CN110184476A - A method of eliminating furnace knot in sedimentation electric furnace - Google Patents
A method of eliminating furnace knot in sedimentation electric furnace Download PDFInfo
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- CN110184476A CN110184476A CN201910404495.7A CN201910404495A CN110184476A CN 110184476 A CN110184476 A CN 110184476A CN 201910404495 A CN201910404495 A CN 201910404495A CN 110184476 A CN110184476 A CN 110184476A
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- 238000004062 sedimentation Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000002893 slag Substances 0.000 claims abstract description 56
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims abstract description 47
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 43
- 239000000956 alloy Substances 0.000 claims abstract description 43
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000010949 copper Substances 0.000 claims abstract description 27
- 229910052802 copper Inorganic materials 0.000 claims abstract description 25
- 229910052742 iron Inorganic materials 0.000 claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000003723 Smelting Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005864 Sulphur Substances 0.000 claims abstract description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 2
- 239000012634 fragment Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 230000005484 gravity Effects 0.000 abstract description 15
- 230000008030 elimination Effects 0.000 abstract description 5
- 238000003379 elimination reaction Methods 0.000 abstract description 5
- 229910000805 Pig iron Inorganic materials 0.000 abstract description 4
- 238000009856 non-ferrous metallurgy Methods 0.000 abstract description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 33
- 238000006722 reduction reaction Methods 0.000 description 19
- 230000009467 reduction Effects 0.000 description 18
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 10
- 239000002699 waste material Substances 0.000 description 10
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 238000007664 blowing Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910000570 Cupronickel Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 description 4
- 239000011028 pyrite Substances 0.000 description 4
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 4
- 229910052683 pyrite Inorganic materials 0.000 description 4
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- YGHCWPXPAHSSNA-UHFFFAOYSA-N nickel subsulfide Chemical compound [Ni].[Ni]=S.[Ni]=S YGHCWPXPAHSSNA-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 240000007817 Olea europaea Species 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 241000722270 Regulus Species 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- XXWDKWAUNILFEM-UHFFFAOYSA-N S.[Au+3] Chemical compound S.[Au+3] XXWDKWAUNILFEM-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003818 cinder Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009867 copper metallurgy Methods 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001535 kindling effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- -1 magnesium aluminate Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0054—Slag, slime, speiss, or dross treating
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/006—Pyrometallurgy working up of molten copper, e.g. refining
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to a kind of methods for eliminating furnace knot in sedimentation electric furnace, belong to technical field of non-ferrous metallurgy.The blend melt of the smelting slag of output during copper weld pool and sulfonium is sent into the clarified separation that sedimentation electric furnace carries out slag sulfonium, when melt temperature in control electric furnace carries out the sedimentation of sulfonium within the set range, iron sulphur alloy is put into molten bath, iron sulphur alloy is the alloy that fe and ferrous sulfide are constituted, wherein iron 61%~70%, sulphur 25%~35% in iron sulphur alloy；The specific gravity of iron sulphur alloy is 5.3~7.0 grams/cm3, fusing point is 900~1300 DEG C, 1~40mm of granularity.It can guarantee the furnace bottom furnace knot thickness control of sedimentation electric furnace in 300mm hereinafter, slag-drip opening, sulfonium mouth is unimpeded does not block by row using method of the invention；Furnace knot fusing speed is fast, whole to eliminate furnace knot.Furnace knot is eliminated with the pig iron, can generate dell, unfavorable whole elimination furnace knot in furnace knot layer.
Description
Technical field
The present invention relates to a kind of methods for eliminating furnace knot in sedimentation electric furnace, belong to technical field of non-ferrous metallurgy.
Background technique
It is convergence of the desulfurization except iron and oxide gangue by the chemical nature of raw material copper metallurgy of copper-sulphide ores.Traditional smelting
Method for example electric furnace, blast furnace, reverberatory smelting because rate of driving it is little, the oxygen gesture of system is lower, and the harm of magnetic iron oxide is not
It is prominent.And the development trend of modern metallurgy of copper is Strong oxdiative melting, since system oxygen gesture is high, rate of driving is big, matte grade is high,
It is that Copper in Slag is caused to increase and formed the major reason of furnace knot that the content of magnetic iron oxide, which increases, in smelting slag.Through peroxidation
It answers, a part of iron forms Fe in furnace charge3O4, Fe3O4Fusing point high (1597 DEG C) deposited in slag with Fe-O complicated ions state
When the amount thereof is large, slag melting can be made to increase, specific gravity increases, and is degrading slag and separates with the supernatant of sulfonium.When smelting slag is sent into
Settle electric furnace, the Fe in melt3O4It can partially be precipitated and be sunken to furnace bottom formation furnace knot, the composition of furnace knot is other than magnetic iron oxide, also
Oxide containing magnesium aluminate spinel and Cu, Ni and Co.
Furnace bottom furnace knot thickens the normal operating that can endanger sedimentation electric furnace, and furnace knot thickness maintains 200mm~300mm to protection
Furnace bottom is advantageous.The blocked up furnace knot formed in sedimentation EAF bottom how is efficiently and safely eliminated, is the coke of modern metallurgy of copper concern
Point and technical problem.
It is the addition pyrite, high-quality copper concentrate, life into molten bath with the conventional method that reduction-sulfurization technology eliminates furnace knot
The one kind of these substances or several such as iron, ferrosilicon, silicon carbide, coke, coal, oils reducing agent, natural gas, acidity or basic solvent
Kind, the mode of addition is divided into furnace roof and is sprinkled into, is brought into chute with smelting slag, spraying into these types of mode with spray gun insertion molten bath.By
It is limited to settle the structure of electric furnace and the physicochemical property of admixture, these method defects are obvious:
The pig iron, ferrosilicon ratio be great can to pass through molten slag layer and molten matte layer sinks to bottom oven knot, to Fe3O4It is restored, but not
Tool make to the cupro-nickel cobalt/cobalt oxide in furnace knot the ability of sulfonium.The pig iron, ferrosilicon fusing point are high, under the operation temperature of sedimentation electric furnace
Slowly, reaction rate is low for fusing.
Silicon carbide, coke, coal can be to the Fe in furnace knot without the participation of flux3O4It is restored, but these three substances
Specific gravity is small, can float on upper layer in the melt, it is difficult to touch furnace knot, in order to obtain good reacting dynamics condition, need to use
These three substances are sent to furnace bottom with plug-in type spray gun by gas stirring molten bath, but melt splash is inevitably caused to exist
Furnace wall furnace roof generates serious dross, while also disturbing the environment of slag sulfonium standing sedimentation separation, causes electric furnace waste containing valuable
Metal is high.
Ferrous sulfide in pyrite, high-quality copper concentrate needs the participation by silica flux, could be in furnace knot
Fe3O4It is restored.Since the specific gravity of silica is less than the specific gravity of slag, pyrite and copper concentrate also sink to be needed less than furnace bottom, therefore also
To stir molten bath well by compress wind could eliminate furnace knot using pyrite, copper concentrate.
Diesel oil, natural gas are used as reducing agent and eliminates furnace knot, needs that diesel oil or natural gas are sent to furnace bottom with spray gun, it is raw
Problem appear to is that slag splash causes furnace wall furnace roof dross in production, spray gun scaling loss is serious, and rifle position control is inaccurate, and Fe3O4's goes back
Former rate is low.
Also slag can be allowed to contact with furnace knot as far as possible, while lower shift electrode improves electric furnace function using slag face is reduced in production
Rate kindling temperature relied on hot slag to change furnace knot.This measure can only eliminate the furnace knot of finite region below electrode district, energy consumption
Height, melt discharge are relatively difficult.
Periodical blowing out empties melt, is cleared up furnace knot by being manually entered in electric furnace to be proved be more reliable way,
But this way furnace outage time is long, it is difficult to utilize mechanization device, labor intensity is big, and the cleaning peering inner lining of furnace of furnace damages
Wound.
Summary of the invention
In view of the above problems and insufficient, the present invention provides a kind of method for eliminating furnace knot in sedimentation electric furnace.This hair
It is bright to be achieved through the following technical solutions.
A method of furnace knot in sedimentation electric furnace being eliminated, step includes:
The blend melt of the smelting slag of output during copper weld pool and sulfonium is sent into the clarification point that sedimentation electric furnace carries out slag sulfonium
From controlling the melt temperature in electric furnace when carrying out the sedimentation of sulfonium within the set range, investment iron sulphur alloy is into molten bath, iron sulphur alloy
It is the alloy that fe and ferrous sulfide are constituted, wherein iron 61%~70%, sulphur 25%~35% in iron sulphur alloy；Iron sulphur alloy
Specific gravity be 5.3~7.0 grams/cm3, fusing point is 900~1300 DEG C, 1~40mm of granularity.
Specifically:
By iron sulphur alloy Fe-FeS alloy (5.3~7.0 grams/cm of specific gravity3) from the slag inlet of electric furnace furnace roof and two sides plus
Expect that hole puts into molten bath, alloy passes through slag blanket (3.3~3.7 grams/cm of specific gravity3) and matte layer (4.7~5.2 grams/cm of specific gravity3) reach bottom
Portion furnace knot surface, under the bath temperature (1150~1300 DEG C) of sedimentation electric furnace, alloy melted by heat is closed along furnace knot surface spreading
The Fe in Fe simple substance and furnace knot in gold3O4It is reacted:
FeS in alloy and the oxide of the Cu, Ni and Co in furnace knot, which carry out making sulfonium, to react:
Cu2O+FeS=Cu2S+FeO (2)
3NiO+3FeS=Ni3S2+3FeO+1/2S2 (3)
CoO+FeS=CoS+FeO (4)
The FeO that above-mentioned reaction generates floats and the SiO in melt2In conjunction with generation iron olive pulls stone and imports clinker:
Make the Cu that sulfonium reaction generates2S、Ni3S2, CoS and FeS dissolve each other to form matte.
The magnetic iron oxide in furnace knot can be made smoothly to restore slag making using the above method, make the cupro-nickel cobalt/cobalt oxide in furnace knot
Sulfonium is made, furnace knot melts, and is converted into fusing point low-gravity small slag and sulfonium.
The blend melt of the smelting slag and sulfonium adds an iron sulphur daily and closes when settling the sedimentation of electric furnace progress sulfonium
Gold was completed to add iron sulphur alloy in 15 minutes, and during adding iron sulphur alloy, the row's of avoiding sulfonium, iron sulphur alloy adds 10 points of delay
Zhong Hou just can arrange sulfonium into smelting slag and deslagging by the normal operating system of sedimentation electric furnace.
Sedimentation electric furnace will be discharged daily, give off copper matte regulus and slag respectively.Due to the temperature field in each region in molten bath
It is distributed variant, the furnace knot thickness in each region of furnace bottom is different, and when copper matte regulus face and the top of the slag drop to low level, the sedimentation electric furnace is visited
Bar surveys furnace knot thickness distribution, adjusts the ladle refining amount of corresponding region, then freely falls formula investment from each charging aperture of furnace roof
The iron sulphur alloy fragment of metering.
It is above-mentioned to contain Fe3O4Smelting slag and flux be added sedimentation electric furnace after, part Fe under the action of carbon pole3O4Energy
Reduction slag making reaction is enough carried out, remaining is distributed in slag, molten sulfonium and precipitation and forms furnace knot.Furnace knot thicken speed by slag type,
The influence of furnace temperature, Electrode Operation system, melt discharge system.Enter the iron-content and exclude electric furnace that electric furnace is respectively expected daily using statistics
The iron-content respectively expected, the difference of the two can be considered that iron enters the amount of furnace knot, by the Fe-FeS for reacting (1) formula and combination iron sulphur alloy
The content of fe in alloy calculates the total dosage of alloy of furnace knot of processing daily.
Above-mentioned iron sulphur alloy the preparation method comprises the following steps:
The blowing slag, troilite and coal base reduction agent of the blowing refinement of the matte process output are sent into side-blown dilution converter by step 1,
It is 1150 DEG C~1300 DEG C progress, one section of weak reduction melting in temperature, weak reduction melting has been dissolved matte after terminating deslagging
Fe-S-O melt；Detailed process are as follows:
Melting blowing slag is packed into furnace from the fire door of side-blown dilution converter with cinder ladle, hopper adds troilite from fire door
Into in furnace, the mixture of air and fuel is sprayed into furnace using the burning spray gun being arranged on side-blown dilution converter headwall and carries out furnace
Temperature is adjusted, and coal base reduction agent is sprayed into molten bath deep, control reduction from the air port compressed air or nitrogen of side-blown dilution converter
Atmosphere carries out one section of weak reduction, reduction reaction to the magnetic iron oxide in blowing slag are as follows:
Chemically react (5) inner reactant S2Thermal decomposition from troilite:
The atmosphere of control system is weakly reducing atmosphere, that is, controls the additional amount of reducing agent coal, and reaction (9) is difficult to occur, iron
Olive rock ballast is not decomposed in one section of weak reduction operation.The furnace entering volume for controlling troilite allows the sulphur in melt in suitable range, guarantee
There is suitable FeO in melt, FeS and FeO is allowed to form the Fe-S-O melt to dissolve each other completely.Cupro-nickel cobalt/cobalt oxide in blowing slag is made
Sulfonium:
Sulfonium is dissolved in Fe-S-O melt.One section of weak reduction terminates, and two layers of melt is formed in molten bath, upper layer is that specific gravity is small
Slag based on silicate, lower layer are the heavy Fe-S-O melts for having trapped sulfonium, this two layers of melt is because of mutual not phase
The difference of molten and specific gravity and be layered.Weak reduction melting terminates the Fe-S-O melt that matte (sulfonium) has been dissolved after deslagging.
Step 2, the Fe-S-O melt for having dissolved matte for obtaining step 1 are 1150 DEG C~1300 DEG C in temperature and carry out two
The strong reduction melting of section, is prepared iron sulphur alloy；Specifically:
Upper layer silicate slag is discharged rotary furnace, leaves Fe-S-O melt, into two sections strong reduction operation.Control furnace
Mild strongly reducing atmosphere restores the FeO in Fe-S-O melt:
FeS cannot be restored by charcoal.The fe that strong reduction generates dissolves each other with FeS, Fe-FeS alloy is formed, containing Cu, Ni and Co
Sulfonium also dissolves in the alloy.Two sections strong reduction terminates, and iron sulphur alloy melt, which discharges out of the furnace, carries out water quenching, obtains granular iron sulphur and closes
Gold.
One section of weak reduction melting controls CO/CO in the step 12Percent by volume is 0.1~0.2:1.
Two sections strong reduction melting controls CO/CO in the step 22Percent by volume is 1.5~2.0:1.
The iron sulphur alloy specific gravity is 5.3~7.0 grams/cm3, sulfur-bearing 25%~35%, fusing point is 900~1300 DEG C, grain
Spend 1~40mm.
Furnace knot can be eliminated using the above method and so that the magnetic iron oxide in waste is reduced to 6.5wt% hereinafter, electric furnace is abandoned
Copper in Slag is controlled in 0.55wt% or less.
The beneficial effects of the present invention are:
(1) it can guarantee the furnace bottom furnace knot thickness control for settling electric furnace in 300mm hereinafter, deslagging using method of the invention
Mouthful, sulfonium mouth is unimpeded does not block by row；Furnace knot fusing speed is fast, whole to eliminate furnace knot.Furnace knot is eliminated with the pig iron, can be produced in furnace knot layer
Raw dell, unfavorable whole elimination furnace knot.
(2) ferrous sulfide that Fe-FeS alloy is brought into carries out the cupro-nickel cobalt/cobalt oxide in furnace knot to make sulfonium reaction, is conducive to
Improve the rate of recovery of Cu, Ni and Co.
(3) Fe-FeS alloy price is low, is lower than the expense of existing various methods come treatment furnace knot operating cost with alloy.
Specific embodiment
With reference to embodiment, the invention will be further described.
The matched sedimentation electric furnace of matte production procedure that oxygen-enriched top blowing produces 200000 tons of copper per year (is also referred to as dilution electricity in industry
Furnace), size of burner hearth is 22.28 × 5.81 × 4.5 meters, 6 electrodes.Traditional handicraft is that electric furnace receiving per hour is sent by top blast furnace
110 tons of slag sulfonium blend melts (blend melt cupric 23.52%, iron content 26.73%, wherein smelting slag be containing magnetic iron oxide
7.8%), keep furnace temperature at 1180 DEG C~1220 DEG C, furnace power maintains 4870 kilowatt hour per hour, and slag sulfonium blend melt exists
During electric furnace keeps the temperature clarified separation, restored from furnace roof insertion oil gun into molten bath, slotting oil gun restores twice daily, morning 9:00
Start to restore for the first time, afternoon, 13:00 started second of reduction, every time reduction 50 minutes, and diesel consumption is 10 liters/min.Often
Hour obtains 45.5 tons of matte (copper grade 56wt%, containing full iron 18.6wt%) and 63 tons of wastes, waste contain Cu0.568wt%,
Containing full iron 32.3wt%, wherein contain Fe3O47.0wt%.Furnace bottom furnace knot layer is being thickeied by daily 3-5mm, area near row's sulfonium mouth
Domain, furnace knot is most thick to arrive 500mm or so, and when slag-drip opening zone furnace knot thickness highest reaches 800mm or so.
Embodiment 1
The method that the elimination settles furnace knot in electric furnace, step include:
Sedimentation electric furnace receives the mixing that the smelting slag and sulfonium of output during 110 tons of copper weld pools are sent by top blast furnace per hour
Melt (blend melt cupric 23.47wt%, iron content 27.10wt%, wherein smelting slag is 7.8wt% containing magnetic iron oxide) is sent into
The clarified separation that electric furnace carries out slag sulfonium is settled, keeps furnace temperature at 1180 DEG C~1220 DEG C, furnace power maintains per hour 4850
Kilowatt hour adds 3 tons in 15 minutes after the period of 13:00~14:00 completes the process of sedimentation electric furnace slag input sulfonium blend melt
Iron sulphur alloy (iron content 67wt%, sulphur 28wt%, 1100 DEG C of fusing point, 6.4 grams/cm of specific gravity3, granularity 5mm~40mm).It is clear through electric furnace
Sorting is from obtaining 45.1 tons of matte (copper grade 56.4wt%, containing full iron 17.83wt%) per hour and 65 tons of wastes, waste contain
Cu0.548wt%, contain full iron 35.8wt%, wherein contain Fe3O46.2wt%.Detection electric furnace bottom furnace knot eliminates feelings after production 96 hours
Condition arranges sulfonium mouth near zone, and furnace knot thickness is in 250mm or so, and slag-drip opening zone furnace knot thickness is in 350mm or so, advantageous protection
Furnace bottom and the working of a furnace are smooth.
Embodiment 2
The method that the elimination settles furnace knot in electric furnace, step include:
Sedimentation electric furnace receives the mixing that the smelting slag and sulfonium of output during 110 tons of copper weld pools are sent by top blast furnace per hour
Melt (blend melt cupric 24.55wt%, iron content 26.27wt%, wherein smelting slag is 8.5wt% containing magnetic iron oxide) is sent into
The clarified separation that electric furnace carries out slag sulfonium is settled, keeps furnace temperature at 1180 DEG C~1220 DEG C, furnace power maintains per hour 4850
Kilowatt hour adds 3.5 in 15 minutes after the period of 13:00~14:00 completes the process of sedimentation electric furnace slag input sulfonium blend melt
Ton iron sulphur alloy (iron content 61wt%, S35 wt%, 1150 DEG C of fusing point, 5.8 grams/cm of specific gravity3, granularity 1mm~20mm).Through electric furnace
Clarified separation obtains 39.5 tons of matte per hour and (copper grade 67wt%, contains containing full iron 10.1wt%) and 72.6 tons of wastes, waste
Cu0.546wt%, contain full iron 36.97wt%, wherein contain Fe3O46.4wt%.Detection electric furnace bottom furnace knot eliminates feelings after production 7 days
Condition arranges sulfonium mouth near zone, and furnace knot thickness is in 250mm or so, and slag-drip opening zone furnace knot thickness is in 300mm or so, furnace knot thickness
Control is reasonable.
Embodiment 3
The method that the elimination settles furnace knot in electric furnace, step include:
Sedimentation electric furnace receives the mixing that the smelting slag and sulfonium of output during 110 tons of copper weld pools are sent by top blast furnace per hour
Melt (blend melt cupric 24.10wt%, iron content 26.72wt%, wherein smelting slag is 7.2wt% containing magnetic iron oxide) is sent into
The clarified separation that electric furnace carries out slag sulfonium is settled, keeps furnace temperature at 1180 DEG C~1220 DEG C, furnace power maintains per hour 4860
Kilowatt hour adds 2.5 in 15 minutes after the period of 13:00~14:00 completes the process of sedimentation electric furnace slag input sulfonium blend melt
Ton iron sulphur alloy (iron content 70wt%, sulphur 25wt%, 1200 DEG C of fusing point, 6.7 grams/cm of specific gravity3, granularity 5mm~20mm).Through electric furnace
Clarified separation obtains 49 tons of matte per hour and (copper grade 53.3wt%, contains containing full iron 20.7wt%) and 62.8 tons of wastes, waste
Cu0.53wt%, contain full iron 32.3wt%, wherein contain Fe3O45.7wt%.Detection electric furnace bottom furnace knot eliminates situation after production 7 days,
Sulfonium mouth near zone is arranged, furnace knot thickness is in 250mm or so, and slag-drip opening zone furnace knot thickness is in 300mm or so, furnace knot thickness control
Rationally.
Above the embodiment of the present invention is explained in detail, but the present invention is not limited to above-mentioned embodiment party
Formula can also be made without departing from the purpose of the present invention within the knowledge of a person skilled in the art
Various change out.
Claims (3)
1. a kind of method for eliminating furnace knot in sedimentation electric furnace, it is characterised in that step includes:
The blend melt of the smelting slag of output during copper weld pool and sulfonium is sent into the clarified separation that sedimentation electric furnace carries out slag sulfonium, control
When melt temperature in electric furnace processed carries out the sedimentation of sulfonium within the set range, iron sulphur alloy is put into molten bath, iron sulphur alloy is single
The alloy that matter iron and ferrous sulfide are constituted, wherein iron 61%~70%, sulphur 25%~35% in iron sulphur alloy；The ratio of iron sulphur alloy
Weight is 5.3~7.0 grams/cm3, fusing point is 900~1300 DEG C, 1~40mm of granularity.
2. the method according to claim 1 for eliminating furnace knot in sedimentation electric furnace, it is characterised in that: the smelting slag and sulfonium
Blend melt adds an iron sulphur alloy when settling the sedimentation of electric furnace progress sulfonium daily, completes in 15 minutes plus iron sulphur closes
Gold, during adding iron sulphur alloy, the row's of avoiding sulfonium, iron sulphur alloy adds delay after ten minutes, just can be by the normal of sedimentation electric furnace
Operating duty arranges sulfonium into smelting slag and deslagging.
3. the method according to claim 1 for eliminating furnace knot in sedimentation electric furnace, it is characterised in that: the sedimentation electric furnace is visited
Bar surveys furnace knot thickness distribution, adjusts the ladle refining amount of corresponding region, then freely falls formula investment from each charging aperture of furnace roof
The iron sulphur alloy fragment of metering.
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