CN107555482A - A kind of method and additive that Manganese Ferrite spinel is prepared using high lead high phosphorus promoter manganese - Google Patents
A kind of method and additive that Manganese Ferrite spinel is prepared using high lead high phosphorus promoter manganese Download PDFInfo
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- CN107555482A CN107555482A CN201710811984.5A CN201710811984A CN107555482A CN 107555482 A CN107555482 A CN 107555482A CN 201710811984 A CN201710811984 A CN 201710811984A CN 107555482 A CN107555482 A CN 107555482A
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- manganese
- lead
- additive
- phosphorus
- dephosphorization
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- 239000011572 manganese Substances 0.000 title claims abstract description 116
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 107
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 81
- 239000011574 phosphorus Substances 0.000 title claims abstract description 74
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000000654 additive Substances 0.000 title claims abstract description 41
- 230000000996 additive effect Effects 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 31
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 24
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 23
- 239000011029 spinel Substances 0.000 title claims abstract description 23
- 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
- 238000005054 agglomeration Methods 0.000 claims abstract description 3
- 230000002776 aggregation Effects 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 67
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical group [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 34
- 229910052742 iron Inorganic materials 0.000 claims description 30
- 229910000616 Ferromanganese Inorganic materials 0.000 claims description 24
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- 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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- 229910052681 coesite Inorganic materials 0.000 claims description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims description 9
- 238000000926 separation method Methods 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
- 238000005728 strengthening Methods 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 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
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 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
- 230000003014 reinforcing effect Effects 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
- 229910021646 siderite Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 235000002908 manganese Nutrition 0.000 description 77
- 239000011133 lead Substances 0.000 description 72
- 239000000463 material Substances 0.000 description 20
- 229910052500 inorganic mineral Inorganic materials 0.000 description 13
- 229910052745 lead Inorganic materials 0.000 description 13
- 235000010755 mineral Nutrition 0.000 description 13
- 239000011707 mineral Substances 0.000 description 13
- 239000002131 composite material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- 238000005245 sintering Methods 0.000 description 7
- 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
- 239000012535 impurity Substances 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 4
- BFXLJWUGRPGMFU-UHFFFAOYSA-N dipropoxyphosphinothioyl n,n-diethylcarbamodithioate;sulfane Chemical compound S.CCCOP(=S)(OCCC)SC(=S)N(CC)CC BFXLJWUGRPGMFU-UHFFFAOYSA-N 0.000 description 4
- 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
- 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
- 229910021538 borax Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application 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
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction 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
- 239000000126 substance Substances 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
- 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
- 238000004458 analytical method 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
- 239000003153 chemical reaction reagent Substances 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
- 238000005516 engineering process 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
- 230000005389 magnetism Effects 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
- 239000002245 particle Substances 0.000 description 1
- 229910052585 phosphate mineral Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002360 preparation method Methods 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
- 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 method and additive that Manganese Ferrite spinel is prepared using high lead high phosphorus promoter manganese；Additive is made up of iron compound, calc-flux and sodium salt；It is by after high lead high phosphorus promoter manganese fine grinding and additive mixing agglomeration, drying, roasting to take off lead to prepare the method for Manganese Ferrite spinel using the high lead high phosphorus promoter manganese dephosphorization of reinforced by additive, it is calcined block to separate through ore grinding, magnetic separation, obtains Manganese Ferrite spinel and the tailings rich in lead phosphorus；This method can be with middle the 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 height, magnetic property are good after magnetic separation；And this method raw material sources are extensive, technique is simple, cost is low, it is easy to accomplish industrialized production.
Description
Technical field
The present invention relates to a kind of additive for being used to strengthen the de- lead dephosphorization of high lead high phosphorus promoter manganese, more particularly to one kind passes through
Add the additive being made up of iron compound, calc-flux and sodium salt to be calcined to strengthen high lead high phosphorus promoter manganese, pass through and regulate and control to roast
Burning-magnetic separation process realizes that de- lead dephosphorization obtains the method for jakobsite material, belongs to mineral processing, metallurgical engineering and material
Preparation field.
Background technology
Manganese is a kind of important strategic resource, and 90% manganese disappears as the deoxidier and desulfurizing agent and alloying element of molten steel
Consume in steel industry, 10% is used for other relevant industries.It is 64351.7 ten thousand t that China's manganese ore, which adds up proved reserves, reserves
592040000 t, the provinces and regions such as Guangxi, Hunan, Guizhou, Sichuan, Liaoning, Yunnan are mainly distributed on, account for national manganese resource gross reserves
90%.
At present, as the development of economy and industrial expansion, particularly steel industry, market are got over to the demand of manganese ore
Come bigger.Thus, the breach between the consumption and Ore Yield of Chinese manganese ore increases year by year, and China relies on import within 2014
Manganese ore amount be up to 6,470,000 t.The main reason for causing this situation is that China's manganese ore grade is low, the high-quality rich manganese ore of high-grade
Resource does not almost have, and 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 manganese ore of content overproof 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, some gangue minerals can be removed 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 with having
The simple Ferromanganese Ore of the evil embedding cloth of element, the separation of ferromanganese mineral and gangue can be realized using the beneficiation method of routine.But by
The close symbiosis of ferrimanganic in China's ferrimanganic ore resources, disseminated grain size is thin, and the smelting harmful element such as lead, phosphorus is substituted with lattice more, class
Matter with elephant form preservation in iron, manganese mineral, be having for difficult to realize ferromanganese and harmful element only by conventional 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 height is, it is necessary to disappear
Substantial amounts of fuel and reducing agent are consumed, produces substantial amounts of solid, gas pollutant.
Manganese anode slime is also the manganese resource of a kind of high lead-type.In electrolytic manganese production process, oxygen is separated out 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 of anode discharge generation2
The product deposited on positive plate.The earth of positive pole that often 1 ton of electrolytic manganese of production can produce 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, therefore, annual to produce electrolysis anode sludge 6~9.6 ten thousand ton or so,
Cumulant has reached more than 920,000 tons.These earth of positive pole are complicated because of its composition, it is difficult to are used, generally as dangerous debris dump
Deposit, steel-making additive or undersell, preferably do not developed and comprehensively utilized, not only the wasting of resources, and 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 wave filter magnetic core, magnetic core of transformer, radio magnetic core, and tape
Recording and video recording head etc., and the critical material of magnetic recording element.Hard magnetic material is mainly used in the phonographic recorder in telecommunications devices,
Sound pick-up, loudspeaker, the magnetic core of various instrument etc..
It is to use high temperature solid phase synthesis using analyzing pure or high-purity mineral dust to prepare the method for such material at present
Prepared by the mode through multistage roasting ore grinding, directly preparing jakobsite material using low-grade manganese ore is rarely reported.Pass
System solid reaction process prepares jakobsite material to analyze pure, ultrahigh quality mineral as raw material.But it is pure and mild to prepare analysis
The separating-purifying of mineral needs technological process, the substantial amounts of chemical reagent of consumption grown very much, causes cost height, efficiency low.
The content 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 present invention are to be to provide a kind of additive for being used to strengthen high lead high phosphorus promoter manganese roasting, and the additive can
To regulate and control the migration of the generation of iron and manganese oxides and objectionable impurities elements, realize 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 realize above-mentioned technical purpose, it is used to strengthen the de- lead dephosphorization of high lead high phosphorus promoter manganese the 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.
The high lead high phosphorus promoter manganese that is used to strengthen of the present invention takes off the additive of lead dephosphorization mainly by iron content, calcic and containing sodium
Material composition, iron compound major control regulation and control and Mn/Fe mass ratioes in the sinter mixture of high lead high phosphorus promoter manganese, to promote
The generation of ferromanganese composite oxides, prevent gangue mineral from entering in roasting process in ferromanganese composite oxides, and can regulate and control
The magnetic of ferromanganese composite oxides, be advantageous to follow-up magnetic separation separation.And calcareous solvent and sodium salt mainly adjust sintering system
In (CaO+Na2O)/SiO2Mass ratio, so as to 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 ferromanganese composite oxides and the migration of impurity element, harmful element can be migrated from iron mineral to arteries and veins
In stone ore thing, separate ferro manganese composite oxides 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.
Preferable 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 AR.Iron content
Material is not limited to analyze pure Fe2O3、Fe3O4Deng iron-bearing mineral and iron content secondary resource also are adapted for additive component requirement.
Preferable scheme, the calc-flux are quick lime and/or lime stone.
Preferable scheme, the sodium salt include at least one of sodium carbonate, sodium sulphate, Boratex, sodium oxalate.
Preferable scheme, the sodium salt comprise at least sodium oxalate.
Preferable scheme, the weight/mass percentage composition of the sodium salt mesoxalic acid sodium is 50%~90%.
Present invention also offers a kind of side for strengthening high lead high phosphorus promoter manganese and taking off lead dephosphorization and preparing Manganese Ferrite spinel
Method, this method be by after high lead high phosphorus promoter manganese fine grinding with described additive mixing agglomeration；Gained life block after drying, is placed in
In air atmosphere, it is calcined at a temperature of 1200~1300 DEG C, roasting block separates by ore grinding, magnetic separation, produces Manganese Ferrite
Spinel；Wherein, the mass ratio of each component meets relation after high lead high phosphorus promoter manganese mixes 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
For 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
Two phosphorus measure.
Preferable 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., it is readily applicable to the manganese ore money of phosphorus content high (0.001%~5%)
Source, it can equally be effectively applicable to the higher manganese resource of phosphorus, lead content.
Preferable 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, need preferentially by levigate to the required particle diameter of the granularity of raw material, solid phase reaction is fully carried out, while ensure by compound system
Standby green briquette has certain intensity in dry and roasting process.
Preferable scheme, roasting block ore grinding to granularity meet that the mass percentage content of -325 mesh grades is not less than
99%.Ore grinding to appropriate granularity is advantageous to the magnetic separation separation of Manganese Ferrite spinel.
Preferable scheme, the magnetic field intensity that the magnetic separation separation uses is 500~800Gs.Can be with by adjusting Mn-Fe ratio
The preferable Manganese Ferrite spinel of magnetic is obtained, can realize that magnetic separation separates under relatively low magnetic field.
Tailings is the enrichment tailings of lead and phosphorus after magnetic separation separation in technical scheme.
Additive component is preferably also finely ground to the quality percentage that granularity meets -325 mesh grades in technical scheme
It is not less than 95% than content, and specific surface area is not less than 2500cm2/g。
Roasting time is 2~5h in technical scheme.
The liquid phase growing amount of material is 5%~25% in roasting process in technical scheme.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 ferromanganese composite oxides
Migration of elements, harmful element can be migrated into gangue mineral from iron mineral.
Technical scheme is first using high lead high phosphorus promoter manganese as direct material, in Additive and appropriate roasting
Under temperature conditionss, efficiently de- lead dephosphorization is carried out, obtains the Manganese Ferrite spinel of high-quality.The present invention 1200 DEG C~
It is calcined under 1300 DEG C of hot conditions, the additive being made up of iron compound, calc-flux and sodium salt gives full play to its reinforcing
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
Deng harmful element to gangue mineral migrate.Because the chemical property of iron, manganese element is extremely similar, easily in high-temperature calcination process
Mutually substitution, iron compound may advantageously facilitate ferromanganese composite oxides and mutually generates, and gangue mineral be difficult in roasting process into
Enter in ferromanganese composite oxides lattice, it can generate the liquid phase of low melting point with a small amount of iron, manganese mineral, by regulating and controlling sintering temperature
With (CaO+Na+O)/SiO in material2Mass ratio, the size and partial liquid phase of amount of liquid phase in roasting agglomerate can be adjusted
Interfacial property, and then regulate and control the growth of ferromanganese composite oxides and the migration of impurity element, harmful element can move from iron mineral
Move in gangue mineral.So as to provide mineralogy bar for roasting agglomerate mill ore magnetic selection separation ferro manganese composite oxides and P elements
Part.In addition, carrying out dispensing to manganese source and source of iron, Mn/Fe mass ratioes in compound are controlled to be between 0.40~0.65, in this
Ferromanganese composite oxides magnetic in the range of Mn/Fe ratios is very strong, is easy to realize ferromanganese combined oxidation under very weak magnetic field intensity
Thing and gangue efficiently separate.
Compared with the prior art, the advantageous effects that technical scheme is brought：
1) additive that technical scheme 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 of high-quality point
Spinel；Dephosphorization takes off lead efficiency and is up to more than 98%；
2) technical scheme is first that raw material realizes that a step prepares the manganese of high-quality using high lead high phosphorus promoter manganese
Hercynite material, realize the efficient increment processing of low-grade promoter manganese；
3) technical scheme 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 separates in middle high lead high phosphorus promoter manganese, and obtains relatively high magnetism, can be carried out by low-intensity magnetic field
The Manganese Ferrite spinel of magnetic separation separation.
4) technical scheme is simple to operate, cost is low, added value is high, is advantageous to industrialized production.
Brief description of the drawings
Fig. 1 is the magnetic sample obtained in embodiment 1, embodiment 2, comparative example 1, comparative example 2 magnetic at room temperature
Hysteresis curves collection of illustrative plates.
Embodiment
Following examples are intended to further illustrate present invention, rather than the protection model of limitation the claims in the present invention
Enclose.
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%th, P 1.0%), additive (60% iron-containing resource：Bloodstone, magnetic iron ore；30% calc-flux：Quick lime；10% sodium
Salt：The sodium oxalate of 10% sodium carbonate+90%) dispensing is carried out, the composition of compound is TMn21%, TFe42%, (CaO+Na2O)/
SiO2=0.05, weight/mass percentage composition shared by the mesh grade of compound -325 is 95%, specific surface area 2600cm2/ g, with addition of
Pelletizing after 0.25% bentonite and 8% moisture, is then dried, by dried sample in Muffle kiln roasting, roasting temperature
Spend for 1300 DEG C, roasting time 2h, the levigate extremely weight/mass percentage composition shared by -325 mesh grades of sample will be calcined after cooling is
99.5%, magnetic separation is carried out in the magnetic field that magnetic field intensity is 500Gs, the magnetic product of gained is more stratiform jakobsite materials
Material.The magnetic property of the magnetic product obtained under the conditions of this 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%th, P 0.9%), additive (65% iron-containing resource：Bloodstone, magnetic iron ore；25% calc-flux：Quick lime；10% sodium
Salt：The sodium oxalate of+10% borax of 10% sodium sulphate+80%) dispensing is carried out, the composition of compound is TMn16%, TFe40%, (CaO
+Na2O)/SiO2=0.45, weight/mass percentage composition shared by the mesh grade of compound -325 is 95%, specific surface area 2500cm2/ g,
Pelletizing after bentonite and 8% moisture with addition of 0.25%, is then dried, by dried sample in Muffle kiln roasting, roasting
It is 1200 DEG C, roasting time 5h to burn temperature, and the levigate extremely weight/mass percentage composition shared by -325 mesh grades of sample will be calcined after cooling and is
100%, magnetic separation is carried out in the magnetic field that magnetic field intensity is 800Gs, the magnetic product of gained is more stratiform jakobsite materials
Material.The magnetic property of the magnetic product obtained under the conditions of this 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%th, 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：The sodium oxalate of+5% borax of 5% sodium sulphate+90%) dispensing is carried out, the composition of compound is TMn20%,
TFe31%, (CaO+Na2O)/SiO2=0.30, weight/mass percentage composition shared by the mesh grade of compound -325 is 95%, specific surface area
For 2650cm2/ g, pelletizing after the bentonite and 8% moisture with addition of 0.25%, is then dried, by dried sample in Muffle
Kiln roasting, sintering temperature are 1250 DEG C, roasting time 5h, and it is levigate to quality shared by -325 mesh grades that sample will be calcined after cooling
Percentage composition is 100%, carries out magnetic separation in the magnetic field that magnetic field intensity is 700Gs, the magnetic product of gained is more Layered Manganeses
Hercynite material.The magnetic property of the magnetic product obtained under the conditions of this is good, and the removal efficiency of lead and phosphorus is up to 99.2% respectively
With 98.9%.
Comparative example 1
In the comparative example calcium additive is free of in additive combination
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%th, P 0.9%), additive (75% iron-containing resource：Bloodstone, magnetic iron ore；25% sodium salt：10% sodium sulphate, 10% boron
Sand, 80% sodium oxalate) dispensing is carried out, the composition of compound is TMn19%, TFe35%, (CaO+Na2O)/SiO2=0.25, mix
Weight/mass percentage composition shared by closing -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 dried sample in Muffle kiln roasting, sintering temperature is 1275 DEG C, during roasting
Between 4h, will be calcined after cooling sample it is levigate to weight/mass percentage composition shared by -325 mesh grades be 100%, be in magnetic field intensity
Carry out magnetic separation in 650Gs magnetic field, jakobsite phase content only 80% in the magnetic product of gained.Lead and phosphorus under the conditions of being somebody's turn to do
Removal efficiency respectively only 78.4% and 67.9%.
Comparative example 2
In the comparative example sodium salt additive is free of in additive combination
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%th, P 0.9%), additive (60% iron-containing resource：Bloodstone, magnetic iron ore；40% calc-flux：Quick lime；) matched somebody with somebody
Material, the composition of compound is TMn19%, TFe35%, CaO/SiO2=0.25, quality percentage shared by the mesh grade of compound -325
Content is 95%, specific surface area 2570cm2/ g, pelletizing after the bentonite and 8% moisture with addition of 0.25%, is then dried,
By dried sample in Muffle kiln roasting, sintering temperature is 1225 DEG C, roasting time 4.5h, sample mill will be calcined after cooling
Thin extremely weight/mass percentage composition shared by -325 mesh grades is 100%, and magnetic separation, gained are carried out in the magnetic field that magnetic field intensity is 600Gs
Magnetic product in jakobsite phase content only 85.0%.The removal efficiency of lead and phosphorus difference only 76.7% He under the conditions of this
73.4%.
Comparative example 3
In the comparative example sodium oxalate is free of in the combination of sodium salt additive
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%th, P 0.9%), additive (60% iron-containing resource：Bloodstone, magnetic iron ore；30% calc-flux：Quick lime；10% sodium
Salt：100% sodium carbonate) dispensing is carried out, the composition of compound is TMn19%, TFe35%, (CaO+Na2O)/SiO2=0.25, mix
Weight/mass percentage composition shared by closing -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 dried sample in Muffle kiln roasting, sintering temperature is 1250 DEG C, during roasting
Between 4.5h, will be calcined after cooling sample it is levigate to weight/mass percentage composition shared by -325 mesh grades be 100%, be in magnetic field intensity
Carry out magnetic separation in 600Gs magnetic field, jakobsite phase content only 87.6% in the magnetic product of gained.Should under the conditions of lead and
The removal efficiency difference only 80.4% and 78.9% of phosphorus.
Claims (10)
1. a kind of be used to strengthen the additive that high lead high phosphorus promoter manganese takes off lead dephosphorization, it is characterised in that：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 additive for being used to strengthen the de- lead dephosphorization of high lead high phosphorus promoter manganese according to claim 1, its feature exist
In：The iron compound includes Fe2O3、Fe3O4, magnetic iron ore, bloodstone, goethite, limonite, siderite, high-phosphorus iron ore, contain
At least one of iron secondary resource.
A kind of 3. additive strengthened high lead high phosphorus promoter manganese and take off lead dephosphorization according to claim 1, it is characterised in that：Institute
It is quick lime and/or lime stone to state calc-flux.
4. the high lead high phosphorus promoter manganese of a kind of reinforcing according to any one of claims 1 to 3 takes off the additive of lead dephosphorization, it is special
Sign is：The sodium salt includes at least one of sodium carbonate, sodium sulphate, Boratex, sodium oxalate.
A kind of 5. additive strengthened high lead high phosphorus promoter manganese and take off lead dephosphorization according to claim 4, it is characterised in that：Institute
State sodium salt and comprise at least sodium oxalate.
A kind of 6. additive strengthened high lead high phosphorus promoter manganese and take off lead dephosphorization according to claim 5, it is characterised in that：Institute
The weight/mass percentage composition for stating sodium salt mesoxalic acid sodium is 50%~90%.
A kind of 7. 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 the additive mixing agglomeration described in any one of claim 1~6；Gained gives birth to block through drying
Afterwards, it is placed in air atmosphere, is calcined at a temperature of 1200~1300 DEG C, roasting block separates by ore grinding, magnetic separation, produces
Manganese Ferrite spinel；
Wherein, the mass ratio of each component meets relation after high lead high phosphorus promoter manganese mixes 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
For 0.001%~3%, and lead is measured with lead oxide, and phosphorus is measured with phosphorus pentoxide.
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 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.
9. 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 high lead high phosphorus promoter manganese is finely ground to granularity and meets the mass percentage content of -325 mesh grades not
Less than 95%, and specific surface area is not less than 2500cm2/g。
10. 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：It is calcined block ore grinding to granularity and meets that the mass percentage content of -325 mesh grades is not less than 99%；
The magnetic field intensity that the magnetic separation separation uses is 500~800Gs.
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| CN110642298A (en) * | 2019-11-07 | 2020-01-03 | 郑州大学 | Method for preparing in-situ reinforced spinel type composite ferrite material |
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