OA17667A - Method for recovering a copper sulfide from an ore containing an iron sulfide. - Google Patents

Method for recovering a copper sulfide from an ore containing an iron sulfide. Download PDF

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OA17667A
OA17667A OA1201600010 OA17667A OA 17667 A OA17667 A OA 17667A OA 1201600010 OA1201600010 OA 1201600010 OA 17667 A OA17667 A OA 17667A
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hydrogen peroxide
added
copper
pulp
flotation
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OA1201600010
Inventor
Gerhard Arnold
Ingo Hamann
Alan Hitchiner
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Evonik Degussa Gmbh
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Publication of OA17667A publication Critical patent/OA17667A/en

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Abstract

In a method for recovering a copper sulfide concentrate by froth flotation from an ore containing an iron sulfide, hydrogen peroxide is added to the conditioned mineral pulp before or during flotation in an amount effective to lower the redox potential of the conditioned mineral pulp in order to improve concentrate grade and recovery of copper sulfides.

Description

The présent invention is directed to a method of recovering a copper sulfide concentrate from an ore containing an iron sulfide which provides an improvement in concentrate grade and recovery of copper sulfides and has a low consumption of processing chemicals.
Background of the Invention
The most common method for recovering a copper sulfide concentrate from an ore is by froth flotation. The ore is wet ground to form a minerai pulp, which is usually conditioned with a collector compound that adsorbs to the surface of copper sulfide minerais and makes the surface of copper sulfide minerais more hydrophobie. A gas is then passed through the minerai pulp to form gas bubbles, hydrophobie particles of the minerai pulp attach predominantly to the gas/liquid phase boundary of the bubbles and are carried with the gas bubbles to the froth that forms on top of the minerai pulp. The froth is removed from the liquid surface to recover a copper sulfide concentrate.
Most copper sulfide ores contain iron sulfides in addition to copper sulfides and one aims at achieving sélective flotation of copper sulfides, with iron sulfides remaining in the flotation tailings.
US 5,110,455 discloses a method for separating copper sulfide from rimmed iron sulfide which uses conditioning of the minerai pulp with an oxidant that is preferably hydrogen peroxide. The document teaches to add an oxidant »
in an amount that raises the redox potential of the minerai pulp by 20 to 500 mV.
A Uribe-Salas et al., Int. J. Miner. Process. 59 (2000) 69-83 describe an improvement in the selectivity for the flotation of chalcopyrite from an ore of pyrite matrix by raising the redox potential of the minerai pulp by 0.1 V through an addition of hydrogen peroxide before flotation. The amount of hydrogen peroxide added is adjusted to provide a constant redox potential.
Summary of the Invention
The inventors of the présent invention hâve found that addition of small amounts of hydrogen peroxide to the conditioned minerai pulp before or during flotation, which do not raise the redox potential of the pulp but to the contrary effect a lower redox potential, surprisingly provide a substantial improvement in concentrate grade and recovery of copper suifides.
The présent invention is therefore directed to a method for recovering a copper sulfide concentrate from an ore containing an iron sulfide, which method comprises the steps of
a) wet grinding the ore with grinding media to form a minerai pulp,
b) conditioning the minerai pulp with a collector compound to form a conditioned minerai pulp, and
c) froth flotation of the conditioned minerai pulp to form a froth and a flotation tailing, separating the froth from the flotation tailing to recover a copper sulfide concentrate, wherein hydrogen peroxide is added to the conditioned minerai pulp between steps b) and c) or during step c) in an amount effective to lower the redox potential of the conditioned minerai pulp.
Brief Description of the Drawings
Figure 1 shows redox potential Eh plotted against the amount of added hydrogen peroxide for the experiments of example 1.
Figure 2 shows curves for cumulated copper concentrate grade (y-axis) plotted against cumulated copper recovery (x-axis) for examples 2 and 3.
Figure 3 shows redox potential Eh plotted against the amount of added hydrogen peroxide for the experiments of example 4.
Figure 4 shows curves for cumulated copper concentrate grade (y-axis) plotted against cumulated copper recovery (x-axis) for examples 5 to 7.
Figure 5 shows redox potential Eh.plotted against the amount of added hydrogen peroxide for the experiments of example 8.
Figure 6 shows curves for cumulated copper concentrate grade (y-axis) plotted against cumulated copper recovery (x-axis) for examples 9 and 10.
Figure 7 shows redox potential Eh plotted against the amount of added hydrogen peroxide for the experiments of example 11.
Figure 8 shows curves for cumulated copper concentrate grade (y-axis) plotted against cumulated copper recovery (x-axis) for examples 12 and 13.
Detailed Description of the Invention
The method of the invention recovers a copper sulfide concentrate from an ore containing an iron sulfide using three method steps.
In the first step of the method of the invention, the ore is ground with grinding media to form a minerai pulp, i.e. an aqueous suspension of ground ore. Suitable grinding media for grinding ores are known from the prior art. Preferably, the grinding media comprise a grinding surface made of steel or cast iron having an iron content of at least 90 % by weight. Grinding can be carried out in any mill known from the art that uses grinding media. Suitable mills are bail mills using balls as grinding media or rod mills using rods as grinding media, with bail mills being preferred. The mill preferably has a lining of an abrasion résistant material.
The ore is wet milled to form a minerai pulp, i.e. an aqueous suspension of ground ore. The ore may be fed to the mill together with water. Alternatively, ore and water are fed separately. Milling is carried out typically to a médian particle size of 50-200 pm. Preferably, the ore is ground to what is called the libération size, i.e. the maximum médian particle size where essentially ail copper sulfide is exposed to the particle surface and essentially no copper sulfide remains encapsulated inside a particle.
In the second step of the method of the invention, the ore is conditioned with a collector compound to form a conditioned minerai pulp. Collector compounds are compounds which after addition to the minerai pulp adsorb to the surface of copper sulfides and render the surface hydrophobie. Collector compounds suitable for froth flotation of copper sulfides are known from the prior art.
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Preferably, an alkali métal alkyl xanthate is used as collector, such as potassium amyl xanthate or sodium ethyl xanthate. Conditioning is typically carried out by adding the conditioner to the minerai pulp and mixing for a time period sufficient to achieve adsorption of the conditioner to the minerai surface, typically for less than 15 minutes. Preferably for 0.5 to 15 minutes. Alternatively, the collector is added in the first step of grinding and conditioning is carried out by retaining the minerai pulp for a corresponding time.
Further reagents, such as frothers, pH regulators, depressants and mixtures thereof may be added in the grinding step, the conditioning step or in both steps. Frothers are compounds that stabilize the froth formed in a froth flotation. Suitable frothers are commercially available, e.g. from Huntsman under the trade name Polyfroth®. Depressants are compounds that render the surface of unwanted minerais more hydrophilic. Polyamines known from the prior art, such as diethylenetriamine or triethylenetetraamine, may be used as depressants for iron sulfides. pH regulators, such as calcium oxide, calcium hydroxide or sodium carbonate, may be added to adjust the pH of the minerai pulp to a desired value, preferably to a value in the range from 7 to 11.
In the third step of the method of the invention, the conditioned minerai pulp is subjected to froth flotation to form froth and a flotation tailing, with hydrogen peroxide being added to the conditioned minerai pulp during froth flotation or between the second step of conditioning the minerai pulp and the step of froth flotation. The froth is separated from the flotation tailing to recover a copper sulfide concentrate. Froth flotation may be carried out using equipment and procedures known to a person skilled in the art for the froth flotation of copper ores.
Froth flotation may be carried out as a single stage flotation or as a multiple stage flotation, using e.g. rougher, scavenger and cleaner stages. In a multiple stage froth flotation, hydrogen peroxide is preferably added before the first flotation stage or during the first flotation stage.
Hydrogen peroxide is added to the conditioned pulp in an amount that is effective to lower the redox potential of the conditioned minerai pulp. Preferably, hydrogen peroxide is added in an amount lowering the redox potential by at least 10 mV. When the ore is ground with grinding media comprising a grinding surface made of steel or cast iron with an iron content of at least 90 % by weight, the amount of hydrogen peroxide added is preferably adjusted to provide a maximum lowering of redox potential after hydrogen peroxide addition. The redox potential of the minerai pulp can be determined with methods known from the prior art. Preferably, the redox potential is determined with a redox electrode that uses an electrochemical cell.
The method of the invention requires only small amounts of hydrogen peroxide. In general, less than 100 g hydrogen peroxide per ton of ore are needed and preferably less than 50 g/t are used. The method can be carried out with as little as 2 g/t hydrogen peroxide per ton of ore and preferably at least 5 g/t are used.
When hydrogen peroxide is added between the step of conditioning the minerai pulp and the step of froth flotation, the time period between addition of hydrogen peroxide and froth flotation is preferably less than 15 min, more preferably less than 3 min and most preferably less than 1 min. Limiting the time period between addition of hydrogen peroxide and froth flotation improves both concentrate grade and recovery of copper suifides.
In a preferred embodiment of the method of the invention, froth flotation is carried out continuously and hydrogen peroxide is added continuously during froth flotation.
Hydrogen peroxide is preferably added as an aqueous solution comprising 0.5 to 5 % by weight hydrogen peroxide. Adding such a dilute hydrogen peroxide solution provides better concentrate grade and recovery than obtained with the same amount of a more concentrated hydrogen peroxide solution. Therefore, it is preferred to dilute a commercial hydrogen peroxide solution comprising 30 to 70 % by weight hydrogen peroxide to a dilute solution comprising 0.5 to 5 % by weight hydrogen peroxide before adding it in the method of the invention.
üsually there will be an optimum amount of hydrogen peroxide per ton of ore that dépends on the ore composition. Increasing the amount of added hydrogen peroxide up to the optimum amount will lead to an increase in concentrate grade and recovery of copper sulfides, whereas increasing the amount of added hydrogen peroxide beyond the optimum amount will not lead to any further improvement, but in general will even lead to a reduced concentrate grade and recovery of copper sulfides.
The prior art teaches that hydrogen peroxide shall be added to a flotation process for copper sulfide ores in amounts increasing the redox potential of the ore in order to improve the recovery of copper sulfides. The inventors of the présent invention hâve found that addition of hydrogen peroxide to the conditioned minerai pulp in small amounts that do not increase the redox potential of the minerai pulp, but effect a lowering of the redox potential, surprisingly provides a substantial increase in the concentrate grade and recovery of copper sulfides. Even more surprisingly, for most copper sulfide ores the addition of hydrogen peroxide in an amount lowering the redox potential of the conditioned ore will lead to a better concentrate grade and recovery of copper sulfides than addition of a large amount of hydrogen peroxide that raises in the redox potential.
In addition to providing an improvement in the concentrate grade and recovery of copper sulfides, the method of the invention can also provide an improved recovery of gold from the ore and reduce the content of iron sulfides and arsenic minerais in the copper sulfide concentrate.
The following examples illustrate the invention, but are not intended to limit the scope of the invention.
Examples
In ail flotation experiments, ores were ground to a particle size P80 of 200 pm with a laboratory Magotteaux Mill® using 16*1 inch forged carbon steel rods as grinding media. The resulting minerai pulp was transferred to a laboratory flotation cell and mixed for two minutes to homogenize. Sodium ethyl xanthate was added as collector at 21 g per ton of ore, followed by 5 g per ton of POLYFROTH® H27 frother from Huntsman. The resulting minerai pulp was conditioned for 1 min before flotation was started by introducing air. Four timed concentrâtes were collected during flotation over intervals given in the examples. Each concentrate was collected by hand scraping the froth from the surface of the pulp once every 10 seconds. Concentrâtes were weighed and assayed and cumulated grades and recoveries were calculated from these data. Grades were plotted against recovery and the values for grades at a spécifie copper recovery and recoveries at a spécifie copper grade given in the tables below were read from these curves.
Examples 1 to 3
Flotation was carried out with a sedimentary copper/gold ore having a head assay of 1.74 % Cu, 9.95 % Fe, 3.27 ppm Au, 168 ppm Bi, and 3.21 % S.
In example 1, varying amounts of hydrogen peroxide were added immediately before starting flotation and the redox potential (Eh) was determined immediately after flotation was started. The results are summarized in table 1. Figure 1 shows the values of Eh plotted against the amount of added hydrogen peroxide. Figure 1 shows Eh decreasing upon addition of small amounts of hydrogen peroxide and increasing upon addition of larger amounts.
Table 1
Variation of added hydrogen peroxide amount
H2O2 added [g/t] Example 1 Eh[mV]
0 241
7.5 230
15 220
30 226
60 222
90 227
120 239
In examples 2 and 3, flotation was carried out with concentrâtes collected over intervals of 0.5, 2, 5, and 10 minutes. No hydrogen peroxide was added in example 2. In example 3, a 1 % by weight aqueous hydrogen peroxide solution was added in an amount of 75 g/t ore immediately before starting flotation.
Figure 2 shows the curves for cumulated copper concentrate grade plotted against cumulated copper recovery for examples 2 and 3. Tables 2 and 3 compare these results at 85 % copper recovery and at 18 % concentrate copper grade.
Table 2
Copper and gold concentrate grades and gold and diluent recoveries at 85 % copper recovery
Example H2O2 added Grade Recovery
Cu [%] Au [ppm] Au [%] Bi [%] IS [%] NSG [%]
2* 0 g/t 18.2 25.0 62.5 69.2 18.8 3.6
3 75 g/t 19.2 26.0 55.0 65.0 13.6 3.4
* Not according to the invention,
IS = iron sulfides, NSG = non sulfide gangue
Table 3
Copper and gold recovery and concentrate gold and diluents grade at 18 % concentrate copper grade
Example H2O2 added Recovery Grade
Cu [%] Au [%] Au [ppm] Bi [ppm] IS [%] NSG [%]
2* 0 g/t 85.7 58.8 24.7 1420 6.2 41.5
3 75 g/t 89.3 63.3 24.7 1310 4.7 42.8
* Not according to the invention,
IS = iron sulfides, NSG = non sulfide gangue
Examples 4 to 7
Flotation was carried out with a volcanogenic sulfide deposit ore having a head assay of 2.63 % Cu, 19.2 % Fe, and 15.9 % S.
In example 4, varying amounts of hydrogen peroxide were added immediately before starting flotation and the redox potential (Eh) was determined immediately after flotation was started. The results are summarized in table 4. Figure 3 shows the values of Eh plotted against the amount of added hydrogen peroxide. Figure 3 shows Eh decreasing upon addition of small amounts of hydrogen peroxide and increasing upon addition of larger amounts.
Table 4
Variation of added hydrogen peroxide amount
H2O2 added [g/t ] Example 4 Eh[mV]
0 250
30 243
60 237
120 239
180 235
240 236
300 240
360 245
In examples 5 to 7, flotation was carried out with concentrâtes collected over intervals of 0.5, 2, 4, and 7 minutes. No hydrogen peroxide was added in example 5. In examples 6 and 7, a 1 % by weight aqueous hydrogen peroxide solution was added in amounts of 15 g/t ore and 240 g/t ore immediately before starting flotation.
Figure 4 shows the curves for cumulated copper concentrate grade plotted against cumulated copper recovery for examples 5 to 7. Tables 5 and 6 compare these results at 90 % copper recovery and at 18 % concentrate copper grade.
Table 5
Copper and iron concentrate grades and diluent recoveries at 90 % copper recovery
Example H2O2 added Grade Recovery
Ou [%1 Fe [%] Fe [%] IS [%] NSG [%]
5* 0 g/t 15.5 26.8 18.2 10.0 4.5
6 15 g/t 20.5 28.8 17.7 7.7 4.1
7 240 g/t 21.1 27.6 16.4 8.0 3.9
* Not according to the invention,
IS = iron sulfides, NSG = non sulfide gangue
Table 6
Copper and iron recovery and concentrate diluents grade at % concentrate copper grade
Example H2O2 added Recovery Grade
Cu [%] Fe [%] Fe [%] IS [%] NSG [%]
5* 0 g/t 91.0 18.8 26.8 19.0 28.4
6 15 g/t 93.5 20.2 28.1 18.0 26.4
7 240 g/t 94.6 19.5 26.9 20.0 27.5
* Not according to the invention,
IS = iron sulfides, NSG = non sulfide gangue
Examples 8 to 10
Flotation was carried out with a porphyry copper/gold ore having a head assay of 0.43 % Cu, 5.4 % Fe, 0.18 ppm Au and 5.0 % S.
In example 8, varying amounts of hydrogen peroxide were added immediately before starting flotation and the redox potential (Eh) was determined immediately after flotation was started. The results are summarized in table 7. Figure shows the values of Eh plotted against the amount of added hydrogen peroxide. Figure 5 shows Eh decreasing upon addition of small amounts of hydrogen peroxide and increasing upon addition of larger amounts.
Table 7
Variation of added hydrogen peroxide amount
H2O2 added [g/t] Example 8 Eh[mV]
0 224
7.5 203
15 186
30 199
60 190
120 201
180 210
240 225
In examples 9 and 10, flotation was carried out with concentrâtes collected over intervals of 0.5, 2, 4, and 9 minutes. No hydrogen peroxide was added in example 9. In example 10, a 1 % by weight aqueous hydrogen peroxide solution was added in an amount of 120 g/t ore immediately before starting flotation.
Figure 6 shows the curves for cumulated copper concentrate grade plotted against cumulated copper recovery for examples 9 and 10. Tables 8 and 9 compare these results at 10 70 % copper recovery and at 9 % concentrate copper grade.
Table 8
Copper and gold concentrate grades and gold and diluent recoveries at 70 % copper recovery
Example H2O2 added Grade Recovery
Cu [%] Au [ppm] Au [%] IS [%] NSG [%]
9* 0 g/t 6.2 1.3 35.0 14.5 3.1
10 120 g/t 7.2 1.7 46.0 11.2 2.6
* Not according to the invention,
IS = iron sulfides, NSG = non sulfide gangue
Table 9
Copper and gold recovery and concentrate gold and diluents grade at 9 % concentrate copper grade
Example H2O2 added Recovery Grade
Cu [%] Au [%J Au [ppm] IS [%] NSG [%]
9* 0 g/t 60.0 27.5 1.7 33.0 41.0
10 120 g/t 67.0 42.5 2.0 27.0 47.0
* Not according to the invention,
IS = iron sulfides, NSG = non sulfide gangue
Table 9 shows an additional improvement in the recovery of copper and gold.
Examples 11 to 13
Flotation was carried out with an iron oxide hosted copper/gold ore having a head assay of 0.83 % Cu, 21.7 % Fe, 0.39 ppm Au, 568 ppm As, and 4.0 % S.
In example 11, varying amounts of hydrogen peroxide were added immediately before starting flotation and the redox potential (Eh) was determined immediately after flotation was started. The results are summarized in table 10. Figure 7 shows the values of Eh plotted against the amount of added hydrogen peroxide. Figure 7 shows Eh decreasing upon addition of small amounts of hydrogen peroxide and increasing upon addition of larger amounts.
Table 10
Variation of added hydrogen peroxide amount
H2O2 added [g/t] Example 11 Eh [mV]
0 233
7.5 216
15 203
30 200
60 206
90 214
120 224
In examples 12 and 13, flotation was carried out with concentrâtes collected over intervals of 0.5, 2, 4, and 8 minutes. No hydrogen peroxide was added in example 12. In example 13 a 1 % by weight aqueous hydrogen peroxide solution was added in an amount of 50 g/t ore immediately before starting flotation.
Figure 8 shows the curves for cumulated copper concentrate grade plotted against cumulated copper recovery for examples 12 and 13. Tables 11 and 12 compare these results at 80 % copper recovery and at 13 % concentrate copper grade.
Table 11
Copper and gold concentrate grades and gold and diluent recoveries at 80 % copper recovery
Example H2O2 added Grade Recovery
Cu [%] Au [ppm] Au [%] As [%] IS [%] NSG [%]
12* 0 g/t 10.5 3.7 60.0 33.9 46.3 1.8
13 50 g/t 12.0 3.9 59.0 27.5 38.0 1.4
* Not according to the invention,
IS = iron sulfides, NSG = non sulfide gangue
Table 12
Copper and gold recovery and concentrate gold and diluents grade at 13 % concentrate copper grade
Example H2O2 added Recovery Grade
Cu [%] Au [%] Au [ppm] As [ppm] IS [%J NSG [%]
12* 0 g/t 57.5 36.0 3.8 2740 42.8 19.1
13 50 g/t 75.0 53.0 4.0 2780 41.8 20.1
* Not according to the invention,
IS = iron sulfides, NSG = non sulfide gangue

Claims (5)

Claims:
1) A method for recovering a copper sulfide from an ore containing an iron sulfide, comprising the steps of
a) wet grinding the ore with grinding media to form a minerai pulp,
b) conditioning the minerai pulp with a collector compound to form a conditioned minerai pulp, and
c) froth flotation of the conditioned minerai pulp to form a froth and a flotation tailing, separating the froth from the flotation tailing to recover a copper sulfide concentrate, wherein hydrogen peroxide is added to the conditioned minerai pulp between steps b) and c) or during step c) in an amount effective to lower the redox potential of the conditioned minerai pulp.
2) The method of claim 1, wherein hydrogen peroxide is added in an amount lowering the redox potential by at least 10 mV.
3) The method of claim 1 or 2, wherein the hydrogen peroxide is added less than 15 minutes before a gas is introduced for froth flotation.
4) The method of claim 1 or 2, wherein froth flotation is carried out continuously and hydrogen peroxide is added continuously during froth flotation.
5) The method of any one of claims 1 to 4, wherein hydrogen peroxide is added as an aqueous solution comprising 0.5 to 5 % by weight hydrogen peroxide.
6) The method of any one of claims 1 to 5, wherein an alkali métal alkyl xanthate is used as collector.
7) The method of any one of daims 1 to 5, wherein the grinding media comprise a grinding surface made of steel or cast iron having an iron content of at least 90 % by weight.
5 8) The method of claim 7, wherein the amount of hydrogen peroxide added is adjusted to provide a maximum lowering of redox potential after hydrogen peroxide addition.
Method for recovering a copper sulfide from an ore containing an iron sulfide
OA1201600010 2013-07-19 2014-07-11 Method for recovering a copper sulfide from an ore containing an iron sulfide. OA17667A (en)

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