CN102806150A - Collecting agent for copper-zinc separation flotation of copper-zinc ore - Google Patents
Collecting agent for copper-zinc separation flotation of copper-zinc ore Download PDFInfo
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- CN102806150A CN102806150A CN2012102747068A CN201210274706A CN102806150A CN 102806150 A CN102806150 A CN 102806150A CN 2012102747068 A CN2012102747068 A CN 2012102747068A CN 201210274706 A CN201210274706 A CN 201210274706A CN 102806150 A CN102806150 A CN 102806150A
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Abstract
The invention relates to a high-efficiency collecting agent for copper-zinc separation flotation of copper-zinc ores, which consists of the following materials in parts by weight: 35-55 parts of diethylamino methyl xanthate, 30-50 parts of alkyl allyl thiourethane and 5-15 parts of ethyl alkyl xanthate formate. The collecting agent has the characteristics of collecting and foaming dual attributes, good selectivity to copper sulfide minerals, strong collecting capacity and weaker collecting capacity to zinc sulfide ores and pyrites, can realize high-efficiency separation of copper and zinc within the range of pH value of 7-11, can effectively improve the grade and recovery rate of copper and zinc concentrates, and is a copper-zinc ore collecting agent with a wider application range.
Description
Technical field
The present invention relates to a kind of copper zinc ore beneficiation collecting agent, particularly a kind of collecting agent that is used for copper zinc ore copper zinc separating flotation.
Background technology
To the enrichment in the copper sulfide zinc ore, copper smelting zinc metal is the main production method of present copper zinc metal then through floatation process.Because copper zinc content is low in the nature copper zinc ore product resource, must the metal in the ore be carried out enrichment through floatation process.Controling differential flotation process for copper is adopted in the flotation of copper zinc ore usually, under suitable pH condition, suppresses zinc mineral with sodium sulfite, zinc sulfate, and xanthate, ester class collecting agent use separately or mix and use the diffeential floatation copper mineral, select the copper mine tailing to select zinc.This method has been widely used in commercial production at present, to ore of high grade, that mineral composition is fairly simple, can obtain the higher copper of the grade and the rate of recovery, zinc concentrate.Yet, for the copper zinc ore of some difficult choosing, as follows pig copper content copper sulfide zinc ore higher or slightly weathering oxidation; Adopt xanthate or single ester class collecting agent, flotation effect is very undesirable, and copper, zinc concentrate contain height mutually; Mainly be to contain the zinc height in the copper concentrate; Cupric is high in the zinc concentrate, and copper, zinc metal recovery rate are low, is unfavorable for improving the comprehensive utilization ratio of copper sulfide zinc ore resource.Therefore, research and development are suitable for the high-efficient collecting agent that the dealing with complicated difficulty is selected the copper sulfide zinc ore, and reasonable development copper zinc ore is produced resource, improve copper zinc ore mountain overall economic efficiency, have crucial meaning.
Summary of the invention
Technical problem to be solved by this invention is to avoid the deficiency of prior art, and a kind of effectively separating copper, zinc vulcanizing mine are provided, and is applicable to that particularly complicated difficulty selects a kind of collecting agent that is used for copper zinc ore copper zinc separating flotation of copper sulfide zinc ore.
The technical scheme that the present invention is taked for its technical problem of solution is:
A kind of collecting agent that is used for copper zinc ore copper zinc separating flotation, form by the material of following weight portion:
35-55 parts of diethylin methyl xanthogenic acids
30-50 parts of alkyl pi-allyl thiourethanes
5-15 parts of alkyl xanthogenic acid Ethyl formates.
In above-mentioned collector composition, preferred weight part of diethylin methyl xanthogenic acid is 50 parts, and preferred weight part of alkyl pi-allyl thiourethane is 40 parts, and preferred weight part of alkyl xanthogenic acid Ethyl formate is 10 parts.
It is propyl group pi-allyl thiourethane or isobutyl group pi-allyl thiourethane that said alkyl pi-allyl thiourethane is selected from.
It is ethoxy-dithioformic acid Ethyl formate, isopropyl xanthan acid Ethyl formate or butyl xanthic acid Ethyl formate that said alkyl xanthogenic acid Ethyl formate is selected from.
Described a kind of collecting agent that is used for copper zinc ore copper zinc separating flotation is prepared from following method:
At normal temperatures and pressures, diethylin methyl xanthogenic acid, alkyl pi-allyl thiourethane and alkyl xanthogenic acid Ethyl formate are added in the stirred tank by above-mentioned weight portion, mixed under the room temperature 1～1.5 hour, promptly get said copper zinc ore copper zinc separating flotation collecting agent.
Diethylin methyl xanthogenic acid is the good sulfide mineral collector of a kind of selectivity; Copper sulfide mineral (comprising chalcopyrite, vitreous copper, covellite etc.) had stronger selectivity collecting effect; Has frothing capacity; A little less than zinc sulfide mineral (comprising zincblende, marmatite) collecting effect, when being used for flotation cupric, zinc vulcanizing mine, can significantly improve the separating effect of copper sulfide mineral and zinc sulfide mineral; Reduce copper concentrate, zinc concentrate and contain (reduce in the copper concentrate in the zinc content and zinc concentrate concentrate copper content), raising copper, zinc concentrate grade and the rate of recovery mutually; Alkyl pi-allyl thiourethane is a kind of sulfide mineral collector; Be mainly used in copper, lead, gold, silver sulfide flotation; To the pyrite collecting ability a little less than, when the copper zinc vulcanizing mine carried out flotation below pulp alkalinity pH9, zinc sulfide mineral was non-rising basically; Can realize the high efficiency separation of copper sulfide, zinc mineral, reduce zinc sulfide mineral inhibitor consumption significantly.The alkyl xanthogenic acid Ethyl formate is a kind of sulfide mineral collector, has foaming characteristic concurrently, is mainly used in the flotation of copper, lead, Ni sulphide mine and association gold and silver.The above-mentioned weight portion scope of the combination of these components and each component; Confirm through a large amount of tests; The composite novel combination medicament that forms of principle of effective combination results cooperative effect of the different medicaments of foundation through amalgamation mechanism and common adsorption mechanism etc., has improved the selectivity of medicament; Strengthened collecting ability; Especially copper sulfide mineral there is stronger selectivity collecting effect, in the scope of pH value 7-12, all can realizes the high efficiency separation of copper, zinc, can effectively improve copper, zinc concentrate grade and the rate of recovery.
The present invention is good to the copper sulfide mineral selectivity, and collecting ability is strong, and to zinc sulfide ore and pyrite collecting ability a little less than, it is applied to the copper zinc ore floating, can reduce copper, zinc concentrate to contain mutually, improves copper, zinc recovery 1-3%.Beneficiation test with Xinjiang copper-zinc ore (cupric 1.27%, zinc 3.59%, sulphur 23.35%) is an example, adopts the collecting agent of being invented to substitute conventional butyl xanthate and ester 105, and the copper concentrate copper grade has improved 1.05%, and the rate of recovery improves 2.65%; Zinc concentrate zinc grade improves 3.50%, and the rate of recovery has improved 1.62%.
The specific embodiment
Below principle of the present invention and characteristic are described, institute gives an actual example and only is used to explain the present invention, is not to be used to limit scope of the present invention.
In following examples, just the weight portion of raw material changes, and the method for preparing said collecting agent is constant.Parts by weight of raw materials changes the influence to mineral processing index among the different embodiment in order to describe more intuitively; Select for use the Inner Mongol copper-zinc ore to carry out beneficiation test under the same conditions; List the grade and the rate of recovery of copper, zinc concentrate respectively, through the performance of the synthetic collecting agent of the variation reflection different material weight portion of copper, zinc concentrate mineral processing index.Copper, zinc concentrate contain low mutually, and copper, zinc recovery height explain that said collecting agent selectivity is good, and collecting ability is strong, and copper zinc separating flotation is effective.
Embodiment 1:
1, preparation diethylin methyl yellow ortho acid
The 14.6Kg diethylamine is joined in the agitated reactor, slowly add 6Kg formaldehyde at normal temperatures, about 0.5h adds, and heats up then, is no more than 60 ℃ with reaction temperature and is advisable insulation reaction 2h; Logical refrigerated brine is cooled to 30 ℃, adds carbon disulfide 15.2Kg, slowly adds potassium hydroxide powder 11.2 Kg, and about 1h adds, and gets product diethylin methyl yellow ortho acid at 40 ℃ of insulation reaction 1h, and this reaction diethylin methyl yellow ortho acid effective content can reach 90%.
2, preparation isobutyl group pi-allyl thiourethane
In airtight stainless steel cauldron, add isothiocyanates 28.7Kg (main content is greater than 98%) and 19.7g butyl titanate, 90～100 ℃ of control temperature add isobutanol at a slow speed; 1.5h about dropwise, the isobutanol addition is 21.4Kg, keeping reaction temperature is 115～125 ℃; Reaction 3h promptly reacts end, and after room temperature was reduced in cooling, can was to Plastic Drum; Gained brown oily product is an isobutyl group pi-allyl thiourethane, and this reaction isobutyl group pi-allyl thiourethane effective content can reach 85%.
3, preparation alkyl xanthogenic acid Ethyl formate
11.5Kg isopropyl xanthate and 12Kg ethanol are joined in the agitated reactor, slowly add the 15.6Kg chloro ethyl formate at normal temperatures; About 1h adds, and is no more than 35 ℃ with reaction temperature and is advisable insulation reaction 3h; Leave standstill the back and divide the impurity that goes to the bottom; Supernatant liquid reclaims ethanol 50～60 ℃ of distillations, and remaining liq is an oily yellow transparent liquid isopropyl xanthan acid Ethyl formate, and this product is filled in the Plastic Drum; This reaction isopropyl xanthan acid Ethyl formate effective content can reach 85%, and productive rate is more than 93%.
The diethylin methyl yellow ortho acid 35kg that 4, will prepare as stated above at normal temperatures and pressures, propyl group pi-allyl thiourethane 50kg, isopropyl xanthan acid Ethyl formate 12kg mixed under the room temperature 1.5 hours, promptly got collector composition of the present invention.
5. with this collecting agent Inner Mongol copper sulfide zinc ore is carried out beneficiation test, raw ore cupric 0.87%, zinc 3.16%, sulphur 10.61%.Adopt and preferentially to select copper, select the copper mine tailing to select the principle technological process of zinc, concrete technological process is the copper one roughing, scans for twice, and twice selected; The zinc one roughing is scanned triple cleaning twice.Selecting copper medicament lime is pH values of pulp adjustment agent and pyrite inhibitor, and sodium sulfite, zinc sulfate are the zinc sulfide mineral inhibitor, collecting agent of the present invention; Select zinc medicament lime, copper sulphate, butyl xanthate, 2
#Oil.Carry out beneficiation test according to above-mentioned technological process, the collecting agent of being invented makes an addition to copper one roughing and primary cleaning, and consumption is 190 g/t, and the beneficiation test result is following: copper concentrate cupric 21.07% contains zinc 4.97, copper recovery 83.60%; Zinc concentrate contains zinc 55.62%, cupric 0.82%, zinc recovery 86.19%.
Embodiment 2:
The diethylin methyl yellow ortho acid 50kg that will prepare by the method for embodiment 1 at normal temperatures and pressures; Isobutyl group pi-allyl thiourethane 40kg, isopropyl xanthan acid Ethyl formate 10kg adds in the stirred tank; Mixed under the room temperature 1.5 hours, and promptly got collector composition of the present invention.Beneficiation test is carried out in technological process according to embodiment 1, and the collecting agent of being invented makes an addition to copper one roughing and primary cleaning, and consumption is 180 g/t, and the beneficiation test result is following: copper concentrate cupric 23.75% contains zinc 3.69%, copper recovery 85.32%; Zinc concentrate contains zinc 56.91%, cupric 0.52%, zinc recovery 88.23%.
Embodiment 3:
The diethylin methyl yellow ortho acid 55kg that will prepare by the method for embodiment 1 at normal temperatures and pressures; Isobutyl group pi-allyl thiourethane 30kg, ethoxy-dithioformic acid Ethyl formate 10kg adds in the stirred tank; Mixed under the room temperature 1.5 hours, and promptly got collector composition of the present invention.Mineral processing circuit according to embodiment 1; With this collecting agent Inner Mongol copper sulfide zinc ore is carried out beneficiation test; The collecting agent of being invented makes an addition to copper one roughing and primary cleaning, and consumption is 170 g/t, and the beneficiation test result is following: copper concentrate cupric 23.31%; Contain zinc 3.75%, copper recovery 85.64%; Zinc concentrate contains zinc 56.76%, cupric 0.58%, zinc recovery 88.09%.
Embodiment 4:
The diethylin methyl yellow ortho acid 40kg that will prepare by the method for embodiment 1 at normal temperatures and pressures; Propyl group pi-allyl thiourethane 35kg, butyl xanthic acid Ethyl formate 11kg adds in the stirred tank; Mixed under the room temperature 1.5 hours, and promptly got collector composition of the present invention.Mineral processing circuit according to embodiment 1; With this collecting agent Inner Mongol copper sulfide zinc ore is carried out beneficiation test; The collecting agent of being invented makes an addition to copper one roughing and primary cleaning, and consumption is 200 g/t, and the beneficiation test result is following: copper concentrate cupric 23.46%; Contain zinc 3.81%, copper recovery 84.53%; Zinc concentrate contains zinc 56.52%, cupric 0.65%, zinc recovery 87.80%.
Embodiment 5:
The diethylin methyl yellow ortho acid 50kg that will prepare by the method for embodiment 1 at normal temperatures and pressures; Isobutyl group pi-allyl thiourethane 35kg, isopropyl xanthan acid Ethyl formate 5kg adds in the stirred tank; Mixed under the room temperature 1.5 hours, and promptly got collector composition of the present invention.Mineral processing circuit according to embodiment 1; With this collecting agent Inner Mongol copper sulfide zinc ore is carried out beneficiation test; The collecting agent of being invented makes an addition to copper one roughing and primary cleaning, and consumption is 160 g/t, and the beneficiation test result is following: copper concentrate cupric 22.89%; Contain zinc 3.99%, copper recovery 84.59%; Zinc concentrate contains zinc 55.68%, cupric 0.70%, zinc recovery 87.31%.
Embodiment 6:
The diethylin methyl yellow ortho acid 45kg that will prepare by the method for embodiment 1 at normal temperatures and pressures; Propyl group pi-allyl thiourethane 40kg, ethoxy-dithioformic acid Ethyl formate 15kg adds in the stirred tank; Mixed under the room temperature 1.5 hours, and promptly got collector composition of the present invention.Mineral processing circuit according to embodiment 1; With this collecting agent Inner Mongol copper sulfide zinc ore is carried out beneficiation test; The collecting agent of being invented makes an addition to copper one roughing and primary cleaning, and consumption is 150 g/t, and the beneficiation test result is following: copper concentrate cupric 23.39%; Contain zinc 3.86%, copper recovery 85.19%; Zinc concentrate contains zinc 56.67%, cupric 0.59%, zinc recovery 87.68%.
The beneficiation test data declaration of above embodiment; Said collectors application is in the copper zinc ore floating, can realize effectively separating of copper sulfide and zinc sulfide mineral, improves the sorting index of copper, zinc; Significantly improve the comprehensive utilization ratio of copper sulfide zinc ore product resource; Reduce reagent consumption simultaneously, alleviate pollution, for bargh creates good economic benefit and social benefit environment.
Claims (5)
1. collecting agent that is used for copper zinc ore copper zinc separating flotation, it is characterized in that: the raw material by following weight portion is formed:
35-55 parts of diethylin methyl yellow ortho acid
30-50 parts of alkyl pi-allyl thiourethanes
5-15 parts of alkyl xanthogenic acid Ethyl formates.
2. a kind of collecting agent that is used for copper zinc ore copper zinc separating flotation according to claim 1, it is characterized in that: the weight portion proportioning of said raw material is:
50 parts of diethylin methyl yellow ortho acid
40 parts of alkyl pi-allyl thiourethanes
10 parts of alkyl xanthogenic acid Ethyl formates.
3. a kind of collecting agent that is used for copper zinc ore copper zinc separating flotation according to claim 1 and 2 is characterized in that said alkyl pi-allyl thiourethane is propyl group pi-allyl thiourethane, isobutyl group pi-allyl thiourethane.
4. a kind of collecting agent that is used for copper zinc ore copper zinc separating flotation according to claim 1 and 2 is characterized in that said alkyl xanthogenic acid Ethyl formate is a kind of in ethoxy-dithioformic acid Ethyl formate, isopropyl xanthan acid Ethyl formate or the butyl xanthic acid Ethyl formate.
5. a kind of collecting agent that is used for copper zinc ore copper zinc separating flotation according to claim 1 and 2 is characterized in that being prepared from following method:
At normal temperatures and pressures, diethylin methyl xanthogenic acid, alkyl pi-allyl thiourethane and alkyl xanthogenic acid Ethyl formate are added in the stirred tank by above-mentioned weight portion, mixed under the room temperature 1～1.5 hour, divide water, get said collecting agent.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012102747068A CN102806150A (en) | 2012-08-03 | 2012-08-03 | Collecting agent for copper-zinc separation flotation of copper-zinc ore |
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| CN2012102747068A CN102806150A (en) | 2012-08-03 | 2012-08-03 | Collecting agent for copper-zinc separation flotation of copper-zinc ore |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104056725A (en) * | 2014-05-15 | 2014-09-24 | 中南大学 | Ether group thionocarbamates collecting agent, as well as preparation and application method thereof |
| CN104772222A (en) * | 2015-03-11 | 2015-07-15 | 铜陵鑫腾矿业科技有限公司 | Flotation agent for copper-zinc separate flotation of copper-zinc ore |
| CN109647627A (en) * | 2019-01-04 | 2019-04-19 | 福州大学 | A kind of covellite separates collecting agent and preparation method with flotation of pyrite |
| CN111905932A (en) * | 2020-07-16 | 2020-11-10 | 沈阳有色金属研究院有限公司 | Beneficiation method for complex copper zinc sulfide ore |
| CN112588448A (en) * | 2020-12-18 | 2021-04-02 | 中南大学 | Composite collecting agent and application thereof in chalcopyrite flotation |
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| US5074994A (en) * | 1990-10-18 | 1991-12-24 | The Doe Run Company | Sequential and selective flotation of sulfide ores |
| CN101091935A (en) * | 2007-07-26 | 2007-12-26 | 长春黄金研究院 | Combined capturing and collecting agent |
| CN101992151A (en) * | 2010-11-11 | 2011-03-30 | 西北矿冶研究院 | High-sulfur copper ore collecting agent |
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2012
- 2012-08-03 CN CN2012102747068A patent/CN102806150A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5074994A (en) * | 1990-10-18 | 1991-12-24 | The Doe Run Company | Sequential and selective flotation of sulfide ores |
| CN101091935A (en) * | 2007-07-26 | 2007-12-26 | 长春黄金研究院 | Combined capturing and collecting agent |
| CN101992151A (en) * | 2010-11-11 | 2011-03-30 | 西北矿冶研究院 | High-sulfur copper ore collecting agent |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104056725A (en) * | 2014-05-15 | 2014-09-24 | 中南大学 | Ether group thionocarbamates collecting agent, as well as preparation and application method thereof |
| CN104056725B (en) * | 2014-05-15 | 2016-06-29 | 中南大学 | A kind of ether thiourethane collecting agent and methods for making and using same thereof |
| CN104772222A (en) * | 2015-03-11 | 2015-07-15 | 铜陵鑫腾矿业科技有限公司 | Flotation agent for copper-zinc separate flotation of copper-zinc ore |
| CN109647627A (en) * | 2019-01-04 | 2019-04-19 | 福州大学 | A kind of covellite separates collecting agent and preparation method with flotation of pyrite |
| CN111905932A (en) * | 2020-07-16 | 2020-11-10 | 沈阳有色金属研究院有限公司 | Beneficiation method for complex copper zinc sulfide ore |
| CN112588448A (en) * | 2020-12-18 | 2021-04-02 | 中南大学 | Composite collecting agent and application thereof in chalcopyrite flotation |
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Application publication date: 20121205 |