CN107555482B - A kind of method and additive preparing Manganese Ferrite spinel using high lead high phosphorus promoter manganese - Google Patents
A kind of method and additive preparing Manganese Ferrite spinel using high lead high phosphorus promoter manganese Download PDFInfo
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- CN107555482B CN107555482B CN201710811984.5A CN201710811984A CN107555482B CN 107555482 B CN107555482 B CN 107555482B CN 201710811984 A CN201710811984 A CN 201710811984A CN 107555482 B CN107555482 B CN 107555482B
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- manganese
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- phosphorus
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- dephosphorization
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- 239000011572 manganese Substances 0.000 title claims abstract description 121
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 112
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 80
- 239000011574 phosphorus Substances 0.000 title claims abstract description 73
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000000654 additive Substances 0.000 title claims abstract description 35
- 230000000996 additive effect Effects 0.000 title claims abstract description 35
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 29
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 28
- 239000011029 spinel Substances 0.000 title claims abstract description 28
- 238000007885 magnetic separation Methods 0.000 claims abstract description 19
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 19
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 150000002506 iron compounds Chemical class 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000005054 agglomeration Methods 0.000 claims abstract description 3
- 230000002776 aggregation Effects 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 67
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 34
- 229910052742 iron Inorganic materials 0.000 claims description 30
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000292 calcium oxide Substances 0.000 claims description 17
- 235000012255 calcium oxide Nutrition 0.000 claims description 17
- 229910000616 Ferromanganese Inorganic materials 0.000 claims description 12
- 238000005728 strengthening Methods 0.000 claims description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 229910052681 coesite Inorganic materials 0.000 claims description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 9
- 229940039790 sodium oxalate Drugs 0.000 claims description 9
- 229910052682 stishovite Inorganic materials 0.000 claims description 9
- 229910052905 tridymite Inorganic materials 0.000 claims description 9
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims description 8
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 7
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 235000019738 Limestone Nutrition 0.000 claims description 3
- 239000006028 limestone Substances 0.000 claims description 3
- -1 Boratex Chemical compound 0.000 claims description 2
- OJGLOFBKLCHJFP-UHFFFAOYSA-L disodium;2-oxopropanedioate Chemical compound [Na+].[Na+].[O-]C(=O)C(=O)C([O-])=O OJGLOFBKLCHJFP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052598 goethite Inorganic materials 0.000 claims description 2
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 claims description 2
- 229910000464 lead oxide Inorganic materials 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 235000002908 manganese Nutrition 0.000 description 78
- 239000011133 lead Substances 0.000 description 73
- 239000000463 material Substances 0.000 description 19
- 239000000203 mixture Substances 0.000 description 16
- 229910052745 lead Inorganic materials 0.000 description 13
- 239000004615 ingredient Substances 0.000 description 12
- 229910052500 inorganic mineral Inorganic materials 0.000 description 12
- 235000010755 mineral Nutrition 0.000 description 12
- 239000011707 mineral Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- 239000000440 bentonite Substances 0.000 description 6
- 229910000278 bentonite Inorganic materials 0.000 description 6
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000005453 pelletization Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910001655 manganese mineral Inorganic materials 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001608 iron mineral Inorganic materials 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910021538 borax Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013070 direct material Substances 0.000 description 2
- 229910001691 hercynite Inorganic materials 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004484 Briquette Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000406668 Loxodonta cyclotis Species 0.000 description 1
- 235000003283 Pachira macrocarpa Nutrition 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 241001083492 Trapa Species 0.000 description 1
- 235000014364 Trapa natans Nutrition 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052585 phosphate mineral Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 235000009165 saligot Nutrition 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Magnetic Ceramics (AREA)
Abstract
The invention discloses a kind of methods and additive that Manganese Ferrite spinel is prepared using high lead high phosphorus promoter manganese；Additive is made of iron compound, calc-flux and sodium salt；Using the high lead high phosphorus promoter manganese dephosphorization of reinforced by additive take off the lead method for preparing Manganese Ferrite spinel be will be after high lead high phosphorus promoter manganese fine grinding and additive mixing agglomeration, drying, roasting, it roasts block to separate through ore grinding, magnetic separation, obtains Manganese Ferrite spinel and the tailings rich in lead phosphorus；This method can be with the middle harmful element lead and phosphorus of the high lead high phosphorus promoter manganese of efficient removal, and prepares Manganese Ferrite spinel simultaneously, and gained jakobsite purity is high, magnetic property are good after magnetic separation；And this method raw material sources extensively, it is simple process, at low cost, it is easy to accomplish industrialized production.
Description
Technical field
The present invention relates to a kind of additive for taking off lead dephosphorization for strengthening high lead high phosphorus promoter manganese, in particular to one kind passes through
Addition is roasted by the additive that iron compound, calc-flux and sodium salt form to strengthen high lead high phosphorus promoter manganese, is roasted by regulation
Burning-magnetic separation process realizes method that de- lead dephosphorization obtains jakobsite material, belongs to mineral processing, metallurgical engineering and material
Preparation field.
Background technique
Manganese is a kind of important strategic resource, and 90% manganese disappears as the deoxidier and desulfurizing agent and alloying element of molten steel
It consumes in steel industry, 10% is used for other relevant industries.It is 64351.7 ten thousand t, reserves that China's manganese ore, which adds up proved reserves,
592040000 t are mainly distributed on the provinces and regions such as Guangxi, Hunan, Guizhou, Sichuan, Liaoning, Yunnan, Zhan Quanguo manganese resource gross reserves
90%.
Currently, the especially development of steel industry, the demand of manganese ore is got in market with economy and industrial expansion
Come bigger.The notch between the consumption and Ore Yield of Chinese manganese ore increases year by year as a result, and China relies on import within 2014
Manganese ore amount be up to 6,470,000 t.The main reason for leading to this situation is that China's manganese ore grade is low, the high-quality rich manganese ore of high-grade
Resource is almost without the manganese ore 100% for producing medium-low carbon ferromanganese depends on import.Resource it is poor, miscellaneous, thin the features such as constrain
The efficient utilization of manganese ore.The average grade of China's manganese ore generally contains higher Si, Fe, P, Pb, wherein P 20% or so
The exceeded manganese ore of content accounts for 49.6%.In addition, ferrimanganic polymetallic ore resource often altogether, associated silver, lead, zinc, cobalt etc., manganese average grade
Only 15%, reserves account for 19%.
Low-grade iron ore could be used for Mn series alloy smelting after must carrying out ore dressing.The ore dressing of manganese ore has gravity treatment, Qiang Ci
The techniques such as choosing, again-magnetic separation, strong magnetic-flotation can remove some gangue minerals by ore dressing, improve manganese grade.But China's manganese
Ore structures are complicated, and disseminated grain size is thin, and valuable mineral is combined closely with gangue, selects smelting difficulty larger, for iron, manganese mineral and has
The evil simple Ferromanganese Ore of the embedding cloth of element, the separation of ferrous manganese ore object and gangue may be implemented using conventional beneficiation method.But by
The close symbiosis of ferrimanganic in China's ferrimanganic ore resources, disseminated grain size is thin, and lead, phosphorus etc. smelt harmful element mostly with lattice substitution, class
Matter with elephant form preservation in iron, manganese mineral, be only having for difficult to realize manganese iron and harmful element by routine ore-dressing technique
Effect separation.Although Mn-rich slag method can effectively remove the harmful elements such as lead, phosphorus, Mn-rich slag method smelting temperature is high, needs to disappear
A large amount of fuel and reducing agent are consumed, a large amount of solid, gas pollutant is generated.
Manganese anode slime is also the manganese resource of a kind of high lead-type.In electrolytic manganese production process, oxygen is precipitated in anode, and have
A small amount of earth of positive pole deposition.This earth of positive pole is dark brown color substance, is a small amount of Mn in electrolytic process2+In the MnO that anode discharge generates2
The product deposited on anode plate.The earth of positive pole that 1 ton of electrolytic manganese of every production can generate the high rate containing manganese is 0.05~0.08 ton, in recent years
To come, China's electrolytic manganese metal yield maintains 1,200,000 tons or so, and it is therefore, annual to generate electrolysis anode sludge 6~9.6 ten thousand ton or so,
Cumulant has reached 920,000 tons or more.These earth of positive pole are because of its complicated composition, it is difficult to be used, generally as dangerous debris dump
It deposits, steel-making additive or undersell, is not preferably developed and comprehensively utilized, not only the wasting of resources, but also handle not
When easily causing considerable degree of environmental pollution.
In addition, ferrimanganic base spinel type ferrite purposes is very wide, wide in variety, quantity is big, a kind of high ferrite of the output value
Material.Soft magnetic materials is mainly used as various inductance elements, such as filter magnetic core, magnetic core of transformer, radio magnetic core and tape
The critical material of recording and video recording head etc. and magnetic recording element.Hard magnetic material is mainly used for the phonographic recorder in telecommunications devices,
Sound pick-up, loudspeaker, the magnetic core etc. of various instrument.
The method for preparing such material at present is to use to analyze pure or high-purity mineral dust using high temperature solid phase synthesis
Mode through multistage roasting ore grinding directlys adopt low-grade manganese ore and prepares jakobsite material and be rarely reported to prepare.It passes
System solid reaction process prepares jakobsite material as raw material to analyze pure, ultrahigh quality mineral.But preparation analysis is pure and mild
Process flow that the separating-purifying of mineral needs to grow very much, a large amount of chemical reagent of consumption, lead at high cost, low efficiency.
Summary of the invention
Hardly possible is separated with manganese mineral for harmful elements such as lead, phosphorus in high lead high phosphorus promoter manganese ore dressing process in the prior art
Problem, the purpose of the invention is to provide a kind of for strengthening the additive of high lead high phosphorus promoter manganese roasting, which can
To regulate and control the generation of iron and manganese oxides and the migration of objectionable impurities elements, realizes that high lead high phosphorus promoter manganese dephosphorization takes off lead, obtain height
Quality Manganese Ferrite spinel.
Another object of the present invention is to be to provide one kind using high lead high phosphorus promoter manganese as direct material, by efficiently taking off
Phosphorus takes off the method that lead obtains high-quality Manganese Ferrite spinel simultaneously.
In order to achieve the above technical purposes, lead dephosphorization is taken off for strengthening high lead high phosphorus promoter manganese the present invention provides a kind of
Additive, the additive is by following content of component: 60~80 parts of iron compound；15~30 parts of calc-flux；Sodium salt 5~10
Part.
Of the invention takes off the additive of lead dephosphorization mainly by iron content, calcic and containing sodium for strengthening high lead high phosphorus promoter manganese
Material composition, iron compound mainly control regulation and Mn/Fe mass ratio in the sinter mixture of high lead high phosphorus promoter manganese, to promote
The generation of manganese iron compound oxide prevents gangue mineral from entering in manganese iron compound oxide in roasting process, and can regulate and control
The magnetism of manganese iron compound oxide is conducive to subsequent magnetic separation separation.And calcareous solvent and sodium salt mainly adjust sintering system
In (CaO+Na2O)/SiO2Mass ratio, thus adjust roasting agglomerate in amount of liquid phase size and partial liquid phase it is interface characteristics
Matter, and then regulate and control the growth of manganese iron compound oxide and the migration of impurity element, harmful element can be migrated from iron mineral to arteries and veins
In stone ore object, ferro manganese composite oxides are separated for roasting agglomerate mill ore magnetic selection and P elements provide mineralogy condition.Therefore, originally
The additive of invention can strengthen the de- lead dephosphorization of high lead high phosphorus promoter manganese, promote the generation of Manganese Ferrite spinel.
Preferred scheme, the iron compound include Fe2O3、Fe3O4, magnetic iron ore, bloodstone, goethite, limonite, water chestnut
At least one of iron ore, high-phosphorus iron ore, iron content secondary resource.Wherein, Fe2O3、Fe3O4Selected from commercially available analytical reagents.Iron content
Substance is not limited to analyze pure Fe2O3、Fe3O4Deng iron-bearing mineral and the also suitable additive component requirement of iron content secondary resource.
Preferred scheme, the calc-flux are quick lime and/or lime stone.
Preferred scheme, the sodium salt include at least one of sodium carbonate, sodium sulphate, Boratex, sodium oxalate.
Preferred scheme, the sodium salt include at least sodium oxalate.
Preferred scheme, the mass percentage of the sodium salt mesoxalic acid sodium are 50%~90%.
The present invention also provides a kind of sides for strengthening the de- lead dephosphorization of high lead high phosphorus promoter manganese and preparing Manganese Ferrite spinel
Method, this method be by after high lead high phosphorus promoter manganese fine grinding with the additive mixing agglomeration；The raw block of gained after drying, is placed in
It in air atmosphere, is roasted at a temperature of 1200~1300 DEG C, roasting block is by ore grinding, magnetic separation separation to get Manganese Ferrite
Spinel；Wherein, the mass ratio of each component meets relationship after high lead high phosphorus promoter manganese is mixed with additive: 0.40≤
Mn/Fe≤0.65,0.05≤(CaO+Na2O)/SiO2≤0.45；The mass percentage content of lead in the high lead high phosphorus promoter manganese
It is 0.001%~15%, the mass percentage content of phosphorus is 0.001%~3%, and lead is measured with lead oxide, and phosphorus is with five oxidations
The metering of two phosphorus.
Preferred scheme, the high lead high phosphorus promoter manganese include manganese oxide ore, manganese carbonate ore, Ferromanganese Ore, electrolytic manganese anode
At least one of mud, electrolytic zinc anode mud, manganese sinter.The 15% manganese ore money being up to present invention may apply to aoxidize lead content
Source, such as electrolytic manganese anode mud, electrolytic zinc anode mud etc. are readily applicable to the manganese ore money of phosphorus content high (0.001%~5%)
Source can equally be effectively applicable to the higher manganese resource of phosphorus, lead content.
Preferred scheme, the high lead high phosphorus promoter manganese are finely ground to the mass percentage content that granularity meets -325 mesh grades
Not less than 95%, and specific surface area is not less than 2500cm2/g.Manganese, lead, Phosphate minerals Khenpo granularity in high lead high-phosphorus manganese resource
Carefully, preferentially that the granularity of raw material is levigate to required partial size is needed, carries out solid phase reaction sufficiently, while being guaranteed by mixture system
Standby green briquette has certain intensity in dry and roasting process.
Preferred scheme, the mass percentage content that roasting block ore grinding to granularity meets -325 mesh grades are not less than
99%.Ore grinding to appropriate granularity is conducive to the magnetic separation separation of Manganese Ferrite spinel.
Preferred scheme, the magnetic field strength that the magnetic separation separation uses is 500~800Gs.It can be with by adjusting Mn-Fe ratio
Magnetic preferable Manganese Ferrite spinel is obtained, can realize that magnetic separation separates under lower magnetic field.
Tailings is the enrichment tailings of lead and phosphorus after magnetic separation separation in technical solution of the present invention.
Additive component is preferably also finely ground to the quality percentage that granularity meets -325 mesh grades in technical solution of the present invention
It is not less than 95% than content, and specific surface area is not less than 2500cm2/g。
Calcining time is 2~5h in technical solution of the present invention.
The liquid phase production quantity of material is 5%~25% in roasting process in technical solution of the present invention.It is roasted by adjusting
The size of amount of liquid phase and the interfacial property of partial liquid phase in agglomerate are burnt, and then regulates and controls growth and the impurity of manganese iron compound oxide
Migration of elements, harmful element can be migrated from iron mineral into gangue mineral.
Technical solution of the present invention is for the first time using high lead high phosphorus promoter manganese as direct material, in Additive and appropriate roasting
Under the conditions of temperature, efficiently de- lead dephosphorization is carried out, the Manganese Ferrite spinel of high-quality is obtained.Of the invention 1200 DEG C~
It is roasted under 1300 DEG C of hot conditions, its reinforcing is given full play to by the additive that iron compound, calc-flux and sodium salt form
The effect of high lead high phosphorus promoter manganese roasting, on the one hand promotes the generation of ferrimanganic iron compound oxide phase, on the other hand promotes lead, phosphorus
Equal harmful elements are migrated to gangue mineral.Since the chemical property of iron, manganese element is extremely similar, easily in high-temperature calcination process
Mutually replace, iron compound may advantageously facilitate manganese iron compound oxide and mutually generates, and gangue mineral be difficult in roasting process into
Enter in manganese iron compound oxide lattice, the liquid phase of low melting point can be generated with a small amount of iron, manganese mineral, by regulating and controlling maturing temperature
With (CaO+Na+O)/SiO in material2Mass ratio, the size and partial liquid phase of amount of liquid phase in adjustable roasting agglomerate
Interfacial property, and then regulate and control the growth of manganese iron compound oxide and the migration of impurity element, harmful element can be moved from iron mineral
It moves in gangue mineral.To provide mineralogy item for roasting agglomerate mill ore magnetic selection separation ferro manganese composite oxides and P elements
Part.In addition, carrying out ingredient to manganese source and source of iron, controls Mn/Fe mass ratio in mixture and be between 0.40~0.65, be in this
Mn/Fe is very stronger than the manganese iron compound oxide magnetism in range, convenient for realizing manganese iron combined oxidation under very weak magnetic field strength
Object and gangue efficiently separate.
Compared with the prior art, technical solution of the present invention bring advantageous effects:
1) additive that technical solution of the present invention provides can strengthen high lead high phosphorus promoter manganese roasting process, realize high lead
The efficiently de- lead dephosphorization of high phosphorus promoter manganese and the generation for promoting Manganese Ferrite spinel, to obtain the Manganese Ferrite point of high-quality
Spinel；Dephosphorization takes off lead efficiency and is up to 98% or more；
2) technical solution of the present invention is for the first time that raw material realizes that a step prepares the manganese of high-quality using high lead high phosphorus promoter manganese
Hercynite material realizes the efficient increment processing of low-grade promoter manganese；
3) technical solution of the present invention by using additive and controls the conditions such as sintering temperature, realizes high temperature solid state reaction
The impurity such as manganese and lead phosphorus efficiently separate in middle high lead high phosphorus promoter manganese, and obtain magnetic stronger, can be carried out by low-intensity magnetic field
The Manganese Ferrite spinel of magnetic separation separation.
4) technical solution of the present invention is easy to operate, at low cost, added value is high, is conducive to industrialized production.
Detailed description of the invention
Fig. 1 is embodiment 1, embodiment 2, comparative example 1, the magnetic sample obtained in comparative example 2 magnetic at room temperature
Hysteresis curves map.
Specific embodiment
Following embodiment is intended to further illustrate the content of present invention, rather than limits the protection model of the claims in the present invention
It encloses.
Embodiment 1
By high lead promoter manganese (the Manganese anode slime TMn 40.4%, Pb 10.5% of high phosphorus；Ferromanganese Ore TMn 20.6%, Pb
3.5%, P 1.0%), additive (60% iron-containing resource: bloodstone, magnetic iron ore；30% calc-flux: quick lime；10% sodium
Salt :+90% sodium oxalate of 10% sodium carbonate) ingredient is carried out, the ingredient of mixture is TMn21%, TFe42%, (CaO+Na2O)/
SiO2=0.05, mass percentage shared by -325 mesh grade of mixture is 95%, specific surface area 2600cm2/ g, with addition of
Pelletizing after 0.25% bentonite and 8% moisture, is then dried, by the sample after drying in Muffle kiln roasting, roasting temperature
Degree is 1300 DEG C, calcining time 2h, and mass percentage shared by levigate extremely -325 mesh grades of sample will be roasted after cooling and is
99.5%, magnetic separation is carried out in the magnetic field that magnetic field strength is 500Gs, resulting magnetic product is multilayer shape jakobsite material
Material.The magnetic property of the magnetic product obtained under this condition is good, and the removal efficiency of lead and phosphorus is up to 98.7% and 99.4% respectively
Embodiment 2
By high lead promoter manganese (the Manganese anode slime TMn 43.2%, Pb 9.6% of high phosphorus；Ferromanganese Ore TMn 14.4%, Pb
2.8%, P 0.9%), additive (65% iron-containing resource: bloodstone, magnetic iron ore；25% calc-flux: quick lime；10% sodium
Salt :+80% sodium oxalate of+10% borax of 10% sodium sulphate) ingredient is carried out, the ingredient of mixture is TMn16%, TFe40%, (CaO
+Na2O)/SiO2=0.45, mass percentage shared by -325 mesh grade of mixture is 95%, specific surface area 2500cm2/ g,
Bentonite with addition of 0.25% and 8% moisture after pelletizing, then dry, by the sample after drying in Muffle kiln roasting, roasting
Burning temperature is 1200 DEG C, calcining time 5h, and mass percentage shared by levigate extremely -325 mesh grades of sample will be roasted after cooling and is
100%, magnetic separation is carried out in the magnetic field that magnetic field strength is 800Gs, resulting magnetic product is multilayer shape jakobsite material
Material.The magnetic property of the magnetic product obtained under this condition is good, and the removal efficiency of lead and phosphorus is up to 98.5% and 99.2% respectively.
Embodiment 3
By high lead promoter manganese (the Manganese anode slime TMn 40.8%, Pb 8.3% of high phosphorus；Ferromanganese Ore TMn 14.4%, Pb
2.8%, P 0.9%), additive (80% iron-containing resource: high-phosphor oolitic hematite, magnetic iron ore；10% calc-flux: quick lime,
Lime stone；10% sodium salt :+90% sodium oxalate of+5% borax of 5% sodium sulphate) ingredient is carried out, the ingredient of mixture is TMn20%,
TFe31%, (CaO+Na2O)/SiO2=0.30, mass percentage shared by -325 mesh grade of mixture is 95%, specific surface area
For 2650cm2/ g, bentonite with addition of 0.25% and 8% moisture after pelletizing, then dry, by the sample after drying in Muffle
Kiln roasting, maturing temperature are 1250 DEG C, calcining time 5h, and it is levigate to quality shared by -325 mesh grades that sample will be roasted after cooling
Percentage composition is 100%, carries out magnetic separation in the magnetic field that magnetic field strength is 700Gs, resulting magnetic product is more Layered Manganeses
Hercynite material.The magnetic property of the magnetic product obtained under this condition is good, and the removal efficiency of lead and phosphorus is up to 99.2% respectively
With 98.9%.
Comparative example 1
Calcium additive is free of in additive combination in the comparative example
By high lead promoter manganese (the Manganese anode slime TMn 38.8%, Pb 8.9% of high phosphorus；Ferromanganese Ore TMn 10.2%, Pb
2.8%, P 0.9%), additive (75% iron-containing resource: bloodstone, magnetic iron ore；25% sodium salt: 10% sodium sulphate, 10% boron
Sand, 80% sodium oxalate) ingredient is carried out, the ingredient of mixture is TMn19%, TFe35%, (CaO+Na2O)/SiO2=0.25, it mixes
Closing mass percentage shared by -325 mesh grades of material is 95%, specific surface area 2550cm2/ g, with addition of 0.25% bentonite and
Pelletizing after 8% moisture, is then dried, and by the sample after drying in Muffle kiln roasting, maturing temperature is 1275 DEG C, when roasting
Between 4h, it to mass percentage shared by -325 mesh grades is 100% that it is levigate that sample will be roasted after cooling, is in magnetic field strength
Magnetic separation is carried out in the magnetic field of 650Gs, jakobsite phase content only 80% in resulting magnetic product.Lead and phosphorus under this condition
Removal efficiency respectively only 78.4% and 67.9%.
Comparative example 2
Not sodium salt additive in additive combination in the comparative example
By high lead promoter manganese (the Manganese anode slime TMn 38.8%, Pb 8.9% of high phosphorus；Ferromanganese Ore TMn 10.2%, Pb
2.8%, P 0.9%), additive (60% iron-containing resource: bloodstone, magnetic iron ore；40% calc-flux: quick lime；) matched
Material, the ingredient of mixture are TMn19%, TFe35%, CaO/SiO2=0.25, quality percentage shared by -325 mesh grade of mixture
Content is 95%, specific surface area 2570cm2/ g, bentonite with addition of 0.25% and 8% moisture after pelletizing, then dry,
By the sample after drying in Muffle kiln roasting, maturing temperature is 1225 DEG C, calcining time 4.5h, will roast sample mill after cooling
Mass percentage shared by thin extremely -325 mesh grades is 100%, carries out magnetic separation, gained in the magnetic field that magnetic field strength is 600Gs
Magnetic product in jakobsite phase content only 85.0%.The removal efficiency of lead and phosphorus distinguishes only 76.7% He under this condition
73.4%.
Comparative example 3
Sodium oxalate is free of in the combination of sodium salt additive in the comparative example
By high lead promoter manganese (the Manganese anode slime TMn 38.8%, Pb 8.9% of high phosphorus；Ferromanganese Ore TMn 10.2%, Pb
2.8%, P 0.9%), additive (60% iron-containing resource: bloodstone, magnetic iron ore；30% calc-flux: quick lime；10% sodium
Salt: 100% sodium carbonate) ingredient is carried out, the ingredient of mixture is TMn19%, TFe35%, (CaO+Na2O)/SiO2=0.25, it mixes
Closing mass percentage shared by -325 mesh grades of material is 95%, specific surface area 2570cm2/ g, with addition of 0.25% bentonite and
Pelletizing after 8% moisture, is then dried, and by the sample after drying in Muffle kiln roasting, maturing temperature is 1250 DEG C, when roasting
Between 4.5h, it to mass percentage shared by -325 mesh grades is 100% that it is levigate that sample will be roasted after cooling, is in magnetic field strength
Magnetic separation is carried out in the magnetic field of 600Gs, jakobsite phase content only 87.6% in resulting magnetic product.Under this condition lead and
The removal efficiency of phosphorus respectively only 80.4% and 78.9%.
Claims (9)
1. a kind of method strengthened the de- lead dephosphorization of high lead high phosphorus promoter manganese and prepare Manganese Ferrite spinel, it is characterised in that: will
After high lead high phosphorus promoter manganese fine grinding with additive mixing agglomeration；The raw block of gained after drying, is placed in air atmosphere, 1200~
It is roasted at a temperature of 1300 DEG C, roasting block is by ore grinding, magnetic separation separation to get Manganese Ferrite spinel；
Wherein, the mass ratio of each component meets relationship after high lead high phosphorus promoter manganese is mixed with additive:
0.40≤Mn/Fe≤0.65,0.05≤(CaO+Na2O)/SiO2≤0.45；
The mass percentage content of lead is 0.001%~15% in the high lead high phosphorus promoter manganese, the mass percentage content of phosphorus
It is 0.001%~3%, and lead is measured with lead oxide, phosphorus is measured with phosphorus pentoxide；
The additive is by following content of component:
60~80 parts of iron compound；
15~30 parts of calc-flux；
5~10 parts of sodium salt.
2. a kind of de- lead dephosphorization of high lead high phosphorus promoter manganese of strengthening according to claim 1 prepares Manganese Ferrite spinel
Method, it is characterised in that: the high lead high phosphorus promoter manganese include manganese oxide ore, manganese carbonate ore, Ferromanganese Ore, electrolytic manganese anode mud,
At least one of electrolytic zinc anode mud, manganese sinter.
3. a kind of de- lead dephosphorization of high lead high phosphorus promoter manganese of strengthening according to claim 1 prepares Manganese Ferrite spinel
Method, it is characterised in that: the high lead high phosphorus promoter manganese is finely ground to granularity and meets the mass percentage content of -325 mesh grades not
Lower than 95%, and specific surface area is not less than 2500cm2/g。
4. a kind of de- lead dephosphorization of high lead high phosphorus promoter manganese of strengthening according to claim 1 prepares Manganese Ferrite spinel
Method, it is characterised in that: the mass percentage content that roasting block ore grinding to granularity meets -325 mesh grades is not less than 99%；Institute
It states magnetic separation and separates the magnetic field strength used as 500~800Gs.
5. a kind of de- lead dephosphorization of high lead high phosphorus promoter manganese of strengthening according to claim 1 prepares Manganese Ferrite spinel
Method, it is characterised in that: the iron compound includes Fe2O3、Fe3O4, magnetic iron ore, bloodstone, goethite, limonite, sparring
At least one of mine, high-phosphorus iron ore, iron content secondary resource.
6. a kind of de- lead dephosphorization of high lead high phosphorus promoter manganese of strengthening according to claim 1 prepares Manganese Ferrite spinel
Method, it is characterised in that: the calc-flux is quick lime and/or lime stone.
7. according to claim 1,5,6 it is described in any item it is a kind of strengthen high lead high phosphorus promoter manganese and take off lead dephosphorization prepare Manganese Ferrite point
The method of spinel, it is characterised in that: the sodium salt includes at least one of sodium carbonate, sodium sulphate, Boratex, sodium oxalate.
8. a kind of de- lead dephosphorization of high lead high phosphorus promoter manganese of strengthening according to claim 7 prepares Manganese Ferrite spinel
Method, it is characterised in that: the sodium salt includes at least sodium oxalate.
9. a kind of de- lead dephosphorization of high lead high phosphorus promoter manganese of strengthening according to claim 8 prepares Manganese Ferrite spinel
Method, it is characterised in that: the mass percentage of the sodium salt mesoxalic acid sodium is 50%~90%.
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| JPS5739108A (en) * | 1980-08-20 | 1982-03-04 | Sumitomo Metal Ind Ltd | Preparation of pig iron for casting |
| EP0630856A1 (en) * | 1993-06-28 | 1994-12-28 | SANIMET S.p.A. | Process for removing iron and manganese from acid solutions of zinc salts |
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| JPS5739108A (en) * | 1980-08-20 | 1982-03-04 | Sumitomo Metal Ind Ltd | Preparation of pig iron for casting |
| EP0630856A1 (en) * | 1993-06-28 | 1994-12-28 | SANIMET S.p.A. | Process for removing iron and manganese from acid solutions of zinc salts |
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