CN103938081B - For the ambrose alloy iron alloy of making steel and preparation method - Google Patents
For the ambrose alloy iron alloy of making steel and preparation method Download PDFInfo
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- CN103938081B CN103938081B CN201310657483.8A CN201310657483A CN103938081B CN 103938081 B CN103938081 B CN 103938081B CN 201310657483 A CN201310657483 A CN 201310657483A CN 103938081 B CN103938081 B CN 103938081B
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- iron
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- copper
- nickel
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Abstract
<b/><b/><b/><b/><b/> the present invention is to provide webbite---ambrose alloy iron alloy.Its preparation method makes raw material with nickelous sulfide, copper-sulphide ores (containing tantalite power), adds flux make sweetening agent with squama iron.A step pyrometallurgical smelting ambrose alloy iron alloy in a furnace.The consumption of sweetening agent adds comparing for 1:0.3-0.8 containing oxygen of flux according to sulphur content in sulphide ores used and squama iron, and the ratio of squama iron and flux is between 1:1-5.So not only remove the sulphur in nickel, copper iron, retain the iron that mineral bring alloy into simultaneously.For make steel can reach nickel, copper alloying while, can also output of steel be increased.The carbonaceous fuel of 5%-10% of furnace charge total amount also will be added in furnace charge.Nickeliferous and copper 2%-50% in alloy, surplus is iron and inevitable impurity.Also can production of copper iron and Rhometal in this approach, for the alloying constituent of making steel.Make the alloying constituent of making steel with ambrose alloy iron of the present invention, steel cost can be reduced.There are good economic benefit and social benefit.
Description
Technical field
The present invention is ambrose alloy iron alloy for making steel and preparation method, belongs to chemical metallurgy technical field.
Background technology
Nickel and copper belong to nonferrous heavy metal, and their physico-chemical property, smelting technology, mineral wealth are all quite similar, and again with being all steelmaking alloy element, they can form alloy with silicon, iron etc. again.This provides favourable condition and scientific basis to the manufacture of research and production nickel and copper.
The production method that they produce ambrose alloy iron with ore or concentrate is more, has summed up pyrogenic process and the large class of wet method two.Pyrogenic process produces nickel and copper is main method, accounts for more than 80% (quality is as follows) of ambrose alloy output.The pyrogenic process technological process of production of nickel, copper sulfurized ore: the first step, sulphide ores/concentrate roasting; Second step, is smelted into nickel matte or copper matte regulus in a furnace, is the compound of nickel or copper, iron and sulphur; 3rd step, bessemerizes and removes sulphur, iron and other impurity, produce thick nickel or blister copper; 4th step, electrorefining produces electric nickel, copper.
At present, except pyrogenic process produces nickel, copper, still additive method is had.As Rhometal, be produce by carbothermic method, raw material used is only limited to nickel oxide ore and silicate nickel minerals; Also have the ambrose alloy iron alloy that pyrogenic process is produced, it makes flux with lime and the iron in mineral than 0.25--0.5%, and in alloy siliceous 5%, this alloy is to use in without silicon steel and low-silicon steel.In the iron alloy of steel-making, siliceous less than 5% is impurity.If use this alloy in steel-making comprehensively, silica removal process must be carried out; Also the technology had is a pyrometallurgical smelting blister copper, is impure more with the blister copper of lime or the production of lime masonry sweetening agent.Must electrolysis could use in steel-making; Now commercially also have ambrose alloy iron alloy, it makes a kind of alloy with the waste material secondary remelting of pure metal.Owing to yielding poorly by resource limit, price is not cheap yet.Above-mentioned technology nickel, copper and the alloy produced due to impurity more, the reasons such as production cost is high, and price is more expensive, not yet can use, still make alloying constituent with pure metallic nickel and copper at present in steel-making.
Summary of the invention
The object of the invention is to add flux desulfurization with squama iron, a step pyrogenic process produces ambrose alloy iron alloy, for webbite, substitutes nickel and the copper of pure metal.Production technique is simple, and production cost is low, can create better economic benefit and social benefit.
The ambrose alloy iron alloy that the present invention produces, makes raw material, with squama iron (containing FeO, Fe with the sulphide ores (concentrate) of ambrose alloy
2o
3, Fe
3o
4) and flux (as: lime, Wingdale, calcium carbide, fluorite etc.), with the use of making sweetening agent.In smelting furnace (as blast furnace, reverberatory furnace, electric furnace etc.), single stage method melting ambrose alloy iron alloy.When making raw material with oxidized ore, by their oxidized ore through sulfidation roasting process, then carry out pyrometallurgical smelting.
Ambrose alloy iron produced by the present invention's sulphide ores, and its principle is: cupric sulfide (CuS), nickelous sulfide (NiS), at about 500 DEG C, generate cuprous sulfide (Cu
2s), the sub-nickel (Ni of sulfuration
2s) i.e. 4CuS → 2Cu
2s+S
2with 4NiS → 2Ni
2s+S
2.When the sub-nickel of cuprous sulfide and sulfuration is more than 1150 DEG C, the oxygen in squama iron and flux is combined with the sulphur in the sub-nickel of cuprous sulfide sulfuration, and generation sulfurous gas is overflowed, and copper and iron are in conjunction with generating nickel copper-iron alloy.That is: Cu
2s+Ni
2s+2FeO=2FeCuNi+SO
2↑.
Squama iron and flux with the use of sweetening agent, one, increase the activity of Strong ferric oxide, improve squama iron sweetening power, two, oxygen in flux in oxide compound also participates in desulfurization, three, slag fluidity is good.Want sulfur-bearing in sulphide ores too high (>=20%), large by squama iron, make iron content in copper-iron alloy too high.At this moment can use squama iron less, add flux, reduce the iron level in alloy.How many squama iron and flux proportionings, should change according to the content of iron in sulphide ores and sulphur and change.Between the ratio 1:1--5 of squama iron and flux.
Sulphur content in nickel sulfide ore used (containing fine ore) or cupric sulfide (containing fine ore), the ratio adding the oxygen level in flux with squama iron is 1:0.3--0.8.The carbonaceous fuel of 5%-10% also will be added, as coal, coke etc. in furnace charge.
Nickel is similar to the physics and chemistry behavior of copper, and mineralogical property is similar, and production technique is substantially identical, can form alloy again with iron.Nickel, copper mine mostly are mineral intergrowth, containing a small amount of copper in nickel minerals, containing a small amount of nickel in copper mine, claim ambrose alloy sulphide ores.Therefore, a small amount of nickel or copper is contained in alloy.The composition of nickel to be improved in alloy, nickel minerals consumption can be increased.Will improve the composition of copper in alloy, can increase copper mine consumption, making alloy is ambrose alloy iron alloy.
Improve nickel or copper content in alloy, when not reaching alloying constituent with nickel, copper mine and tantalite power, ice nickel or matte can be selected to substitute their mineral.
Secondary remelting can be carried out with copper iron or ferronickel and metallic copper, nickel, make ambrose alloy iron alloy.
At present, production of copper, nickel technique are: dropped in smelting furnace by sulphide ores raw material, produce compound---ice nickel or the matte of nickel or copper, iron, sulphur.Matte or ice nickel are dropped into converter melting, is being blown into oxygen-rich air and removes sulphur in matte or ice nickel, make blister copper or thick nickel.In desulfurization simultaneously, the steel-making useful element oxidations by air such as a large amount of iron in matte or ice nickel and a small amount of cobalt, chromium are become slag to remove.Material for steel-making is kind of a wasting of resources.The present invention with squama iron and flux with the use of, only slough the sulphur in matte or ice nickel, retaining iron can increase output of steel.Meanwhile, converter removing impurities and refining two procedures is eliminated again.
Not containing copper in some nickel minerals, not containing nickel in copper mine, or containing trace, available preparation method of the present invention, produces ferronickel or copper-iron alloy, for the copper alloy of making steel and nickelalloy.
In a word, the present invention makes raw material with nickel sulfide ore or copper-sulphide ores (containing tantalite power), coordinate with squama iron and flux and make sweetening agent, add the ratio 1:0.3--0.8 of the oxygen level in flux according to sulphur content in sulphide ores used and squama iron, the ratio of squama iron and flux is between 1:1--5.One step pyrometallurgical smelting ferronickel, copper iron or ambrose alloy iron alloy.Contain nickel and the copper of 2%-50% in the alloy, surplus is iron and inevitable impurity.Summation≤4% of silicon, carbon, sulphur, phosphorus in impurity.If in alloy during sulfur-bearing >=0.5%, sodium carbonate can be added in liquation bag, sodium hydroxide, sodium-chlor carries out the process such as sulphur removal, existing maturation process.
It is identical that one step pyrometallurgical smelting ambrose alloy iron alloy and pyrogenic process produce matte.
Embodiment
Below by specific embodiment, the present invention is described.In embodiment, the drying of nickel, copper ore concentrates, roasting, kneading and melting equipment and operating procedure and production nickel, copper are identical, so no longer describe in detail in an embodiment.
Embodiment 1
Charge composition: brass concentrate (CuFeS
2) 100kg, containing Cu29%, Fe25%, S31%, Ni3%, SiO
26%.Squama iron 50kg, about containing Fe
2o
320%, Fe
3o
450%, FeO40%, containing oxygen total amount 17% in squama iron.Lime 20kg.Containing CaO82%, calcium oxide containing oxygen about 6%.Coke 10kg, returning charge 100kg.Mix, drop into melting 1 hours in closed blast furnace.To come out of the stove casting mold, through chemical examination alloying constituent:
Cu35%, Fe61%, Ni2%, impurity 2%.S0.04%, Si1.5%, C0.5%, P0.03% in impurity, also have Ni, Co, Cr etc. of trace.SO
2collect.
Embodiment 2
Charge composition: sintering nickel yellow iron ore concentrate [(FeNi)
9s
8] 100kg, containing Ni32%, Cu2%, Fe31%, S30%.Returning charge 100kg, squama iron 10kg, Wingdale 50kg, coal grain 15kg.Above-mentioned furnace charge is mixed, drops into melting in closed blast furnace.
Alloying constituent: Ni41%, Fe52%, Cu3%, total impurities 4%.
Embodiment 3
Charge composition: low nickel matte 100kg, containing Ni17%, Cu4%, Fe47%, S24%.Chalcopyrite 50kg, containing Cu29%, Fe25%, S31%.Return furnace charge 120kg, squama iron 10kg, lime 60kg, nut coke 15kg.Mixed by furnace charge, drop into melting in closed blast furnace, chemical examination alloying constituent of coming out of the stove: Ni21%, Cu20%, Fe57%, all the other are impurity.Also raw material can be made with matte and ice nickel, melting ambrose alloy iron alloy.
Embodiment 4
Charge composition: copper sulfide concentrate 100kg, containing Cu23%, Fe28%, S29%, returning charge 100kg, squama iron 20kg, Wingdale 60kg, coke 25kg.Furnace charge is mixed, drops into melting in reverberatory furnace.To come out of the stove chemical examination alloying constituent: Cu42%, Fe55%, all the other are impurity.
Embodiment 5
Charge composition: the copper iron 100kg that embodiment 1 is produced, metallic nickel 30kg.Drop into electrosmelting of intermediate frequency, chemical examination alloying constituent of coming out of the stove: Ni23%, Cu28%, surplus is Fe and impurity.
Embodiment 6
Certain steel mill produces X70 pipe line steel, and former ton steel adds metallic nickel 1.9kg, metallic copper 1.8kg, close Renminbi about 2800 yuan, with the embodiment of the present invention 3 ambrose alloy iron alloy, ton steel adds 9.5kg, close Renminbi 2750 yuan, ton steel reduces costs 50 yuan, ton steel increase yield 6kg.
Claims (1)
1. the preparation method of ambrose alloy iron alloy for making steel, it is characterized in that: in ambrose alloy iron alloy, containing weight percent 2-50% nickel and copper, surplus is iron and inevitable impurity, its preparation method is: make raw material with the sulphide ores of nickel, copper or tantalite power, add flux with squama iron and make sweetening agent, containing FeO, Fe in described squama iron
2o
3, Fe
3o
4, pyrogenic process makes ambrose alloy iron alloy in a furnace, and in the sulfide of nickel and copper, sulphur content and squama iron add the weight ratio of oxygen level in flux is 1:0.3-0.8, and squama iron and flux are than being 1:1-5.
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| CN115747542B (en) * | 2022-11-02 | 2023-11-07 | 中南大学 | Method for preparing Fe-Ni-Co-Cu high-entropy alloy by reducing nickel converting slag |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3846185A (en) * | 1968-09-11 | 1974-11-05 | Mitsubishi Electric Corp | Method of producing semi-hard magnetic ni-cu-fe alloys and the resulting product |
| JP3038441B2 (en) * | 1990-06-26 | 2000-05-08 | 株式会社トーキン | Alloy material having large Barkhausen effect and method of manufacturing alloy wire for magnetic wire pulsar using the same |
| JPH0625793A (en) * | 1992-07-08 | 1994-02-01 | Kobe Steel Ltd | Fe-cu-ni compound powder for powder metallurgy and its manufacture as well as sintered body using the same powder |
| CN101250658A (en) * | 2008-03-28 | 2008-08-27 | 常州武帆合金有限公司 | Nickel copper alloy |
| CN100590216C (en) * | 2008-10-17 | 2010-02-17 | 河北上大再生资源科技有限公司 | Nickel-copper intermediate alloy and smelting purification processing method thereof |
| CN101935796A (en) * | 2008-10-17 | 2011-01-05 | 河北上大再生资源科技有限公司 | Ni14 nickel-iron intermediate alloy |
| CN101892423A (en) * | 2010-07-29 | 2010-11-24 | 大连理工大学 | Cu-containing Fe-Ni stainless steel alloy |
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