CN101545045B - Method for producing microalloy ferro-silicon by using a ferrous metasilicate electric stove integral deoxidation and reduction - Google Patents
Method for producing microalloy ferro-silicon by using a ferrous metasilicate electric stove integral deoxidation and reduction Download PDFInfo
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- CN101545045B CN101545045B CN2009101172273A CN200910117227A CN101545045B CN 101545045 B CN101545045 B CN 101545045B CN 2009101172273 A CN2009101172273 A CN 2009101172273A CN 200910117227 A CN200910117227 A CN 200910117227A CN 101545045 B CN101545045 B CN 101545045B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention relates to a method for producing microalloy ferro-silicon by using a ferrous metasilicate electric stove integral deoxidation and reduction, including the steps as follows: a. heating a nickel smelting waste slag or a nickel, copper and cobalt smelting waste slag to a molten state, or fetching the nickel smelting waste slag or a nickel, copper and cobalt smelting waste slagof the molten state to place in a thermal slag ladle directly; b. holding the slag in the molten state by heat insulation, at the same time infusing oxygen or air into the waste slag to react to generate solid residue to purify; c removing the solid residue; d. cooling the remained part and then crushing; e. producing the ferro-silicon through the deoxidation and reduction of the remained part asiron raw material and other raw material. For the method of the invention, firstly the nickel smelting waste slag is purified, then the purified copper smelting waste slag may be used to replace the iron raw material such as steel shaving, iron scale, sintered ball cluster and the like for the ferro-silicon production, thus it is capable of reducing the dosage of dinas rock or rock quartz; it hasbeen found that the ferro-silicon (FeSi75) produced by the method meets the national standard completely; the invention provides a novel method for producing ferroalloy.
Description
Technical field
The present invention relates to non-ferrous metal metallurgy waste (nickel smelting waste slag, copper smelting waste slag, nickel, copper, cobalt smelting waste slag) comprehensive utilization technique, particularly a kind of method of utilizing ferrous metasilicate electric stove integral deoxidation and reduction to produce microalloy ferro-silicon.
Background technology
Nickel smelting waste slag and nickel, copper, cobalt smelting waste slag are the smelting waste slags that nickel is smelted discharging in the production, are a kind of industrial solid castoffs.Along with the development of producing, solid waste increases year by year, the nickel smelting waste slag of enormous amount is stored up in the open in smelting enterprise periphery slag field, except that minute quantity water supply mud factory makes additive (replacement iron ore), all the other overwhelming majority do not obtain utilizing, and have caused the serious environmental issue to enterprise's periphery ecotope, human settlement.
Measuring and calculating contains a large amount of irony elements and silicon-dioxide in nickel smelting waste slag and nickel, copper, the cobalt smelting waste slag by analysis, contains metallic elements such as minor amount of nickel, copper, cobalt, lead, zinc in addition.With the about 1,600,000 tons waste of certain super-huge smelting enterprise is example, and wherein metal, nonmetal theoretical storage are: 620,000 tons of iron content, 4917 tons in nickel, 6273 tons of copper, 1864 tons of cobalts, 337 tons in lead, 5976 tons on zinc, 590,000 tons of silicon-dioxide.This is the huge wasting of resources, shows that also nickel smelting waste slag has huge value of exploiting and utilizing simultaneously, the difficult problem yet the comprehensive utilization of nickel smelting waste slag has at present become international in fact.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing ferrous metasilicate electric stove integral deoxidation and reduction to produce microalloy ferro-silicon, this method can make full use of depleted nickel smelting waste slag and nickel, copper, cobalt smelting waste slag resource, avoid the wasting of resources and the environmental influence that bring thus, produce qualified silicon iron product with lower cost.
For achieving the above object, the technical solution used in the present invention is:
A kind of method of utilizing ferrous metasilicate electric stove integral deoxidation and reduction to produce microalloy ferro-silicon is characterized in that, comprises the steps:
A, nickel smelting waste slag or nickel, copper, cobalt smelting waste slag are heated to molten state, or directly get the nickel smelting waste slag of molten state or nickel, copper, cobalt smelting waste slag, be positioned in the warm sludge bag;
B, insulation make waste keep molten state, thus simultaneously in waste aerating oxygen or air generate solid residue with purification and impurity removal;
C, remove solid residue;
D, the part cooling back fragmentation that will be left;
E, produce ferrosilicon with other raw material by the deoxidation and reduction method as ferriferous raw material then.
Wherein before step c, also need to shake the warm sludge bag 30-40 minute, left standstill then 8-12 minute.
Wherein behind step c, also to remove the heavy metal layer that molten state waste lower floor accounts for waste gross weight 4-6%.
Wherein behind step b, also to be incubated and make waste keep molten state, thereby in waste, feed chlorine simultaneously and generate solid residue with purification and impurity removal, the consumption of chlorine is a waste 0.1-0.25 cubic meter per ton, aeration time is 5-10 minute, or feeding chlorine meets the requirements until foreign matter content in waste.
Wherein the consumption of aerating oxygen is a waste 0.4-1 cubic meter per ton in step b, and aeration time is 5-10 minute, or aerating oxygen meets the requirements until foreign matter content in waste.
Wherein the consumption of bubbling air is a waste 2-5 cubic meter per ton in step b, and aeration time is 5-10 minute, or bubbling air meets the requirements until foreign matter content in waste.
Wherein use graphitized carbon cellulosic material gas duct to stretch in this warm sludge bag among the step b with ventilation.
Wherein the waste of molten state is meant that the waste temperature is at 1150 ℃-1300 ℃.
Wherein other raw material is meant silica and reductive agent among the step e, or quartz and reductive agent.
Wherein reductive agent adopts blue carbon, metallurgical coke or bottle coal Jiao.
The inventive method is at first with the waste purification and impurity removal, be used for ferrosilicon then and produce ferriferous raw materials such as alternative steel cuttings, iron scale, agglomerates of sintered pellets, reduce silica (or quartzy) consumption simultaneously, experiment showed, that the ferrosilicon (FeSi75) that adopts the inventive method to produce meets national standard fully.In addition, the ferrosilicon that adopts the present invention to produce still is a kind of microalloy ferro-silicon, contains the micro-nickel element, can improve the steel-making quality to a certain extent with microalloy ferro-silicon steel-making.Microalloy ferro-silicon is used for stainless steel, when special steel is produced, can saves the consumption of nickel, cobalt, thereby reduces steel-making cost.This can reduce the production power consumption as the vitreous state grog significantly waste after the removal of impurities when producing ferrosilicon, thereby reduces the ferrosilicon production cost significantly, reduces emission of carbon-dioxide.
Adopt method of the present invention efficiently comprehensively to reclaim elements such as the iron in the waste, silicon, nickel, copper, cobalt.Wherein the silicon rate of recovery is more than 95%, and iron recovery is more than 96%, and nickel recovery is more than 92%, and copper recovery is more than 90%, and the cobalt rate of recovery is more than 93%.Reached the purpose of large industrial solid castoff recycling, existing smelting enterprise deposits nickel smelting waste slag and has taken a large amount of soils, adopt the inventive method not only to contain waste constantly engulfing to the soil, can also progressively discharge the soil that occupied originally by handling original waste, this not only produces economic benefit, also produces corresponding environmental benefit and social benefit.
Embodiment
The inventive method to the principle of waste purification and impurity removal is: utilize furnace outer refining technology, high pressure oxygen, high pressure chlorine successively are blown into respectively in the waste of molten state, quantitatively it is carried out purification and impurity removal handles in batches, detrimental impurity (as aluminum oxide, magnesium oxide, calcium oxide, sulfide etc.) in the waste is fully reacted, promote to generate the less new compound of proportion by even, slight concussion simultaneously, new compound floats on above the waste and separates out, and heavy metal deposition is in lower floor.With this technology the detrimental impurity in the waste is reduced in the specialized range, makes waste obtain purifying, the main component behind the purifying is that (molecular formula is FeSiO to ferrous metasilicate
32FeOSiO
2) product.
Reaction equation is
FeS+3Fe
3O
4+ 5SiO
2+ 5O
2=5 (2FeOSiO
2)+SO
2↑ (under the high temperature fused state)
2Ca+O
2=2CaO (under the high temperature fused state)
2Mg+O
2=2MgO (under the high temperature fused state)
4Al+3O
2=2Al
2O
3(under the high temperature fused state)
2K+Cl
2=2KCl (under the high temperature fused state)
2Na+Cl
2=2NaCl (under the high temperature fused state)
The principle that the inventive method is produced ferrosilicon is:
Ferrous metasilicate, silica, coke and the blue carbon (or other reductive agent) of release mesh are prepared burden in proportion at the batching station, compound is delivered to throat platform, by the shuttle-type belt compound is unloaded to furnace top bin again through charging belt.Furnace charge is interrupted through the material pipe and adds in the electric arc furnace, and under the high arc temperature state, ferro element in the ferrous metasilicate and element silicon are reduced by carbon simultaneously, and the element silicon in the silicon-dioxide is also determined the ferrosilicon that mixes by carbon reduction generation ratio.
Reaction equation is
C+O
2=CO
2↑+heat (under the conditions at the arc)
C+CO
2=2CO ↑-heat
FeSiO
32FeOSiO
2+ 7CO=3Fe+2Si+7CO
2↑-heat (under the conditions at the arc)
SiO
2+ 2CO=Si+2CO
2↑-heat (under the conditions at the arc)
The inventive method mainly is the steel cuttings during the ferrous metasilicate behind the waste purification and impurity removal is produced as the existing ferrosilicon smelting of ferriferous raw material replacement, iron scale, ferriferous raw materials such as agglomerates of sintered pellets, certainly also substituted simultaneously the part silica raw material, because the content of silicon and iron is determined in the ferrous metasilicate, therefore can calculate the consumption of other raw material easily, with silicon, the proportion relation and the prior art of iron calculating stock yard are identical, and in addition have other raw material (as reductive agent) of deoxidation and reduction smelting duriron now, all proportion of raw materials, all identical with processing parameter etc. with prior art.
Below for producing low nickel matte, hot waste is the chemical component table of the electric furnace warm sludge composition representative value of ferronickel slag:
Electric furnace warm sludge composition (%) in three months
Embodiment 1:
A, nickel smelting waste slag is heated to 1150 ℃ molten state;
B, be positioned in the warm sludge bag insulation at 1150 ℃, stretch into warm sludge bag bottom aerating oxygen (high pressure oxygen) in nickel smelting waste slag by graphitized carbon cellulosic material gas duct simultaneously, the consumption of oxygen is 0.4 cubic metre of a nickel smelting waste slag per ton, and control oxygen is at the uniform velocity mobile, and aeration time is 5 minutes;
C, even, slight level were shaken the warm sludge bag 30 minutes, left standstill then 8 minutes;
D, remove the solid residue that the nickel smelting waste slag upper strata generates;
E, part (the being mainly ferrous metasilicate) cooling that will be left, broken again back requires to make the ball piece of suitable size according to existing ferrosilicon smelting;
F, then ferrous metasilicate ball piece is made ferrosilicon by the ratio of existing ferrosilicon smelting requirements by the smelting of deoxidation and reduction method with silica and blue carbon as ferriferous raw material.
Embodiment 2:
A, nickel smelting waste slag is heated to 1300 ℃ molten state;
B, be positioned in the warm sludge bag insulation at 1300 ℃, stretch into warm sludge bag bottom aerating oxygen in nickel smelting waste slag by graphitized carbon cellulosic material gas duct simultaneously, the consumption of oxygen is 1 cubic metre of a nickel smelting waste slag per ton, and control oxygen is at the uniform velocity mobile, and aeration time is 10 minutes;
C, even, slight level were shaken the warm sludge bag 40 minutes, left standstill then 12 minutes;
Rest part is identical with embodiment 1.
Embodiment 3:
A, nickel smelting waste slag is heated to 1200 ℃ molten state;
B, be positioned in the warm sludge bag insulation at 1200 ℃, stretch into warm sludge bag bottom aerating oxygen in nickel smelting waste slag by graphitized carbon cellulosic material gas duct simultaneously, the consumption of oxygen is 0.8 cubic metre of a nickel smelting waste slag per ton, and control oxygen is at the uniform velocity mobile, and aeration time is 8 minutes;
C, even, slight level were shaken the warm sludge bag 35 minutes, left standstill then 10 minutes;
Rest part is identical with embodiment 1.
Embodiment 4:
A, nickel smelting waste slag is heated to 1150 ℃ molten state;
B, be positioned in the warm sludge bag insulation at 1150 ℃, stretch into warm sludge bag bottom bubbling air (high-pressure air) in nickel smelting waste slag by graphitized carbon cellulosic material gas duct simultaneously, the consumption of air is 2 cubic metres of nickel smelting waste slags per ton, and control air is at the uniform velocity mobile, and aeration time is 5 minutes;
C, continuation insulation feed chlorine (removing sodium, potassium impurity) then at 1150 ℃ in nickel smelting waste slag, the consumption of chlorine (high pressure chlorine) is 0.1 cubic metre of a nickel smelting waste slag per ton, and aeration time is 5 minutes;
D, even, slight level were shaken the warm sludge bag 30 minutes, left standstill then 8 minutes;
E, remove the solid residue that the nickel smelting waste slag upper strata generates;
Rest part is identical with embodiment 1.
Embodiment 5:
A, nickel smelting waste slag is heated to 1300 ℃ molten state;
B, be positioned in the warm sludge bag insulation at 1300 ℃, stretch into warm sludge bag bottom bubbling air in nickel smelting waste slag by graphitized carbon cellulosic material gas duct simultaneously, the consumption of air is 5 cubic metres of nickel smelting waste slags per ton, and control air is at the uniform velocity mobile, and aeration time is 10 minutes;
C, continuation insulation feed chlorine (removing sodium, potassium impurity) then at 1300 ℃ in nickel smelting waste slag, the consumption of chlorine is 0.25 cubic metre of a nickel smelting waste slag per ton, and aeration time is 10 minutes;
D, even, slight level were shaken the warm sludge bag 40 minutes, left standstill then 12 minutes;
E, remove the solid residue that the nickel smelting waste slag upper strata generates;
Rest part is identical with embodiment 1.
Embodiment 6:
A, nickel smelting waste slag is heated to 1200 ℃ molten state;
B, be positioned in the warm sludge bag insulation at 1200 ℃, stretch into warm sludge bag bottom bubbling air in nickel smelting waste slag by graphitized carbon cellulosic material gas duct simultaneously, the consumption of air is 3 cubic metres of nickel smelting waste slags per ton, and control air is at the uniform velocity mobile, and aeration time is 7 minutes;
C, continuation insulation feed chlorine (removing sodium, potassium impurity) then at 1200 ℃ in nickel smelting waste slag, the consumption of chlorine is 0.2 cubic metre of a nickel smelting waste slag per ton, and aeration time is 8 minutes;
D, even, slight level were shaken the warm sludge bag 36 minutes, left standstill then 11 minutes;
E, remove the solid residue that the nickel smelting waste slag upper strata generates;
Rest part is identical with embodiment 1.
Embodiment 7:
A, directly get the nickel smelting waste slag of 1150 ℃ molten state;
B, be positioned in the warm sludge bag insulation at 1150 ℃, stretch into warm sludge bag bottom aerating oxygen in nickel smelting waste slag by graphitized carbon cellulosic material gas duct simultaneously, the consumption of oxygen is 0.8 cubic metre of a nickel smelting waste slag per ton, and control oxygen is at the uniform velocity mobile, and aeration time is 8 minutes;
C, remove the solid residue that the nickel smelting waste slag upper strata generates, also will remove the heavy metal layer that molten state nickel smelting waste slag lower floor accounts for nickel smelting waste slag gross weight 5%;
D, part (the being mainly ferrous metasilicate) cooling that will be left, broken again back requires to make the ball piece of suitable size according to existing ferrosilicon smelting;
E, then ferrous metasilicate ball piece is made ferrosilicon by the ratio of existing ferrosilicon smelting requirements by the smelting of deoxidation and reduction method with quartz and metallurgical coke as ferriferous raw material.
Embodiment 8:
A, directly get nickel, copper, the cobalt smelting waste slag of 1200 ℃ molten state;
B, be positioned in the warm sludge bag insulation and stretch into warm sludge bag bottom bubbling air in waste by graphitized carbon cellulosic material gas duct simultaneously at 1200 ℃, the consumption of air is 3 cubic metres of wastes per ton, and control air is at the uniform velocity mobile, and aeration time is 7 minutes;
C, continuation insulation feed chlorine (removing sodium, potassium impurity) then at 1200 ℃ in waste, the consumption of chlorine is 0.2 cubic metre of a waste per ton, and aeration time is 8 minutes;
D, remove the solid residue that the waste upper strata generates, also will remove the heavy metal layer that molten state waste lower floor accounts for waste gross weight 6%;
E, part (the being mainly ferrous metasilicate) cooling that will be left, broken again back requires to make the ball piece of suitable size according to existing ferrosilicon smelting;
F, then ferrous metasilicate ball piece is made ferrosilicon by the ratio of existing ferrosilicon smelting requirements by the smelting of deoxidation and reduction method with the gentle coal tar of quartz as ferriferous raw material.
Embodiment 9:
A, directly get nickel, copper, the cobalt smelting waste slag of 1200 ℃ molten state;
B, be positioned in the warm sludge bag insulation and stretch into warm sludge bag bottom bubbling air in waste by graphitized carbon cellulosic material gas duct simultaneously, meet the requirements until foreign matter content at 1200 ℃;
C, continuation insulation feed chlorine (removing sodium, potassium impurity) then at 1200 ℃ in waste, meet the requirements until foreign matter content;
D, even, slight level were shaken the warm sludge bag 36 minutes, left standstill then 11 minutes;
E, part (the being mainly ferrous metasilicate) cooling that will be left, broken again back requires to make the ball piece of suitable size according to existing ferrosilicon smelting;
F, then ferrous metasilicate ball piece is made ferrosilicon by the ratio of existing ferrosilicon smelting requirements by the smelting of deoxidation and reduction method with silica and metallurgical coke, blue carbon as ferriferous raw material.
By the ferrosilicon that adopts the foregoing description technical scheme to smelt is analyzed, under the situation of not removing the heavy metal layer of waste lower floor (being mainly nickel, cobalt etc.), the product that the present invention smelts is a microalloy ferro-silicon, country does not still have the microalloy ferro-silicon product standard at present, the microalloy ferro-silicon product is as the substitute products of common ferrosilicon, bring certain benefit to turn into the nickel, cobalt element of usefulness except that containing trace to steel products, all the other indexs are all identical with common 75% ferrosilicon, so the silicon iron product technical qualification of inventive method preparation meet the GB2272-87 specified standards.
Accordingly, under the situation of the heavy metal layer of removing waste lower floor, the product index that the present invention smelts is all identical with common 75% ferrosilicon, meets the GB2272-87 specified standards.
Claims (7)
1. a method of utilizing ferrous metasilicate electric stove integral deoxidation and reduction to produce microalloy ferro-silicon is characterized in that, comprises the steps:
A, nickel smelting waste slag or nickel, copper, cobalt smelting waste slag are heated to molten state, or directly get the nickel smelting waste slag of molten state or nickel, copper, cobalt smelting waste slag, be positioned in the warm sludge bag;
B, insulation make waste keep molten state, thereby use graphitized carbon cellulosic material gas duct to stretch in this warm sludge bag in waste aerating oxygen simultaneously or air generates solid residue with purification and impurity removal;
C, remove solid residue;
D, the part cooling back fragmentation that will be left;
E, produce microalloy ferro-silicon with other raw material by the deoxidation and reduction method as ferriferous raw material then, wherein other raw material is meant silica and reductive agent, or quartz and reductive agent, and reductive agent adopts metallurgical coke.
2. the method for utilizing ferrous metasilicate electric stove integral deoxidation and reduction to produce microalloy ferro-silicon as claimed in claim 1 is characterized in that: wherein also need to shake the warm sludge bag 30-40 minute before step c, left standstill then 8-12 minute.
3. the method for utilizing ferrous metasilicate electric stove integral deoxidation and reduction to produce microalloy ferro-silicon as claimed in claim 1 is characterized in that: wherein also will remove the heavy metal layer that molten state waste lower floor accounts for waste gross weight 4-6% behind step c.
4. the method for utilizing ferrous metasilicate electric stove integral deoxidation and reduction to produce microalloy ferro-silicon as claimed in claim 1, it is characterized in that: wherein behind step b, also will be incubated and make waste maintenance molten state, thereby in waste, feed chlorine simultaneously and generate solid residue with purification and impurity removal, the consumption of chlorine is a waste 0.1-0.25 cubic meter per ton, aeration time is 5-10 minute, or feeding chlorine meets the requirements until foreign matter content in waste.
5. the method for utilizing ferrous metasilicate electric stove integral deoxidation and reduction to produce microalloy ferro-silicon as claimed in claim 1, it is characterized in that: wherein the consumption of aerating oxygen is a waste 0.4-1 cubic meter per ton in step b, aeration time is 5-10 minute, or aerating oxygen meets the requirements until foreign matter content in waste.
6. the method for utilizing ferrous metasilicate electric stove integral deoxidation and reduction to produce microalloy ferro-silicon as claimed in claim 1, it is characterized in that: wherein the consumption of bubbling air is a waste 2-5 cubic meter per ton in step b, aeration time is 5-10 minute, or bubbling air meets the requirements until foreign matter content in waste.
7. as any described method of utilizing ferrous metasilicate electric stove integral deoxidation and reduction to produce microalloy ferro-silicon in the claim 1 to 6, it is characterized in that: wherein the waste of molten state is meant that the waste temperature is at 1150 ℃-1300 ℃.
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|---|---|---|---|
| CN2009101172273A CN101545045B (en) | 2009-02-12 | 2009-02-12 | Method for producing microalloy ferro-silicon by using a ferrous metasilicate electric stove integral deoxidation and reduction |
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