CN102698877B - Copper-lead separation flotation inhibitor and applications thereof - Google Patents
Copper-lead separation flotation inhibitor and applications thereof Download PDFInfo
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Abstract
The invention belongs to the field of complicated copper-lead-zinc sulphide ore beneficiation separation and provides a copper-lead separation flotation inhibitor and applications thereof. The copper-lead separation flotation inhibitor is formed by mixing polymeric ferric sulfate solution with a mass concentration of 5.0%-6.0% and glycerin solution with a mass concentration of 0.8%-1.2%, wherein the mass ratio of the polymeric ferric sulfate solution to the glycerin solution is 1:1-4. Addition of the inhibitor in copper-lead separation operation can remarkably improve copper and lead concentrate qualities, evidently lower mutual containing of copper and lead, and improve flotation recovery rate of copper and lead minerals. The copper-lead separation flotation inhibitor and the applications thereof have the advantages that the copper-lead separation flotation inhibitor is environment-friendly, efficient in sorting, low in reagent cost, easy to operate and the like and applicable to the complicated copper-lead-zinc sulphide ore beneficiation separation.
Description
Technical field
The invention belongs to technical field of mineral processing, relate to complicated copper-lead zinc Mineral separation field, be mainly used in the separation field of copper sulfide and vulcanized lead mineral, a kind of depressing agent and application thereof of copper-lead separation are specifically provided.
Background technology
Along with social development, resource utilization increases day by day, and ore properties becomes increasingly complex, and technique of preparing difficulty is increasing.Complicated copper-lead zinc mineral original ore property is changeable, and symbiosis is close, explanation mutually, and particularly copper and lead minerals character are closely similar, and usually with fine grain teeth cloth symbiosis, separating difficulty is very large.
The application more widely method of the separated medicament of copper-lead has dichromate titration, cyanide process and heating method; Heating method complicated operation, is difficult to control, and application difficulty is large.Bichromate and cyanide all belong to deadly poisonous compound, very serious to ecological environmental pollution; And consumption is large, production cost is high.Therefore, need the separated inhibitor of copper-lead of development of new high-efficiency environment friendly badly.
At present, single inhibitor is difficult to meet the mineralogical property of current complexity, and combination medicament application is more and more extensive.Dissimilar inhibitor is used in combination, gives full play to their synergy to reach the object of efficient separation, strengthen the separating effect of object mineral, improve valuable mineral flotation recovery rate, increase the economic benefit of enterprise.Therefore, combination medicament is an important directions of the separated inhibitor of copper-lead of development of new non-toxic efficient, and the development of the plumbous zinc ore dressing of complex copper sulphide is significant.
Summary of the invention
The technical problem to be solved in the present invention is that the defect existing for the separated inhibitor of current copper-lead, has invented a kind of novel Flotation Separation of Cu-Pb inhibitor and suppressed vulcanized lead mineral, can significantly improve copper-lead separating effect, can solve the separated difficult problem of copper-lead.
Technical scheme of the present invention is:
A kind of Flotation Separation of Cu-Pb inhibitor, be called for short CXM, the glycerine water solution that the bodied ferric sulfate aqueous solution that is 5.0%-6.0% by mass concentration and mass concentration are 0.8%-1.2% mixes and forms, and the mass ratio of the wherein said bodied ferric sulfate aqueous solution and glycerine water solution is 1: 1～4.
Bodied ferric sulfate molecular formula: [Fe
2(OH) n (SO
4)
3-n/2]
mthe molecular formula of (wherein n < 2, m=f (n)) glycerine: C
3h
8o
3, structural formula is:
The mass concentration of the described bodied ferric sulfate aqueous solution is preferably 5.0%, and the mass concentration of glycerine water solution is preferably 1.0%.The mass ratio of the described bodied ferric sulfate aqueous solution and glycerine water solution is preferably 1: 1.5～and 3.
Flotation Separation of Cu-Pb of the present invention suppresses the using method of (CXM), is selected from one of following 2 kinds of methods:
The concrete steps of method a are:
(1) raw ore obtains Copper-lead mixed concentrate by copper-lead bulk flotation;
(2) in Copper-lead mixed concentrate, add the vulcanized sodium of 1000～1500 grams/ton and the active carbon of 200～300 grams/ton, stir 5～8 minutes; Add the CXM of 150～200 grams/ton, stir 3～6 minutes, add the Z-200 of 15～30 grams/ton
#, stir and within 3～6 minutes, carry out copper-lead separation and roughly select operation;
(3) roughly selecting concentrate carries out 2-3 selected operation and obtains copper concentrate; Selected operation for the first time adds the CXM of 80～150 grams/ton; Selected operation for the second time adds the CXM of 40～70 grams/ton; Selected operation for the third time adds the CXM of 0～20 gram/ton; Rougher tailings adds the Z-200 of 3～6 grams/ton
#for collecting agent carries out 2～3 times, scan operation, obtaining bottom land product is lead concentrate;
The concrete steps of method b are:
The diffeential floatation method that raw ore adopts one roughing triple cleaning to scan for twice is selected copper, and copper is roughly selected with 600～1000 grams of/ton of sodium sulfites, 600～1000 grams of/ton of zinc sulfate, 40～70 grams of/ton of Z-200
#for collecting agent, the CXM that the selected interpolation of copper is 100～160 grams/ton and 400～500 grams of/ton of zinc sulfate are as inhibitor; The CXM that selected two interpolation of copper is 60～100 grams/ton and 200～250 grams of/ton of zinc sulfate are as inhibitor, and copper selected three adds the CXM of 15～30 grams/ton, scans operation one and scans operation two and respectively add the Z-200 of 8～12 grams/ton
#;
In method a or b, CXM refers to the described Flotation Separation of Cu-Pb inhibitor of one of claim 1-3, and it is 5% aqueous solution that sodium sulfite, potassium bichromate, zinc sulfate, sodium carbonate and vulcanized sodium are all prepared mass concentration, and the preparation mass concentration of xanthate is 1% aqueous solution, Z-200
#for directly adding.
" gram/ton " of the present invention refers to the addition with respect to raw ore, and for example the CXM of 75 grams/ton, refers in one ton of raw ore and add CXM 75g.
The concrete steps that the described raw ore of method a step (1) obtains Copper-lead mixed concentrate by copper-lead bulk flotation are preferably: raw ore is milled to-180 orders to-220 orders and accounts for 70%-90%, then add the vulcanized sodium of 600～1000g/t sodium carbonate, 600～1000g/t zinc sulfate and 200～400g/t as inhibitor, the xanthate of 8～15g/t and the Z-200 of 20～35g/t
#as collecting agent, carry out copper-lead bulk flotation operation, obtain Copper-lead mixed concentrate.
Described in method a or b, in raw ore, the quality percentage composition of copper is preferably 0.25%～1.5%, and plumbous quality percentage composition is preferably 1.5%～5.0%, and the quality percentage composition of zinc is preferably 2.8%～7.0%.
Below the present invention will be further explained:
Know-why of the present invention is: first, bodied ferric sulfate surface ionization goes out a small amount of ferric ion can improve pulp potential, the lead salt PbX of the lyophobic dust collecting agent on vulcanized lead mineral surface in bulk concentrate under high potential
2can decompose, generate hydroaropic substance Pb (OH)
2and X
2, vulcanized lead mineral are suppressed; And the hydrophobic substance CuX on copper sulfide mineral surface
2still can stable existence under high potential, so copper sulfide mineral still keeps hydrophobicity under high potential.Secondly, glycerine and copper sulfide, lead minerals can be had an effect: it can with lead ion generation hydrogen bond action and the chemisorbed of galena surface ionization, thereby suppressed the flotation of vulcanized lead mineral; And only there is hydrogen bond action with the copper ion on copper sulfide mineral surface, when consumption is less, on almost not impact of the flotation of chalcopyrite.Finally, bodied ferric sulfate and glycerine are combined according to a certain percentage, can produce the synergy between medicament, the powder performance of bodied ferric sulfate and glycerine is all significantly improved, strengthened their selective inhibitories to lead minerals, combination medicament is on the almost not impact of the floatability of copper simultaneously.
Compared with prior art, advantage of the present invention is:
1), according to the synergy of medicament, coordinate inorganic inhibitor bodied ferric sulfate and organic inhibitor glycerine as the inhibitor of lead minerals.This inhibitor has good inhibitory action to vulcanized lead mineral, and copper sulfide mineral is not almost had to inhibitory action, reaches the object of copper-lead separation.
2) the separated inhibitor bichromate of traditional copper-lead or cyanide, cost is high, large usage quantity, and be hypertoxicity medicament, environmental pollution is serious, and cost for wastewater treatment is also high.
3) inhibitor of the present invention (CXM) is environmentally friendly medicament, and low price.When obtaining same copper-lead concentrate product, consumption is only bichromate 0.2-0.4 times, has greatly saved beneficiation cost.
4) adopt after this medicament and method, process raw ore cupric 0.25～1.50%, leaded 2.0～5.0% raw ore, can obtain copper concentrate copper recovery > 75.00%, copper grade > 22.00%, leaded < 5.00%.
Accompanying drawing explanation
Fig. 1 is the mineral processing circuit figure that the embodiment of the present invention 1 adopts;
Fig. 2 is the mineral processing circuit figure that the embodiment of the present invention 2 adopts;
Fig. 3 is the mineral processing circuit figure that the embodiment of the present invention 3 adopts.
The specific embodiment
Below by the specific embodiment, the present invention will be further explained, and unless otherwise indicated, percentage composition described in embodiment refers to quality percentage composition, and in enforcement, CXM represents Flotation Separation of Cu-Pb inhibitor of the present invention." gram/ton " described in embodiment refers to the addition with respect to raw ore, and for example the CXM of 75 grams/ton, refers in one ton of raw ore and add CXM75g.
Embodiment 1:
Adopt the present invention to reclaim copper mineral in the complex lead zinc ores of Jiangxi as raw ore, raw ore cupric 0.30～0.80%, leaded 2.00～4.50%, containing zinc 3.00～6.50%, original ore property is complicated, each valuable mineral disseminated grain size is inhomogeneous, part mineral are fine grain teeth cloth, and copper mineral and lead minerals symbiosis are complicated, and disseminated grain size is thin, lead minerals floatability is very good, and copper-lead mineral separating difficulty is very large.
(1) raw ore adopt bulk flotation more separated technique select copper-lead mineral; Raw ore is milled to-200 orders and accounts for 82.15%, then add the vulcanized sodium of 600 grams of/ton of sodium carbonate, 600 grams of/ton of zinc sulfate and 200g/t as inhibitor, the Z-200 of the xanthate of 10 grams/ton and 30 grams/ton
#as collecting agent, carry out copper-lead bulk flotation operation.
(2) Copper-lead mixed concentrate is carried out to copper-lead detached job: concrete copper-lead separating technology is shown in accompanying drawing 1, copper-lead separation is roughly selected and is added successively the vulcanized sodium of 1000 grams/ton and the active carbon of 250 grams/ton, stir 6 minutes, add again the CXM of 150 grams/ton, stir 3 minutes, then add the Z-200 of 15 grams/ton
#, stir 2 minutes; Selected one and selected two add respectively the CXM of 80 grams/ton and the CXM of 40 grams/ton, and mixing time is all 3 minutes; Selected three is blank selected; Scan operation and add 3 grams of/ton of Z-200
#, stir 1 minute.Wherein, the compound concentration of sodium sulfite, potassium bichromate, zinc sulfate, sodium carbonate and vulcanized sodium is the 5wt% aqueous solution, and the compound concentration of xanthate is the 1wt% aqueous solution, Z-200
#for directly adding.Wherein, the glycerine water solution that the bodied ferric sulfate aqueous solution that CXM is 5wt.% by concentration and concentration are 1wt.% is to mix at 1: 1.5 by weight.
The ore-dressing technique that the CXM of take is inhibitor and existingly press down comparative test result that plumbous inhibitor carries out copper-lead detached job to Copper-lead mixed concentrate in Table 1 with other, other condition is constant, changes inhibitor and consumption thereof.
Table 1 comparative test result (%)
As known from Table 1, take combination medicament CXM during as inhibitor: the copper concentrate that lead concentrate test obtains is best in quality, and Cu Concentrate Grade is the highest, and leaded minimum in copper concentrate, the rate of recovery of copper is also the highest; Lead concentrate cupric is minimum, and the plumbous rate of recovery is the highest, and plumbous grade is also higher.The index that its index obtains while being obviously better than take potassium bichromate or sodium sulfite as inhibitor.Illustrating that CXM has extraordinary inhibitory action to lead minerals, is the vulcanized lead mineral inhibitor of high-quality.
Embodiment 2:
The complicated copper/lead/zinc ore in Qinghai is as raw ore, and raw ore cupric 0.60～1.00% is leaded 2.80～5.00%, containing zinc 4.00～6.80%.In raw ore, between copper/lead/zinc ore thing, inlay and be related to complexity, disseminated grain size is extremely tiny.First adopt copper-lead bulk flotation to obtain Copper-lead mixed concentrate (with embodiment 1), and then carry out copper-lead detached job.
Concrete copper-lead separating technology is shown in accompanying drawing 2, and copper-lead detached job adopts one roughing, and twice selected, once purging selection operation.For the Copper-lead mixed concentrate obtaining, first add 300 grams of/ton of active carbons and 1200 grams of/ton of vulcanized sodium, stir 6 minutes, then add the CXM of 150 grams/ton, stir 5 minutes, then add the Z-200 of 15 grams/ton
#, stir and carry out copper-lead separation after 2 minutes and roughly select operation; Roughly select and carry out twice selected operation after operation again and obtain copper concentrate product, twice selected operation adds 90 grams of/ton of CXM and 45 grams of/ton of CXM successively, stirs 3 minutes; Scan operation and add 4 grams of/ton of Z-200
#, stir 2 minutes.The glycerine water solution that the bodied ferric sulfate aqueous solution that CXM is 5wt.% by concentration and concentration are 1wt.% is to mix at 1: 2.5 by weight, and other medicament compound concentrations are identical with embodiment 1.
The result of the test that the ore-dressing technique that the CXM of take is inhibitor and the potassium bichromate of take carry out copper-lead detached job to Copper-lead mixed concentrate as inhibitor is in Table 2, and other condition is constant, changes inhibitor and consumption thereof.
Table 2 comparative test result (%)
As seen from the above table, the CXM of take is leaded only 4.72% as inhibitor separating copper lead minerals can obtain, and copper grade reaches 25.97% high-quality copper concentrate, take potassium bichromate during as inhibitor, copper concentrate is leaded 7.94%, and thus, CXM will obviously be better than potassium bichromate to the separating effect of Copper-lead mixed concentrate.
Embodiment 3:
Gansu Complicated Copper lead zinc sulphur ore is as raw ore, and raw ore cupric 0.36～0.59% is leaded 1.82～3.21%, containing zinc 2.00～4.50%.The main copper sulfide mineral of raw ore is tetrahedrite, secondly for the tetrahedrite behind chalcopyrite ，Cheng ore deposit again by pyrite, mispickel, magnetic iron ore, zincblende, the galena of many phases time cut apart, parcel, corrode, make it very complicated on Structural Tectonics.Chalcopyrite is interrupted raindrop shape and is distributed in gangue, and character is comparatively simple.
Raw ore adopts one to roughly select three selected two controling differential flotation process for copper of scanning and select copper, and concrete copper-lead separating technology is shown in accompanying drawing 3, roughly selects with 1000 grams of/ton of sodium sulfites, 1000 grams of/ton of zinc sulfate, 60 grams of/ton of Z-200
#for collecting agent, selected 150 grams of/ton of CXM of interpolation and 400 grams of/ton of zinc sulfate are as inhibitor; Selected two 75 grams of/ton of CXM of interpolation and 200 grams of/ton of zinc sulfate are as inhibitor, and selected three add 20 grams of/ton of CXM, scan operation one and scan operation two and respectively add the Z-200 of 10 grams/ton
#.On the basis of above-mentioned technique, the CXM of selected employing is replaced with to potassium bichromate, the consumption of each operation is 3 times of CXM consumption.The glycerine water solution that the bodied ferric sulfate aqueous solution that CXM is 5wt.% by concentration and concentration are 1wt.% is to mix at 1: 3 by weight.
Table 3 is to take respectively the comparison of the copper concentrate quality that CXM and potassium bichromate obtain during as inhibitor, and other condition is constant, changes inhibitor and consumption thereof.
Table 3 comparative test result (%)
Can find out as shown in Table 3, the copper concentrate quality when copper concentrate quality obtaining during inhibitor that the CXM of take is selected lead is significantly better than take potassium bichromate as inhibitor, copper concentrate lead tolerance is low, and copper recovery is high.
Claims (3)
1. the using method of a Flotation Separation of Cu-Pb inhibitor, the glycerine water solution that the bodied ferric sulfate aqueous solution that Flotation Separation of Cu-Pb inhibitor is 5.0%-6.0% by mass concentration and mass concentration are 0.8%-1.2% mixes and forms, and the mass ratio of the wherein said bodied ferric sulfate aqueous solution and glycerine water solution is 1:1 ~ 4; It is characterized in that, be specifically selected from one of following 2 kinds of methods:
The concrete steps of method a are:
(1) raw ore obtains Copper-lead mixed concentrate by copper-lead bulk flotation;
(2) in Copper-lead mixed concentrate, add the vulcanized sodium of 1000～1500 grams/ton and the active carbon of 200～300 grams/ton, stir 5～8 minutes; Add the Flotation Separation of Cu-Pb inhibitor of 150～200 grams/ton, stir 3～6 minutes, add the Z-200 of 15～30 grams/ton
#, stir and within 3～6 minutes, carry out copper-lead separation and roughly select operation;
(3) roughly selecting concentrate carries out 2-3 selected operation and obtains copper concentrate; Selected operation for the first time adds the Flotation Separation of Cu-Pb inhibitor of 80～150 grams/ton; Selected operation for the second time adds the Flotation Separation of Cu-Pb inhibitor of 40～70 grams/ton; Selected operation for the third time adds the Flotation Separation of Cu-Pb inhibitor of 0～20 gram/ton; Rougher tailings adds the Z-200 of 3～6 grams/ton
#for collecting agent carries out 2～3 times, scan operation, obtaining bottom land product is lead concentrate;
The concrete steps of method b are:
The diffeential floatation method that raw ore adopts one roughing triple cleaning to scan for twice is selected copper, and copper is roughly selected with 600～1000 grams of/ton of sodium sulfites, 600～1000 grams of/ton of zinc sulfate, 40～70 grams of/ton of Z-200
#for collecting agent, the Flotation Separation of Cu-Pb inhibitor that the selected interpolation of copper is 100～160 grams/ton and 400～500 grams of/ton of zinc sulfate are as inhibitor; The Flotation Separation of Cu-Pb inhibitor that selected two interpolation of copper is 60～100 grams/ton and 200～250 grams of/ton of zinc sulfate are as inhibitor, copper selected three adds the Flotation Separation of Cu-Pb inhibitor of 15～30 grams/ton, scans operation one and scans operation two and respectively add the Z-200 of 8～12 grams/ton
#.
2. the using method of Flotation Separation of Cu-Pb inhibitor described in claim 1, it is characterized in that, the concrete steps that the described raw ore of method a step (1) obtains Copper-lead mixed concentrate by copper-lead bulk flotation are: raw ore is milled to-180 orders to-220 orders and accounts for 70%-90%, then add the vulcanized sodium of 600～1000g/t Tan Suan Na ﹑ 600～1000g/t zinc sulfate and 200～400g/t as inhibitor, the xanthate of 8～15g/t and the Z-200 of 20～35g/t
#as collecting agent, carry out copper-lead bulk flotation operation, obtain Copper-lead mixed concentrate.
3. the using method of Flotation Separation of Cu-Pb inhibitor described in claim 1, it is characterized in that, described in method a or b, in raw ore, the quality percentage composition of copper is 0.25%～1.5%, and plumbous quality percentage composition is 1.5%～5.0%, and the quality percentage composition of zinc is 2.8%～7.0%.
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