide) 1min, add collecting agent stirring 2min, flotation 2min, selected according to the conclusion of embodiment 2
Collecting agent concentration is selected for 10mg/L, flotation obtains froth pulp, and collecting agent concentration is 10mg/L, during pH=9, the collecting of embodiment 1
Agent is 73.88% to the flotation recovery rate of chalcopyrite, and the flotation recovery rate to pyrite is 56.95%.
It was found from shown in Fig. 4~5, the collecting agent shown in the embodiment of the present invention 1, as slurry pH increases, formula (Ia) institute
Show that new collector changes little to chalcopyrite flotation recovery rate, it is interval (5.6-11) in whole pH value, chalcopyrite is kept
Higher collecting ability；With the rise of pH value, new collector declines to the collecting ability of pyrite.When pH value is 9, catch
The collecting ability difference that agent is received to chalcopyrite and pyrite is larger, possesses the possibility that shallow crust structures are realized under the conditions of low alkali.By
This is visible, and new collector shown in formula (Ia) has preferable selectivity.
It is understood that the principle that embodiment of above is intended to be merely illustrative of the present and the exemplary implementation that uses
Mode, but the invention is not limited in this.For those skilled in the art, the essence of the present invention is not being departed from
In the case of refreshing and essence, various changes and modifications can be made therein, and these variations and modifications are also considered as being comprised in the present invention's
In protection domain.
Claims (10)
1. copper-sulphide ores flotation collector, it is characterised in that concrete structure formula is：
R1For aryl alkyl.
2. copper-sulphide ores flotation collector according to claim 1, it is characterised in that the R1For C6‐12Aryl C1‐6Alkane
Base.
3. copper-sulphide ores flotation collector according to claim 1, it is characterised in that the R1For isobutyl phenenyl ethyl,
Phenyl propyl, propyloxy phenyl base, phenyl normal-butyl, phenyl t-butyl or phenyl isobutyl base.
4. copper-sulphide ores flotation collector according to claim 1, it is characterised in that its concrete structure formula is：
5. a kind of preparation method of any copper-sulphide ores flotation collector of Claims 1 to 4, it is characterised in that specific step
It is rapid as follows：
Occur substitution reaction with sodium chloroacetate (formula (III)) and xanthogen sodium (formula (II)), produce intermediate propyl group xanthan
Sour sodium acetate (formula (IV))；It is eventually adding organic amine (formula (V)) and occurs aminolysis reaction with xanthogen sodium acetate (formula (IV)),
Produce target product (formula (I)).
6. the preparation method of collecting agent according to claim 5, it is characterised in that the condition that the substitution reaction occurs is
PH=8.0, in stirring reaction at 30 DEG C；The sodium chloroacetate (formula (III)) and the mol ratio of xanthogen sodium (formula (II))
For 1:1.
7. the preparation method of collecting agent according to claim 5, it is characterised in that the condition that the aminolysis reaction occurs is
Organic amine is added using dropwise addition mode, in reaction at 30~35 DEG C；The organic amine (formula (V)) and sodium chloroacetate (formula (III))
Mole be 1:1.
8. a kind of application of any described copper-sulphide ores flotation collector of Claims 1 to 4, it is characterised in that described sulphur
Change application of the Copper ore flotation collector in floating cupric sulfide mineral and recovery copper-sulphide ores.
9. application according to claim 8, it is characterised in that the collecting agent carries out the specific steps of copper-sulphide ores flotation
It is as follows：
Lime is first added into ore deposit, the pH value of ore pulp is adjusted in 5.6~11, regulator is added after stirring, collecting agent is added and floats
Choosing, collecting agent concentration is 5~10mg/L, and flotation obtains froth pulp.
10. application according to claim 9, it is characterised in that the collecting agent concentration is 10mg/L, the slurry pH
For 9.0；The regulator is sodium hydroxide, and 2min is stirred before adding regulator, and it is 1min to add mixing time after regulator,
Add after collecting agent stirring 2min, flotation time is 3min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109675723A (en) * | 2019-01-29 | 2019-04-26 | 中南大学 | Collecting agent and its preparation method and application with amide groups and thioamides base |
| CN111672635A (en) * | 2020-05-25 | 2020-09-18 | 西部矿业股份有限公司 | Efficient collecting agent for collecting copper and gold from copper smelting slag and preparation method thereof |
| CN117884259A (en) * | 2024-03-14 | 2024-04-16 | 中国矿业大学(北京) | Multi-metal ore dressing and separating agent and preparation method and application thereof |
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|---|---|---|---|---|
| CN106076646A (en) * | 2016-06-20 | 2016-11-09 | 曹飞 | A kind of screening technique of new copper sulfur collecting agent |
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2017
- 2017-07-06 CN CN201710546519.3A patent/CN107141241B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106076646A (en) * | 2016-06-20 | 2016-11-09 | 曹飞 | A kind of screening technique of new copper sulfur collecting agent |
Non-Patent Citations (1)
| Title |
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| KATHARINA BREME: "Identification of New, Odor-Active Thiocarbamates in Cress Extracts and Structure−Activity Studies on Synthesized Homologues", 《J. AGRIC. FOOD CHEM.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109675723A (en) * | 2019-01-29 | 2019-04-26 | 中南大学 | Collecting agent and its preparation method and application with amide groups and thioamides base |
| CN111672635A (en) * | 2020-05-25 | 2020-09-18 | 西部矿业股份有限公司 | Efficient collecting agent for collecting copper and gold from copper smelting slag and preparation method thereof |
| CN117884259A (en) * | 2024-03-14 | 2024-04-16 | 中国矿业大学(北京) | Multi-metal ore dressing and separating agent and preparation method and application thereof |
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| CN107141241B (en) | 2019-04-30 |
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