CN103143447B - Beneficiation method of high-oxygenation-efficiency complicated copper ore containing co-associated metal - Google Patents
Beneficiation method of high-oxygenation-efficiency complicated copper ore containing co-associated metal Download PDFInfo
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- CN103143447B CN103143447B CN201310029605.9A CN201310029605A CN103143447B CN 103143447 B CN103143447 B CN 103143447B CN 201310029605 A CN201310029605 A CN 201310029605A CN 103143447 B CN103143447 B CN 103143447B
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Abstract
The invention discloses a beneficiation method of a high-oxygenation-efficiency complicated copper ore containing co-associated metal. The method comprises the following steps of: grinding a raw ore to be selected and blending into ore slurry I; carrying out copper sulfide select flotation on the ore slurry I to obtain copper sulfide ore concentrate I, copper sulfide middling and copper sulfide tailings; carrying out copper oxide select flotation on the copper sulfide tailings to obtain copper oxide ore concentrate I, copper oxide middling and copper oxide tailings; and carrying out fine selection on the copper sulfide middling and the copper oxide middling to respectively obtain sulfide ore concentrate II and copper oxide ore concentrate II. The copper sulfide middling and the copper oxide middling are respectively and independently processed to obtain high-grade copper sulfide ore concentrate and high-grade copper oxide ore concentrate; and meanwhile, low-grade copper sulfide ore concentrate and low-grade copper oxide ore concentrate are obtained. The high-grade copper sulfide ore concentrate, the low-grade copper sulfide ore concentrate and the copper oxide ore concentrates are separated, so that a subsequent metallurgy process flow is simplified, the recycling rate of copper is improved, a co-associated metal resource is enhanced and the recycling of noble metal is particularly enhanced; and the production cost is reduced, and the economic benefit is improved.
Description
Technical field
The present invention relates to technical field of mineral processing, in particular to the beneficiation method of the complicated copper mine of a kind of high oxidation rate that contains common associated metal.
Background technology
The copper reserves of China is many, but the average grade of copper mine is only 0.87%, is greater than the ultra-large type copper ore grade of 200 tons substantially all lower than 1%.Because most Copper Resources is complicated intergrowth mineral, middle-size and small-size ore deposit is in the majority, and large ore deposit only accounts for 2.7%, medium-sized mineral deposit accounts for 8.9%, Small Ore Deposits accounts for 88.4%, and wherein a large portion belongs to vulcanization-oxidization mixing copper ore type, and these copper mine compositions are more complicated and oxygenation efficiency is high.Traditional copper ore floatation technology has only considered that single copper-sulphide ores (comprises primary chalcopyrite, secondary vitreous copper, covellite etc.) flotation or the flotation of single cupric oxide ore, ignore a series of features that vulcanization-oxidization copper mineral mixing ore deposit and associated resources reclaim, reclaimed above-mentioned mineral by ore dressing merely and have the problems such as the rate of recovery is low, copper grade is low, beneficiation reagent consumption large, associated resources can not comprehensively be reclaimed, deficiency in economic performance.So the thinking breaking traditions, selects smelting to be combined into a break-through point.Although the external ore dressing of recent year is combined aspect and is studied with pyrometallurgy and hydrometallurgy, obtain larger success, but mix the complicated refractory ore of the compositions such as copper mine during in selecting smelting combination PROCESS FOR TREATMENT oxidation-sulfuration, there is the technical problem that technological process more complicated and cost are higher.
Summary of the invention
The present invention aims to provide the beneficiation method of the complicated copper mine of a kind of high oxidation rate that contains common associated metal, to solve the technical problem that ore-dressing technique complexity, copper recovery are lower and production cost is higher existing in prior art.
To achieve these goals, according to an aspect of the present invention, provide the beneficiation method of the complicated copper mine of a kind of high oxidation rate that contains common associated metal, comprised the following steps: raw ore to be selected is ground and be modulated into ore pulp one; Ore pulp one is carried out to copper sulfide flotation, obtain copper sulfide concentrate one, copper sulfide chats and copper sulfide mine tailing; Copper sulfide mine tailing is carried out to cupric oxide flotation, obtain cupric oxide concentrate one, cupric oxide chats and cupric oxide mine tailing; And copper sulfide chats and cupric oxide chats are carried out selected, obtain respectively copper sulfide concentrate two and cupric oxide concentrate two.
Further, the particle that in ore pulp one, particle diameter is less than 0.074mm accounts for 68%～73% of total particle weight, and the concentration of ore pulp one is 24～36%.
Further, copper sulfide flotation step comprises: ore pulp one is carried out to copper sulfide and roughly select, obtain copper sulfide rough concentrate and copper sulfide mine tailing; Copper sulfide rough concentrate is carried out selected, obtain the selected chats of copper sulfide concentrate one and copper sulfide; Copper sulfide mine tailing is scanned, obtained copper sulfide scavenger concentrate and copper sulfide and scan mine tailing; And the selected chats of copper sulfide and the merging of copper sulfide scavenger concentrate, obtain copper sulfide chats.
Further, cupric oxide flotation step comprises: copper sulfide mine tailing is carried out to cupric oxide and roughly select, obtain cupric oxide rough concentrate and cupric oxide mine tailing; Cupric oxide rough concentrate is carried out selected, obtain the selected chats of cupric oxide concentrate one and cupric oxide; Cupric oxide mine tailing is scanned, obtained cupric oxide scavenger concentrate and cupric oxide and scan mine tailing; And selected cupric oxide chats and cupric oxide scavenger concentrate are merged, obtain cupric oxide chats.
Further, also comprise to copper sulfide chats is carried out ball milling and is modulated into the step of chats ore pulp two before copper sulfide chats is carried out to selected step, the particle that in chats ore pulp two, particle diameter is less than 0.044mm accounts for 95～98% of total particle weight.
Further, copper sulfide chats carries out selected step and comprises: copper sulfide chats is carried out to primary vulcanization copper chats selected, obtain the selected concentrate of copper sulfide chats and the selected mine tailing of copper sulfide chats; Wherein, the selected mine tailing of copper sulfide chats returns to cupric oxide flotation step; The selected concentrate of copper sulfide chats is carried out to copper sulfide chats is selected for the second time, obtain selected two concentrate of copper sulfide chats and selected two mine tailings of copper sulfide chats; Wherein, selected two mine tailings of copper sulfide chats return to the selected step of primary vulcanization copper chats; And selected two concentrate of copper sulfide chats are carried out to copper sulfide chats is selected for the third time, and obtain selected three mine tailings of copper sulfide concentrate two and copper sulfide chats, wherein selected three mine tailings of copper sulfide chats return to the selected step of copper sulfide chats for the second time.
Further, adopt amyl group xanthic acid Ethyl formate as collecting agent in the selected step of primary vulcanization copper chats, terpenic oil is as foaming agent; Wherein the addition of amyl group xanthic acid Ethyl formate is 50～70g/t raw ore, and the addition of terpinol is 20～40g/t raw ore; For the second time the selected step of copper sulfide chats and for the third time the selected step of copper sulfide chats all adopt calgon as inhibitor, the addition of calgon is 100～200g/t raw ore.
Further, copper sulfide mine tailing is carried out all adopting vulcanized sodium as vulcanizing agent in cupric oxide is roughly selected and cupric oxide rougher tailings is scanned step, hydrogen sulfide ammonium is as activator, and the combination medicament that diphenyl phosphonic acid and hydroxamic acid sodium form is as collecting agent.
Further, the selected step of cupric oxide chats comprises: cupric oxide chats is carried out to cupric oxide chats is selected for the first time, obtain the selected concentrate of cupric oxide chats and the selected mine tailing of cupric oxide chats; Wherein, the selected mine tailing of cupric oxide chats returns to cupric oxide flotation step; The selected concentrate of cupric oxide chats is carried out to cupric oxide chats is selected for the second time, obtain selected two concentrate of cupric oxide chats and selected two mine tailings of cupric oxide chats; Wherein, selected two mine tailings of cupric oxide chats return to the selected step of cupric oxide chats for the first time; And selected two concentrate of cupric oxide chats are carried out to cupric oxide chats is selected for the third time, and obtain selected three mine tailings of cupric oxide concentrate two and cupric oxide chats, wherein, selected three mine tailings of cupric oxide chats return to the selected step of cupric oxide chats for the second time.
Further, adopt vulcanized sodium as vulcanizing agent for the first time in the selected step of cupric oxide chats, hydrogen sulfide ammonium is as activator, and the combination medicament that diphenyl phosphonic acid and hydroxamic acid sodium form is as collecting agent; Wherein the addition of vulcanized sodium is 200-400g/t raw ore, and the addition of hydrogen sulfide amine is 100～300g/t raw ore, and the addition of the combination medicament that diphenyl phosphonic acid and hydroxamic acid sodium form is 60～100g/t raw ore; The selected step of cupric oxide chats adopts the combination medicament of diphenyl phosphonic acid and the formation of hydroxamic acid sodium as collecting agent for the second time, and the addition of the combination medicament that diphenyl phosphonic acid and hydroxamic acid sodium form is 30～60g/t raw ore; The selected step of cupric oxide chats adopts calgon as inhibitor for the third time, and the addition of calgon is 100～300g/t raw ore.
The present invention by being recovered to the valuable mineral of easily choosing in concentrate in mineral processing circuit, by the sorting mineral not dissociating in chats, chats is processed separately, obtain high-grade copper sulfide concentrate and high-grade cupric oxide concentrate, obtain low-grade copper sulfide concentrate and low-grade cupric oxide concentrate simultaneously.In the high-grade copper sulfide concentrate wherein obtaining, Cu+Fe+S accounts for 94% left and right, approach or be better than matte chemical composition, can dispense routine " matte smelting " operation of follow-up pyrometallurgical smelting, directly enter " sulfonium blowing " operation, significantly simplify the technique of pyrometallurgical smelting; High-grade cupric oxide concentrate cupric 45% left and right, malachite, chrysocolla content are about 90%, are better than general cupric oxide ore chemistry and become.The low-grade copper concentrate obtaining in converting furnace with Cu
2s produces cross reaction can directly produce blister copper, the convenient metallurgical output that simultaneously reduces hydrometallurgy copper.Ore-dressing technique of the present invention is due to high-grade is separated with low-grade copper sulfide concentrate and cupric oxide concentrate, significantly simplify follow-up metallurgical technology flow process, not only improve the rate of recovery of copper, and strengthen the recovery to common associated metal resource, especially noble metal, reduce production cost, improved economic benefit.
Brief description of the drawings
The Figure of description that forms the application's a part is used to provide a further understanding of the present invention, and schematic description and description of the present invention is used for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows the mineral processing circuit figure of the complicated copper mine of the high oxidation rate that contains common associated metal of the exemplary embodiments according to the present invention.
Detailed description of the invention
It should be noted that, in the situation that not conflicting, the feature in embodiment and embodiment in the application can combine mutually.Describe below with reference to the accompanying drawings and in conjunction with the embodiments the present invention in detail.
In the present invention, the complicated copper mine of the high oxidation rate that contains common associated metal of indication refers to the copper mine that in copper mineral, cupric oxide ore proportion is greater than 40%, also contains some callable associated metals altogether in this copper mine.Mineral processing circuit of the present invention, is not only applicable to the complicated copper mine of high oxidation rate, applicable equally for some common copper mines.
According to a kind of exemplary embodiment of the present invention, as shown in Figure 1, the beneficiation method of the complicated copper mine of high oxidation rate that contains common associated metal comprises the following steps: will treat that raw ore grinds and be modulated into ore pulp one; Ore pulp one is carried out to copper sulfide flotation, obtain copper sulfide concentrate one, copper sulfide chats and copper sulfide mine tailing; Copper sulfide mine tailing is carried out to cupric oxide flotation, obtain cupric oxide concentrate one, cupric oxide chats and cupric oxide mine tailing; And copper sulfide chats and cupric oxide chats are carried out selected, obtain respectively copper sulfide concentrate two and cupric oxide concentrate two.
By the valuable mineral of easily choosing being recovered in concentrate in mineral processing circuit, by the sorting mineral not dissociating in chats, chats is processed separately, obtain high-grade copper sulfide concentrate one and high-grade cupric oxide concentrate one, obtain low-grade copper sulfide concentrate two and more low-grade cupric oxide concentrate two simultaneously.In the high-grade copper sulfide concentrate wherein obtaining, Cu+Fe+S accounts for 94% left and right, approach or be better than matte chemical composition, can dispense routine " matte smelting " operation of follow-up pyrometallurgical smelting, directly enter " sulfonium blowing " operation, significantly simplify the technique of pyrometallurgical smelting; High-grade cupric oxide concentrate cupric 45% left and right, malachite, chrysocolla content are about 90%, are better than general cupric oxide ore chemistry and become.The low-grade copper concentrate obtaining in converting furnace with Cu
2s produces cross reaction can directly produce blister copper, the convenient metallurgical output that simultaneously reduces hydrometallurgy copper.Ore-dressing technique of the present invention is due to high-grade is separated with low-grade copper sulfide concentrate and cupric oxide concentrate, ore dressing and follow-up metallurgical technology flow process are significantly simplified, not only improve the rate of recovery of copper, and strengthen the recovery to common associated metal resource, especially noble metal, reduce production cost, improved economic benefit.
A preferred embodiment of the invention, the particle that in ore pulp one, particle diameter is less than 0.074mm accounts for 68%～73% of total particle weight, and the concentration of ore pulp one is 24%～36%.Raw ore ore grinding is also modulated into ore pulp one by adding water, in the time that the mass percent concentration of ore pulp one is 24%～36%, this ore pulp one is sent into flotation cell and is added floating agent to carry out flotation.By the grain fineness in ore pulp one and mass percent concentration be controlled at the object product that contributes in above-mentioned scope in ore pulp quickly and efficiently with floating agent in conjunction with and float up, saved flotation time, improved flotation effect.
According to a kind of exemplary embodiment of the present invention, as shown in Figure 1, copper sulfide flotation step comprises: ore pulp one is carried out to copper sulfide and roughly select, obtain copper sulfide rough concentrate and copper sulfide mine tailing; Copper sulfide rough concentrate is carried out selected, obtain the selected chats of copper sulfide concentrate one and copper sulfide; Copper sulfide mine tailing is scanned, obtained that copper sulfide is scanned chats and copper sulfide is scanned mine tailing; And the selected chats of copper sulfide and copper sulfide scan chats and merge, obtain copper sulfide chats.
Copper sulfide is roughly selected and is adopted amyl group xanthic acid Ethyl formate as collecting agent, and consumption is 100 grams/ton-120 grams/ton, and terpenic oil is as foaming agent, and consumption is 40-60g/t raw ore; Copper sulfide is scanned and is divided into twice, wherein copper sulfide is scanned an employing sodium carbonate as adjusting agent, consumption is 300-500g/t raw ore, amyl group xanthic acid Ethyl formate is as collecting agent, consumption is 40-60g/t raw ore, and terpenic oil is as foaming agent, and consumption is 30-40g/t raw ore, copper sulfide is scanned two employing amyl group xanthic acid Ethyl formates as collecting agent, and consumption is 40-60g/t raw ore.The selected calgon that all adopts of cupric oxide rough concentrate is as inhibitor, and consumption is 100-300g/t raw ore.
The main purpose of roughly selecting is that the copper mineral after ore grinding is reclaimed, and one roughing enough makes 60～90% copper mineral flotation out.Concrete operations are sent into flotation cell for having certain density ore pulp, in the ore pulp system in flotation cell, add collecting agent and foaming agent while stirring, adding collecting agent is for the copper sulfide emersion in ore pulp is come, the action principle of collecting agent is that collecting agent and copper mineral surface action form chemisorbed, increases the hydrophobicity of copper mineral and then adheres on foam and float therewith; Adding foaming agent is in order to increase foam volume and viscosity thereof in bubbling process, is conducive to copper mineral and adheres to the surface of foam.In the process of flotation, to stir ore pulp system, stirring is for the floating agent such as collecting agent and foaming agent is mixed more fully with ore pulp, general mixing time is 1～3 minute, to be controlled at the time within the scope of this and enough make copper mineral mix fully with floating agent, long or too shortly all be unfavorable for the flotation of medicament to mineral.The valuable mineral of easily choosing can be recovered in copper sulfide concentrate one by this process, and scan in chats with copper sulfide during the sorting mineral not dissociating is selected to copper sulfide.The step that wherein copper sulfide is scanned is the rate of recovery in order to improve copper.
According to another kind of exemplary embodiment of the present invention, as shown in Figure 1, cupric oxide flotation step comprises: copper sulfide mine tailing is carried out to cupric oxide and roughly select, obtain cupric oxide rough concentrate and cupric oxide mine tailing; Cupric oxide rough concentrate is carried out selected, obtain the selected chats of cupric oxide concentrate one and cupric oxide; Cupric oxide mine tailing is scanned, obtained cupric oxide scavenger concentrate and cupric oxide and scan mine tailing; And selected cupric oxide chats and cupric oxide scavenger concentrate are merged, obtain cupric oxide chats.
Mud in the cupric oxide ore obtaining after copper sulfide flotation is many, more difficult with respect to the flotation of copper-sulphide ores.Can be by being manually that rough concentrate is poured in the flotation cell of selected operation by the froth pulp of flotation in rougher process, or by foam tank with water jets under high pressure be punched in next foam tank, carry out selected.Roughly select the rough concentrate obtaining and again carry out selected quality and the efficiency that has ensured floatation process.
According to a kind of exemplary embodiment of the present invention, before copper sulfide chats is carried out to selected step, also comprise to copper sulfide chats is carried out ball milling and is modulated into the step of chats ore pulp two, the particle that in chats ore pulp two, particle diameter is less than 0.044mm accounts for 95～98% of total particle weight.Copper sulfide chats ore pulp is carried out to the effect that ball milling has ensured that next step is selected, improve the liberation degree of minerals of the superfine adhesion mineral of disseminated grain size, various mineral are fully dissociated, in refining process, use inhibitor, a part of gangue mineral can be suppressed, thus the content of raising Cu Concentrate Grade and associated metal.
Preferably, copper sulfide chats carries out selected step and comprises: copper sulfide chats is carried out to primary vulcanization copper chats selected, obtain the selected concentrate of copper sulfide chats and the selected mine tailing of copper sulfide chats; Wherein, the selected mine tailing of copper sulfide chats returns to cupric oxide flotation step; The selected concentrate of copper sulfide chats is carried out to copper sulfide chats is selected for the second time, obtain selected two concentrate of copper sulfide chats and selected two mine tailings of copper sulfide chats; Wherein, selected two mine tailings of copper sulfide chats return to the selected step of primary vulcanization copper chats; And selected two concentrate of copper sulfide chats are carried out to copper sulfide chats is selected for the third time, and obtain selected three mine tailings of copper sulfide concentrate two and copper sulfide chats, wherein selected three mine tailings of copper sulfide chats return to the selected step of copper sulfide chats for the second time.
Copper sulfide chats is carried out to triple cleaning step and finally obtained copper sulfide concentrate two, although this copper sulfide concentrate two is lower with respect to copper sulfide concentrate one purity, but with respect to prior art, but tool has greatly improved, in the ore-dressing technique of prior art, generally have to copper sulfide concentrate one, remaining is as mine tailing.The present invention is by the change of ore-dressing technique, obtain the middle copper sulfide concentrate two lower but higher with respect to the purity of mine tailing than copper sulfide concentrate one purity, in this copper sulfide concentrate two, contain more high-grade associated metal resource altogether, as cobalt, nickel, gold, silver etc., by secondary, copper sulfide concentrate is carried out selectedly, improved the rate of recovery of common associated metal.Obtain copper products by metallurgical method, avoided the large shortcoming of traditional handicraft productive rate; Simultaneously more traditional ore-dressing technique, has increased the recovery of common associated metal resource, significantly reduces the production of follow-up metallurgical technology, has increased economic benefit.
Further preferably, adopt amyl group xanthic acid Ethyl formate as collecting agent in the selected step of primary vulcanization copper chats, terpenic oil is as foaming agent; Wherein the addition of amyl group xanthic acid Ethyl formate is 50～70g/t raw ore, and the addition of terpinol is 20～40g/t raw ore; For the second time the selected step of copper sulfide chats and for the third time the selected step of copper sulfide chats all adopt calgon as inhibitor, the addition of calgon is 100～200g/t raw ore.
According to a kind of exemplary embodiment of the present invention, copper sulfide mine tailing is carried out all adopting vulcanized sodium as vulcanizing agent in cupric oxide is roughly selected and cupric oxide rougher tailings is scanned step, hydrogen sulfide ammonium is as activator, and the combination medicament that diphenyl phosphonic acid and hydroxamic acid sodium form is as collecting agent.In ore pulp, add hydrogen sulfide ammonium, can not only in the time of flotation malachite, strengthen the activation of hydrogen sulphion, greatly accelerate the speed of vulcanization reaction, also can eliminate or reduce the unfavorable factor of residual hydrogen sulfide, avoid the malachite that excess sulphur ion pair cured, the inhibitory action of chrysocolla, made the sulfide film of malachite, chrysocolla Surface Creation more solid, stable.Above-mentioned effect is conducive to malachite, chrysocolla and collecting agent effect.According to agent molecule design theory, can calculate the most suitable carbon chain lengths of collecting agent for flotation malachite, its calculated value is between 11～12.The present invention selects diphenyl phosphonic acid as collecting agent, its carbon number is just between this, it is selectively better than straight-chain alkyl phosphinic acids class collecting agent, form combined capturing and collecting agent with hydroxamic acid sodium, have complementary advantages, contribute to improve the concentrate grade of cupric oxide and do not affect copper recovery, increasing the rate of recovery of associated metal resource.
The vulcanized sodium of middle employing roughly selected by cupric oxide and the amount of hydrogen sulfide amine is followed successively by 600-800g/t raw ore, 200-400g/t raw ore; The consumption of collecting agent diphenyl phosphonic acid and hydroxamic acid sodium is followed successively by 80-120g/t raw ore, 40-60g/t raw ore.In the step that cupric oxide rougher tailings is scanned, scan the vulcanized sodium of an employing and the consumption of hydrogen sulfide amine is followed successively by 200-400g/t raw ore and 100-150g/t raw ore, the consumption of collecting agent diphenyl phosphonic acid and hydroxamic acid sodium is followed successively by 50-80g/t raw ore and 20-40g/t raw ore; The vulcanized sodium of two employings scanned by cupric oxide and the consumption of hydrogen sulfide amine is followed successively by 100-300g/t raw ore and 40-80g/t raw ore, and the consumption of collecting agent diphenyl phosphonic acid and hydroxamic acid sodium is followed successively by 40-60g/t raw ore, 10-30g/t raw ore.
A preferred embodiment of the invention, the selected step of cupric oxide chats comprises: cupric oxide chats is carried out to cupric oxide chats is selected for the first time, obtain the selected concentrate of cupric oxide chats and the selected mine tailing of cupric oxide chats; Wherein, the selected mine tailing of cupric oxide chats returns to cupric oxide flotation step; The selected concentrate of cupric oxide chats is carried out to cupric oxide chats is selected for the second time, obtain selected two concentrate of cupric oxide chats and selected two mine tailings of cupric oxide chats; Wherein, selected two mine tailings of cupric oxide chats return to the selected step of cupric oxide chats for the first time; And selected two concentrate of cupric oxide chats are carried out to cupric oxide chats is selected for the third time, and obtain selected three mine tailings of cupric oxide concentrate two and cupric oxide chats, wherein, selected three mine tailings of cupric oxide chats return to the selected step of cupric oxide chats for the second time.
By design mineral processing circuit, cupric oxide chats is carried out further selected, obtain cupric oxide concentrate two, this cupric oxide concentrate two is lower with respect to the purity of cupric oxide concentrate one, but higher with respect to the purity of cupric oxide mine tailing.Cupric oxide concentrate two can be processed through simple, and the metallurgical operation that enters next step greatly reduces conventional method and directly enter the treating capacity of metallurgical operation, reduces the investment of metallurgical technology.Cupric oxide chats is carried out further selected, can reclaim to greatest extent copper resource, cupric oxide concentrate product for different grades can adopt diverse ways to process, bring larger saving space to follow-up metallurgy, and the associated resources (as cobalt, nickel, gold, silver etc.) of copper is reclaimed to greatest extent.
Preferably, adopt vulcanized sodium as vulcanizing agent for the first time in the selected step of cupric oxide chats, hydrogen sulfide amine is as activator, and the combination medicament that diphenyl phosphonic acid and hydroxamic acid sodium form is as collecting agent; Wherein the addition of vulcanized sodium is 200-400g/t raw ore, and the addition of hydrogen sulfide amine is 100-300g/t raw ore; The addition of the combination medicament that diphenyl phosphonic acid and hydroxamic acid sodium form is 60～100g/t raw ore; The selected step of cupric oxide chats adopts the combination medicament of diphenyl phosphonic acid and the formation of hydroxamic acid sodium as collecting agent for the second time, and the addition of the combination medicament that diphenyl phosphonic acid and hydroxamic acid sodium form is 30～60g/t raw ore; The selected step of cupric oxide chats adopts calgon as inhibitor for the third time, and the addition of calgon is 100～300g/t raw ore.
Due to cupric oxide ore, the mud that especially chrysocolla contains is more, is mainly desliming in floatation process, so adopt some conventional collecting agent flotation more difficult, is difficult to be effective.The present invention adopts the combination medicament of diphenyl phosphonic acid and the formation of hydroxamic acid sodium as collecting agent, high to the well selective and rate of recovery of copper oxide mineral, can carry out preferably flotation.After twice selected step, add inhibitor to suppress some impurity gangue minerals, it is separated with object mineral, improve the rate of recovery of copper.
Further illustrate beneficial effect of the present invention below in conjunction with specific embodiment
Embodiment 1
Raw ore cupric 3.42%, copper oxygenation efficiency is 43.38%, containing cobalt 0.16%.
Beneficiation steps is as follows:
(1) by 1 ton of raw ore through ball mill ore grinding, mog accounts for 73% of total particle weight to the particle that particle diameter in ore pulp is less than 0.074mm, the mass percent concentration of ore pulp enters flotation cell and carries out flotation while being 36%.
(2) in ore pulp, add amyl group xanthic acid Ethyl formate 120g, terpenic oil 60g, carries out the copper sulfide of 3 minutes and roughly selects, and obtains copper sulfide rough concentrate and copper sulfide rougher tailings.
In copper sulfide rougher tailings, add sodium carbonate 500g, amyl group xanthic acid Ethyl formate 60g, terpenic oil 20g carries out primary vulcanization copper and scans, 3 minutes time, obtains copper sulfide scavenger concentrate one and copper sulfide and scans mine tailing one, scans and in mine tailing one, adds amyl group xanthic acid Ethyl formate 60g to copper sulfide, stir, 2 minutes time, obtains copper sulfide scavenger concentrate two and final copper sulfide mine tailing, and wherein copper sulfide scavenger concentrate two returns to copper sulfide and roughly selects step.
By copper sulfide rough concentrate carry out 3 times selected, obtain copper sulfide concentrate one and the selected chats of copper sulfide.
Copper sulfide scavenger concentrate and the selected chats merging of copper sulfide are carried out to ball milling, obtain the ore pulp that particle that particle diameter is less than 0.044mm accounts for total particle weight 98%, carry out afterwards primary vulcanization copper chats selected, add amyl group xanthic acid Ethyl formate 70g, terpenic oil 40g, flotation 2 minutes, selected and the selected inhibitor calgon that all adds of copper sulfide chats for the third time of copper sulfide chats for the second time, addition is followed successively by 200g and 100g, and flotation time is 1 minute, obtains copper sulfide concentrate two.
(3) sulphide ore is roughly selected and is scanned after operation completes copper sulfide mine tailing is carried out to oxide ore flotation operation.Wherein cupric oxide is roughly selected and is added vulcanized sodium 800g, hydrogen sulfide amine 400g, 120 grams/ton of collecting agent diphenyl phosphonic acids, 60 grams/ton, hydroxamic acid sodium, and flotation time 3 minutes, obtains cupric oxide rough concentrate and cupric oxide rougher tailings;
Cupric oxide rougher tailings is carried out to cupric oxide to be scanned, wherein cupric oxide is scanned an addition agent vulcanized sodium 400g, hydrogen sulfide amine 150g, collecting agent diphenyl phosphonic acid 80g, hydroxamic acid sodium 40g, flotation time 3 minutes, obtain cupric oxide scavenger concentrate one and cupric oxide and scan mine tailing one, cupric oxide is scanned to mine tailing one to carry out cupric oxide for the second time and scans, wherein add vulcanized sodium 300g, hydrogen sulfide amine 80g, collecting agent diphenyl phosphonic acid 60g, hydroxamic acid sodium 30g, flotation 2 minutes, obtains cupric oxide and scans chats two and mine tailing.
Cupric oxide rough concentrate is carried out selected, add inhibitor calgon 300g, flotation time is 2 minutes, obtains the selected chats of cupric oxide concentrate one and cupric oxide.
(4) selected cupric oxide chats and cupric oxide scavenger concentrate are merged to carry out cupric oxide chats selected, wherein cupric oxide chats adds vulcanized sodium 400g in selected for the first time, hydrogen sulfide amine 300g, collecting agent diphenyl phosphonic acid 60g, hydroxamic acid sodium 40g, flotation time 3 minutes; Cupric oxide chats adds diphenyl phosphonic acid 40g, hydroxamic acid sodium 20g, flotation time 2 minutes in selected for the second time; Cupric oxide chats adds calgon 300g in selected for the third time, flotation time 2 minutes, wherein the selected cleaner tailings obtaining of cupric oxide chats turns back to cupric oxide through ball milling and roughly selects step for the first time, wherein grinding of ball grinder to particle diameter is less than 0.074 particle and accounts for 95% of total particle weight, for the second time cupric oxide chats selected and for the third time the selected cleaner tailings order obtaining of cupric oxide chats return to upper level operation, finally obtain cupric oxide concentrate two.
The experimental data that embodiment 1 obtains is in table 1.
Table 1
As can be seen from Table 1, apply mineral processing circuit of the present invention, high-grade copper sulfide concentrate one and cupric oxide concentrate one are obtained, low-grade copper sulfide concentrate two and cupric oxide concentrate two have been obtained simultaneously, in reclaiming to large extent copper resource, also common associated metal cobalt resource is reclaimed, make cobalt there is the higher rate of recovery.
Embodiment 2
Raw ore cupric 2.22%, copper oxygenation efficiency is 57.19%, 68.93 grams of/ton of raw ores of argentiferous.
Beneficiation steps is as follows:
(1) by 1 ton of raw ore through ball mill ore grinding, mog accounts for 68% of total particle weight to the particle that particle diameter in ore pulp is less than 0.074mm, the mass percent concentration of ore pulp enters flotation cell and carries out flotation while being 24%.
(2) in ore pulp, add amyl group xanthic acid Ethyl formate 100g, terpenic oil 40g, flotation time is 3 minutes, obtains copper sulfide rough concentrate and copper sulfide rougher tailings.
In copper sulfide rougher tailings, add sodium carbonate 300g, amyl group xanthic acid Ethyl formate 40g, terpenic oil 30g carries out primary vulcanization copper and scans, 3 minutes time, obtain copper sulfide scavenger concentrate one and copper sulfide and scan mine tailing one, scan in mine tailing one and add amyl group xanthic acid Ethyl formate 40g flotation 2 minutes to copper sulfide, obtain copper sulfide scavenger concentrate two and final copper sulfide mine tailing, copper sulfide scavenger concentrate two returns to copper sulfide and roughly selects step.
By copper sulfide rough concentrate carry out 3 times selected, obtain copper sulfide concentrate one and the selected chats of copper sulfide.
Copper sulfide scavenger concentrate and the selected chats merging of copper sulfide are carried out to ball milling, obtain the ore pulp that particle that particle diameter is less than 0.044mm accounts for total particle weight 95%, carry out afterwards primary vulcanization copper chats selected, add amyl group xanthic acid Ethyl formate 50g, terpenic oil 20g, flotation 2 minutes, for the second time copper sulfide chats selected and for the third time copper sulfide chats all add inhibitor calgon in selected, addition is followed successively by 150g and 100g, and flotation time is 1 minute, obtains copper sulfide concentrate two.
(3) sulphide ore is roughly selected and is scanned after operation completes copper sulfide mine tailing is carried out to oxide ore flotation operation.Wherein cupric oxide is roughly selected and is added vulcanized sodium 600g, aluminum sulfate 400g, hydrogen sulfide ammonium 200g, collecting agent diphenyl phosphonic acid 80g, hydroxamic acid sodium 40g, and flotation time 3 minutes, obtains cupric oxide rough concentrate and cupric oxide rougher tailings;
Cupric oxide rougher tailings is carried out to cupric oxide to be scanned, wherein cupric oxide adds vulcanized sodium 200g, hydrogen sulfide amine 100g in scanning for the first time, collecting agent diphenyl phosphonic acid 50g, hydroxamic acid sodium 20, flotation time 3 minutes, obtain cupric oxide scavenger concentrate one and cupric oxide and scan mine tailing one, cupric oxide is scanned to mine tailing one to carry out cupric oxide for the second time and scans, wherein add vulcanized sodium 100g, hydrogen sulfide amine 40g, collecting agent diphenyl phosphonic acid 40g, hydroxamic acid sodium 10g, flotation 2 minutes, obtains cupric oxide scavenger concentrate two and mine tailing.
Cupric oxide rough concentrate is carried out selected, add inhibitor calgon 100g, flotation time is 2 minutes, obtains the selected chats of cupric oxide concentrate one and cupric oxide.
(4) selected cupric oxide chats and the merging of cupric oxide scavenger concentrate are obtained to cupric oxide chats, carry out selected to cupric oxide chats, wherein cupric oxide chats adds vulcanized sodium 200g in selected for the first time, hydrogen sulfide amine 100g, collecting agent diphenyl phosphonic acid 40g, hydroxamic acid sodium 20g, flotation time 3 minutes; Cupric oxide chats adds diphenyl phosphonic acid 20g, hydroxamic acid sodium 10g, flotation time 2 minutes in selected for the second time; Cupric oxide chats adds calgon 100g in selected for the third time, flotation time 2 minutes, the cleaner tailings that wherein cupric oxide chats obtains in selected for the first time turns back to cupric oxide through ball milling and roughly selects step, wherein grinding of ball grinder to particle diameter is less than 0.074 particle and accounts for 93% of total particle weight, for the second time cupric oxide chats selected and for the third time the selected cleaner tailings order obtaining of cupric oxide chats return to upper level operation, finally obtain cupric oxide concentrate two.
The experimental data that embodiment 1 obtains is in table 1
Table 2
Can find out from above description and experimental data, adopt technical scheme of the present invention can make the total rate of recovery of copper up to 92.12%, the rate of recovery of associated silver is 88.45%, makes copper and silver all obtain good recovery.The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (9)
1. a beneficiation method that contains the complicated copper mine of high oxidation rate of common associated metal, is characterized in that, comprises the following steps:
Raw ore to be selected is ground and is modulated into ore pulp one;
Described ore pulp one is carried out to copper sulfide flotation, obtain copper sulfide concentrate one, copper sulfide chats and copper sulfide mine tailing;
Described copper sulfide mine tailing is carried out to cupric oxide flotation, obtain cupric oxide concentrate one, cupric oxide chats and cupric oxide mine tailing; And
Described copper sulfide chats and described cupric oxide chats are carried out selected, obtain respectively copper sulfide concentrate two and cupric oxide concentrate two;
Wherein, described cupric oxide flotation step comprises: copper sulfide mine tailing is carried out to cupric oxide and roughly select, obtain cupric oxide rough concentrate and cupric oxide mine tailing; Described cupric oxide rough concentrate is carried out selected, obtain the selected chats of cupric oxide concentrate one and cupric oxide; Described cupric oxide mine tailing is scanned, obtained cupric oxide scavenger concentrate and cupric oxide and scan mine tailing; And selected described cupric oxide chats and described cupric oxide scavenger concentrate are merged, obtain cupric oxide chats;
Described copper sulfide mine tailing carried out to cupric oxide is roughly selected and described cupric oxide chats is carried out when selected, adopting combination medicament that diphenyl phosphonic acid and hydroxamic acid sodium forms as collecting agent.
2. method according to claim 1, is characterized in that, the particle that in described ore pulp one, particle diameter is less than 0.074mm accounts for 68%～73% of total particle weight, and the concentration of described ore pulp one is 24%～36%.
3. method according to claim 2, is characterized in that, described copper sulfide flotation step comprises:
Described ore pulp one is carried out to copper sulfide and roughly select, obtain copper sulfide rough concentrate and copper sulfide mine tailing;
Described copper sulfide rough concentrate is carried out selected, obtain the selected chats of copper sulfide concentrate one and copper sulfide;
Described copper sulfide mine tailing is scanned, obtained copper sulfide scavenger concentrate and copper sulfide and scan mine tailing; And
The selected chats of described copper sulfide and described copper sulfide scavenger concentrate merge, and obtain copper sulfide chats.
4. method according to claim 3, it is characterized in that, before described copper sulfide chats is carried out to selected step, also comprise to described copper sulfide chats is carried out ball milling and is modulated into the step of chats ore pulp two, the particle that in described chats ore pulp two, particle diameter is less than 0.044mm accounts for 95%～98% of total particle weight.
5. according to the method in any one of claims 1 to 3, it is characterized in that, described copper sulfide chats carried out to selected step and comprise:
Described copper sulfide chats is carried out to primary vulcanization copper chats selected, obtain the selected concentrate of copper sulfide chats and the selected mine tailing of copper sulfide chats; Wherein, the selected mine tailing of described copper sulfide chats returns to cupric oxide flotation step;
The selected concentrate of described copper sulfide chats is carried out to copper sulfide chats is selected for the second time, obtain selected two concentrate of copper sulfide chats and selected two mine tailings of copper sulfide chats; Wherein, selected two mine tailings of copper sulfide chats return to the selected step of primary vulcanization copper chats; And
Selected two concentrate of described copper sulfide chats are carried out to copper sulfide chats is selected for the third time, obtain selected three mine tailings of copper sulfide concentrate two and copper sulfide chats, wherein selected three mine tailings of copper sulfide chats return to the selected step of copper sulfide chats for the second time.
6. method according to claim 5, is characterized in that,
In the selected step of described primary vulcanization copper chats, adopt amyl group xanthic acid Ethyl formate as collecting agent, terpenic oil is as foaming agent; The addition of wherein said amyl group xanthic acid Ethyl formate is 50～70g/t raw ore, and the addition of described terpenic oil is 20～40g/t raw ore;
The selected step of the described chats of copper sulfide for the second time and the selected step of the described chats of copper sulfide for the third time all adopt calgon as inhibitor, and the addition of described calgon is 100～200g/t raw ore.
7. method according to claim 1, it is characterized in that, described copper sulfide mine tailing is carried out all adopting vulcanized sodium as vulcanizing agent in cupric oxide is roughly selected and described cupric oxide rougher tailings is scanned step, hydrogen sulfide ammonium is as activator, and the combination medicament that diphenyl phosphonic acid and hydroxamic acid sodium form is as collecting agent.
8. according to the method in any one of claims 1 to 3, it is characterized in that, described cupric oxide chats carried out to selected step and comprise:
Described cupric oxide chats is carried out to cupric oxide chats is selected for the first time, obtain the selected concentrate of cupric oxide chats and the selected mine tailing of cupric oxide chats; Wherein, the selected mine tailing of described cupric oxide chats returns to described cupric oxide flotation step;
The selected concentrate of described cupric oxide chats is carried out to cupric oxide chats is selected for the second time, obtain selected two concentrate of cupric oxide chats and selected two mine tailings of cupric oxide chats; Wherein, selected two mine tailings of described cupric oxide chats return described in the selected step of cupric oxide chats for the first time; And
Selected two concentrate of described cupric oxide chats are carried out to cupric oxide chats is selected for the third time, obtain selected three mine tailings of cupric oxide concentrate two and cupric oxide chats, wherein, the selected step of cupric oxide chats for the second time described in selected three mine tailings of described cupric oxide chats return.
9. method according to claim 8, is characterized in that,
In the selected step of the described chats of cupric oxide for the first time, adopt vulcanized sodium as vulcanizing agent, hydrogen sulfide ammonium is as activator, and the combination medicament that diphenyl phosphonic acid and hydroxamic acid sodium form is as collecting agent; The addition of wherein said vulcanized sodium is 200-400g/t raw ore, and the addition of described hydrogen sulfide amine is 100～300g/t raw ore, and the addition of the combination medicament that described diphenyl phosphonic acid and hydroxamic acid sodium form is 60～100g/t raw ore;
The selected step of the described chats of cupric oxide for the second time adopts the combination medicament of diphenyl phosphonic acid and the formation of hydroxamic acid sodium as collecting agent, and the addition of the combination medicament that described diphenyl phosphonic acid and hydroxamic acid sodium form is 30～60g/t raw ore;
The selected step of the described chats of cupric oxide for the third time adopts calgon as inhibitor, and the addition of described calgon is 100～300g/t raw ore.
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| CN104772229B (en) * | 2015-04-16 | 2017-09-22 | 江西理工大学 | Silver ore middle-low grade association copper recovery process |
| CN107486338B (en) * | 2017-08-30 | 2019-06-04 | 厦门紫金矿冶技术有限公司 | A kind of floatation process of high efficiente callback complex copper oxide ore |
| CN107930859B (en) * | 2018-01-12 | 2020-03-27 | 东北大学 | Non-sulfurized mineral flotation collector and application thereof |
| CN108802288B (en) * | 2018-06-14 | 2021-08-03 | 湖南科技大学 | Method for analyzing product quality based on mineral characteristics |
| CN110681477B (en) * | 2018-07-06 | 2021-08-10 | 厦门紫金矿冶技术有限公司 | Dressing and smelting combined treatment method for recovering complex copper oxide ore |
| CN111790517A (en) * | 2020-06-02 | 2020-10-20 | 中国恩菲工程技术有限公司 | Method for sorting copper oxide and copper sulfide mixed ore |
| CN112642583A (en) * | 2020-12-29 | 2021-04-13 | 黑龙江省宝泉岭农垦溢祥石墨有限公司 | Graphite flotation middling treatment process and device |
| CN113333153B (en) * | 2021-07-15 | 2023-04-25 | 紫金矿业集团股份有限公司 | Ore dressing method for fine-grained chalcopyrite in plateau area |
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