CN104342560B - A kind of metallurgical composite slag one step reduction obtains molten iron and the technique of sulfonium phase - Google Patents
A kind of metallurgical composite slag one step reduction obtains molten iron and the technique of sulfonium phase Download PDFInfo
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- ferrum
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Abstract
A kind of metallurgical composite slag one step reduction obtains molten iron and the technique of sulfonium phase, belongs to Ferrous Metallurgy and technical field of non-ferrous metallurgy.Relate to the separation and recovery that metallurgical composite slag is realized during molten point of reduction ferrum and non-ferrous metal.By allocating Calx into after levigate for metallurgy composite slag, carbonaceous reducing agent prepares carbonaceous pelletizing, realizes slag sulfonium ferrum three-phase layering, be separately recovered ferrum and non-ferrous metal after carbonaceous pelletizing direct-reduction in molten point of stove.This kind of technique can not only realize ferrum and separate with non-ferrous metal, moreover it is possible to non-ferrous metal is enriched in sulfonium mutually in, play the effect to multiple metallic element synthetical recovery.The stacking of metallurgical slag not only causes serious environmental problem, also creates the significant waste of resource, and this technique utilizes present situation by greatly change metallurgical slag, produces considerable economic benefit and social benefit, has broad application prospects.
Description
Technical field
The invention belongs to Ferrous Metallurgy and technical field of non-ferrous metallurgy, particularly relate to a kind of metallurgical composite slag one step also
The former technique obtaining molten iron and sulfonium phase, make in metallurgical composite slag the comprehensive reutilization of metallic element, particularly ferrum with
The reduction of non-ferrous metal copper, nickel etc. and separation and recovery.
Technical background
Pyrometallurgical smelting is topmost metallurgy of copper mode, and its copper yield accounts for the 80% of total copper yield, domestic even up to
97%, the copper ashes yield of ton copper is about 2.2t, and the quantity of slag is huge.Copper ashes ferrum, copper grade are respectively 30%～40% and
0.5%～2%, there is the highest recycling and be worth.The Iron grade of nickel slag is suitable with copper ashes, possibly together with 0.2%～0.7%
Nickel.
The Land use systems of copper ashes mainly includes pyrogenic process dilution and mill float glass process.The former reduces slag by reduction or sulfuration enrichment
In copper content, copper is recovered with the form of sulfide.Mill float glass process is a kind of physical treatment mode, can effectively return
Receive sulfide and the metal of copper, but invalid to oxide.Therefore, both the above method has selection to the recovery of copper
Property.Up to the present, the molten point mode of reduction is still that the process maximally effective means of copper ashes, but copper almost all enters
Molten iron forms copper-iron alloy, and both separate difficulty.Nickel is close with the character of copper, is easily formed ferronickel in reduction process
Alloy.There are some researches show, when carbon content forms the layering of molten iron and sulfonium in molten iron when reaching certain content, add
FeS-MS (M is alkali metal or alkaline-earth metal) flux can strengthen non-ferrous metal further between sulfonium with molten iron phase
Distribution ratio, promote non-ferrous metal separate with ferrum.
Summary of the invention
It is an object of the invention to provide a kind of metallurgical composite slag one step reduction and obtain molten iron and the technique of sulfonium phase, this work in skill, copper ashes, nickel slag is reduced with the form of carbonaceous pelletizing, molten point (molten point, be to complete after material melts completely Slag separates with melt) after obtain molten iron and sulfonium phase (copper matte regulus, nickel matte), and other trace non-ferrous metal element is rich Combine in sulfonium mutually in, it is achieved that the synthetical recovery of metal.
The present invention relates to during molten point of reduction, realize metallurgical composite slag the separation and recovery of ferrum and non-ferrous metal.Will
Allocate Calx into after metallurgical composite slag is levigate, carbonaceous reducing agent prepares carbonaceous pelletizing, molten after carbonaceous pelletizing direct-reduction
Realize slag-sulfonium-ferrum three-phase layering in dividing stove, be separately recovered ferrum and non-ferrous metal.This kind of technique can not only realize ferrum and have
The separation of non-ferrous metal, moreover it is possible to non-ferrous metal is enriched in sulfonium mutually in, play the effect to multiple metallic element synthetical recovery.
The stacking of metallurgical slag not only causes serious environmental problem, also creates the significant waste of resource, and this technique is by pole
Greatly change metallurgical slag utilizes present situation, produces considerable economic benefit and social benefit, before having wide application
Scape.
Metal-oxide and sulfide in composite slag are all reduced, and during molten point, molten iron is in the case of carbon is saturated
Realize the three-phase layering of slag-ferrum-sulfonium, and non-ferrous metal enrichment of element in sulfonium mutually in, reach metallic element is comprehensively returned
The purpose received.Concrete technology and the technical parameter controlled in process are as follows:
A carbonaceous pelletizing is reductase 12 0～30mins within the temperature range of 1250 DEG C～1300 DEG C, copper in composite slag, nickel,
The oxide of the elements such as ferrum and sulfide are reduced thoroughly:
Cu2S+CaO+C=2Cu+CO+CaS (1)
ΔGθ=116478-125T
Ni3S2+ 2CaO+2C=3Ni+2CO+2CaS (2)
ΔGθ=199376-250T
FeS+CaO+C=Fe+CO+CaS (3)
ΔGθ=141310-154T
Cu2O+C=2Cu+CO (4)
ΔGθ=57540-161T
NiO+C=Ni+CO (5)
ΔGθ=119062-171T
2FeO·SiO2+ 2CaO+2C=2Fe+2CO+2CaO SiO2 (6)
ΔGθ=209711-325T
B metallized pellet is molten within the temperature range of 1400 DEG C～1450 DEG C to be divided, it is achieved the separation that slag-ferrum is biphase；
C molten iron carburizing in the presence of having coke layer reaches saturated, and the sulfur in molten iron and carbon have alternative and formed
Fe-FeS two-phase, it is achieved ferrum, sulfonium separate；
The sulfide of the metals such as d copper, nickel is more higher than the sulfide stability of ferrum, and vulcanization reaction occurs
[FeS]+2 [Cu]=[Fe]+[Cu2S] (7)
2 [FeS]+3 [Ni]=2 [Fe]+[Ni3S2] (8)
The metal such as copper, nickel enters sulfonium phase, it is achieved non-ferrous metal separates with ferrum；
The raw material of the present invention reduces in the way of carbonaceous pelletizing, the existence of coke layer must be had to ensure in molten point of stove
The carbon content of molten iron, meanwhile, the sulfur part needed for vulcanization reaction comes from slag itself, and not enough part is by combustion
The sulfur that material strip enters supplements, and finally realizes the three-phase layering of slag-sulfonium-ferrum, reaches the purpose of comprehensive recovery of metallic elements.
Accompanying drawing explanation
Fig. 1 is copper ashes, the reduction of nickel slag one step, molten divisional processing flow chart.
Fig. 2 is the liquidus curve of FeS-MS binary system.
Fig. 3 is three-phase metallurgy principle schematic diagram.
Detailed description of the invention
Embodiment 1
Yunnan granulated copper slag, TFe content is 40.57%, and copper content is 0.75%, and natural alkalinity is 0.15.By copper
Slag is ground to granularity less than the powder of 0.125mm, and prepares basicity after adding a certain amount of Calx and coal blending and be
The carbonaceous pelletizing of 1.0.It is dried 4h in the carbonaceous pelletizing prepared is placed in 200 DEG C of baking ovens, puts into tubular electric resistance afterwards
In stove 1400 DEG C, graphite crucible inside holding 40mins carry out molten point.The granulated iron quality obtained after weighing molten point, really
Determine the recovery rate of ferrum, determined the copper content of sample by chemical titration analysis.Analysis result shows, when basicity is 1.0
The recovery rate of ferrum increases with the prolongation of temperature retention time, and reaching recovery rate during 40mins is 91%, granulated iron copper content with
The prolongation of temperature retention time and reduce, be reduced to 0.4% during 40mins, in molten iron, the removal efficiency of copper is close to 80%.
Embodiment 2
Jiangyin copper ashes, TFe content is 42.94%, and copper content is 0.69%, and natural alkalinity is 0.07.By river copper ashes
It is ground to granularity less than the powder of 0.125mm, and prepares carbonaceous pelletizing after adding a certain amount of Calx and coal blending.
The carbonaceous pelletizing prepared is placed in 200 DEG C of baking ovens and is dried 4h, put into afterwards tube type resistance furnace 1400 DEG C,
Graphite crucible inside holding 40mins carries out molten point.The granulated iron quality obtained after weighing molten point, determines the recovery rate of ferrum,
The copper content of sample is determined by chemical titration analysis.Analysis result shows, when basicity is 1.0, the recovery rate of ferrum is
92.3%, granulated iron copper content is reduced to 0.38%, and in molten iron, the removal efficiency of copper is more than 75%.
Embodiment 3
The nickelic slag in Jinchang, TFe content is 32.97%, and nickel content is 0.639%, and natural alkalinity is 0.59.By copper ashes
It is ground to granularity less than the powder of 0.125mm, and prepares carbonaceous pelletizing after adding a certain amount of Calx and coal blending.
The carbonaceous pelletizing prepared is placed in 200 DEG C of baking ovens and is dried 4h, put into afterwards tube type resistance furnace 1400 DEG C,
Graphite crucible inside holding 40mins carries out molten point.The granulated iron quality obtained after weighing molten point, determines the recovery rate of ferrum,
The nickel content of sample is determined by chemical titration analysis.Analysis result shows, when basicity is 1.0, the recovery rate of ferrum is
88%, granulated iron nickel content is reduced to 0.21%, and in molten iron, the removal efficiency of nickel is 85%.
Claims (2)
1. metallurgical composite slag one step reduction obtains molten iron and the technique of sulfonium phase, it is characterised in that technique and in work
The technical parameter controlled in skill is as follows:
A carbonaceous pelletizing is reductase 12 0～30mins within the temperature range of 1250 DEG C～1300 DEG C, copper in composite slag, nickel,
The oxide of ferrum element and sulfide are reduced thoroughly:
Cu2S+CaO+C=2Cu+CO+CaS (1)
ΔGθ=116478-125T
Ni3S2+ 2CaO+2C=3Ni+2CO+2CaS (2)
ΔGθ=199376-250T
FeS+CaO+C=Fe+CO+CaS (3)
ΔGθ=141310-154T
Cu2O+C=2Cu+CO (4)
ΔGθ=57540-161T
NiO+C=Ni+CO (5)
ΔGθ=119062-171T
2FeO·SiO2+ 2CaO+2C=2Fe+2CO+2CaO SiO2 (6)
ΔGθ=209711-325T
B metallized pellet is molten within the temperature range of 1400 DEG C～1450 DEG C to be divided, it is achieved the separation that slag-ferrum is biphase；
C molten iron carburizing in the presence of having coke layer reaches saturated, and the sulfur in molten iron and carbon have alternative and formed
Fe-FeS two-phase, it is achieved ferrum, sulfonium separate；
D copper, nickel metal sulfide more higher than the sulfide stability of ferrum, occur vulcanization reaction
[FeS]+2 [Cu]=[Fe]+[Cu2S] (7)
2 [FeS]+3 [Ni]=2 [Fe]+[Ni3S2] (8)
Copper, nickel metal enter sulfonium phase, it is achieved non-ferrous metal separates with ferrum.
Method the most according to claim 1, it is characterised in that raw material reduces in the way of carbonaceous pelletizing,
The existence of coke layer must be had in molten point of stove to ensure the carbon content of molten iron, meanwhile, the sulfur part needed for vulcanization reaction
Coming from slag itself, the sulfur that not enough part is brought into by fuel supplements, and finally realizes the three-phase layering of slag-sulfonium-ferrum,
Reach the purpose of comprehensive recovery of metallic elements.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107151743A (en) * | 2017-04-25 | 2017-09-12 | 昆明理工大学 | A kind of pyrite vulcanization corronil waste material makes copper matte regulus and the method for reclaiming dilval |
| CN107641718A (en) * | 2017-10-10 | 2018-01-30 | 东北大学 | A kind of method by the nickeliferous mixing slag production with iron |
| CN107699702A (en) * | 2017-10-10 | 2018-02-16 | 东北大学 | A kind of method that valuable component is reclaimed by cupric slag |
| CN109055720B (en) * | 2018-09-06 | 2019-10-25 | 钢研晟华科技股份有限公司 | A method of iron powder is prepared based on the modified copper ashes with cryogenic vulcanization reduction of alkaline process |
| CN110205432B (en) * | 2019-05-15 | 2020-12-25 | 昆明理工大学 | Method for producing iron-sulfur alloy |
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| CN103627835A (en) * | 2013-11-12 | 2014-03-12 | 金川集团股份有限公司 | Method for treating nickel smelting furnace slag |
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| CN101629222A (en) * | 2009-08-14 | 2010-01-20 | 吕鲁平 | Method for obtaining chromated nickel base material by treatment of chrome slag with smelting reduction process |
| CN101792863A (en) * | 2010-01-22 | 2010-08-04 | 北京科技大学 | Method for extracting valuable elements from slag of melted high-iron high-silicon nonferrous metal |
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