CN101549322A - Process of using sulphur lead-zinc containing tailings to prepare sulphur iron ore concentrate - Google Patents
Process of using sulphur lead-zinc containing tailings to prepare sulphur iron ore concentrate Download PDFInfo
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- CN101549322A CN101549322A CNA2009100944534A CN200910094453A CN101549322A CN 101549322 A CN101549322 A CN 101549322A CN A2009100944534 A CNA2009100944534 A CN A2009100944534A CN 200910094453 A CN200910094453 A CN 200910094453A CN 101549322 A CN101549322 A CN 101549322A
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- 239000012141 concentrate Substances 0.000 title claims abstract description 51
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 18
- BFUPQMKQJRHLRA-UHFFFAOYSA-N [Pb]=S.[Zn] Chemical compound [Pb]=S.[Zn] BFUPQMKQJRHLRA-UHFFFAOYSA-N 0.000 title claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 130
- 229910052742 iron Inorganic materials 0.000 claims abstract description 65
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 57
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000005864 Sulphur Substances 0.000 claims abstract description 19
- 238000011084 recovery Methods 0.000 claims abstract description 17
- 239000011593 sulfur Substances 0.000 claims description 38
- 229910052717 sulfur Inorganic materials 0.000 claims description 38
- 238000005188 flotation Methods 0.000 claims description 20
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 13
- 239000011707 mineral Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 229910020218 Pb—Zn Inorganic materials 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 8
- 238000003801 milling Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 claims description 6
- 230000005484 gravity Effects 0.000 claims description 6
- 239000004088 foaming agent Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000007885 magnetic separation Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 230000008719 thickening Effects 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 3
- 208000032005 Spinocerebellar ataxia with axonal neuropathy type 2 Diseases 0.000 claims description 2
- 208000033361 autosomal recessive with axonal neuropathy 2 spinocerebellar ataxia Diseases 0.000 claims description 2
- 238000010494 dissociation reaction Methods 0.000 claims description 2
- 230000005593 dissociations Effects 0.000 claims description 2
- 239000006148 magnetic separator Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 238000004513 sizing Methods 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 abstract description 6
- 238000007667 floating Methods 0.000 abstract description 4
- 235000011149 sulphuric acid Nutrition 0.000 abstract 2
- 239000001117 sulphuric acid Substances 0.000 abstract 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 229910052725 zinc Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 6
- 229910052683 pyrite Inorganic materials 0.000 description 6
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 6
- 239000011028 pyrite Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000003818 cinder Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910001608 iron mineral Inorganic materials 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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Abstract
The objective of the invention is to provide a process of using sulphur lead-zinc containing tailings to prepare sulphur iron ore concentrate, using magnet-floating combination process or magnet-gravity-floating combination process to produce sulphur iron ore concentrate containing more than 90% sulphur and iron, using the sulphur iron ore concentrate to produce sulphuric acid, getting 98% sulphuric acid of national standard while getting iron ore concentrate power containing more than 60% iron, and sulphur in the tailings is reduced to less than 2%, recovery rate of sulphur iron in ore concentrate is more than 86%. The invention make comprehensive recovery and use of sulphur iron in the lead-zinc tailings.
Description
One, technical field
The present invention relates to a kind of method with sulphur lead-zinc containing tailings to prepare sulphur iron ore concentrate, belongs to technical field of mineral processing.
Two, background technology
China is the abundant relatively country of plumbous zinc resource, wherein most of mine association pyrite, magnetic iron ore and valuable metals such as magnetic iron ore or bloodstone.Because sulphur, iron ore are lower with respect to the value of plumbous zinc metal, so comprehensive reutilization is not carried out to sulphur, the iron ore of association in present a lot of plumbous zinc ore dressing plant.When the bulk flotation flow process is adopted in the plumbous zinc of part ore dressing plant, also only reclaim as by-product from stage or sulphur, zinc separation phase output sulphur concentrate leaded, zinc at plumbous, sulphur content, and the sulphur and the iron rule that enter in the mine tailing do not have to recycle substantially, directly are stored in the mine tailing.The annual lead-zinc ore raw ore of handling in the ore dressing plant in the whole nation reaches tens million of tons, the Pb-Zn tailings ore of output sulfur-bearing iron also has tens million of tons simultaneously, because sulphur iron resource does not wherein obtain effective comprehensive reutilization, not only cause the bigger wasting of resources, and because the oxidation of sulphur forms acid water in the mine tailing storehouse, tailing water effluxes and also causes certain environmental pollution in the process.
Sulphur iron ore (pyrite, magnetic iron ore) has close floatability with lead-zinc sulfide ore stone, in the ore dressing practice, no matter be diffeential floatation or bulk flotation, in the process of flotation of lead zinc, all to suppress sulphur iron ore, good especially sulphur iron ore enters into lead and zinc concentrate to have only the sub-fraction floatability, to enter into flotation tailing after most of sulphur iron ore is suppressed, and make sulphur iron ore in mine tailing, obtain enrichment.According to the height difference of raw ore sulfur-bearing grade, the sulfur-bearing grade in the Pb-Zn tailings does not wait from 4%～30%, and ferrous grade and sulfur-bearing grade are approaching.
Troilite is the raw material of preparation sulfuric acid, generally requires the sulfur-bearing grade to reach 30%～35% troilite mark ore deposit and gets final product.Plumbous, sulphur content from or sulphur, the zinc sulphur concentrate that separates output can be used as the relieving haperacidity raw material and be sold to sulfuric acid plant and produce sulfuric acid, also have the part ore dressing plant to carry out simple flotation or gravity treatment to containing pyrite tailing, the sulphur concentrate of output sulfur-bearing 30% uses to sulfuric acid plant as production marketing.Because the troilite mineral purity in troilite mark ore deposit only has about 70%, wherein still contain gangue minerals such as more calcium, magnesium, silicon, aluminium, behind the preparation sulfuric acid with the pyrite cinder of output iron content 40%～50%, the requirement that this burning slag iron content does not reach iron-smelting raw material, usually only can be as the additive of cement, the resource value of iron fails to find full expression.
Guangdong Province's mineral products Applied Research Laboratory was once carried out the research that gravity separation method reclaims sulphur in the Pb-Zn tailings, with spiral chute the Pb-Zn tailings of sulfur-bearing 27%～30% is carried out one roughing and once purging selection, obtained the sulphur concentrate of sulfur-bearing 44%～47%, sulfur recovery rate 80%～82%.Float test is not carried out in this research, does not relate to the subsequent treatment process of sulphur concentrate yet.
Yiming Xing Mine Metallargical Equipment and Kunming University of Science and Technology have invented the production method of cinder of sulfur iron ore in high iron and low sulfur type and have obtained the invention patent mandate (patent No.: ZL200410079520.4) in 2004, the comprehensive utilization of low-grade single troilite raw ore or grade magnetic iron ore raw ore of the middle end did not relate to the method for preparing high-quality sulphur iron ore concentrate with the sulfur-bearing Pb-Zn tailings during this patent was mainly concerned with.
Three, summary of the invention
The object of the present invention is to provide a kind of method with sulphur lead-zinc containing tailings to prepare sulphur iron ore concentrate, adopt magnetic-floating process integration or magnetic-weight-floating process integration, producing sulfur-bearing iron adds up to grade greater than 90% sulphur iron ore concentrate, when preparing sulfuric acid with this concentrate, but the output iron content reaches sulphur in the Pb-Zn tailings, the comprehensive purpose that reclaims and utilize of iron resource greater than 60% fine iron breeze.
The present invention realizes by following technical scheme.
(1), earlier mine tailing is fed stir in the agitator and size mixing, pulp density is 20～50%, removes+coarse fraction of 0.15mm with sifted, obtains the undersize of granularity≤0.15mm.If mineral surfaces has oxidative phenomena, then mine tailing is fed ore grinding in the ore mill, the ore grinding time is 0.5 minute～5 minutes kinds, obtains degree of dissociation of mineral monomer and reaches ore milling product more than 80%;
(2), if undersize or ore milling product contain magnetic iron ore and the magnetic iron ore approaching with magnetic iron ore magnetic, then reclaim wherein magnetic iron ore and magnetic iron ore in advance with the low intensity magnetic separation machine, obtain magnetic concentrate and magnetic tailing;
(3), if undersize, ore milling product or magnetic tailing contain mud 〉=30%, then throw tail as the gravitational separation equipment desliming with spiral chute, obtain the gravity treatment rough concentrate;
(4), undersize, ore milling product, gravity treatment rough concentrate and magnetic tailing are carried out flotation, size mixing with mixing drum, pulp density is 20～40%, and adding sulfuric acid 2000～4000g/t adjustment slurry pH is 5～6, sulphur iron ore is activated, adding butyl xanthate 100～400g/t is collecting agent, and sulphur iron ore is carried out collecting, adds terpenic oil or 730 foaming agents, 50～100g/t as foaming agent, roughly select 1～2 time, scan 2～3 times, selected 3～5 times, the concentrate and tailings that obtains.The chats of each section operation turns back to an operation in proper order.Flotation can be carried out in agitation impeller flotator, also can adopt the column-type floatation machine to carry out flotation;
(5), the concentrate that obtains of flotation can merge with magnetic concentrate, send sulfuric acid plant to prepare sulfuric acid behind thickening filtration, obtains the fine iron breeze of GB 98 sulfuric acid and iron content 〉=60%.
Adopt the present invention to handle the sulfur-bearing Pb-Zn tailings, can obtain the sulphur iron ore concentrate of sulphur iron grade 〉=90%, the sulfur-bearing in the mine tailing is reduced in 2%, the rate of recovery of sulphur iron in concentrate reaches more than 86%.
Advantage of the present invention and good effect
(1), the present invention carries out further joint disposal to the sulfur-bearing Pb-Zn tailings, prepare sulfur-bearing, iron mineral purity reaches the high-quality sulphur iron ore concentrate more than 90%, the sulfur-bearing that selects mine tailing is again reduced in 2%, the rate of recovery of sulphur iron in concentrate reaches more than 86%, sulphur in the mine tailing, iron resource have obtained comprehensive recovery, when preparing sulfuric acid with this high-quality sulphur iron ore concentrate, but the coproduction iron content is fully utilized the sulphur iron resource in the Pb-Zn tailings greater than 60% fine iron breeze fully.
(2), the mine tailing after the present invention handles, its residual sulfur mainly exists with sulphate form, character is relatively stable, be not easy oxidation, mine tailing wastewater significantly reduces the influence of environment, not only can create remarkable economic efficiency, and meet recycling economy and sustainable development objective requirement comprehensive utilization of resources.
Four, description of drawings:
Fig. 1 is a process chart of the present invention.
Five, the specific embodiment
Mine tailing sulfur-bearing 7.50% behind embodiment 1, certain plumbous zinc ore dressing plant flotation of lead zinc, iron content 10.82%, containing sulfur mineral mainly is pyrite and magnetic iron ore, iron-bearing mineral mainly is pyrite, magnetic iron ore and a spot of magnetic iron ore.Sift out+the 0.15mm grade with screening machine, undersize is used the drum magnetic separator preliminary election after agitator is sized mixing, and obtains the magnetic separation sulphur iron ore concentrate of iron content 50.30%, sulfur-bearing 41.50%, iron recovery 42.16%, sulfur recovery rate 35.68%.Magnetic tailing contains mud 38%, throw tail with the spiral chute desliming, rough concentrate is sized mixing with agitator and is carried out flotation, add 2500g/t sulfuric acid and adjust pH values of pulp=5.5, adding butyl xanthate 150g/t is collecting agent, and adding terpenic oil 60g/t is foaming agent, through one roughing, secondary is scanned with four times selected, obtained the high-sulfur iron ore concentrate of sulfur-bearing 46.50%, iron content 44.60%, sulfur recovery rate 53.68%, iron recovery 44.60%, the true tailings sulfur-bearing after the flotation reduces to 0.94%.After magnetic concentrate and flotation concentrate merged, obtained the sulphur iron ore concentrate of sulfur-bearing 44.50%, iron content 47.88%, the comprehensive recovery of sulphur and iron has reached 89.36% and 86.76% respectively.The sulphur iron ore concentrate that merges prepares sulfuric acid through behind the thickening filtration as raw material supplying sulfuric acid plant, and when obtaining GB 98 sulfuric acid, the fine iron breeze of output iron content 〉=62% has been obtained satisfied comprehensive reutilization effect.
The average sulfur-bearing 12.80% of mine tailing behind embodiment 2, certain plumbous zinc ore dressing plant flotation of lead zinc, iron content 11.18%, containing sulfur mineral mainly is troilite, iron-bearing mineral also is a troilite, magnetic iron ore and total amount＜1% of magnetic iron ore.Because the time of storing up is long, the troilite mineral surfaces has the oxidation imagination.Ball mill with φ 2100 * 2700 carries out ore grinding to mine tailing, product clay content behind the ore grinding is 26%, carry out flotation after sizing mixing with agitator, add 3200g/t sulfuric acid and adjust pH values of pulp=5.5, add butyl xanthate 200g/t, add terpenic oil 80g/t, through secondary roughly select, scan for three times with five times selected, sulfur-bearing 48.62%, iron content 42.47%, sulphur iron mixing grade 90.89% have been obtained, the sulphur iron ore concentrate of the rate of recovery 88.87% of sulphur and iron, the true tailings sulfur-bearing after the flotation reduces to 1.86%.The sulphur iron ore concentrate prepares sulfuric acid through behind the thickening filtration as raw material supplying sulfuric acid plant, and when obtaining GB 98 sulfuric acid, the fine iron breeze of output iron content 〉=61% has been obtained satisfied comprehensive reutilization effect.
Claims (3)
1, a kind of method with sulphur lead-zinc containing tailings to prepare sulphur iron ore concentrate, it is characterized in that: it is pressed following technical scheme and realizes,
(1), earlier mine tailing is fed stir in the agitator and size mixing, pulp density is 20～50%, removes+coarse fraction of 0.15mm with sifted, obtains the undersize of granularity≤0.15mm; Mineral surfaces is had the mine tailing ore grinding of oxidative phenomena, and the ore grinding time is 0.5 minute～5 minutes kinds, obtains degree of dissociation of mineral monomer and reaches ore milling product more than 80%;
(2), undersize or ore milling product contained magnetic iron ore and magnetic iron ore reclaim wherein magnetic iron ore and magnetic iron ore in advance with the low intensity magnetic separation machine, obtain magnetic concentrate and magnetic tailing;
(3), with clay content 〉=30% in undersize, ore milling product or the magnetic tailing, throw tail with spiral chute as the gravitational separation equipment desliming, obtain the gravity treatment rough concentrate;
(4), undersize, ore milling product, gravity treatment rough concentrate and magnetic tailing are carried out flotation, size mixing with mixing drum, pulp density is 20～40%, and adding sulfuric acid 2000～4000g/t adjustment slurry pH is 5～6, sulphur iron ore is activated, adding butyl xanthate 100～400g/t is collecting agent, and sulphur iron ore is carried out collecting, adds terpenic oil or 730 foaming agents, 50～100g/t, roughly select 1～2 time, scan 2～3 times, selected 3～5 times, obtain concentrate and tailings;
(5), the concentrate that obtains of flotation and magnetic concentrate merge, and send sulfuric acid plant to prepare sulfuric acid behind thickening filtration, obtains the fine iron breeze of GB 98 sulfuric acid and iron content 〉=60%.
2, method with sulphur lead-zinc containing tailings to prepare sulphur iron ore concentrate according to claim 1, it is characterized in that: raw material Pb-Zn tailings sulfur-bearing 7.50%, iron content 10.82%, through screening, undersize is sized mixing with agitator, use the drum magnetic separator preliminary election again, obtain iron content 50.30%, sulfur-bearing 41.50%, iron recovery 42.16%, the magnetic separation sulphur iron ore concentrate of sulfur recovery rate 35.68%, magnetic tailing contains mud 38%, throw tail with the spiral chute desliming, rough concentrate is sized mixing with agitator and is carried out flotation, adds 2500g/t sulfuric acid and adjusts pH values of pulp=5.5, adding butyl xanthate 150g/t is collecting agent, adding terpenic oil 60g/t is foaming agent, through one roughing, secondary scan with four times selected, obtained sulfur-bearing 46.50%, iron content 44.60%, sulfur recovery rate 53.68%, the sulphur iron ore concentrate of iron recovery 44.60%.
3, method with sulphur lead-zinc containing tailings to prepare sulphur iron ore concentrate according to claim 1, it is characterized in that: raw material Pb-Zn tailings sulfur-bearing 12.80%, iron content 11.18%, there is oxide layer on the mine tailing surface, use the ball mill ore grinding of φ 2100 * 2700 earlier, product clay content behind the ore grinding is 26%, carry out flotation after sizing mixing with agitator, add 3200g/t sulfuric acid and adjust pH values of pulp=5.5, add butyl xanthate 200g/t, add terpenic oil 80g/t, roughly select through secondary, scan for three times with five times selected, obtained sulfur-bearing 48.62%, iron content 42.47%, sulphur iron mixes grade 90.89%, the sulphur iron ore concentrate of the rate of recovery 88.87% of sulphur and iron.
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