CN103084274B - Preparation method of high grade copper oxide concentrate - Google Patents
Preparation method of high grade copper oxide concentrate Download PDFInfo
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- CN103084274B CN103084274B CN201310029762.XA CN201310029762A CN103084274B CN 103084274 B CN103084274 B CN 103084274B CN 201310029762 A CN201310029762 A CN 201310029762A CN 103084274 B CN103084274 B CN 103084274B
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- 239000012141 concentrate Substances 0.000 title claims abstract description 143
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 139
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 139
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000005188 flotation Methods 0.000 claims abstract description 155
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 76
- 239000011707 mineral Substances 0.000 claims abstract description 76
- 238000000034 method Methods 0.000 claims abstract description 55
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 27
- 238000000227 grinding Methods 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 22
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 16
- NTZRDKVFLPLTPU-UHFFFAOYSA-N CC[Na] Chemical compound CC[Na] NTZRDKVFLPLTPU-UHFFFAOYSA-N 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 161
- 239000010949 copper Substances 0.000 claims description 161
- 229910052802 copper Inorganic materials 0.000 claims description 159
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 66
- 239000003112 inhibitor Substances 0.000 claims description 54
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 46
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- 229910052708 sodium Inorganic materials 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
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- 239000000395 magnesium oxide Substances 0.000 abstract description 19
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 19
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- 230000000694 effects Effects 0.000 abstract description 10
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- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 abstract description 5
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 abstract description 5
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- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 10
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- 239000003795 chemical substances by application Substances 0.000 description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
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- QRMLKVVWCJUMPR-UHFFFAOYSA-N BrCC[Na] Chemical compound BrCC[Na] QRMLKVVWCJUMPR-UHFFFAOYSA-N 0.000 description 3
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- 239000013522 chelant Substances 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910001779 copper mineral Inorganic materials 0.000 description 3
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
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- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
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- 230000002411 adverse Effects 0.000 description 1
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- RSIPQHOWTCNEBI-UHFFFAOYSA-N n-hydroxypropanamide Chemical compound CCC(=O)NO RSIPQHOWTCNEBI-UHFFFAOYSA-N 0.000 description 1
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- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- BVIXLMYIFZGRBH-UHFFFAOYSA-M sodium;2-chloroethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCl BVIXLMYIFZGRBH-UHFFFAOYSA-M 0.000 description 1
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- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method of high grade copper oxide concentrate. The preparation method sequentially comprises complex copper oxide crude ore grinding, copper sulphide flotation and copper oxide flotation. The copper oxide flotation comprises rough flotation and fine flotation, wherein the rough flotation includes that flotation reagents are added into tailings of copper sulphide flotation after the copper sulphide flotation, and rough concentrate and rougher tailings are obtained after mixing, stirring and separating. The fine flotation includes that gangue mineral depressants are added into the rough concentrate to be stirred, and the gangue mineral depressants are halogenate ethyl sodium sulfonate. According to the preparation method, in the fine flotation process, the halogenate ethyl sodium sulfonate is added to serve as the depressants, impurity gangue minerals are water loving, and therefore the separating effect of target minerals and the impurity gangue minerals is improved in the fine flotation process. The method drastically reduces contents of silica, calcium oxide, magnesium oxide and other impurity gangue minerals, and obtains the high grade copper oxide concentrate. The mineral processing process is low in cost, and simple and feasible in operation.
Description
Technical Field
The invention relates to the technical field of ore dressing, in particular to a preparation method of high-grade copper oxide concentrate.
Background
In copper resources in China, copper oxide ores account for about one third of copper ore resources, most copper ore deposits have oxidation zones, even independent large and medium copper oxide ore deposits are formed in some copper ore deposits, and with the increasing exhaustion of copper sulfide ore resources and the increasing demand of copper metal in China, the copper oxide ore resources are developed and utilized efficiently.
The treatment process of copper oxide mainly comprises the following major categories: 1. direct leaching, and producing copper by adopting wet smelting; 2. mineral separation is carried out to produce copper concentrate (about 8% -25% of copper), then the concentrate is leached, and wet smelting is adopted to produce copper; 3. the ore dressing produces copper concentrate (about 18% -25% copper), and then the copper concentrate is reduced and smelted in an electric furnace to produce blister copper. Under the same condition, if the copper concentrate with relatively high grade can be produced, the method of electric furnace reduction smelting is most economical.
Copper oxide ore is generally found in an oxidation zone at the upper part of a copper deposit, and the flotation effect of the copper oxide ore is not ideal due to extremely complex physical and chemical conditions, uneven mineral granularity, easy over-crushing in the crushing and grinding process, serious argillization and the like. The difficulty of producing high-grade copper oxide concentrate is high. Therefore, if the beneficiation can produce high-grade copper oxide concentrate, the beneficiation has great significance for pyrometallurgy.
The flotation index of the copper oxide ore is low mainly because: the copper oxide ore has loose and fragile structure and more water, and particularly when mud gangue is contained, the mud is seriously formed in the ore grinding process and the flotation is difficult; useful minerals are embedded with fine granularity, generally in a gel or soil state, and some minerals are in a state of penetrating into gangue or surrounding rocks and are difficult to separate and recover; the copper oxide ore has high solubility, and the concentration of copper ions in ore pulp is higher, so that the consumption of a medicament is increased, and the selectivity in the flotation process is destroyed; the copper oxide ore has complex composition, various useful minerals, large difference of floatability, complex composition of gangue, siliceous, calcareous and ferruginous gangue, and great influence on flotation.
Disclosure of Invention
The invention aims to provide a preparation method of high-grade copper oxide concentrate, and aims to solve the technical problems that the gangue mineral impurities such as calcium, magnesium and the like are high and the copper grade is low when the copper oxide concentrate is prepared in the prior art.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a method for preparing a high-grade copper oxide concentrate, which comprises, in order, complex copper oxide raw ore grinding, copper sulfide flotation, and copper oxide flotation, wherein the copper oxide flotation comprises: roughing, adding a flotation reagent into copper sulfide flotation tailings obtained by copper sulfide flotation, mixing, stirring and separating to obtain rough concentrate and roughing tailings; and fine selection, namely adding a gangue mineral inhibitor into the rough concentrate and stirring, wherein the gangue mineral inhibitor is halogenated ethyl sodium sulfonate.
Furthermore, the addition amount of the halogenated ethyl sodium sulfonate is 20-150 g/ton of copper sulfide flotation tailings.
Further, before adding the halogenated ethyl sodium sulfonate, the method also comprises the following steps: adding a siliceous gangue inhibitor into the rough concentrate, and stirring, wherein the siliceous gangue inhibitor is oxalic acid, and the adding amount of the oxalic acid is 60-150 g/ton of copper sulfide flotation tailings.
Further, the step of fine selection sequentially comprises four steps of first copper fine selection, second copper fine selection, third copper fine selection and fourth copper fine selection; wherein the first copper concentration comprises the steps of adding oxalic acid serving as an inhibitor into the rough concentrate, mixing, stirring and separating to obtain a first concentration concentrate and a first concentration middling; the second copper concentration comprises the steps of adding oxalic acid serving as an inhibitor into the first concentrate, mixing, stirring and separating to obtain second concentrate and second middling; the third copper concentration comprises the steps of adding halogenated ethyl sodium sulfonate serving as an inhibitor into the second concentrate, mixing, stirring and separating to obtain a third concentrate and a third middling; and the fourth copper concentration comprises the steps of adding halogenated ethyl sodium sulfonate serving as an inhibitor into the third concentrated ore, mixing, stirring and separating to obtain high-grade copper oxide concentrate and four concentrated middlings.
Further, combining the first middling, the second middling, the third middling and the fourth middling obtained in the concentration step to obtain a concentrated middling, grinding the concentrated middling and modulating the concentrated middling into middling pulp, and performing flotation on the middling pulp to obtain copper oxide middling flotation concentrate and copper oxide middling flotation tailings; wherein, the copper oxide middling flotation concentrate returns to the first copper concentration step; and returning the copper oxide middling flotation tailings to the ore grinding step of concentrating middling.
Further, the flotation step of the middling pulp sequentially comprises the first copper middling roughing, the second copper middling roughing and the copper middling blank concentration; the first copper middling roughing comprises the steps of adding a flotation reagent into middling pulp, mixing, stirring and separating to obtain a first copper middling rough concentrate and a first copper middling roughing tailings; the second copper middling roughing comprises the steps of adding a flotation reagent into the first copper middling roughing tailings, mixing, stirring, and separating to obtain second copper middling roughing concentrates and second copper middling roughing tailings; combining the first copper middling rough concentrate and the second copper middling rough concentrate, and then carrying out blank concentration on the copper middling to obtain copper oxide middling flotation concentrate and copper oxide middling flotation tailings; and returning the copper oxide middling flotation concentrate to the first copper concentration step, and returning the copper oxide middling flotation tailings to the first copper middling roughing step.
Further, the method also comprises the step of adding a flotation agent into the rougher tailings for scavenging.
Further, the flotation reagent comprises a regulator, a collector and a foaming agent; the modifier is sodium sulfide, the collector is a combined reagent formed by xanthate and hydroximic acid, and the foaming agent is terpineol oil.
Further, in the step of complex copper oxide raw ore grinding, the mineral aggregate ground to the fineness of less than 0.074mm accounts for 70-85% of the total ground mineral aggregate mass.
The invention adopts the processes of complex copper oxide raw ore grinding, copper sulfide flotation, copper oxide flotation and the like, and adds halogenated ethyl sodium sulfonate as an inhibitor in the concentration process of the copper oxide flotation to make impurity gangue minerals hydrophilic, thereby improving the separation effect of target minerals and the impurity gangue minerals in the concentration process. The method greatly reduces the content of gangue minerals such as silicon dioxide, calcium oxide, magnesium oxide and the like in the copper oxide concentrate, so that the removal rate of the impurities is up to more than 95 percent, and the high-grade copper oxide concentrate is obtained without reducing the recovery rate of the copper concentrate. After the grade of the copper oxide concentrate is improved, the crude copper can be produced by adopting a pyrometallurgical process of electric furnace reduction smelting, and because the grade of the concentrate is improved, the slag amount in the smelting process is obviously reduced, the copper carried away by the slag amount is obviously reduced, and the smelting recovery rate is increased; the electric energy required by the process for melting the slag is correspondingly reduced, so that the energy efficiency is higher. Because the crude copper can be produced only by adopting the electric furnace reduction smelting, the construction investment of a smelting plant is greatly reduced compared with wet smelting. The production of the high-purity copper oxide concentrate lays a foundation for simplification and optimization of a metallurgical process flow, and has a wide application prospect.
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:
fig. 1 shows a schematic flow diagram of a process for the preparation of high grade copper oxide concentrate according to an exemplary embodiment of the present invention;
fig. 2 shows a detailed flow diagram of a process for the preparation of high grade copper oxide concentrate according to an exemplary embodiment of the present invention;
FIG. 3 shows SiO in the Rough copper ore, copper concentration one concentrate, copper concentration two concentrate, copper concentration three concentrate and high grade copper oxide concentrate obtained in example 1 of the present invention2A trend graph of MgO and CaO; and
FIG. 4 shows SiO in the blister copper ore, copper concentration one concentrate, copper concentration two concentrate, copper concentration three concentrate and high grade copper oxide concentrate obtained in example 2 of the present invention2And a trend chart of MgO and CaO.
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.
The high-grade copper oxide concentrate refers to copper oxide concentrate with higher copper grade obtained by flotation of copper sulfide flotation tailings.
According to an exemplary embodiment of the invention, the preparation method of the high-grade copper oxide concentrate is shown in fig. 1, and comprises the steps of grinding a complex copper oxide raw ore, performing copper sulfide flotation and performing copper oxide flotation in sequence, wherein the copper oxide flotation comprises roughing and concentrating, the roughing comprises adding a flotation reagent into copper sulfide flotation tailings obtained by copper sulfide flotation, mixing, stirring and separating to obtain a rough concentrate and a roughing tailings; and the fine separation comprises adding gangue mineral inhibitor into the rough concentrate and stirring, wherein the gangue mineral inhibitor is halogenated ethyl sodium sulfonate.
The invention adopts the processes of complex copper oxide raw ore grinding, copper sulfide flotation, copper oxide flotation and the like, and adds a flotation reagent into copper sulfide flotation tailings to perform copper oxide flotation, aiming at leading copper oxide minerals to be adhered to foams to float out under the action of the flotation reagent. In the process, part of gangue minerals float upwards due to reasons such as foam entrainment and the like, some impurity gangue minerals float upwards along with the gangue minerals, the floated impurity gangue minerals and the copper oxide minerals are mixed together, in order to separate target minerals and the impurity gangue minerals in a floated foam product, an inhibitor is added to inhibit the impurity gangue minerals in the process of concentrating rough concentrate, the addition of the inhibitor can change the surface potential of a flotation product, and particles with different surface properties can be mutually repelled due to the difference of the surface potentials, so that the separation is realized. The inhibitor is added during the concentration process to effectively separate the gangue minerals as impurities from the target minerals.
The existing method generally selects a combined medicament formed by conventional tannic acid and starch or other medicaments as an inhibitor in the concentration process, but because the structure of the copper oxide ore is loose and fragile, more water is contained, especially more mud gangue is contained, the argillization is serious in the grinding process, and the mineral embedding granularity is fine, so that the separation and the recovery are difficult; in addition, the copper oxide ore has high solubility, the concentration of copper ions in ore pulp is high, and the conventional inhibitors are difficult to realize the effective separation of the copper oxide ore and impurity gangue minerals in the complex copper oxide ore due to self reasons, so that the finally obtained copper sulfide concentrate has high impurity content and low copper grade.
The invention adopts halogenated ethyl sodium sulfonate as gangue mineral inhibitor in the concentration process, wherein the halogenated ethyl sodium sulfonate refers to chloroethyl sodium sulfonate and bromoethyl sodium sulfonate. The halogenated ethyl sodium sulfonate is selected because the halogenated ethyl sodium sulfonate has the characteristic of inhibiting calcium and magnesium gangue minerals, and the action principle is that on one hand, sodium sulfonate groups of the halogenated ethyl sodium sulfonate selectively form adsorption with the surfaces of the calcium and magnesium gangue minerals; on the other hand, the halogenated group is hydrophilic, and forms a bidirectional action mode of hydrophilicity while hydrophilicity, so that the calcium and magnesium-containing mineral is hydrophilic. Therefore, the halogenated ethyl sodium sulfonate can effectively inhibit the flotation of calcium and magnesium impurity minerals without reducing the recovery rate of the copper concentrate, improve the flotation efficiency of copper oxide and obtain high-grade copper oxide concentrate.
The invention adopts the complex copper oxide ore as raw ore, and adds the halogenated ethyl sodium sulfonate impurity inhibitor in the copper oxide concentration process through the processes of ore grinding, copper sulfide flotation, copper oxide flotation and the like, so that the impurity gangue minerals are effectively precipitated from the floated foam, and the separation effect of the target minerals and the impurity gangue minerals is improved. The method greatly reduces the content of gangue minerals such as silicon dioxide, calcium oxide, magnesium oxide and the like in the copper oxide concentrate, so that the removal rate of the impurities is up to more than 95 percent, and the high-grade copper oxide concentrate is obtained without reducing the recovery rate of the copper concentrate. In addition, the beneficiation process is low in cost, simple and feasible in operation, and provides a wider prospect for application of high-purity copper oxide concentrate.
Preferably, the addition amount of the halogenated ethyl sodium sulfonate is 20-150 g/ton of copper sulfide flotation tailings. In the step of fine selection of the copper oxide rough concentrate, the addition amount of the inhibitor has a remarkable influence on a pulp system, the control of the addition amount of the inhibitor within the range is realized by considering the factors such as the grade and the recovery rate of copper, and if the content of the halogenated ethyl sodium sulfonate is more than 150 g/ton of copper sulfide flotation tailings, the recovery rate of copper is influenced; if the content of the halogenated ethyl sodium sulfonate is less than 20 g/ton of copper sulfide flotation tailings, the copper grade can be influenced, because the inhibition of calcium and magnesium impurity gangue minerals is not thorough, the copper grade is low, and the smelting cost is high. The addition amount of the halogenated ethyl sodium sulfonate is controlled within the range, otherwise, the copper grade in the finally obtained target product is low, the impurity content is high, and the waste of copper resources is caused by the high copper content in tailings.
According to a preferred embodiment of the present invention, before adding the sodium haloethyl sulfonate, further comprising: adding a siliceous gangue inhibitor into the rough concentrate, and stirring, wherein the siliceous gangue inhibitor is oxalic acid, and the adding amount of the oxalic acid is 60-150 g/ton of copper sulfide flotation tailings.
From the cause of copper oxide ore, oxygenThe copper ore has high mud content and fine granularity, and the mud can generate adverse effect during the flotation of the sulphide ore, so that the flotation recovery rate of the copper oxide ore is not high, and the copper grade is very low. When the rough concentrate is selected, the siliceous gangue inhibitor is added and stirred, and the halogenated ethyl sodium sulfonate inhibitor is added, so that the factors that most siliceous gangue minerals are inhibited firstly to save the dosage of subsequent inhibitors are considered, the ore dressing cost is reduced, the influence of the siliceous gangue minerals on flotation is reduced, and the subsequent inhibition of the calcareous magnesium gangue is better. Firstly, oxalic acid is added into the rough concentrate for concentration, and then halogenated ethyl sodium sulfonate is added for concentration, compared with the method of simply adding halogenated ethyl sodium sulfonate as an inhibitor for concentration, SiO can be reduced fundamentally2And the content of impurities such as MgO, CaO and the like, so that the removal rate of the impurities is as high as 95 percent, and finally the copper oxide concentrate with high copper grade is obtained.
The present invention is preferably, but not limited to, the above-mentioned siliceous inhibitor, and oxalic acid is selected because it has a chelating group capable of chelating ions dissolved on the surface of the silicate mineral to form a water-soluble chelate. The adding amount of the siliceous gangue inhibitor is controlled within the range of 60-150 g/ton of copper sulfide flotation tailings, so that the separation of impurity siliceous gangue and target minerals can be realized to the maximum extent, and the waste of the inhibitor can not be generated. The inhibitors employed in the present invention achieve the effect of low dosage addition and maximum separation relative to conventional inhibitors of the prior art.
According to an exemplary embodiment of the present invention, as shown in fig. 2, the concentration step includes four steps of first copper concentration, second copper concentration, third copper concentration and fourth copper concentration in sequence; wherein the first copper concentration comprises the steps of adding oxalic acid serving as an inhibitor into the rough concentrate, mixing, stirring and separating to obtain a first concentration concentrate and a first concentration middling; the second copper concentration comprises the steps of adding oxalic acid serving as an inhibitor into the first concentrate, mixing, stirring and separating to obtain second concentrate and second middling; the third copper concentration comprises the steps of adding halogenated ethyl sodium sulfonate serving as an inhibitor into the second concentrate, mixing, stirring and separating to obtain a third concentrate and a third middling; and the fourth copper concentration comprises the steps of adding halogenated ethyl sodium sulfonate serving as an inhibitor into the third concentrated ore, mixing, stirring and separating to obtain high-grade copper oxide concentrate and four concentrated middlings.
The addition of the inhibitor is generally adjusted according to the concentration of the pulp system during roughing and concentration, for example, the addition of oxalic acid is adjusted according to the concentration of the pulp system during roughing. Wherein the amount of oxalic acid inhibitor added in the second copper beneficiation step is less than the amount of oxalic acid inhibitor added in the first copper beneficiation step; similarly, the amount of the sodium haloethyl sulfonate added in the fourth copper concentration step is less than that added in the third copper concentration step, because the impurity gangue minerals contained in the ore pulp system gradually decrease with the increase of the concentration times, and the adding amount of the sodium haloethyl sulfonate is generally adjusted according to the concentration of the ore pulp system. The fine selection step of the copper oxide rough concentrate is divided into four steps, a siliceous inhibitor is added to realize the separation of siliceous impurity gangue minerals, and calcium and magnesium impurity gangue minerals are added to separate calcium oxide, magnesium oxide and other impurity minerals, so that the quick and effective flotation is realized, the process flow is saved, the large consumption of medicaments is avoided, and the high-grade copper oxide concentrate is obtained on the premise of not reducing the copper recovery rate.
According to another exemplary embodiment of the present invention, as shown in fig. 2, the first middling concentration, the second middling concentration, the third middling concentration and the fourth middling concentration obtained in the concentration step are combined to obtain a concentrated middling, the concentrated middling is ground and prepared into middling pulp, and the middling pulp is subjected to flotation to obtain copper oxide middling flotation concentrate and copper oxide middling flotation tailings; wherein, the copper oxide middling flotation concentrate returns to the first copper concentration step; and returning the copper oxide middling flotation tailings to the step of concentrating middling roughing.
And (2) feeding the concentrated middling into a ball mill for ball milling to obtain middling pulp, wherein the pulp fineness of the middling pulp is that ore materials with the particle size smaller than 0.074mm account for 75-85% of the total ore grinding ore materials, then carrying out flotation on the middling pulp, returning the obtained copper oxide middling flotation concentrate to the copper concentration step for concentration again, and returning the obtained copper oxide middling flotation tailings to the copper middling flotation step for flotation again. The middling regrinding process effectively ensures the effective dissociation of the copper oxide minerals and the gangue minerals in the middling, and meanwhile, the return site of the copper middling flotation concentrate obtained by flotation after the regrinding of the copper oxide middling ensures the recovery rate of the copper concentrate, and improves the dissociation degree of the copper oxide ores and the copper grade in the copper oxide concentrate.
Preferably, as shown in fig. 2, the flotation step of the middling pulp comprises a first copper middling roughing, a second copper middling roughing and a copper middling blank concentration in sequence; wherein the first copper middling roughing comprises adding a flotation reagent into the ore pulp, mixing, stirring and separating to obtain a first copper middling rough concentrate and a first copper middling roughing tailings; the second copper middling roughing comprises adding a flotation reagent into the copper middling roughing tailings, mixing, stirring, and separating to obtain a copper middling rough concentrate II and a copper middling roughing tailings II; combining the first copper middling rough concentrate and the second copper middling rough concentrate, and then carrying out blank concentration on the copper middling to obtain copper oxide middling flotation concentration and copper oxide middling flotation tailings; and returning the copper oxide middling flotation concentrate to the first copper concentration step, and returning the copper oxide middling flotation tailings to the first copper middling roughing step.
The method is mainly used for enabling copper minerals with poor floatability (such as the peacock stone) to act with a collecting agent again, recovering the copper minerals as much as possible and improving the recovery rate of copper by carrying out two times of rough concentration and one time of blank concentration on the copper oxide middlings.
According to a preferred embodiment of the invention, the method further comprises the step of adding a flotation agent to the rougher tailings for scavenging. Adding a flotation reagent into the rougher tailings and stirring, returning the copper scavenged middlings obtained through flotation to the copper oxide rougher flotation step and entering the flotation process again, and scavenging the rougher tailings to improve the recovery rate of copper.
Preferably, the flotation agent comprises a conditioning agent, a collector, and a frother; the modifier is sodium sulfide, the collector is a combined reagent formed by xanthate and hydroximic acid, and the foaming agent is terpineol oil. According to the invention, sodium sulfide, pentoxanthin, hydroximic acid and terpineol oil are used as flotation reagents in the copper oxide roughing, the scavenging of the roughing tailings and the flotation of the beneficiated middlings obtained by merging in the beneficiation process. Wherein the addition amount of sodium sulfide in the copper oxide roughing step is 500-800 g/ton of copper sulfide flotation tailings; the addition amount of a combined reagent formed by the xanthate and the hydroximic acid is 130-200 g/ton of copper sulfide flotation tailings, wherein the mass ratio of the xanthate to the hydroximic acid is 1-12: 5; the terpineol is used as a bubbling agent, and the addition amount of the terpineol is 30-50 g/ton of copper sulfide flotation tailings. The adding amount of sodium sulfide in the scavenging step of the copper oxide rougher tailings is 200-500 g/ton of copper sulfide flotation tailings; the addition amount of a combined reagent formed by the xanthate and the hydroximic acid is 100-160 g/ton of copper sulfide flotation tailings, wherein the mass ratio of the xanthate to the hydroximic acid is 1-5: 2; the addition amount of the terpineol is 20-40 g/ton of copper sulfide flotation tailings. The amount of sodium sulfide added in flotation of the selected middlings obtained by merging in the selection process is 200-400 g/ton of copper sulfide flotation tailings, and the addition amount of a combined reagent formed by the xanthate and the hydroximic acid is 50-90 g/ton of copper sulfide flotation tailings, wherein the mass ratio of the xanthate to the hydroximic acid is 1-12: 5; the terpineol is used as a bubbling agent, and the addition amount of the terpineol is 20-40 g/ton of copper sulfide flotation tailings.
The present invention is preferably, but not limited to, the above-mentioned flotation agents, which are selected because they have the following advantages:
during the flotation process, firstly, the sodium sulfide can quickly form a sulfide film on the surface of the mineral and promote the collecting agent to be firmly adsorbed, so that the floating speed and the flotation efficiency of the refractory copper mineral are increased; and secondly, the interference of the slime to the flotation process can be eliminated, and the selectivity and the collecting capability of the copper oxide minerals are enhanced. The penta-yellow chemical is a common chemical agent for flotation of copper sulphide ores, and the flotation of copper oxide ores by using the yellow chemical under the condition of sulfuration has poor sorting index mainly because of 'over sulfuration' (inhibition generation) or 'incomplete sulfuration' (insufficient floating), so that the single copper sulphide ore is only used for flotationThe collecting agent is difficult to adapt to the flotation requirement of the complex copper oxide ore, and the contradiction between selectivity and collecting force cannot be unified. Hydroximic acid is selected as the collecting agent because it can form salt with various metals to form N-O type and O-O type chelate complexes, the stability constant of which is different according to the cationic species on the surface of useful minerals or gangue minerals, wherein the ethyl hydroximic acid and Cu are2+The chelate stability constant of (A) is 7.9, indicating that ethyl hydroxamic acid has good selectivity for the flotation of copper oxide, and that hydroximic acid tends to bind Cu when bound to copper oxide minerals2+Form chemical adsorption with stronger covalency, so that the hydroximic acid has strong collecting capability. Hydroximic acid-pentaxanthate mixed reagent is used to generate the comprehensive collecting effect on the complex copper oxide ore mixed with oxygen and sulfur, the co-adsorption is generated on the surface of the copper ore, a Cu-hydroximic acid-pentaxanthate (composite) complex is formed, the section width of a polar group is increased, the coverage area of the collecting agent on the copper ore is enlarged, and the flotation performance is improved.
The copper sulfide flotation tailings adopted by the invention are obtained by grinding and copper sulfide flotation of some complex copper oxide minerals. According to a typical embodiment of the invention, in the step of complex copper oxide raw ore grinding, the mineral aggregate ground to the fineness of the mineral aggregate with the particle size of less than 0.074mm accounts for 70-85% of the total ground mineral aggregate. And carrying out copper sulfide flotation on the ore pulp with the grinding fineness within the range, and then adding a flotation reagent to carry out copper oxide flotation when the ore pulp of copper sulfide flotation tailings is controlled to be 24-36%. When the grinding fineness is less than 70-0.074 mm during grinding, the flotation of copper sulfide ore and copper oxide ore in the next step is not facilitated; if the fineness of the ground ore is more than 85-0.074 mm, crushing and energy waste are caused.
The following examples are provided to further illustrate the beneficial effects of the present invention.
Example 1
The copper sulfide flotation tailings contain 3.26% of copper.
Roughing copper sulfide flotation tailings: 1 ton of copper sulfide flotation tailing pulp is sent into a flotation tank for roughing, and 500g of sodium sulfide is added while stirring80g of xanthate, 50g of hydroximic acid and 30g of pine oil to obtain copper oxide rougher tailings and foamy copper oxide rougher concentrate floating on the tailings; obtaining the copper oxide rough concentrate, wherein the copper grade in the copper oxide rough concentrate is 11.86 percent, and SiO225.36 percent of the content, 10.29 percent of MgO and 13.84 percent of CaO.
Four times of concentration of rough concentrates: adding 60g of oxalic acid serving as an inhibitor into the foamy rough concentrate while stirring, and carrying out first copper concentration operation; to obtain a first concentration concentrate and a first concentration middling. And adding 30g of oxalic acid into the first concentration concentrate while stirring to perform a second copper concentration operation to obtain a second concentration concentrate and a second concentration middling. And adding 20g of chloroethyl sodium sulfonate into the second concentration concentrate to carry out three operations of copper concentration to obtain a third concentration concentrate and a third concentration middling. Scraping three concentrates of concentration, adding 10g of chloroethyl sodium sulfonate while stirring to carry out four operations of copper concentration, and obtaining high-grade copper concentrate and four middlings of concentration.
The recovery of the high grade copper oxide concentrate was 72.34%, the copper grade was 52.69%, the purity relative to malachite was 88.25%, SiO20.91% of CaO, 0.93% of CaO and 0.74% of MgO.
Copper middling flotation: combining the first middling, the second middling, the third middling and the fourth middling to obtain the concentrated middling, grinding the concentrated middling and preparing the concentrated middling into middling pulp, wherein the fineness of mineral aggregates of the middling pulp is that the mineral aggregates with the particle size of less than 0.074mm account for 80% of the total ground mineral aggregates. And (3) performing two times of roughing and one time of blank concentration on the middling pulp, wherein the flotation reagent is the same as that in the copper roughing, and finally, returning the obtained copper oxide middling flotation concentrate to the copper roughing step.
And (4) carrying out scavenging twice on the rougher tailings, wherein the added flotation agent is the same as the copper oxide rougher.
SiO in rough copper ore, first concentrate of copper concentration, second concentrate of copper concentration, third concentrate of copper concentration and final high-grade copper oxide concentrate2The trend of MgO and CaO is shown in FIG. 3.
Example 2
Copper sulfide flotation tailings, which contain 1.42% copper. The process differs from the process of example 1 in that:
when the copper sulfide flotation tailings are roughly selected, 800g of sodium sulfide, 120g of xanthate, 80g of hydroximic acid and 50g of pine oil are added, the copper grade of the obtained copper oxide rough concentrate is 10.776%, and the SiO content of the copper oxide rough concentrate is230.44 percent of the content, 8.91 percent of MgO and 11.86 percent of CaO.
Four times of concentration of rough concentrates: adding 150g of oxalic acid in the first selection operation; adding 75g of oxalic acid in the two selection steps; 150g of bromoethyl sodium sulfonate is added in the three steps of concentration, 75g of bromoethyl sodium sulfonate is added in the four operations of concentration, and finally high-grade copper concentrate and four middlings of concentration are obtained.
The recovery rate of the high-grade copper oxide concentrate is 71.25 percent, the copper grade is 50.76 percent, and SiO is generated21.02% of CaO, 0.76% of CaO and 0.91% of MgO.
SiO in rough copper ore, first concentrate of copper concentration, second concentrate of copper concentration, third concentrate of copper concentration and final high-grade copper oxide concentrate2The trend of MgO and CaO is shown in FIG. 4.
As can be seen from the graphs 1-2, the SiO in the target mineral, i.e. the copper oxide concentrate, increases with the number of concentration steps2The variation tendency of MgO and CaO is obviously reduced, in particular to SiO2The content of the MgO is reduced remarkably in the first two concentration steps, and the content of the MgO and the CaO is reduced remarkably in the second two concentration steps. The chart further shows that the sodium chloroethyl sulfonate inhibitor adopted by the invention has better separation effect.
Example 3
The process of example 1 is different in that the first two dressing steps, i.e., the dressing step in which oxalic acid is added as an inhibitor, are not performed, and the other steps are the same as those of example 1.
The recovery rate of the finally obtained high-grade copper concentrate is 74.20 percent, the copper grade is 40.23 percent, and SiO is generated23.28 percent of CaO, 0.98 percent of CaO,MgO content 1.23%.
Comparative example 1
The same process as in example 1, except that:
the first copper concentration step and the second copper concentration step both adopt a water glass and sodium hexametaphosphate combined reagent as an inhibitor, the addition amount of the inhibitor is 1000 g/ton of copper sulfide flotation tailings, and the mass ratio is 1: 5; copper selection three and copper selection four both use tannin and starch combination agents as inhibitors.
The recovery rate of the finally obtained high-grade copper concentrate is 78.49 percent, the copper grade is 21.88 percent, and SiO is generated216.44 percent of CaO, 5.94 percent of CaO and 4.01 percent of MgO.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
the invention adopts the processes of complex copper oxide raw ore grinding, copper sulfide flotation, copper oxide flotation and the like, and adds halogenated ethyl sodium sulfonate as an inhibitor in the concentration process of copper oxide flotation, so that impurity gangue minerals are effectively precipitated from the floated foam, and the separation effect of target minerals and the impurity gangue minerals is improved. The method greatly reduces the content of gangue minerals such as silicon dioxide, calcium oxide, magnesium oxide and the like in the copper oxide concentrate, so that the removal rate of the impurities is up to more than 95 percent, and the high-grade copper oxide concentrate is obtained without reducing the recovery rate of the copper concentrate. In addition, the beneficiation process is low in cost, simple and feasible in operation, and provides a wider prospect for application of high-purity copper oxide concentrate.
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 (6)
1. The preparation method of the high-grade copper oxide concentrate sequentially comprises the steps of grinding complex copper oxide raw ore, performing copper sulfide flotation and performing copper oxide flotation, and is characterized in that the copper oxide flotation comprises the following steps:
roughing, adding a flotation reagent into the copper sulfide flotation tailings obtained by copper sulfide flotation, mixing, stirring and separating to obtain rough concentrate and roughing tailings; and
selecting, namely adding a gangue mineral inhibitor into the rough concentrate and stirring, wherein the gangue mineral inhibitor is halogenated ethyl sodium sulfonate;
also included prior to adding the sodium haloethyl sulfonate is: adding a siliceous gangue inhibitor into the rough concentrate, and stirring, wherein the siliceous gangue inhibitor is oxalic acid, and the adding amount of the oxalic acid is 60-150 g/ton of copper sulfide flotation tailings;
the concentration step sequentially comprises four steps of first copper concentration, second copper concentration, third copper concentration and fourth copper concentration; wherein,
the first copper concentration comprises the steps of adding oxalic acid serving as an inhibitor into the rough concentrate, mixing, stirring and separating to obtain a first concentration concentrate and a first concentration middling;
the second copper concentration comprises the steps of adding oxalic acid serving as an inhibitor into the first concentrate, mixing, stirring and separating to obtain a second concentrate and a second middling;
the third copper concentration comprises the steps of adding the halogenated ethyl sodium sulfonate into the second concentration concentrate to be used as an inhibitor, mixing, stirring and separating to obtain a third concentration concentrate and a third middling;
the fourth copper concentration comprises the steps of adding the halogenated ethyl sodium sulfonate into the third concentrated concentrate for concentration to serve as an inhibitor, mixing, stirring and separating to obtain high-grade copper oxide concentrate and four concentrated middlings;
combining the first middling obtained in the concentration step, the second middling, the third middling and the fourth middling to obtain a concentrated middling, grinding the concentrated middling and modulating the concentrated middling into middling pulp, and performing flotation on the middling pulp to obtain copper oxide middling flotation concentrate and copper oxide middling flotation tailings; wherein,
returning the copper oxide middling flotation concentrate to the first copper concentration step;
and returning the copper oxide middling flotation tailings to the ore grinding step of the concentrated middling.
2. The method according to claim 1, wherein the amount of the sodium haloethyl sulfonate added in the concentration step is 20-150 g/ton of copper sulfide flotation tailings.
3. The method according to claim 1, wherein the flotation step of the middling pulp comprises a first copper middling roughing, a second copper middling roughing and a copper middling blank concentration in sequence; wherein,
the first copper middling roughing comprises the steps of adding the flotation reagent into the middling pulp, mixing, stirring and separating to obtain a first copper middling rough concentrate and a first copper middling roughing tailings;
the second copper middling roughing comprises the steps of adding the flotation reagent into the first copper middling roughing tailings, mixing, stirring, and separating to obtain second copper middling rough concentrates and second copper middling roughing tailings;
combining the first copper middling rough concentrate and the second copper middling rough concentrate, and then carrying out blank concentration on the copper middling to obtain copper oxide middling flotation concentrate and copper oxide middling flotation tailings; and returning the copper oxide middling flotation concentrate to the first copper concentration step, and returning the copper oxide middling flotation tailings to the first copper middling roughing step.
4. The method of claim 1, further comprising the step of adding the flotation reagent to the rougher tailings for scavenger flotation.
5. The method according to any one of claims 1 to 4,
the flotation reagent comprises a regulator, a collector and a foaming agent; wherein,
the modifier is sodium sulfide, the collector is a combined reagent formed by a pentaxanthate and hydroximic acid, and the foaming agent is terpineol oil.
6. The method as claimed in claim 1, wherein the mineral aggregate ground to a fineness of less than 0.074mm in the step of complex copper oxide raw ore grinding accounts for 70-85% of the total ground mineral aggregate mass.
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| CN104759341B (en) * | 2015-03-24 | 2017-06-16 | 湖南有色金属研究院 | A kind of beneficiation method of the cupric oxide ore containing magnetic impurity |
| CN104815760B (en) * | 2015-03-24 | 2017-08-29 | 湖南有色金属研究院 | A kind of collecting agent for the Oxide Copper Ore Flotation technique containing magnetic impurity |
| CN107309091B (en) * | 2017-06-23 | 2022-07-05 | 湖南有色金属研究院 | Flotation separation method for separating copper oxide ore and talc |
| CN107790292A (en) * | 2017-10-21 | 2018-03-13 | 江西理工大学 | A kind of application of salicylide oxime compound in copper oxide mineral flotation |
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| CN113083512B (en) * | 2021-04-07 | 2022-01-14 | 中南大学 | Method for promoting flotation of copper oxide ores |
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