CN111229471A - Copper collecting agent and flotation process of copper sulfide cobalt ore - Google Patents
Copper collecting agent and flotation process of copper sulfide cobalt ore Download PDFInfo
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- CN111229471A CN111229471A CN202010093361.0A CN202010093361A CN111229471A CN 111229471 A CN111229471 A CN 111229471A CN 202010093361 A CN202010093361 A CN 202010093361A CN 111229471 A CN111229471 A CN 111229471A
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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
- B03D1/004—Organic compounds
- B03D1/012—Organic compounds containing sulfur
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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
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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
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
Abstract
The invention provides a copper collecting agent and a flotation process of copper sulfide cobalt ore. The copper collector comprises, by mass, 70-80% of a black powder, 15-25% of a hydrocarbyl thiocarbamate derivative and 5-15% of an alcohol ether solvent. The alcohol ether solvent is used as an amphiphilic molecule to play a role in dispersing adsorption of the black pigment and the alkyl thiocarbamate on the surface of the copper-containing mineral, so that the black pigment and the alkyl thiocarbamate form a more stable and uniform adsorption layer on the surface of the copper-containing mineral, and the adsorption capacity of the combined black pigment and the alkyl thiocarbamate on the surface of copper sulfide is greater than the sum of the adsorption capacities of the non-combined black pigment and the non-combined alkyl thiocarbamate on the surface of copper sulfide. The excellent selectivity of the black powder and the alkyl thiocarbamate to the copper minerals is fully utilized, and meanwhile, the copper mineral collecting is enhanced through the synergistic effect. Therefore, when the copper sulfide cobalt ore is treated by using the copper collecting agent, the flotation of cobalt floating copper is favorably inhibited, and the grade and the yield of cobalt are improved.
Description
Technical Field
The invention relates to the technical field of mineral separation, and particularly relates to a copper collecting agent and a flotation process of copper sulfide cobalt ore.
Background
Copper-cobalt sulfide ore is one of the important sources of cobalt, and flotation is the main mode for sorting the copper-cobalt sulfide ore. Conventional flotation processes include bulk flotation and preferably flotation. The mixed flotation is to sort copper sulfide minerals and cobalt sulfide minerals into mixed concentrates, and the mixed concentrates are used as final products or are subjected to copper-cobalt separation. And the preferential flotation is to float copper sulfide minerals firstly, and then float cobalt minerals from copper tailings to obtain copper concentrates and cobalt concentrates respectively.
From the current technical reports, copper-cobalt bulk flotation is common, and a dressing plant mainly produces copper-cobalt bulk concentrates. Although the copper sulfide cobalt bulk concentrate can be directly treated by the existing metallurgical process, the problems of loss of metal recovery rate, high cost investment of a metallurgical system and the like exist. Therefore, copper and cobalt separation is generally required for the copper and cobalt mixed concentrate, and at present, the copper and cobalt separation is mainly realized by using a large amount of calcium oxide, so that the cobalt concentrate contains a large amount of calcium oxide, and the acid consumption of the subsequent hydrometallurgy process is increased.
The method for preferentially floating copper sulfide cobalt ore comprises the steps of firstly carrying out flotation separation on copper by adopting a collecting agent, and then carrying out flotation on cobalt ore on tailings after copper flotation to respectively obtain copper concentrate and cobalt concentrate. For example, in the research on the flotation test of the copper-cobalt polymetallic sulphide ore published by Chen Dynasty in the journal of Hunan nonferrous metals, the flotation process flow of inhibiting cobalt and floating copper is adopted. LD is selected as a copper mineral collecting agent, lime and bleaching powder are selected as cobalt-containing mineral inhibitors, and copper floats in an alkaline medium. Namely, two-stage ore grinding and two-stage separation are adopted, wherein the first stage ore grinding is used for recovering copper and most of cobalt, and the second stage ore grinding is used for improving the recovery rate of cobalt. A flotation closed circuit is used for testing the copper-cobalt sulfide ore with the copper grade of 2.765% and the cobalt grade of 0.0386% in the raw ore, so that a good test effect is obtained, the copper grade in the final copper concentrate is 29.07%, and the copper recovery rate reaches 95.78%; the cobalt grade in the sulfur-cobalt concentrate I is 0.31 percent, the recovery rate is 20.74 percent, the cobalt grade in the sulfur-cobalt concentrate II is 0.25 percent, and the recovery rate is 8.23 percent. However, although the problem that the cobalt concentrate contains a large amount of calcium oxide can be avoided by adopting the method to separate copper and cobalt, the finally obtained cobalt concentrate still has the problems of low cobalt grade and low cobalt recovery rate.
Disclosure of Invention
The invention mainly aims to provide a copper collecting agent and a flotation process of copper-cobalt sulfide ore, and aims to solve the problems of low cobalt grade and low cobalt recovery rate in cobalt concentrate obtained by a method for preferably flotation of copper-cobalt sulfide ore in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a copper collector comprising, by mass, 70 to 80% of a black dye, 15 to 25% of a hydrocarbyl thiocarbamate derivative, and 5 to 15% of an alcohol ether solvent.
Further, the above-mentioned black drug is one or more of butylammonium black drug, sodium butyl black drug, isopropylammonium black drug, sodium isopropyl black drug, isobutylammonium black drug, and isobutylsodium black drug.
Further, the hydrocarbyl thiocarbamate derivative is one or more of cyanoethyl N, N-dimethyldithiocarbamate, propionitrile N, N-diethyldithiocarbamate and propenyl N, N-diethyldithiocarbamate.
According to another aspect of the present invention, there is provided a flotation process for copper cobalt sulfide ore, the flotation process comprising step S1 of wet grinding a mixture of copper cobalt sulfide ore and calcium oxide or calcium hydroxide to obtain alkaline ore pulp; step S2, mixing materials including alkaline ore pulp, a first copper collector and a first foaming agent, and performing copper roughing to obtain copper roughing concentrate and copper roughing tailings; step S3, mixing the copper roughing tailings and a second copper collecting agent for copper scavenging to obtain copper tailings, wherein the first copper collecting agent and the second copper collecting agent are the same and are any one of the copper collecting agents; and step S4, carrying out cobalt roughing, cobalt fine selection and cobalt scavenging on the copper tailings in sequence to obtain tailings.
Further, the cobalt roughing in the step S4 includes: mixing materials comprising the copper tailings, the third collecting agent and the second foaming agent, and performing cobalt roughing to obtain cobalt roughing concentrate and cobalt roughing tailings; preferably, the second foaming agent is selected from one or more of methyl isobutyl carbinol, dimethyl benzyl alcohol and sec-octanol; preferably the third collector is selected from any one or more of sodium or potassium hydrocarbyl xanthates, more preferably the hydrocarbyl group is any one of butyl, isobutyl, pentyl and isopentyl; preferably, the mass ratio of the third collecting agent to the copper-cobalt sulfide ore is 1-2: 20000, the mass ratio of the second foaming agent to the copper-cobalt sulfide ore is 1-2: 100000, and the time for roughing cobalt is 3-5 min.
Further, the cobalt concentration of the step S4 includes performing cobalt concentration on the cobalt rougher concentrate to obtain a cobalt concentrate; preferably, the cobalt concentration is carried out twice, preferably, an inhibitor is added in the first cobalt concentration, the mass ratio of the inhibitor to the copper cobalt sulfide ore is preferably 1-30: 100000, and the inhibitor is preferably one or two of sodium carboxymethylcellulose and water glass.
Further, the cobalt scavenging of the step S4 includes mixing the cobalt rougher tailings with a fourth collector to perform cobalt scavenging, so as to obtain tailings; the fourth collector is selected from any one or more of sodium hydrocarbyl xanthate or potassium hydrocarbyl xanthate, more preferably the hydrocarbyl group is any one of butyl, isobutyl, pentyl and isopentyl; preferably, the mass ratio of the fourth collecting agent to the copper cobalt sulfide ore is 3-6: 100000, and the time for scavenging cobalt is 3-5 min.
Further, before the step S4, the flotation process includes a step of adding an activating agent into the copper tailings, wherein the activating agent is preferably one or more of copper sulfate, ferrous sulfate and sulfuric acid, and the mass ratio of the activating agent to the copper cobalt sulfide ore is preferably 1-100: 100000.
Further, in the alkaline ore pulp, the ore particles with the particle size of less than 0.074mm are 65-80% of the total amount of the ore in percentage by mass.
Further, the pH value of the alkaline ore pulp is 11-12, and the solid content of the alkaline ore pulp is preferably 30-40%.
Further, in the step S2, the mass ratio of the first copper collector to the copper cobalt sulfide ore is 1 to 3:50000, the mass ratio of the first foaming agent to the copper cobalt sulfide ore is preferably 1 to 3:100000, the first foaming agent is preferably selected from one or more of methyl isobutyl carbinol, dimethyl benzyl alcohol and sec-octanol, and the time for roughing copper is preferably 3 to 4 min.
Further, in the step S3, the mass ratio of the second copper collector to the copper cobalt sulfide ore is 1-6: 200000, and the time for copper scavenging is preferably 3-4 min.
Further, the flotation process also comprises the step of carrying out copper concentration on the copper roughing concentrate to obtain copper concentrate; preferably, the copper concentration times are twice; preferably, calcium oxide is added in the first copper concentration, and more preferably, the mass ratio of the calcium oxide to the copper cobalt sulfide ore is 1-100: 100000.
By applying the technical scheme of the invention, the black powder with better copper selectivity and the alkyl thiocarbamate are combined, so that the excellent selectivity of the two reagents on copper minerals is fully utilized, and the copper mineral collection is enhanced through synergistic effect. The alcohol ether solvent in the copper collector is used as an amphiphilic molecule to play a role in dispersing the adsorption of the black dye and the hydrocarbyl thiocarbamate on the surface of the copper-containing mineral, so that the black dye and the hydrocarbyl thiocarbamate form a more stable and uniform adsorption layer on the surface of the copper-containing mineral, and the adsorption quantity of the combined black dye and the hydrocarbyl thiocarbamate on the surface of copper sulfide is greater than the sum of the adsorption quantities of the non-combined black dye and the non-combined hydrocarbyl thiocarbamate on the surface of copper sulfide. On the one hand, the high selectivity and high collecting capacity of the black powder and the hydrocarbyl thiocarbamate to copper are fully exerted; on the other hand, the synergistic effect of the copper collecting agent and the copper mineral collecting agent on the function is further promoted, so that the performances of the copper collecting agent and the copper mineral collecting agent are further complemented, the finally obtained copper collecting agent is obviously superior to the simple superposition of the performances of the copper collecting agent and the copper mineral collecting agent, and the copper collecting agent has excellent copper mineral collecting capacity and selectivity.
Therefore, when the copper sulfide cobalt ore is treated by the copper collecting agent, the copper collecting agent can separate copper in the copper sulfide cobalt ore as much as possible, and simultaneously, the floating of the cobalt ore is reduced as much as possible, so that the content of copper in the copper tailings after the copper is roughly selected is reduced, and the content of cobalt in the copper tailings is improved; the method is beneficial to selecting cobalt when the copper tailings are subjected to cobalt flotation, and further improves the grade and yield of the cobalt.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
figure 1 shows a flow chart of the flotation process operation of the copper cobalt sulphide ore of the invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As analyzed by the background art, the problems of low cobalt grade and low cobalt recovery rate in the cobalt concentrate obtained by adopting the method for preferably floating the copper-cobalt sulfide ore exist in the prior art, and in order to solve the problems, the invention provides a copper collecting agent and a flotation process of the copper-cobalt sulfide ore.
In a typical embodiment of the present application, there is provided a copper collector comprising, by mass, 70-80% of a black chemical, 15-25% of a hydrocarbyl thiocarbamate derivative, and 5-15% of an alcohol ether solvent.
Flotation is a mineral separation method which utilizes the action of a collecting agent and active points on the surface of a mineral so as to make the surface of the mineral float up in a hydrophobic manner. The collecting force and the selectivity of the collecting agent are important factors influencing the action of the collecting agent and the active points of the mineral surface.
This application adopts and makes up with alkyl thiocarbamate the better black medicine of copper selectivity, when these two kinds of medicaments of make full use of are to the good selectivity of copper mineral, has strengthened the collection to the copper mineral through the synergistic effect. The alcohol ether solvent in the copper collector is used as an amphiphilic molecule to play a role in dispersing the adsorption of the black dye and the hydrocarbyl thiocarbamate on the surface of the copper-containing mineral, so that the black dye and the hydrocarbyl thiocarbamate form a more stable and uniform adsorption layer on the surface of the copper-containing mineral, and the adsorption quantity of the combined black dye and the hydrocarbyl thiocarbamate on the surface of copper sulfide is greater than the sum of the adsorption quantities of the non-combined black dye and the non-combined hydrocarbyl thiocarbamate on the surface of copper sulfide. On the one hand, the high selectivity and high collecting capacity of the black powder and the hydrocarbyl thiocarbamate to copper are fully exerted; on the other hand, the synergistic effect of the copper collecting agent and the copper mineral collecting agent on the function is further promoted, so that the performances of the copper collecting agent and the copper mineral collecting agent are further complemented, the finally obtained copper collecting agent is obviously superior to the simple superposition of the performances of the copper collecting agent and the copper mineral collecting agent, and the copper collecting agent has excellent copper mineral collecting capacity and selectivity.
Therefore, when the copper sulfide cobalt ore is treated by the copper collecting agent, the copper collecting agent can separate copper in the copper sulfide cobalt ore as much as possible, and simultaneously, the floating of the cobalt ore is reduced as much as possible, so that the content of copper in the copper tailings after the copper is roughly selected is reduced, and the content of cobalt in the copper tailings is improved; the method is beneficial to selecting cobalt when the copper tailings are subjected to cobalt flotation, and further improves the grade and yield of the cobalt.
On one hand, in order to enable the black powder to have the highest possible selectivity, and on the other hand, in order to improve the adsorption capacity of the black powder and the hydrocarbyl thiocarbamate on the surface of the copper-containing mineral and the stability and uniformity of an adsorption layer formed by the black powder and the hydrocarbyl thiocarbamate, so that the black powder and the hydrocarbyl thiocarbamate can be better complemented in function, and further the copper collecting agent has excellent copper mineral collecting capacity and selectivity, the black powder is preferably one or more of butyl ammonium black powder, butyl sodium black powder, isopropyl ammonium black powder, isopropyl sodium black powder, isobutyl ammonium black powder and isobutyl sodium black powder.
In one embodiment of the present application, the hydrocarbyl thiocarbamate derivative is one or more of cyanoethyl N, N-dimethyldithiocarbamate, propionitrile N, N-diethyldithiocarbamate, and propenyl N, N-diethyldithiocarbamate.
The stability and uniformity of the adsorption layer formed by the black drug and the alkyl thiocarbamate derivative on the surface of the mineral have an important influence on the complementation of the functionality of the black drug and the alkyl thiocarbamate derivative. The hydrocarbyl thiocarbamate has high copper collecting capacity, and the hydrocarbyl thiocarbamate molecule and the black powder molecule can form a stable and uniform adsorption layer on the surface of the mineral as much as possible under the assistance of an alcohol ether solvent, so that the hydrocarbyl thiocarbamate molecule and the black powder molecule can achieve a complementary function in function, and the final copper collector has excellent copper mineral collecting capacity and selectivity.
In another exemplary embodiment of the present application, a flotation process of copper-cobalt sulfide ore is provided, as shown in fig. 1, the flotation process includes a step S1 of wet-grinding a mixture of copper-cobalt sulfide ore and calcium oxide or calcium hydroxide to obtain an alkaline ore slurry; step S2, mixing materials including alkaline ore pulp, a first copper collector and a first foaming agent, and performing copper roughing to obtain copper roughing concentrate and copper roughing tailings; step S3, mixing the copper roughing tailings and a second copper collecting agent for copper scavenging to obtain copper tailings, wherein the first copper collecting agent and the second copper collecting agent are the same and are any one of the copper collecting agents; and step S4, carrying out cobalt roughing, cobalt fine selection and cobalt scavenging on the copper tailings in sequence to obtain tailings.
The mineral composition of copper-cobalt sulfide ore is more complex than that of single copper sulfide ore, wherein the floatability of the cobalt ore is close to that of pyrite, and the floatability of copper ions on pyrite and other sulfide minerals is obviously influenced, so the key of copper-cobalt separation is to inhibit the effect of cobalt and iron minerals. According to the method, the ore is treated by adopting a preferential flotation process of floating copper firstly and then floating cobalt, so that on one hand, the high-efficiency copper collecting agent and the foaming agent are utilized to help to preferentially float copper; on the other hand, the basic medium formed by calcium oxide or calcium hydroxide helps to inhibit the cobalt and iron sulfide minerals from floating, so that the copper and cobalt minerals are sufficiently separated. The obtained copper rougher concentrate contains most of copper, and the copper rougher tailings contain extremely small amount of copper and most of cobalt. And the copper collecting agent is further adopted to carry out scavenging on the copper roughing tailings, so that a small amount of copper in the copper roughing tailings is removed, and the copper content in the copper tailings is further reduced. Based on the efficient optimization effect of the copper collecting agent on copper, the finally obtained copper tailings are subjected to conventional cobalt roughing, cobalt concentration and cobalt scavenging in sequence (as shown in figure 1), and compared with the copper tailings obtained by the conventional process, the cobalt tailings are subjected to the same cobalt roughing, cobalt concentration and cobalt scavenging treatment, the grade and yield of cobalt in the obtained cobalt concentrate are obviously improved. The flotation process flow of the copper-cobalt sulfide ore is simple, the recovery of copper minerals is ensured, the recovery of cobalt-containing minerals is facilitated, and the grade of cobalt and the recovery rate of cobalt are improved.
In a preferred embodiment of the present application, as shown in fig. 1, the copper scavenging foam obtained in the copper scavenging step is returned to the copper roughing step to increase the recovery rate of copper.
In an embodiment of the present application, the cobalt roughing in the step S4 includes: mixing materials comprising the copper tailings, the third collecting agent and the second foaming agent, and performing cobalt roughing to obtain cobalt roughing concentrate and cobalt roughing tailings; preferably, the second foaming agent is selected from one or more of methyl isobutyl carbinol, dimethyl benzyl alcohol and sec-octanol; preferably the third collector is selected from any one or more of sodium or potassium hydrocarbyl xanthates, more preferably the hydrocarbyl group is any one of butyl, isobutyl, pentyl and isopentyl; preferably, the mass ratio of the third collecting agent to the copper-cobalt sulfide ore is 1-2: 20000, the mass ratio of the second foaming agent to the copper-cobalt sulfide ore is 1-2: 100000, and the time for roughing cobalt is 3-5 min.
The copper content in the copper tailings obtained by copper roughing and copper scavenging of the copper-cobalt sulfide minerals is very low, and the time for roughing the cobalt, the third collecting agent and the second foaming agent of the types and the mass ratio of the third collecting agent and the second foaming agent to the copper-cobalt sulfide ore are preferably selected, so that most of cobalt in the copper tailings can be selected to the cobalt roughing concentrate as much as possible.
In one embodiment of the present application, the cobalt concentration of the above step S4 includes: carrying out cobalt concentration on the cobalt rough concentration concentrate to obtain cobalt concentrate; preferably, the cobalt concentration is performed twice (the first cobalt concentration is marked as cobalt concentration I, and the second cobalt concentration is marked as cobalt concentration II, as shown in figure 1), an inhibitor is preferably added into the first cobalt concentration, the mass ratio of the inhibitor to the copper sulfide cobalt ore is preferably 1-30: 100000, and the inhibitor is preferably one or two of sodium carboxymethylcellulose and water glass. In the cobalt concentration, in order to further improve the cobalt recovery rate, the first cobalt concentration middlings obtained in the first cobalt concentration step are preferably returned to the cobalt roughing step, and the second cobalt concentration tailings obtained in the second cobalt concentration step are preferably returned to the first cobalt concentration step (as shown in fig. 1).
The cobalt rougher concentrate obtained by the cobalt rougher flotation contains a large amount of third collecting agent and second foaming agent, so that the cobalt blank cleaner concentration is carried out on the cobalt rougher concentrate twice, namely, the cobalt in the cobalt rougher concentrate can be further subjected to flotation, and the obtained cobalt concentrate has higher cobalt grade. In the process of cobalt concentration, an inhibitor can be added into the first cobalt concentration according to actual needs to inhibit the floatability of gangue minerals so as to improve the flotation effect of cobalt. The inhibitor type and the mass ratio of the inhibitor type to the copper cobalt sulfide ore are both beneficial to exerting the inhibition performance of the inhibitor type to the performance of the third collecting agent and the second foaming agent, and improving the cobalt concentration effect.
In an embodiment of the present application, the cobalt scavenging of the step S4 includes: mixing the cobalt roughing tailings with a fourth collecting agent for cobalt scavenging to obtain tailings; the fourth collector is selected from any one or more of sodium hydrocarbyl xanthate or potassium hydrocarbyl xanthate, more preferably the hydrocarbyl group is any one of butyl, isobutyl, pentyl and isopentyl; preferably, the mass ratio of the fourth collecting agent to the copper cobalt sulfide ore is 3-6: 100000, and the time for scavenging cobalt is 3-5 min.
The cobalt grade of the cobalt concentrate obtained by the cobalt roughing and the cobalt concentration of the copper tailings is relatively high, however, in order to further improve the recovery rate of cobalt and reduce the loss of cobalt, the cobalt roughing tailings are scavenged under the conditions, and a cobalt scavenging foam product is returned to the cobalt roughing operation (as shown in fig. 1) until cobalt-containing minerals basically float upwards.
Preferably, before the step S4, the flotation process includes a step of adding an activating agent to the copper tailings, preferably, the activating agent is one or more of copper sulfate, ferrous sulfate and sulfuric acid, and the mass ratio of the activating agent to the copper cobalt sulfide ore is preferably 1-100: 100000.
The activating agent can activate the cobalt minerals in the copper tailings and improve the floatability of the cobalt minerals, thereby being beneficial to fully floating the cobalt in the subsequent cobalt roughing, cobalt concentrating and cobalt scavenging processes and further improving the grade and recovery rate of the cobalt. However, with the increase of the dosage of the activating agent, the grade of the cobalt concentrate is not obviously improved, and after a certain amount is exceeded, the cobalt recovery rate is reduced. Therefore, the mass ratio of the activator to the copper cobalt sulfide ore is limited to the above range.
In an embodiment of the present application, in the alkaline ore slurry, by mass, the ore particles with a particle size of less than 0.074mm are 65-80% of the total amount of the ore.
If the grinding granularity of the alkaline ore pulp is too coarse, the cobalt content in the copper concentrate is too large, which is not beneficial to the separation of copper and cobalt; if the grinding granularity is too fine, the copper-cobalt flotation process is easy to argillization and is not beneficial to copper-cobalt separation, so that the influence of the two factors on the copper-cobalt flotation process is balanced as much as possible, the high-efficiency separation of copper and cobalt is achieved, the high-grade and high-recovery-rate cobalt is obtained, and the grinding granularity in the range is preferably selected.
The alkaline ore pulp with the pH value of 11-12 is beneficial to inhibiting the floating of cobalt minerals while copper minerals are preferentially floated, so that copper and cobalt are separated as much as possible. The solid content of the alkaline ore pulp is preferably 30-40%, and the reasonable control of the viscosity of the alkaline ore pulp is facilitated. Because the ore pulp is too thin, the recovery rate of the product is easily influenced, the grade of the product is easily influenced due to too high ore pulp concentration, and even the flotation environment is deteriorated, so that the minerals are difficult to float upwards.
In one embodiment of the present application, in the step S2, the mass ratio of the first copper collector to the copper cobalt sulfide ore is 1 to 3:50000, preferably the mass ratio of the first foaming agent to the copper cobalt sulfide ore is 1 to 3:100000, preferably the first foaming agent is selected from one or more of methyl isobutyl carbinol, dimethyl benzyl alcohol and sec-octyl alcohol, and preferably the time for roughing copper is 3 to 4 min.
The first copper collector and the first foaming agent in the above-mentioned mass ratio range are preferable to contribute to the improvement of the efficiency of the preferential flotation of copper minerals as much as possible, thereby efficiently separating copper and cobalt. Because the ore pulp is added with calcium oxide or calcium hydroxide, flotation foam is sticky, and the foaming agent with crisp foam is selected to improve the stability of the foam in the flotation process.
In an embodiment of the application, in the step S3, the mass ratio of the second copper collector to the copper cobalt sulfide ore is 1-6: 200000, and the time for copper scavenging is preferably 3-4 min.
The control of the copper scavenging conditions is to further improve the efficiency of copper scavenging, separate the copper in the copper roughing tailings as much as possible, efficiently separate the copper and the cobalt, and contribute to finally obtaining high-grade cobalt.
In an embodiment of the present application, the flotation process further includes performing copper concentration on the copper rougher concentrate to obtain a copper concentrate; preferably, the copper concentration times are twice; preferably, calcium oxide is added in the first copper concentration, and more preferably, the mass ratio of the calcium oxide to the copper cobalt sulfide ore is 1-100: 100000.
Copper concentration of the copper rougher concentrate (the first copper concentration is marked as copper concentration I and the second copper concentration is marked as copper concentration II, as shown in fig. 1) helps to obtain a high-grade copper concentrate. And the calcium oxide is added in the first copper concentration, so that the cobalt mineral is further inhibited from floating along with the copper mineral, and the copper and the cobalt are separated as far as possible. To further increase copper recovery, the first copper concentration middlings obtained from the first copper concentration are preferably returned to the copper rougher step, and the second copper concentration tailings are preferably returned to the first copper concentration step (as shown in fig. 1).
The advantageous effects of the present application will be described below with reference to specific examples and comparative examples.
Example 1
Taking copper-cobalt sulfide ore with copper grade of 1.85% and cobalt grade of 0.086%, adding water and 3000g/t of calcium oxide, and grinding the copper-cobalt sulfide ore to obtain alkaline ore pulp with pH value of 11.5 and solid content of 35%. The ore particles with the particle size of less than 0.074mm in the alkaline ore pulp are 70 percent of the total amount of the ore by mass percentage. And mixing and stirring the alkaline ore pulp, 40g/t of first copper capturing agent and 20g/t of methyl isobutyl carbinol for 3min, and performing copper roughing for 3min to obtain copper roughing concentrate and copper roughing tailings. Wherein the first copper collector comprises 75% butylammonium nigro, 17% azonitrile ester and 8% ethylene glycol butyl ether. And performing blank concentration twice on the copper roughing concentrate, and adding 300g/t of calcium oxide in the first copper concentration process to obtain the copper concentrate. And returning middlings obtained by the first concentration to the rough concentration operation, and returning tailings obtained by the second concentration to the first concentration operation.
And adding 20g/t of second copper collecting agent into the copper roughing tailings, stirring for 4min, then carrying out copper scavenging, wherein the flotation time is 3min, so as to obtain copper tailings and copper scavenging foam, and returning the copper scavenging foam to the copper roughing step. Wherein the second copper collector is identical in composition to the first copper collector. And continuously adding 200g/t of copper sulfate into the copper tailings to improve the floatability of cobalt, adding 80g/t of sodium butyl xanthate and 15g/t of methyl isobutyl carbinol into the copper tailings, and performing flotation for 3min to obtain cobalt rougher concentrate and cobalt rougher tailings. And (2) carrying out cobalt concentration twice on the cobalt roughing concentrate, adding 200g/t of sodium carboxymethyl cellulose in the first cobalt concentration, wherein the time of each cobalt concentration is 4min, so as to obtain the cobalt concentrate, returning the first cobalt concentration middlings to the cobalt roughing step, and returning the second cobalt concentration tailings to the first cobalt concentration step (as shown in figure 1). And continuously adding 40g/t of sodium butyl xanthate into the cobalt roughing tailings for scavenging twice, performing flotation for 4min to obtain tailings, and returning scavenged foam products to the cobalt roughing operation.
And measuring and calculating the yield of the copper concentrate, the cobalt concentrate and the tailings, and the grade and the recovery rate of Cu and Co in the copper concentrate, the cobalt concentrate and the tailings.
Example 2
Example 2 differs from example 1 in that the first copper collector in example 2 comprised 70% butylammonium blackant, 25% azonitrile ester, 5% ethylene glycol butyl ether, and the yields of the above copper concentrate, cobalt concentrate, tailings and the grades and recovery of Cu, Co therein were measured and calculated.
Example 3
Example 3 differs from example 1 in that the first copper collector in example 3 comprised 80% butylammonium blackant, 15% azonitrile ester, 5% ethylene glycol butyl ether, and the yields of the above copper concentrate, cobalt concentrate, tailings and the grades and recovery of Cu, Co therein were measured and calculated.
Example 4
Example 4 differs from example 1 in that the first copper collector in example 4 comprised 70% butylammonium blackant, 15% azonitrile ester, 15% ethylene glycol butyl ether, and the yields of the above copper concentrate, cobalt concentrate, tailings and the grades and recovery of Cu, Co therein were measured and calculated.
Example 5
Example 5 differs from example 1 in that the black powder in example 5 is sodium butyl black powder, and the yields of the above copper concentrate, cobalt concentrate, tailings and the grades and recovery rates of Cu and Co therein were measured and calculated.
Example 6
Example 6 differs from example 1 in that the hydrocarbyl thiocarbamate derivative in example 6 was N, N-diethyldithiocarbamate propenyl ester, and the yields of the above copper concentrate, cobalt concentrate, tailings and the grades and recoveries of Cu and Co therein were measured and calculated.
Example 7
Example 7 is different from example 1 in that the alcohol ether solvent in example 7 is ethylene glycol propyl ether, and the yields of the above copper concentrate, cobalt concentrate, and tailings, and the grades and recovery rates of Cu and Co therein were measured and calculated.
Example 8
Example 8 is different from example 1 in that the mass of calcium oxide added in example 8 is 2000g/t, the pH value of alkaline ore pulp is 11, and the yield of the copper concentrate, the cobalt concentrate and the tailings and the grade and the recovery rate of Cu and Co in the copper concentrate, the cobalt concentrate and the tailings are measured and calculated.
Example 9
Example 9 differs from example 1 in that the mass of calcium oxide added in example 9 is 3500g/t, the pH of the alkaline pulp is 12, and the yields of the above copper concentrate, cobalt concentrate and tailings and the grades and recovery of Cu and Co therein were measured and calculated.
Example 10
Example 10 differs from example 1 in that the mass of calcium oxide added in example 10 is 4000g/t, the pH of the alkaline pulp is 13, and the yields of the above copper concentrate, cobalt concentrate and tailings and the grades and recovery of Cu and Co therein were measured and calculated.
Example 11
Example 11 differs from example 1 in that the mass of calcium oxide added in example 11 is 1500g/t, the pH of the alkaline pulp is 9, and the yields of the above copper concentrate, cobalt concentrate and tailings and the grades and recovery of Cu and Co therein were measured and calculated.
Example 12
Example 12 differs from example 1 in that in example 12 the ore particles with a particle size of less than 0.074mm represent 65% of the total ore, the yield of the above copper concentrate, cobalt concentrate, tailings and the grade and recovery of Cu, Co therein were measured and calculated.
Example 13
Example 13 differs from example 1 in that in example 13 the ore particles with a particle size of less than 0.074mm represent 80% of the total ore, and the yields of the above copper concentrate, cobalt concentrate, tailings and the grades and recovery of Cu, Co therein were measured and calculated.
Example 14
Example 14 differs from example 1 in that in example 14 the ore particles with a particle size of less than 0.074mm represent 60% of the total ore, the yield of the above copper concentrate, cobalt concentrate, tailings and the grade and recovery of Cu, Co therein were measured and calculated.
Example 15
Example 15 differs from example 1 in that in example 15, 20g/t of the first copper capturing agent is added and mixed with 10g/t of methyl isobutyl carbinol, and the yield of the copper concentrate, the cobalt concentrate and the tailings and the grade and recovery rate of Cu and Co in the copper concentrate, the cobalt concentrate and the tailings are measured and calculated.
Example 16
Example 16 differs from example 1 in that in example 16 60g/t of the first copper capturing agent was added and mixed with 30g/t of methyl isobutyl carbinol, and the yields of the copper concentrate, cobalt concentrate and tailings and the grades and recovery rates of Cu and Co therein were measured and calculated.
Example 17
Example 17 differs from example 1 in that in example 17 80g/t of the first copper capturing agent is added and mixed with 30g/t of methyl isobutyl carbinol, and the yield of the copper concentrate, the cobalt concentrate and the tailings and the grade and recovery rate of Cu and Co in the copper concentrate, the cobalt concentrate and the tailings are measured and calculated.
Example 18
Example 18 differs from example 1 in that in example 18, 15g/t of the first copper capturing agent is added and mixed with 5g/t of methyl isobutyl carbinol, and the yield of the copper concentrate, the cobalt concentrate and the tailings and the grade and recovery rate of Cu and Co in the copper concentrate, the cobalt concentrate and the tailings are measured and calculated.
Example 19
Example 19 differs from example 1 in that in example 19, 5g/t of a second copper collector was added and the yields of the above copper concentrate, cobalt concentrate, tailings and the grades and recovery of Cu, Co therein were measured and calculated.
Example 20
Example 20 differs from example 1 in that in example 20 a second copper collector of 30g/t was added and the yields of the copper concentrate, cobalt concentrate, tailings and the grades and recovery of Cu, Co therein described above were measured and calculated.
Example 21
Example 21 differs from example 1 in that in example 21 no second copper collector was added and the yields of the above copper concentrate, cobalt concentrate, tailings and the grades and recovery of Cu, Co therein were measured and calculated.
Example 22
Example 22 differs from example 1 in that in example 22, 40g/t of a second copper collector was added and the yields of the copper concentrate, cobalt concentrate, tailings and the grades and recovery of Cu, Co therein described above were measured and calculated.
Example 23
Example 23 differs from example 1 in that in example 23 1000g/t ferrous sulphate was added, 50g/t sodium butylxanthate and 10g/t methyl isobutyl carbinol were added to the copper tailings, and the yields of the above copper concentrate, cobalt concentrate, tailings and the grades and recovery of Cu and Co therein were measured and calculated.
Example 24
Example 24 differs from example 1 in that in example 24 no copper sulphate was added, 100g/t of sodium butylxanthate and 20g/t of secondary octanol were added to the copper tailings, and the yields of the above copper concentrate, cobalt concentrate, tailings and the grades and recovery of Cu and Co therein were measured and calculated.
Example 25
Example 25 differs from example 1 in that in example 25 no sodium carboxymethylcellulose was added and 60g/t of sodium butylxanthate was added to the cobalt rougher tailings, the yields of the above copper concentrate, cobalt concentrate, tailings and the grades and recovery of Cu, Co therein were measured and calculated.
Example 26
Taking copper-cobalt sulfide ore with copper grade of 1.45% and cobalt grade of 0.078%, adding water and 3000g/t of calcium oxide, and grinding the copper-cobalt sulfide ore to obtain alkaline ore pulp with pH value of 11 and solid content of 30%. The ore particles with the particle size of less than 0.074mm in the alkaline ore pulp are 65 percent of the total amount of the ore by mass percentage. And mixing and stirring the alkaline ore pulp, 40g/t of first copper capturing agent and 20g/t of methyl isobutyl carbinol for 3min, and performing copper roughing for 4min to obtain copper roughing concentrate and copper roughing tailings. Wherein the first copper collector comprises 75% butylammonium nigro, 17% azonitrile ester and 8% ethylene glycol butyl ether. And performing blank concentration twice on the copper roughing concentrate, and adding 300g/t of calcium oxide in the first copper concentration process to obtain the copper concentrate. And returning middlings obtained by the first concentration to the rough concentration operation, and returning tailings obtained by the second concentration to the first concentration operation.
And adding 20g/t of second copper collecting agent into the copper roughing tailings, stirring for 4min, then carrying out copper scavenging, wherein the flotation time is 4min, so as to obtain copper tailings and copper scavenging foam, and returning the copper scavenging foam to the copper roughing step. Wherein the second copper collector is identical in composition to the first copper collector. And continuously adding 200g/t of copper sulfate into the copper tailings to improve the floatability of cobalt, adding 80g/t of sodium butyl xanthate and 15g/t of methyl isobutyl carbinol into the copper tailings, and performing flotation for 5min to obtain cobalt rougher concentrate and cobalt rougher tailings. And (2) carrying out cobalt concentration twice on the cobalt roughing concentrate, adding 200g/t of sodium carboxymethyl cellulose in the first cobalt concentration, wherein the time of each cobalt concentration is 4min, so as to obtain the cobalt concentrate, returning the first cobalt concentration middlings to the cobalt roughing step, and returning the second cobalt concentration tailings to the first cobalt concentration step (as shown in figure 1). And continuously adding 40g/t of sodium butyl xanthate into the cobalt roughing tailings for scavenging twice, performing flotation for 3min to obtain tailings, and returning scavenged foam products to the cobalt roughing operation.
And measuring and calculating the yield of the copper concentrate, the cobalt concentrate and the tailings, and the grade and the recovery rate of Cu and Co in the copper concentrate, the cobalt concentrate and the tailings.
Example 27
Taking copper-cobalt sulfide ore with copper grade of 1.69% and cobalt grade of 0.067%, adding water and 3000g/t of calcium oxide, and grinding the copper-cobalt sulfide ore to obtain alkaline ore pulp with pH value of 11 and solid content of 40%. The ore particles with the particle size of less than 0.074mm in the alkaline ore pulp are 80 percent of the total amount of the ore by mass percentage. Mixing and stirring the alkaline ore pulp, 40g/t of first copper capturing agent and 20g/t of methyl isobutyl carbinol for 4min, carrying out copper roughing, wherein the flotation time is 4min, obtaining copper roughing concentrate, copper roughing tailings and copper scavenging foam, and returning the copper scavenging foam to the copper roughing step. Wherein the first copper collector comprises 75% butylammonium nigro, 17% azonitrile ester and 8% ethylene glycol butyl ether. And performing blank concentration twice on the copper roughing concentrate, and adding 300g/t of calcium oxide in the first copper concentration process to obtain the copper concentrate. And returning middlings obtained by the first concentration to the rough concentration operation, and returning tailings obtained by the second concentration to the first concentration operation.
And adding 20g/t of second copper collecting agent into the copper roughing tailings, stirring for 4min, and then carrying out copper scavenging, wherein the flotation time is 4min, so as to obtain the copper tailings. Wherein the second copper collector is identical in composition to the first copper collector. And continuously adding 200g/t of copper sulfate into the copper tailings to improve the floatability of cobalt, adding 80g/t of sodium butyl xanthate and 15g/t of methyl isobutyl carbinol into the copper tailings, and performing flotation for 5min to obtain cobalt rougher concentrate and cobalt rougher tailings. And (2) carrying out cobalt concentration twice on the cobalt roughing concentrate, adding 200g/t of sodium carboxymethyl cellulose in the first cobalt concentration, wherein the time of each cobalt concentration is 4min, so as to obtain the cobalt concentrate, returning the first cobalt concentration middlings to the cobalt roughing step, and returning the second cobalt concentration tailings to the first cobalt concentration step (as shown in figure 1). And continuously adding 40g/t of sodium butyl xanthate into the cobalt roughing tailings for scavenging twice, performing flotation for 5min to obtain tailings, and returning scavenged foam products to the cobalt roughing operation.
And measuring and calculating the yield of the copper concentrate, the cobalt concentrate and the tailings, and the grade and the recovery rate of Cu and Co in the copper concentrate, the cobalt concentrate and the tailings.
Comparative example 1
Comparative example 1 differs from example 10 in that the first copper collector included 75% butylammonium-blackant, 25% cyanamide, and the yields of the above copper concentrate, cobalt concentrate, tailings, and the grades and recovery of Cu, Co therein were measured and calculated.
Comparative example 2
Comparative example 2 differs from example 10 in that the first copper collector included 80% butylammonium blackant, 20% ethylene glycol butyl ether, and the yields of the above copper concentrate, cobalt concentrate, tailings, and the grades and recovery of Cu, Co therein were measured and calculated.
Comparative example 3
Comparative example 3 differs from example 10 in that the first copper collector included 85% of the phosphazenium ester and 15% of the ethylene glycol butyl ether, and the yields of the above copper concentrate, cobalt concentrate, tailings and the grades and recovery of Cu, Co therein were measured and calculated.
Comparative example 4
Comparative example 4 differs from example 10 in that the first copper collector included 60% butylammonium-blackant, 35% azonitrile ester and 5% ethylene glycol butyl ether, and the yields of the above copper concentrate, cobalt concentrate, tailings and the grades and recovery of Cu, Co therein were measured and calculated.
Comparative example 5
Comparative example 5 differs from example 11 in that 100% butylammonium blackant was included in the first copper collector and the yields of the above copper concentrate, cobalt concentrate, tailings and the grades and recoveries of Cu, Co therein were measured and calculated.
The yields of copper concentrate, cobalt concentrate, tailings and the grades and recovery rates of Cu and Co therein of examples 1-27 and comparative examples 1-5 are shown in Table 1.
TABLE 1
As can be seen from the comparison of the above examples and comparative examples, the absence of a component in the copper collector of the present application, or the change in the proportional relationship between the components, affects the selective flotation ability of the copper collector for copper. When the copper collector has too strong a collecting capacity, cobalt can enter the copper concentrate, resulting in a reduction in the cobalt recovery rate of the cobalt concentrate. When the collecting capacity of the copper collector is weak, copper can enter the cobalt concentrate, so that the cobalt grade of the cobalt concentrate is reduced, and the loss of copper is caused.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
flotation is a mineral separation method which utilizes the action of a collecting agent and active points on the surface of a mineral so as to make the surface of the mineral float up in a hydrophobic manner. The collecting force and the selectivity of the collecting agent are important factors influencing the action of the collecting agent and the active points of the mineral surface.
This application adopts and makes up with alkyl thiocarbamate the better black medicine of copper selectivity, when these two kinds of medicaments of make full use of are to the good selectivity of copper mineral, has strengthened the collection to the copper mineral through the synergistic effect. The alcohol ether solvent in the copper collector is used as an amphiphilic molecule to play a role in dispersing the adsorption of the black dye and the hydrocarbyl thiocarbamate on the surface of the copper-containing mineral, so that the black dye and the hydrocarbyl thiocarbamate form a more stable and uniform adsorption layer on the surface of the copper-containing mineral, and the adsorption quantity of the combined black dye and the hydrocarbyl thiocarbamate on the surface of copper sulfide is greater than the sum of the adsorption quantities of the non-combined black dye and the non-combined hydrocarbyl thiocarbamate on the surface of copper sulfide. On the one hand, the high selectivity and high collecting capacity of the black powder and the hydrocarbyl thiocarbamate to copper are fully exerted; on the other hand, the synergistic effect of the copper collecting agent and the copper mineral collecting agent on the function is further promoted, so that the performances of the copper collecting agent and the copper mineral collecting agent are further complemented, the finally obtained copper collecting agent is obviously superior to the simple superposition of the performances of the copper collecting agent and the copper mineral collecting agent, and the copper collecting agent has excellent copper mineral collecting capacity and selectivity.
Therefore, when the copper sulfide cobalt ore is treated by the copper collecting agent, the copper collecting agent can separate the copper in the copper sulfide cobalt ore as much as possible, so that the content of the copper in the copper tailings after the copper roughing is reduced, and the content of the cobalt in the copper tailings is further improved; the method is beneficial to selecting cobalt when the copper tailings are subjected to cobalt flotation, and further improves the grade and yield of the cobalt.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (13)
1. A copper collector, characterized in that it comprises, in mass percent:
70-80% of black powder;
15-25% of an alkyl thiocarbamate derivative; and
5-15% of an alcohol ether solvent.
2. A copper collector according to claim 1, wherein the blacking agent is one or more of butylammonium blacking agent, sodium butylnigre, isopropylammonium blacking agent, sodium isopropylammonium blacking agent, isobutylammonium blacking agent, isobutylsodium blacking agent.
3. A copper collector according to claim 1, wherein the hydrocarbyl thiocarbamate derivative is one or more of cyanoethyl N, N-dimethyldithiocarbamate, propionitrile N, N-diethyldithiocarbamate, propenyl N, N-diethyldithiocarbamate.
4. The flotation process of the copper-cobalt sulfide ore is characterized by comprising the following steps of:
step S1, wet grinding the mixture of the copper-cobalt sulfide ore and calcium oxide or calcium hydroxide to obtain alkaline ore pulp;
step S2, mixing the materials including the alkaline ore pulp, the first copper collector and the first foaming agent, and performing copper roughing to obtain copper roughing concentrate and copper roughing tailings;
step S3, mixing the copper rougher tailings and a second copper collector for copper scavenging to obtain copper tailings, wherein the first copper collector is the same as the second copper collector, and the first copper collector and the second copper collector are the copper collector according to any one of claims 1 to 3; and
and step S4, performing cobalt roughing, cobalt fine selection and cobalt scavenging on the copper tailings in sequence to obtain tailings.
5. The flotation process according to claim 4, wherein the cobalt rougher flotation of step S4 comprises:
mixing materials comprising the copper tailings, the third collecting agent and the second foaming agent, and performing cobalt roughing to obtain cobalt roughing concentrate and cobalt roughing tailings; preferably, the second foaming agent is selected from one or more of methyl isobutyl carbinol, dimethyl benzyl alcohol and sec-octanol; preferably the third collector is selected from any one or more of sodium or potassium hydrocarbyl xanthates, more preferably the hydrocarbyl group is any one of butyl, isobutyl, pentyl and isopentyl; preferably, the mass ratio of the third collecting agent to the copper cobalt sulfide ore is 1-2: 20000, the mass ratio of the second foaming agent to the copper cobalt sulfide ore is 1-2: 100000, and the time for roughing the cobalt is 3-5 min.
6. The flotation process according to claim 5, wherein the cobalt beneficiation of step S4 comprises:
carrying out cobalt concentration on the cobalt rough concentration concentrate to obtain cobalt concentrate; preferably, the cobalt concentration is performed twice, preferably, an inhibitor is added in the first cobalt concentration, preferably, the mass ratio of the inhibitor to the copper cobalt sulfide ore is 1-30: 100000, and preferably, the inhibitor is one or two of sodium carboxymethylcellulose and water glass.
7. The flotation process according to claim 5, wherein the cobalt scavenging of step S4 comprises:
mixing the cobalt roughing tailings with a fourth collecting agent for cobalt scavenging to obtain tailings; the fourth collector is selected from any one or more of sodium or potassium hydrocarbyl xanthates, more preferably the hydrocarbyl group is any one of butyl, isobutyl, pentyl and isopentyl; preferably, the mass ratio of the fourth collecting agent to the copper cobalt sulfide ore is 3-6: 100000, and the cobalt scavenging time is 3-5 min.
8. The flotation process according to claim 4, wherein before the step S4, the flotation process comprises a step of adding an activating agent into the copper tailings, wherein the activating agent is preferably one or more of copper sulfate, ferrous sulfate and sulfuric acid, and the mass ratio of the activating agent to the copper cobalt sulfide ore is preferably 1-100: 100000.
9. A flotation process according to claim 4, wherein the alkaline pulp contains, in mass percent, 65-80% of the total ore content as ore particles having a particle size of less than 0.074 mm.
10. A flotation process according to claim 4, wherein the pH of the alkaline pulp is 11-12, preferably the solids content of the alkaline pulp is 30-40%.
11. A flotation process according to claim 4, wherein in the step S2, the mass ratio of the first copper collector to the copper cobalt sulfide ore is 1-3: 50000, preferably the mass ratio of the first foaming agent to the copper cobalt sulfide ore is 1-3: 100000, preferably the first foaming agent is selected from one or more of methyl isobutyl carbinol, dimethyl benzyl alcohol and sec-octanol, and preferably the time for roughing the copper is 3-4 min.
12. A flotation process according to claim 4, wherein in the step S3, the mass ratio of the second copper collector to the copper cobalt sulfide ore is 1-6: 200000, and the time for copper scavenging is preferably 3-4 min.
13. The flotation process according to claim 4, further comprising copper concentration of the copper rougher concentrate to obtain a copper concentrate; preferably, the copper concentration times are two times; preferably, calcium oxide is added in the first copper concentration, and more preferably, the mass ratio of the calcium oxide to the copper cobalt sulfide ore is 1-100: 100000.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112275451A (en) * | 2020-09-22 | 2021-01-29 | 商洛学院 | Flotation reagent combination for improving recovery rate of associated cobalt in fine-grained copper sulfide ore |
| CN112588446A (en) * | 2020-11-02 | 2021-04-02 | 中国恩菲工程技术有限公司 | Method for recovering copper-cobalt ore |
| CN113751203A (en) * | 2021-09-13 | 2021-12-07 | 云南迪庆有色金属有限责任公司 | Beneficiation method for copper-molybdenum ore in alpine region |
| CN114918035A (en) * | 2022-01-25 | 2022-08-19 | 铜陵有色金属集团股份有限公司 | Method for recovering chalcopyrite from pyrite and pyrrhotite |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2485083A (en) * | 1946-01-04 | 1949-10-18 | American Cyanamid Co | Froth flotation of copper sulfide ores with lignin sulfonates |
| US7004326B1 (en) * | 2004-10-07 | 2006-02-28 | Inco Limited | Arsenide depression in flotation of multi-sulfide minerals |
| CN103878071A (en) * | 2012-12-19 | 2014-06-25 | 沈阳有色金属研究院 | Combined collector for separation of copper-cobalt sulfide ores |
| CN104826742A (en) * | 2015-05-19 | 2015-08-12 | 烟台恒邦化工助剂有限公司 | Composite collecting agent for sulphide ore and preparing method thereof |
| CN105195331A (en) * | 2015-10-28 | 2015-12-30 | 廖继华 | Preparation method of copper and cobalt flotation agent |
| CN105413854A (en) * | 2015-12-23 | 2016-03-23 | 中国地质科学院矿产综合利用研究所 | Beneficiation method for high-oxidation-rate copper-molybdenum paragenic ore |
| CN106622634A (en) * | 2016-12-05 | 2017-05-10 | 北京矿冶研究总院 | Beneficiation method for copper-cobalt ore |
| CN107961901A (en) * | 2011-10-18 | 2018-04-27 | 塞特克技术公司 | Collector composition and its application method |
| CN109201320A (en) * | 2018-08-23 | 2019-01-15 | 北京矿冶科技集团有限公司 | A kind of beneficiation method of the cobalt ore of copper containing easy-floating gangue |
| CN110038730A (en) * | 2019-05-20 | 2019-07-23 | 北京矿冶科技集团有限公司 | A kind of beneficiation method containing two types copper cobalt sulfide ore containing cobalt mineralss |
-
2020
- 2020-02-14 CN CN202010093361.0A patent/CN111229471A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2485083A (en) * | 1946-01-04 | 1949-10-18 | American Cyanamid Co | Froth flotation of copper sulfide ores with lignin sulfonates |
| US7004326B1 (en) * | 2004-10-07 | 2006-02-28 | Inco Limited | Arsenide depression in flotation of multi-sulfide minerals |
| CN107961901A (en) * | 2011-10-18 | 2018-04-27 | 塞特克技术公司 | Collector composition and its application method |
| CN103878071A (en) * | 2012-12-19 | 2014-06-25 | 沈阳有色金属研究院 | Combined collector for separation of copper-cobalt sulfide ores |
| CN104826742A (en) * | 2015-05-19 | 2015-08-12 | 烟台恒邦化工助剂有限公司 | Composite collecting agent for sulphide ore and preparing method thereof |
| CN105195331A (en) * | 2015-10-28 | 2015-12-30 | 廖继华 | Preparation method of copper and cobalt flotation agent |
| CN105413854A (en) * | 2015-12-23 | 2016-03-23 | 中国地质科学院矿产综合利用研究所 | Beneficiation method for high-oxidation-rate copper-molybdenum paragenic ore |
| CN106622634A (en) * | 2016-12-05 | 2017-05-10 | 北京矿冶研究总院 | Beneficiation method for copper-cobalt ore |
| CN109201320A (en) * | 2018-08-23 | 2019-01-15 | 北京矿冶科技集团有限公司 | A kind of beneficiation method of the cobalt ore of copper containing easy-floating gangue |
| CN110038730A (en) * | 2019-05-20 | 2019-07-23 | 北京矿冶科技集团有限公司 | A kind of beneficiation method containing two types copper cobalt sulfide ore containing cobalt mineralss |
Non-Patent Citations (3)
| Title |
|---|
| 张泾生: "《现代选矿技术手册 第2册 浮选与化学选矿》", 28 February 2011, 北京：冶金工业出版社 * |
| 汪旭光，潘家柱主编: "《21世纪中国有色金属工业可持续发展战略》", 31 December 2001, 北京：冶金工业出版社 * |
| 赵通林: "《浮选》", 30 August 2018 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112275451A (en) * | 2020-09-22 | 2021-01-29 | 商洛学院 | Flotation reagent combination for improving recovery rate of associated cobalt in fine-grained copper sulfide ore |
| CN112275451B (en) * | 2020-09-22 | 2022-03-22 | 商洛学院 | Flotation reagent combination for improving recovery rate of associated cobalt in fine-grained copper sulfide ore |
| CN112588446A (en) * | 2020-11-02 | 2021-04-02 | 中国恩菲工程技术有限公司 | Method for recovering copper-cobalt ore |
| CN113751203A (en) * | 2021-09-13 | 2021-12-07 | 云南迪庆有色金属有限责任公司 | Beneficiation method for copper-molybdenum ore in alpine region |
| CN114918035A (en) * | 2022-01-25 | 2022-08-19 | 铜陵有色金属集团股份有限公司 | Method for recovering chalcopyrite from pyrite and pyrrhotite |
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