CN103993162A - Method for removing iron and phosphorus of high phosphorus ferroniobium concentrate - Google Patents
Method for removing iron and phosphorus of high phosphorus ferroniobium concentrate Download PDFInfo
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- CN103993162A CN103993162A CN201410215362.2A CN201410215362A CN103993162A CN 103993162 A CN103993162 A CN 103993162A CN 201410215362 A CN201410215362 A CN 201410215362A CN 103993162 A CN103993162 A CN 103993162A
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Abstract
The invention relates to a method for removing iron and phosphorus of high phosphorus ferroniobium concentrate. The method is characterized by comprising the two working processes of selective reduction and melt-phase separation, wherein the working process of selective reduction comprises the steps of putting ferroniobium concentrate and semi coke into a silicon carbide reaction tank according to a weight ratio of (50-70):(50-30), reducing in a high temperature furnace at 850-1050 DEG C, and insulating for 40-60 hours; and carrying out solid-state reduction to obtain concentrate clumps containing physical iron, cooling down along with the furnace to be 200-300 DEG C, taking out the reduction product, then cleaning to obtain the reduced block concentrate; the working process of melt-phase separation comprises the steps of uniformly mixing the reduced block concentrate with lime, then putting the mixture into an electric furnace, controlling the alkalinity at 0.5+/-0.1 and the melt-phase separation temperature at 1370-1500 DEG C, insulating for 2-30 minutes, pouring and cooling, so as to obtain phosphorus containing cast iron and low phosphorus and low iron niobium slag. The method has the advantages of no need of prilling, and has low cost, high removal rate of iron and phosphorus, and high yield of niobium, and materials are simple and convenient to load, wherein the niobium yield is greater than 98%, the dephosphorizing rate is greater than 85%, the deferrization rate is greater than 85%, and the alkalinity of the slag former is low, generally 0.5+/-0.1.
Description
Technical field
A kind of method that the present invention relates to high phosphorus ferro-niobium concentrate deferrization dephosphorization, belongs to metallurgical chemistry technical field.
Background technology
China is that niobium consumes big country, but whole dependence on import almost at present.In baiyuneboite, contain a large amount of niobiums, distant view oxide compound (Nb
2o
5) 6,600,000 tons of reserves, but because grade is low, foreign matter content is high, causes it can not directly enter smelting link.Especially in concentrate, the content of Fe, P will directly have influence on niobium grade and niobium phosphorus ratio in ferrocolumbium.
High phosphorus ferro-niobium concentrate iron content 30-50mass%, phosphorous 0.1-1.5mass%, content of niobium 1-5mass%.Because iron, phosphorus content are high, niobium grade is low, causes this kind of mine disaster to reach the requirement of smelting ferrocolumbium.If directly this kind of concentrate directly smelted, phosphorus, iron will be reduced simultaneously and enter alloy with niobium, cause alloy niobium grade low, and phosphorus content is high.In later stage use procedure, also need a large amount of slag former dephosphorizations, increased use cost.
At present, domestic deferrization phosphorus removing method mainly contains beneficiation method, chemical process, biotechnology and smelting process.Beneficiation cost is high, and the rate of recovery is extremely low; Chemical process cost is high and have a waste water handling problem; Although biotechnology environmental protection, energy consumption are low, technical process is long, efficiency is low, cost is high; In the case of smelting process deferrization dephosphorization, what have adds Calcium Fluoride (Fluorspan) in slag former, and under high temperature, Calcium Fluoride (Fluorspan) not only corrodes furnace lining, and contaminate environment.The method (application number 201010534858.8) of a kind of high-phosphorus hematite direct-reduction of Chinese patent dephosphorus iron extraction adopts the method deferrization dephosphorization of cold bound pellet direct-reduction-magnetic separation, but the method adds a large amount of binding agents at home and abroad in cold fixed agglomeration process, while therefore having caused cost rise and smelt, the quantity of slag obviously increases; Under hot conditions, binding agent very easily lost efficacy simultaneously, caused pelletizing to occur the phenomenons such as efflorescence, inner ring formation, had increased labour cost.
Summary of the invention
The object of the invention is to be intended to overcome prior art defect, provide that a kind of technique is simple, the method for dephosphorization rate, deferrization rate is high, niobium yield is high high phosphorus ferro-niobium concentrate deferrization dephosphorization.
For achieving the above object, the technical solution used in the present invention is: adopt selective reduction and molten minute two large operations, selective reduction be by containing ferro-niobium concentrate and blue charcoal by (50-70): weight ratio (50-30) packs in silicon carbide reactor tank, in High Temperature Furnaces Heating Apparatus, under 850～1050 ℃ of conditions, reduce, be incubated 40～60 hours; Solid state reduction becomes the concentrate agglomerate containing physics iron, cools to 200～300 ℃ with the furnace, after reduzate is taken out, clears up the Lumpy concentrate after being reduced; Within molten minute, be to pack electric furnace into after the Lumpy concentrate after reduction and lime are mixed, control basicity 0.5 ± 0.1, between 1370～1500 ℃ of molten minute temperature, soaking time 2～30min, pours into a mould coolingly, obtains the phosphorous pig iron and niobium slag low-phosphorous, low iron.
Described ferro-niobium granularity of concentrate < 150 orders, blue carbon granule degree < 2cm;
Before will packing in silicon carbide reactor tank containing ferro-niobium concentrate and blue charcoal, should at the bottom of tank, spread the blue charcoal particle that 1 ± 0.5 cm is thick, bond when preventing out tank;
Described High Temperature Furnaces Heating Apparatus is resistance furnace or for tunnel furnace or for rotary kiln;
Described electric furnace is medium-frequency induction furnace or is electric arc furnace.
In aforesaid method: niobium yield > 98%, dephosphorization rate > 90%, deferrization rate > 90%.
Owing to adopting technique scheme, the present invention has the following advantages:
(1) adopt pot type selective reduction, do not need pelletizing, feed easy; The reduction of employing semicoke, low cost; After reduction, mixtures of materials is not brought ash content into, the foreign material such as binding agent.
(2) deferrization dephosphorizing rate is high, and niobium yield is high.Niobium yield > 98%, dephosphorization rate > 85%, deferrization rate > 85%.
(3) slag former basicity is low, and basicity is generally 0.5 ± 0.1.
Accompanying drawing explanation
Fig. 1 is the sectional side elevation of silicon carbide reactor tank of the present invention;
Fig. 2 is the cross-sectional figure of silicon carbide reactor tank of the present invention.
In figure: 1, silicon carbide reactor tank, 2, containing ferro-niobium concentrate, 3, blue charcoal.
Embodiment
Embodiment 1
Select high phosphorus ferro-niobium concentrate composition to be: Fe
2o
358.27mass%, FeO1.35mass%, SiO
219.93mass%, Nb
2o
51.26mass%, MgO1.33mass%, TiO
23.69 mass%, CaO1.92 mass%, CaF
21.64mass%, P
2o
52.37 mass%; The reductive agent using is blue charcoal, ash content 12.5%, fugitive constituent 17.52%, fixed carbon 69.98%, granularity 0.45～4mm; Concentrate and blue charcoal weight ratio 50:50, charging schematic diagram as shown in Figure 1, 2.The tank installing is put into resistance furnace and carry out selective reduction, 900 ℃ of reduction temperatures, 60 hours recovery times.Cool to 200 ℃ with the furnace, reduzate is taken out, cleared up.Then the agglomerate after reduction is added to lime and adjust and in the intermediate frequency furnace that basicity to 0.5 joins liner plumbago crucible, melt minute, 1450 ℃ of molten minute temperature, melt and divide a time 10min.Pour into a mould the cooling phosphorous pig iron and the low-phosphorous niobium slag of low iron of obtaining.Dephosphorization rate 92.3% is analyzed and calculated to the phosphorous pig iron and low-phosphorous low iron niobium slag, deferrization rate 94.4%, niobium yield 99%.
Embodiment 2
Select high phosphorus ferro-niobium concentrate composition to be: Fe
2o
348.97mass%, FeO1.6mass%, SiO
221.87mass%, Nb
2o
54.4mass%, MgO1.05mass%, TiO
26.71 mass%, CaO1.34 mass%, CaF
21.50 mass%, P
2o
50.16 mass%; The reductive agent using is blue charcoal, ash content 12.5%, fugitive constituent 17.52%, fixed carbon 69.98%, granularity 0.45～4mm; Concentrate and blue charcoal weight ratio 60:40, charging schematic diagram as shown in Figure 1, 2.The tank installing is put into resistance furnace and carry out selective reduction, 935 ℃ of reduction temperatures, 60 hours recovery times.Cool to 200 ℃ with the furnace, reduzate is taken out, cleared up.Then the agglomerate after reduction is added to lime and adjust and in the intermediate frequency furnace that basicity to 0.4 joins liner plumbago crucible, melt minute, 1400 ℃ of molten minute temperature, melt and divide a time 10min.Pour into a mould the cooling phosphorous pig iron and the low-phosphorous niobium slag of low iron of obtaining.Dephosphorization rate 93.6% is analyzed and calculated to the phosphorous pig iron and low-phosphorous low iron niobium slag, deferrization rate 96.7%, niobium yield 98.8%.
Embodiment 3
Select high phosphorus ferro-niobium concentrate composition to be: Fe
2o
348.97mass%, FeO1.6mass%, SiO
221.87mass%, Nb
2o
54.4mass%, MgO1.05mass%, TiO
26.71 mass%, CaO1.34 mass%, CaF
21.50 mass%, P
2o
50.16 mass%; The reductive agent using is blue charcoal, ash content 12.5%, fugitive constituent 17.52%, fixed carbon 69.98%, granularity 0.45～4mm; Concentrate and blue charcoal weight ratio 64:36, charging schematic diagram as shown in Figure 1, 2.The tank installing is put into resistance furnace and carry out selective reduction, 935 ℃ of reduction temperatures, 60 hours recovery times.Cool to 200 ℃ with the furnace, reduzate is taken out, cleared up.Then the agglomerate after reduction is added to lime and adjust and in the intermediate frequency furnace that basicity to 0.5 joins liner plumbago crucible, melt minute, 1400 ℃ of molten minute temperature, melt and divide a time 10min.Pour into a mould the cooling phosphorous pig iron and the low-phosphorous niobium slag of low iron of obtaining.Dephosphorization rate 90.2% is analyzed and calculated to the phosphorous pig iron and low-phosphorous low iron niobium slag, deferrization rate 95.4%, niobium yield 98.5%.
Embodiment 4
Select high phosphorus ferro-niobium concentrate composition to be: Fe
2o
358.27mass%, FeO1.35mass%, SiO
219.93mass%, Nb
2o
51.26mass%, MgO1.33mass%, TiO
23.69 mass%, CaO1.92 mass%, CaF
21.64mass%, P
2o
52.37 mass%; The reductive agent using is blue charcoal, ash content 12.5%, fugitive constituent 17.52%, fixed carbon 69.98%, granularity 0.45～4mm; Concentrate and blue charcoal weight ratio 55:45, charging schematic diagram as shown in Figure 1, 2.The tank installing is put into resistance furnace and carry out selective reduction, 920 ℃ of reduction temperatures, 50 hours recovery times.Cool to 200 ℃ with the furnace, reduzate is taken out, cleared up.Then the agglomerate after reduction is added to lime and adjust and in the intermediate frequency furnace that basicity to 0.6 joins liner plumbago crucible, melt minute, 1450 ℃ of molten minute temperature, melt and divide a time 10min.Pour into a mould the cooling phosphorous pig iron and the low-phosphorous niobium slag of low iron of obtaining.Dephosphorization rate 93.0% is analyzed and calculated to the phosphorous pig iron and low-phosphorous low iron niobium slag, deferrization rate 94.8%, niobium yield 98.9%.
Claims (4)
1. the method for a high phosphorus ferro-niobium concentrate deferrization dephosphorization, it is characterized in that: adopt selective reduction and molten minute two large operations, selective reduction be by containing ferro-niobium concentrate and blue charcoal by (50-70): weight ratio (50-30) packs in silicon carbide reactor tank, in High Temperature Furnaces Heating Apparatus, under 850～1050 ℃ of conditions, reduce, be incubated 40～60 hours; Solid state reduction becomes the concentrate agglomerate containing physics iron, cools to 200～300 ℃ with the furnace, after reduzate is taken out, clears up the Lumpy concentrate after being reduced; Within molten minute, be to pack electric furnace into after the Lumpy concentrate after reduction and lime are mixed, control basicity 0.5 ± 0.1, between 1370～1500 ℃ of molten minute temperature, soaking time 2～30min, cast, cooling, obtains the phosphorous pig iron and niobium slag low-phosphorous, low iron.
2. the method for high phosphorus ferro-niobium concentrate deferrization dephosphorization according to claim 1, is characterized in that: described ferro-niobium granularity of concentrate < 150 orders, blue carbon granule degree < 2cm.
3. the method for high phosphorus ferro-niobium concentrate deferrization dephosphorization according to claim 1, is characterized in that: described High Temperature Furnaces Heating Apparatus is resistance furnace or for tunnel furnace or be rotary kiln.
4. the method for high phosphorus ferro-niobium concentrate deferrization dephosphorization according to claim 1, is characterized in that: described electric furnace is medium-frequency induction furnace or is electric arc furnace.
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| CN201410215362.2A CN103993162B (en) | 2014-05-21 | 2014-05-21 | A kind of method of high phosphorus ferro-niobium concentrate deferrization dephosphorization |
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| CN103993162B CN103993162B (en) | 2016-04-13 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104762441A (en) * | 2015-04-07 | 2015-07-08 | 内蒙古科技大学 | Niobium-containing slag dephosphorization method |
| CN105803189A (en) * | 2016-05-16 | 2016-07-27 | 贵州大学 | Method for efficiently removing phosphorus from high-phosphorus oolitic hematite |
| CN112322890A (en) * | 2020-10-27 | 2021-02-05 | 长沙矿冶研究院有限责任公司 | Method for producing high-grade niobium concentrate by reducing and melting niobium rough concentrate in two sections |
| CN113215389A (en) * | 2021-05-08 | 2021-08-06 | 包头稀土研究院 | Method for enriching niobium and titanium in iron-containing niobium-titanium ore and application of nickel-containing substance |
| CN113444877A (en) * | 2021-06-07 | 2021-09-28 | 钢研晟华科技股份有限公司 | Method for separating phosphorus and iron from high-phosphorus iron ore |
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| CN102212736A (en) * | 2011-05-12 | 2011-10-12 | 内蒙古科技大学 | Method for preparing niobium microalloy steel by using low-niobium molten iron |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104762441A (en) * | 2015-04-07 | 2015-07-08 | 内蒙古科技大学 | Niobium-containing slag dephosphorization method |
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| CN105803189A (en) * | 2016-05-16 | 2016-07-27 | 贵州大学 | Method for efficiently removing phosphorus from high-phosphorus oolitic hematite |
| CN105803189B (en) * | 2016-05-16 | 2018-06-29 | 贵州大学 | A kind of method of phosphorus in efficient removal high-phosphor oolitic hematite |
| CN112322890A (en) * | 2020-10-27 | 2021-02-05 | 长沙矿冶研究院有限责任公司 | Method for producing high-grade niobium concentrate by reducing and melting niobium rough concentrate in two sections |
| CN112322890B (en) * | 2020-10-27 | 2021-08-31 | 长沙矿冶研究院有限责任公司 | Method for producing high-grade niobium concentrate by reducing and melting niobium rough concentrate in two sections |
| CN113215389A (en) * | 2021-05-08 | 2021-08-06 | 包头稀土研究院 | Method for enriching niobium and titanium in iron-containing niobium-titanium ore and application of nickel-containing substance |
| CN113215389B (en) * | 2021-05-08 | 2022-04-22 | 包头稀土研究院 | Method for enriching niobium and titanium in iron-containing niobium-titanium ore and application of nickel-containing substance |
| WO2022237607A1 (en) | 2021-05-08 | 2022-11-17 | 包头稀土研究院 | Method for enriching niobium-titanium in iron-containing niobium-titanium ore and use of nickel-containing substance |
| JP7541613B2 (en) | 2021-05-08 | 2024-08-28 | 包頭稀土研究院 | Method for enriching niobium titanium in iron-containing niobium titanium ore and use of nickel-containing material |
| CN113444877A (en) * | 2021-06-07 | 2021-09-28 | 钢研晟华科技股份有限公司 | Method for separating phosphorus and iron from high-phosphorus iron ore |
| CN113444877B (en) * | 2021-06-07 | 2022-09-16 | 钢研晟华科技股份有限公司 | Method for separating phosphorus and iron from high-phosphorus iron ore |
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