CN104561602B - The method that ferrosilicon bath step reduces magnesium-smelting silicothermic process coproduction liquid containing ferrochrome - Google Patents
The method that ferrosilicon bath step reduces magnesium-smelting silicothermic process coproduction liquid containing ferrochrome Download PDFInfo
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- 239000007788 liquid Substances 0.000 title claims abstract description 232
- 229910000519 Ferrosilicon Inorganic materials 0.000 title claims abstract description 184
- 238000000034 method Methods 0.000 title claims abstract description 178
- 238000003723 Smelting Methods 0.000 title claims abstract description 92
- 230000008569 process Effects 0.000 title claims abstract description 72
- 229910000604 Ferrochrome Inorganic materials 0.000 title claims abstract description 52
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 224
- 239000011777 magnesium Substances 0.000 claims abstract description 209
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 205
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 164
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 164
- 239000010703 silicon Substances 0.000 claims abstract description 164
- 238000007670 refining Methods 0.000 claims abstract description 126
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 112
- 239000002893 slag Substances 0.000 claims abstract description 109
- 230000009467 reduction Effects 0.000 claims abstract description 90
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 86
- 239000011651 chromium Substances 0.000 claims abstract description 86
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 82
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 41
- 239000010935 stainless steel Substances 0.000 claims abstract description 40
- 229910052742 iron Inorganic materials 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 239000012452 mother liquor Substances 0.000 claims abstract description 13
- 238000013019 agitation Methods 0.000 claims abstract description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 102
- 239000000956 alloy Substances 0.000 claims description 102
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 100
- 239000000395 magnesium oxide Substances 0.000 claims description 50
- 239000007789 gas Substances 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 29
- 238000010304 firing Methods 0.000 claims description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 14
- 239000010459 dolomite Substances 0.000 claims description 13
- 229910000514 dolomite Inorganic materials 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 11
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 239000011733 molybdenum Substances 0.000 claims description 11
- 229910052720 vanadium Inorganic materials 0.000 claims description 11
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- 239000010937 tungsten Substances 0.000 claims description 10
- 229910000838 Al alloy Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910000851 Alloy steel Inorganic materials 0.000 claims description 8
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 8
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000002699 waste material Substances 0.000 claims description 8
- 241001062472 Stokellia anisodon Species 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 239000000292 calcium oxide Substances 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 4
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 235000019738 Limestone Nutrition 0.000 claims description 2
- 239000006028 limestone Substances 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000011819 refractory material Substances 0.000 claims description 2
- 238000012804 iterative process Methods 0.000 claims 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 25
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 25
- 239000011574 phosphorus Substances 0.000 abstract description 25
- 229910000831 Steel Inorganic materials 0.000 abstract description 17
- 239000010959 steel Substances 0.000 abstract description 17
- 238000012546 transfer Methods 0.000 abstract description 15
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 14
- 239000003795 chemical substances by application Substances 0.000 abstract description 13
- 229910052799 carbon Inorganic materials 0.000 abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005864 Sulphur Substances 0.000 abstract description 3
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- 239000011707 mineral Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 230000008901 benefit Effects 0.000 description 10
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- 239000011575 calcium Substances 0.000 description 7
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 6
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 239000001996 bearing alloy Substances 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910005347 FeSi Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910018487 Ni—Cr Inorganic materials 0.000 description 2
- 241001417490 Sillaginidae Species 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 2
- 239000003818 cinder Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
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- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
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- 206010003694 Atrophy Diseases 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- 240000007175 Datura inoxia Species 0.000 description 1
- 206010011906 Death Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910005331 FeSi2 Inorganic materials 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
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- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
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- Silicon Compounds (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The method that ferrosilicon bath step reduces magnesium-smelting silicothermic process coproduction liquid containing ferrochrome, belong to non-ferrous metal magnesium extractive technique field, fall within the technical field that chromium stainless steel in iron and steel industry, ferrochrome are smelted, silicothermic reduction agent and the carrier of chemical reaction are used as using the ferrosilicon bath far above theoretical chemistry requirement, pass through high degree of agitation, increase reaction interface product, enhancing convection heat transfer' heat-transfer by convection, mass transfer ability realize the reinforcing of reduction process.After reduction is finished, magnesium smelting reducing slag is removed, excess silicon iron liquid mixes row refining magnesium again with new a collection of magnesium ore deposit, until the concentration of ferrosilicon liquid is less than poor silicon concentration, poor ferrosilicon liquid is mixed with chrome ore, carries out chromium reduction, obtains chromium stainless steel mother liquor.Refining magnesium, refining ferrochrome are respectively used in high concentration, low concentration using the bath of excessive ferrosilicon, ferrosilicon raw material are fully used, and reaction efficiency is high, more saves, carbon, phosphorus, sulphur are very low in ferrochrome liquid, and the independent sum of the two of cost ratio of magnesium and molten stainless steel coproduction has obvious reduction.
Description
Technical field
The invention belongs to non-ferrous metal magnesium Extraction metallurgy technical field, chromium stainless steel in iron and steel industry, ferrochrome are fallen within
The method of the technical field of alloy smelting, more particularly to magnesium-smelting silicothermic process coproduction liquid containing ferrochrome.
Background technology
Magnesium metal and magnesium alloy are most light structural metallic materials, using the vehicles, electronic product, construction material,
The fields such as Aero-Space, bring the effect of energy-conservation, are described as " the 3rd metal ", " the green metal material of 21st century ".Steel
The mineral resources of the major metal material such as iron, aluminium are progressively tending to be exhausted, and the mineral resources of magnesium metal are enriched very much, moreover
Contain the magnesium resource of more horn of plenty in seawater, be available for the mankind to use more than one thousand years.
The technology of extraction of metal magnesium is divided to two major classes from natural mineral products：Electrolysis and thermal reduction.Electrolysis is general
Magnesium chloride is used for raw material, while electrolysis obtains magnesium metal, by-product chlorine, environmental issue is difficult to overcome, global at present
In magnesium metal yield electrolysis is used only less than 20%.
Several magnesium refining methods of Fig. 1 system introductions, the main technique of thermal reduction is silicothermic process, that is, uses silicon for also
Former agent reduction-oxidation magnesium, obtains metal magnesium vapor under high temperature and vacuum condition, and then condensation obtains the technique of magnesium metal, wherein
Occupy main flow is so-called " Pidgeon process " technique (Pidgeon Process), that is, the horizontal tank cycle silicothermic process of external-heat,
The method is current leading industry technology.In addition, France once developed semi-continuous electrical conductivity of molten slag silicothermic reduction technique
(Magnetherm Process) and industrialization is realized, but the consumption of its ferrosilicon is higher than theoretical value, at present few factories
Using this technique.
The carbothermy for also having Hansgirg of thermal reduction technique is also belonged to ferrosilicon process.Carbothermy refining magnesium is exactly to use carbon
Matter reducing agent reduction-oxidation magnesium, obtains metal magnesium vapor and CO gases, magnesium metal is obtained after fast cooling condensation.Carbothermy refines magnesium
The biggest problem be product for metal magnesium gas and CO gases mixed gas, when cooling down is to obtain magnesium metal, can send out
Raw magnesium-reduced back reaction, causes magnesium reoxidized by CO gases, too many MgO and carbon is mixed with product so that the receipts of magnesium
Yield is substantially reduced, therefore how so that magnesium gas is tried one's best, the quenching operation of fast cooling becomes very crucial.Carbothermic method
The temperature of mixed gas is reduced using the method for the reducibility gas such as a large amount of natural gases, hydrogen dilution, a large amount of foreign gas
Introducing causes cost to increase, therefore this carbothermic method is abandoned by industrial quarters later.In recent years, Australian Union's science with
Industrial research tissue CSIR O scientist, which considers to expand mixed gas by contraction-expanding nozzle, obtains supersonic jet,
So that gas temperature rapid drawdown, and this technique is named as MagSonic techniques, but still it is in the development test stage.
In short, the industrial magnesium refining method for having certain scale yield in history mainly has electrolysis, carbothermic method, skin
The factory of river method and the semicontinuous process for smelting magnesium of Magnetherm, the wherein hot process for smelting magnesium of carbon only in the 1930-1940 ages uses
Cross, mainstream industry method in the world only has electrolysis and Pidgeon process at present.Before nineteen ninety is for mid-term, electrolysis yield is accounted for entirely
Ball magnesium yield more than 80%, Pidgeon process and Magnetherm method yield only have about 20%.Since at the beginning of 21 century, Magnetherm
Technique stops production substantially, and also atrophy is many for electrolysis, and only Pidgeon process yield has accounted for the whole world more than 80%.
Either the semicontinuous process for smelting magnesium of Magnetherm of Pidgeon process technique or France, all particularly siliceous with ferrosilicon
More than 75% ferrosilicon (being usually #75 ferrosilicon) contains MgO ore as refining magnesium raw material, in high-temperature vacuum as reducing agent
Under the conditions of, occur the following chemical reaction of Si reduction magnesia：
2MgO+Si=SiO2+2Mg(gas) (1)
Above formula (1) is basic chemical reaction.Due to only having Mg to turn into gas, quilt at high temperature in reactant, product
Vacuum-pumping system is extracted out, so as to leave conversion zone, the low-temperature zone condensation in vacuum line turns into solid or liquid, so that
Obtain magnesium metal.
Generally, it, using in the form of ferrosilicon as reaction mass, is usually to use dolomite calcination containing magnesium raw material that silicon, which is,
Product CaOMgO afterwards is reacted, and industrial common chemical equation is：
2 (CaOMgO)+Si (+Fe)=2CaOSiO2(+Fe)+2Mg(gas) (2)
Silicon is good reducing agent in metallurgical industry, but because magnesium is active metal, the binding ability with oxygen is very strong, institute
High temperature is needed with Si reduction magnesium at ambient pressure.The partial pressure of product metal magnesium gas is reduced by using vacuum, and
With CaO combinations SiO2Generate stable dicalcium silicate so that above-mentioned reaction (2) if 1200 DEG C of temperature below can carry out work
Industry is produced.
So-called Pidgeon process, is that Canadian metallurgist Pi Jiang is taught in the perfect technique of the 1940's early development, and edge
With so far.Pidgeon process technique is to mix the way of contact of the solid phase such as pressure ball, using outer by siliceous 75% ferrosilicon, magnesium-containing ore etc.
Portion's flame heating, promotes material in horizontal tank to be chemically reacted, material reaction temperature is about 1150~1250 DEG C, and vacuum is general
Less than 13Pa.Existing production of magnesium by pidgeonprocess has following essential defect：
1. reactant ferrosilicon and forge it is white chemically reacted with the solid phase way of contact, reaction rate slowly, typical technique mistake
The reduction reaction cycle is up to 10~12 hours in journey, inefficiency；
2. using flame external heat, heat is by inside is gradually transmitted to outside reactor, and the cycle is long, heat-energy losses
Greatly, heat utilization rate is low, and specialty analysis thinks that the heat utilization rate of typical process only has 20% or so；
3. because the mode of external heat limits reactor volume, typical horizontal tank internal diameter is within 400 millimeters, once
Charge is small, and the former magnesium of one time 10-12 hours outputs of single tank only has 20~30 kilograms, and floor space is big, and field management difficulty is big,
It is difficult to realize large-scale production and do mechanization operation；
4. using containing the ferrosilicon of element silicon 75% as reducing agent, general ton magnesium ferrosilicon consumption is 1.05~1.20 tons, i.e., silicon is remote
Cause to waste more than theoretical consumption figures, while all ferro elements are wasted；
5. horizontal tank typically uses the expensive heat resisting steel containing nickel, chromium, quickly, cost is high for consumption；
6. smoke contamination is serious, work situation is severe, ecological environment around is negatively affected big；
7. needing hand charging, skimming, clear up Crystalline Magnesium, labor intensity is big, it is difficult to realize automated job.
The semicontinuous process for smelting magnesium of Magnetherm of France's exploitation has improved than Pidgeon process, is not only embodied in and uses electric power
Internal heating is carried out, so that energy utilization rate is improved, and also production efficiency obtains very big lifting.But this technique still has several
The deficiency of aspect：It is of prime importance that ferrosilicon is still seriously in excess in theoretical consumption figures, remnants high temperature ferro element is caused all to waste
And the waste of part element silicon.Silicon amount theoretical value 576kg needed for magnesium metal reduction per ton, it is 768kg to convert into #75 ferrosilicon,
And magnesium per ton consumes 1050~1200kg #75~#80 ferrosilicon in actual production, correspondingly siliceous 18 in remaining ferrosilicon~
22%.In addition, Magnetherm process for smelting magnesium is semi-continuous, often produces 1 ton of magnesium metal and about produce 5~6 tons of reducing slags simultaneously,
Need that most of reducing slag is discharged into reaction zone in time, this is accomplished by breaking vacuum, stops smelting, and causes the interruption of production.Also
Have, ferrosilicon, to forge the raw materials such as white powder be to be added to the powder or particle of solid-state in magnesium refining furnace, passes through heat up fusing and then beginning
Reaction is learned, compared with the mode that liquid phase or solid powder are injected into molten bath, its reaction speed is still relatively low.Finally, ferrosilicon is given birth to
Production process is to be discharged with high-temperature fusion liquid from mineral hot furnace, is then added to after being cooled to the solid compared with low temperature in magnesium refining furnace,
The larger energy waste through causing.
South Africa Mintek mechanisms develop MTMP (Mintek Thermal on the basis of Magnetherm techniques
Magnesium Process) technique, it is that vacuumizing is no longer used in stove that it, which protrudes change, but refines magnesium at ambient pressure, so
Tapping process can be carried out under not end-of-life state, as Total continuity technique, and cost is that temperature will be promoted to about 1750 DEG C, is caused
Energy consumption is raised and the fire proof material of furnace lining lost of life, and more multielement is volatized into furnace gas together in company with magnesium, causes the pure of magnesium
Degree declines.And in its reducing agent silicon and the element of iron two waste it is still more serious, siliceous 20% or so in remaining ferrosilicon.
The process for smelting magnesium for being just known as Magnetherm described by United States Patent (USP) US2971833, using under vacuum
Slag resistance heating, once realizes stable commercial scale in multiple countries.But the consumption of its ferrosilicon is higher than theoretical value, specially
Sharp right remaining ferrosilicon siliceous 35% of 69 rows report of P3 pages of specification, has larger amount of remaining ferrosilicon not utilize.United States Patent (USP)
US5090996 is on the basis of Magnetherm process for smelting magnesium, the reduction refining magnesium changed under atmospheric pressure state.United States Patent (USP)
US5383953 patent is described under normal pressure with metal reduction refining magnesium, by controlling the composition of slag to realize, is also considered in all respects as
The improvement of Magnetherm techniques.Above-mentioned patent does not refer to the ferrosilicon consumption of refining magnesium.United States Patent (USP) US3151977 discloses electric heating
The method of reduction refining magnesium, wherein the ferrosilicon for being 70-80% as the ferrosilicon of reducing agent, last siliceous 33% ferrosilicon not by
Utilize.United States Patent (USP) US4699653 describes plasma at ambient pressure as the continuous silicone heat refining magnesium of thermal source, in embodiment
The small experimental data provided shows that silicon can not be depleted by reduction reaction.Chinese patent CN95100495.6 discloses one
The technology of heat refining magnesium in kind, its technique has similarity with Magnetherm, also simply after solid-state furnace charge is loaded, with temperature
Rise, furnace charge can be in molten state.But the reaction system of patent description causes magnesium vapor to be directly condensed into due to condition of high vacuum degree
Solid state crystallization magnesium, easily blocks vacuum system, it is impossible to realize continuous production.Chinese patent CN201010145505.9 proposes one
The method for planting melting and reducing silicon heat refining magnesium, forms multi-unit fused slag system so that reactant and product by being incorporated silicon, aluminum oxide
Ferrosilicon liquid and polynary slag are formed, is liquid phase, is improved in reacting dynamics condition, but its three embodiments because ferrosilicon is excessive
Very big silicon, ferro element is caused to waste, even up to element silicon wastes the ratio of half.
Chinese patent CN201080000976, CN201010255097, CN201010255111 are refined there is provided vacuum circular flow
The method and apparatus of magnesium so that ferrosilicon liquid can be sufficiently mixed with magnesium ore deposit, and realize vacuum and atmospheric pressure environment by dip pipe
Under circulate, obtain good reacting dynamics condition, at the same can also continuous discharging slag, but only to the remnants after refining magnesium
Ferrosilicon provides supplement element silicon so as to the comprehensive Utilization Ways as different silicon-containing ferroalloy, not yet gives full play to silicon as excellent
The chemical functional of matter metallurgy reducing agent.
Pidgeon process technique is used as the main technique of Present Global magnesium metal yield more than 80%, even more method for smelting magnesium by hot process
Absolute prevailing technology, before analyzed deficiency in terms of its energy consumption, material consumption, efficiency, working condition, environmental protection.And have liquid
The a collection of technique of reaction is mutually participated in, using Magnetherm techniques as representative, subsequently there is South Africa MTMP techniques, Chinese patent
CN201010145505.9 etc., has a major progress compared with Pidgeon process in chemical reaction process, but the warp in production practices
Ji advantage is not obvious, using Magnetherm Ji Jia factories even can not with Pidgeon process competition among enterprises and be forced to stop production and close
Close factory.It is also one big to compare high slag ratio in addition to above-mentioned ferrosilicon residue is not utilized effectively, in its technical process
Defect, because the quantity of slag causes molten bath flowing, whipping process to be difficult to far above ferrosilicon amount, have impact on production efficiency.
The main component of metallurgical cinder is many oxide, unreacted mineral aggregate can also be dissolved in various degree in slag or
Liquid is fused into, the viscosity of slag is general in 0.08~2Pas, and the viscosity of the molten metal such as general molten steel, iron liquid only has
0.002~0.008Pas, it is more than 10 times of molten metal to be typically completely melt slag phase viscosity.If oxide melts in furnace charge
Point is higher, or can not all dissolve, with the presence of solid phase particles, then slag often shows the rheology of non-newtonian fluid
Characteristic, apparent viscosity is with temperature, undissolved/unfused solid phase particles property and quantity, stirring operation, foamed slag and void fraction
Etc. having very big fluctuation, or even tens times to up to a hundred times molten metal viscosity so that the mobility of mineral aggregate and slag phase is greatly reduced,
Influence chemical reaction, heat transfer, mass transfer are smoothed out.
As a comparison, in steelmaking process and follow-up external refining, slag phase quality typically only have molten metal 10~
20%, molten bath is using molten metal as main flow media, and metallurgical effect is far better.Due to molten metal bath good fluidity, slag
Amount is small, can be using " process intensification " means such as Bottom Gas Stirring, electromagnetic agitation, top-blown gas jets so that molten bath occurs
Fierce macroscopic view flowing, reaction interface product can increase thousands of times, while heat transfer, mass transfer are carried out with fierce convection type, smelt
Speed is greatly improved.For example, molten slag is when strong agitation, 20-40 when the capacity of heat transmission is static times.Compare again
Such as, oxygen top blown converter steel making has eliminated open hearth steelmaking completely, is exactly because the former forms in fierce Liquid Flow
The emulsification of abundant disperse, core smelting procedure is only needed to 12-15 minutes, and the latter molten bath is " a pool of stagnant water ", core smelter
Sequence will expend several hours.
Either Pidgeon process, or the method for smelting magnesium by hot technology that existing patent is disclosed, is all according to theoretical needed for chemical reaction
Reducing agent calculates supplying ferrosilicon, can be referred to as " chemistry matches somebody with somebody silicon ", it is contemplated that the carried out degree of chemical reaction and silicon
The ratio of free silica in iron, general excessive 30% or so.Generally in refining magnesium raw material dolomite forges white powder, the atomic ratio of calcium and magnesium
Close to 1:1 or slightly above 1, magnesium, which is accounted for, forges the 23~25% of white powder quality, and because the percent reduction of magnesium is generally 80% or so, magnesium ore deposit adds
It is usually 6~6.5 tons of ton magnesium to enter amount, and more than 75% ferrosilicon of ton magnesium supplying only has 1.0~1.1 tons, then even if furnace charge whole
Fusing, the quantity of slag be also in the 600% of metal liquid measure, molten bath slag phase occupy absolute majority, mobility far away from using molten metal as
Main molten bath, causes the efficiency of the chemical reaction in molten bath, heat transfer, mass transfer very low.
In consideration of it, being necessary a kind of new " physics matches somebody with somebody silicon " technique of design to solve the above problems.So-called physics matches somebody with somebody silicon, just
For the several times of oxide furnace charge/slag phase quality to be incorporated ferrosilicon according to the quality of Antaciron liquid in molten bath, with far above
The ferrosilicon bath of theoretical chemistry requirement passes through high degree of agitation so that containing aerobic as silicothermic reduction agent and the carrier of chemical reaction
The magnesium ore deposit highly dispersed mixing for changing magnesium wherein, forms and is similar to emulsion, the disperse system of emulsion, wherein continuous phase medium is low
The ferrosilicon liquid of viscosity, dispersed phase is the slag phase of unreacted/reacted oxide composition, and increase reaction interface product strengthens to spreading
Heat, mass transfer ability, realize the reinforcing of reduction process.After reduction is finished, magnesium smelting reducing slag is removed, excess silicon iron liquid must be repeated
Utilize, return to magnesium refining furnace or stay in always in magnesium refining furnace, row refining magnesium again is mixed with new a collection of magnesium ore deposit, until ferrosilicon liquid is dense
Degree is less than poor silicon concentration.
Silicon is used for refining magnesium in high concentration, and after concentration reduction, its poor ferrosilicon liquid is mixed with chrome ore, chrome ore reduction is carried out,
Obtain ferrochrome liquid or chromium stainless steel mother liquor.Refining magnesium, refining are respectively used in high concentration, low concentration using the bath of excessive ferrosilicon
Ferrochrome, ferrosilicon raw material are fully used, and reaction efficiency is high, more saves, carbon, phosphorus, sulphur are very low in ferrochrome liquid, magnesium and stainless
The cost of molten steel coproduction has obvious reduction than independent sum of the two.
The content of the invention
The technical problem to be solved in the present invention is：For technical side disclosed in existing industry refining magnesium technology and forefathers' patent
The drawbacks of case and deficiency, patent of the present invention disclose the side that a kind of ferrosilicon bath step reduces magnesium-smelting silicothermic process coproduction chrome-bearing alloy steel
Method.
An object of the present invention is to make full use of residual after element silicon and ferro element in reducing agent ferrosilicon, and refining magnesium
The high-temperature physics heat of remaining ferrosilicon.
The purpose of the present invention also includes thoroughly improving the dynamic conditions of reaction so that reactant with liquid liquid phase reactor or
Using mineral as dispersed phase Dispersed precipitate in the formation ferrosilicon bath of ferrosilicon liquid continuous phase, two kinds of reactants are sufficiently mixed, anti-to increase
Interface is answered, convection heat transfer' heat-transfer by convection, mass transfer rate are obviously improved so that production process is rapider, more efficient.
To reach above-mentioned purpose, the invention provides following technical scheme：Ferrosilicon bath step reduction magnesium-smelting silicothermic process coproduction
The method of the liquid containing ferrochrome, it is characterised in that include following technique：
A., the molten alloy liquid for being at least 25-70% containing silicon, two kinds of elements of iron and initial siliceous mass percent is provided,
The molten alloy liquid is placed in vacuum in firing magnesium-smelting furnace, the firing magnesium-smelting furnace and is maintained at 350-50000Pa, and temperature is protected
Hold at 1200-1800 DEG C；
B. the molten alloy liquid and a collection of material containing magnesia are mixed, the molten alloy liquid quality is kept all the time
The quality of slag phase is constituted more than multivariant oxide after unreacted and reaction, and keeps the siliceous quality of molten alloy liquid to be always
Magnesium chemical theory needs 1.5-200 times of siliceous amount in Si reduction slag phase, and Si reduction magnesia, generation magnesium vapor escapes the melting
Aluminium alloy and the collection that is condensed, and the slag phase formed after reaction is isolated into the firing magnesium-smelting furnace；
C. when the silicon concentration in a collection of reacted molten alloy liquid of magnesia is more than a poor silicon concentration, repeat
Technique B；When the silicon concentration in molten alloy liquid is equal to or less than the poor silicon concentration, poor silicon molten alloy liquid is formed, by institute
The poor silicon molten alloy liquid stated is placed in refining chromium reduction furnace, and the poor silicon concentration refers to the siliceous mass percent in molten alloy liquid
Between 15% -50% and less than a concentration of the initial siliceous mass percent of the molten alloy liquid；
D. the poor silicon molten alloy liquid and a collection of material containing chromium oxide of refining chromium reduction furnace, Si reduction are placed in described in mixing
Chromium oxide, generation crome metal is dissolved in the poor silicon molten alloy liquid, obtains liquid containing ferrochrome.
Molten alloy liquid in the technique A is stirred in firing magnesium-smelting furnace by argon gas, electromagnetic force stirring or machinery are stirred
One or more of stirrings in mixing.
Also containing the aluminium element that mass percent is 1-30% in molten alloy liquid in the technique A.
Also containing the nickel element that mass percent is 0.5-20% in molten alloy liquid in the technique A.
In the technique B material containing magnesia for calcining after dolomite, calcining after magnesite, magnesia give up
One or more in old refractory material, the metallurgical slag containing magnesia or the slag melted containing magnesia.
After a collection of magnesia at least 50% in the technique B reacts, the slag phase formed will be just reacted from the refining
Magnesium reducing furnace is separated.
The technique B also includes adding ferrosilicon into the molten alloy liquid, keeps the molten alloy liquid quality all the time
The quality of slag phase is constituted more than multivariant oxide after unreacted and reaction, and keeps the siliceous quality of molten alloy liquid to be always
Magnesium chemical theory needs 1.5-200 times of siliceous amount in Si reduction slag phase.
The mode for separating the slag phase for reacting formation from the firing magnesium-smelting furnace in the technique B includes will be described molten
Melt aluminium alloy and slag phase to discharge together again by the recharge of molten alloy liquid to the firing magnesium-smelting furnace after the firing magnesium-smelting furnace, or
Directly slag phase is separated from the firing magnesium-smelting furnace.
Added in molten alloy liquid in the technique B and contain aluminum oxide and/or contain the material of calcirm-fluoride as slag making
Agent.
Liquid containing ferrochrome in the technique D is smelts the mother liquor of chromium stainless steel, and the liquid containing ferrochrome contains
Chromium mass percent is 10-50%.
Calcined limestone, dolomite are added in the technique D and forges white powder, the material containing calcium oxide or containing magnesia
One or more in material are used as slag former.
Present invention also offers the method that another ferrosilicon bath step reduces magnesium-smelting silicothermic process coproduction chromium stainless steel liquid, bag
Containing following technique：
A., molten alloy liquid at least containing silicon, two kinds of elements of iron and initial siliceous mass percent 25-70%, institute are provided
State molten alloy liquid and be placed in firing magnesium-smelting furnace, the firing magnesium-smelting furnace keep 350-50000Pa vacuum condition and 1200-
1800 degrees Celsius of temperature conditionss；
B. the molten alloy liquid and a collection of material containing magnesia are mixed, the material containing magnesia is step
The reduction slag that D is discharged, keeps the molten alloy liquid quality to be consistently greater than multivariant oxide institute group after unreacted and reaction
Into the quality of slag phase, and the siliceous quality of molten alloy liquid is kept to be always the siliceous amount of magnesium chemical theory need in Si reduction slag phase
1.5-200 times, Si reduction magnesia, generation magnesium vapor escapes the molten alloy liquid and the collection that is condensed, and reaction is formed
Slag phase isolate the firing magnesium-smelting furnace；
C. when the silicon concentration in a collection of reacted molten alloy liquid of magnesia is more than a poor silicon concentration, repeat
Technique B；When the silicon concentration in molten alloy liquid is equal to or less than the poor silicon concentration, poor silicon molten alloy liquid is formed, by institute
The poor silicon molten alloy liquid stated is placed in refining chromium reduction furnace, and the poor silicon concentration refers to the siliceous mass percent in molten alloy liquid
Between 15% -50% and less than a concentration of the initial siliceous mass percent of the molten alloy liquid；
D. mix and described be placed in the poor silicon molten alloy liquid that refines chromium reduction furnace and a collection of at least containing chromium oxide, magnesia
Material, Si reduction chromium oxide, generation crome metal is dissolved in the poor silicon molten alloy liquid, is obtained chromium stainless steel liquid, is contained
The reduction slag of magnesia returns to step B as the melting furnace charge of refining magnesium after being separated with the chromium stainless steel liquid.
Present invention also offers the bath step reduction magnesium-smelting silicothermic process coproduction of another ferrosilicon containing manganese, containing molybdenum, containing vanadium or tungstenic
The method of alloy molten steel, it is characterised in that include following technique：
A., molten alloy liquid at least containing silicon, two kinds of elements of iron and initial siliceous mass percent 25-70%, institute are provided
State molten alloy liquid and be placed in firing magnesium-smelting furnace, the firing magnesium-smelting furnace keep 350-50000Pa vacuum condition and 1200-
1800 degrees Celsius of temperature conditionss；
B. the molten alloy liquid and a collection of material containing magnesia are mixed, the molten alloy liquid quality is kept all the time
The quality of slag phase is constituted more than multivariant oxide after unreacted and reaction, and keeps the siliceous quality of molten alloy liquid to be always
Magnesium chemical theory needs 1.5-200 times of siliceous amount in Si reduction slag phase, and Si reduction magnesia, generation magnesium vapor escapes the melting
Aluminium alloy and the collection that is condensed, and the slag phase for reacting formation is isolated into the firing magnesium-smelting furnace；
C. when the silicon concentration in a collection of reacted molten alloy liquid of magnesia is more than a poor silicon concentration, repeat
Technique B；When the silicon concentration in molten alloy liquid is equal to or less than the poor silicon concentration, poor silicon molten alloy liquid is formed, by institute
The poor silicon molten alloy liquid stated is placed in refining manganese, refining molybdenum, refining vanadium or refining tungsten reduction furnace, and the poor silicon concentration refers in molten alloy liquid
Siliceous mass percent between 15% -50% and less than the one of the initial siliceous mass percent of the molten alloy liquid
Individual concentration；
D. mix and described be placed in refining manganese, refining molybdenum, refining vanadium or refine the poor silicon molten alloy liquid of tungsten reduction furnace and a collection of contain aerobic
Change the material of manganese, molybdenum oxide, vanadium oxide or tungsten oxide, Si reduction manganese oxide, molybdenum oxide, vanadium oxide or tungsten oxide generate metal
Manganese, molybdenum, vanadium or tungsten are dissolved in the poor silicon molten alloy liquid, are obtained containing manganese, containing molybdenum, containing vanadium or tungsten-containing alloy steel liquid.
Compared with prior art, the present invention at least has advantages below：
(1) reducing agent Silicon in Ferrosilicon is enabled to be consumed in refining magnesium link according to theoretical value, excess silicon is completely used for chromium
Reduction, ferro element is fully entered among ferrochrome or chromium stainless steel, and physical sensible heat is fully used；
(2) ferrosilicon obtained from mine heat furnace smelting participates in refining magnesium in liquid hot charging mode, without heat temperature raising remelting, saves
Huge heat needed for ferrosilicon heating fusing；
(3) the liquid phase mode that refining reactive magnesium is bathed with ferrosilicon is carried out, with " physics matches somebody with somebody silicon " replacement " chemistry matches somebody with somebody silicon ", in ferrosilicon liquid
On the premise of abundant excess, magnesium ore deposit is fully incubated with solid phase particles or slag phase drop by ferrosilicon liquid, then using argon bottom-blowing, electricity
" process intensification " means such as magnetic stirring, top-blown gas jet so that interfacial chemical reaction, heat transfer, the speed of mass transfer are in fierceness
It is obviously improved under stirring admixture；
(4) using the inventive method carry out magnesium metal large-scale industrial production, magnesium metal per ton element silicon consumption from
825kg is reduced to 580kg, reduces about 30%；The ferro element of magnesium metal consumption per ton is reduced to almost nil from 275kg；Often
Ton magnesium metal smelting process power consumption only has 6500-7500kwh, and about 80% is reduced than Pidgeon process energy consumption, than Magnetherm half
The techniques such as continuous electric heating reduce 20%；
(5) compare from reaction speed, refining reactive magnesium can be completed in less than 1 minute in the present invention, and Pidgeon process is general
10-12 hours are needed, speed improves more than 300 times；
(6) in terms of efficiency, this method single-reactor can realize 5-20 tons of magnesium of production per hour, and single tank of Pidgeon process is per small
When production capacity there was only 2-3 kilograms, more than 2000 times of improving productivity；
(7) in the mode of production, it is easy to accomplish mechanization, automation, information-based operation, hand labor, environmental protection aspect are substituted
Also had more advantages than Pidgeon process；
(8) from the point of view of coproduction chrome stainless steel, using the reduction by ferrosilicon agent consumption approximate with original refining magnesium, energy resource consumption,
Output magnesium metal, two kinds of important raw metals of molten stainless steel, form inherent two class industries being mutually coupled, and it is passed through
Ji two kinds of products of benefit ratio, which are individually produced, to be significantly improved.
Brief description of the drawings
Fig. 1 is magnesium refining method overview.
Fig. 2 is that silicothermic reduction refines magnesium, refines the free energy of reaction comparative graph of chromium.
Fig. 3 is different ferrosilicon densograms.
Fig. 4 is that ferrosilicon of the present invention bathes the method schematic diagram that step reduces magnesium-smelting silicothermic process coproduction liquid containing ferrochrome.
Each several part sign implication is in Fig. 4：
10 --- vacuum magnesium refining furnace
11 --- magnesium vapor condensation chamber
12 --- deduster
13 --- vavuum pump
20 --- refining chromium stove
100 --- molten silicon iron liquid molten bath in magnesium refining furnace
101 --- magnesium ore deposit, refining magnesium flux (magnesia, calcium oxide, aluminum oxide, calcirm-fluoride etc.)
102 --- the high silicon molten silicon iron liquid for refining magnesium
201 --- chrome ore, refining chromium fluxing agent (chromium oxide, iron oxide, magnesia, calcium oxide etc.)
202 --- the poor silicon molten silicon iron liquid for refining chromium
Fig. 5 is the smelting principle of first embodiment of the invention.
Fig. 6 is the smelting principle of second embodiment of the invention.
Fig. 7 is the smelting principle of third embodiment of the invention.
Fig. 8 is ferrosilicon, the magnesia flow direction of material schematic diagram of fourth embodiment of the invention.
Fig. 9 is the solubility curve figure of carbon in ferrosilicon.
Embodiment
Fig. 1 to Fig. 9 is referred to, ferrosilicon bath step reduction magnesium-smelting silicothermic process coproduction of the present invention is described below in conjunction with the accompanying drawings and contains chromium
The principle and technology contents of the method for aluminium alloy.
Silicon is important reducing agent in metallurgy, in addition to serving as reducing agent in magnesium-smelting silicothermic process, can also be made
For the reducing agent of a lot of other alloying elements, for example, corresponding metal is reduced from chromated oxide, ferriferous oxide.
More than 13% chromium must all be contained in all stainless steels.Contain chromated oxide in chrome ore, pass through thermal reduction
Chromated oxide therein, ferriferous oxide reduction can be entered in ferrous alloy liquid, DIRECT ALLOYING be realized, as stainless steel
Mother liquor.In addition to stainless steel, some other high-alloy steel are also required to higher chromium content.In addition, ferriferous oxide is also can
With directly by Si reduction.Some other high-alloy steel, it is necessary to be incorporated manganese, molybdenum, vanadium, tungsten etc., can also with silicon as reducing agent,
DIRECT ALLOYING is to molten metal from its oxide ore, so as to save ferroalloy production link and heat the energy of fusing repeatedly
Source is wasted.
It is general that the trend that reaction is carried out and the journey carried out are judged using the Gibbs free chemically reacted in metallurgical process
Degree.Fig. 2 shows under the conditions of 0.05 atmospheric pressure silicon heat refining magnesium that the absolute value of the free energy negative value of silicon heat refining magnesium is less than silicon heat refining chromium
Free energy negative value absolute value, that is to say, that Si reduction chromium is easier to make for.
Calculated using the thermodynamic data of reaction equation (1)：Under 1873K, during Si reduction magnesium, under the conditions of pressure 0.05atm,
Minimum silicon activity is about 0.005 in ferrosilicon liquid.The ferrosilicon of this activity value of correspondence, is detected from table 1, ferrosilicon concentration 11.11~
Between 17.65%, the amount of unreacted silicon is that comparison is considerable, because the silicon in ferrosilicon is divided into free silica and FeSi, FeSi2
Deng silicide, consumption and silicon concentration reduction with free silica, silicon activity are reduced rapidly.Silicon activity and silicon as shown in table 1 is dense
The relation of degree, when Silicon in Ferrosilicon concentration is reduced to 0.2 from 0.4, concentration drops to original half, but activity is only original
1/37th.
The Antaciron activity coefficient γ of table 1 and silicon concentration relation (temperature 1873K)
The reaction equation of Si reduction chromium is as follows
Using the thermodynamic data of reaction equation (3), equally under 1873K, during Si reduction chromium, minimum silicon is lived in ferrosilicon liquid
Spend for 0.1ppm, i.e., 10-7, using silicon concentration in table 1 close to the activity coefficient 0.00132 when 0, now remaining silicon can be calculated
Molar fraction be 7.6E-5, mass percent is 0.0038%, it is seen that silicon utilize very fully thoroughly.
Substantially, in the industrial production, thermodynamic equilibrium state can not be fully achieved, and always needs higher silicon dense
Degree is come the reduction process that terminates, thus the usual excess silicon weight of iron percentage of silicon heat refining magnesium is 18-35%, and uses Si reduction chrome ore,
The silicon concentration balanced during terminal is usually in level as 0.5%.It can be said that realizing magnesium metal, ferrochrome with the step reduction of silicon
Order extract, both met the principle of metallurgical thermodynamics, and be also industrially reasonable.
Ferrosilicon bath step reduction magnesium-smelting silicothermic process coproduction liquid containing ferrochrome of the present invention is based on " the step reduction of silicon "
During chemical thermodynamic principle, i.e. Si reduction magnesium, even if under vacuum, as silicon concentration is reduced, the reducing power of silicon declines,
So that the ferrosilicon of low concentration can not participate in reaction, but due to chromium reduction easier than magnesium, it is using the Si reduction chromium in this ferrosilicon
Feasible.Silicon so in ferrosilicon is in high concentration, as the reducing agent of magnesium, in low concentration, as the reducing agent of chromium, also
Ferro element formation ferrochrome liquid in chromium and ferrosilicon after original, is used as stainless steel and the mother liquor of other chrome-bearing alloy steel.
The present invention also solved using " physics match somebody with somebody silicon " method " chemistry is with silicon " of existing silicon heat refining magnesium technology no
Foot, i.e., be no longer incorporated ferrosilicon with the silicon amount needed for chemical reaction, but using in molten bath ferrosilicon liquid as it is main it is uniform continuously
Phase, mineral aggregate and reducing slag are incorporated ferrosilicon liquid as a small number of dispersed phases, to form ferrosilicon bath reaction molten bath.Physics is matched somebody with somebody needed for silicon
The ferrosilicon amount of addition matches somebody with somebody the ferrosilicon addition of silicon considerably beyond chemistry, but superfluous ferrosilicon liquid reacts completely simultaneously in this batch magnesium ore deposit
After being separated with slag, it can always stay in stove or again return in stove, the ferrosilicon of a new round is re-started with new a collection of magnesium ore deposit
The refining reactive magnesium of bath, until the silicon concentration of ferrosilicon is less than the ability no longer after poor silicon concentration with reduction magnesium ore deposit, moves back and is made with it
To refine the reducing agent of chromium.
" physics matches somebody with somebody silicon " method so that the present invention is dramatically different with prior art.First, ferrosilicon liquid is fully excessive, its
The need for quantity matches somebody with somebody silicon far above chemistry, often chemistry matches somebody with somebody 1.5~200 times of silicon amount, and ferrosilicon liquid quality is greater than instead
The quality of slag phase should be formed by multivariant oxide after preceding and reaction, so that using ferrosilicon bath as continuous phase, ease is generated in magnesium vapor
The foam caused by reduction effect that goes out and being stirred vigorously under effect of external source of the gas is blasted, solid particle, the liquid phase drop of slag phase fully divide
Dissipate in ferrosilicon bath, form similar emulsion, the disperse system of emulsion, reaction interface product, convection action, which have, to be significantly increased.The
Two, the silicon concentration of initial silicon iron liquid should not be too high, and prior art typically considers from thermodynamics of reactions angle, tends to higher
Silicon concentration, commonly uses more than 70% ferrosilicon, or even uses 72%, 75%, 78% or even 80% ferrosilicon, and the present invention is due to ferrosilicon mistake
Surplus, after a collection of magnesium ore deposit has been reduced, ferrosilicon liquid be able to will be separated with slag phase, to reuse, so need the close of ferrosilicon liquid
Degree has larger difference, 2500-3000kg/m of general slag density with slag density3, molten metal density need be higher than slag
1500kg/m3Left and right, is conducive to slag phase to separate.Consider both needs, initial silicon iron liquid density is determined in 4000kg/
m3Preferably, with reference to ferrosilicon density in Fig. 3 and the relation of its silicon concentration, ferrosilicon liquid mass ratio should not be higher than 65%, density after fusing
Also decline, typically 10% or so.Refine magnesium process to stir using argon gas, clinker void fraction is higher, can also drop to a certain degree
Low slag phase density.Commercially available ferrosilicon is generally #75, #72, and less less than 70%, liquid ferrosilicon heat is more suitable in this way
Dress refining magnesium, upstream provides the even lower ferrosilicon of mine heat furnace smelting 60% of ferrosilicon, operates very light, and yield is also larger, hot charging
Come over to refine magnesium, save a large amount of heat energy of ferrosilicon heating fusing, because the specific heat of silicon, heat of fusion are much bigger than iron, so liquid
The heat energy that state ferrosilicon hot charging is saved is considerably beyond steel plant's molten iron, molten steel hot charging.
Excess silicon iron liquid needs recycling, can both stay in and reducing slag is pulled down in magnesium refining furnace, what is more optimized is from refining
After flowing out in magnesium stove, then furnace roof is promoted to, from furnace roof is disposable, accomplished continuously or intermittently recharge is in stove, by under the swash of wave of top
Gravitional force and origin of heat, hot ferrosilicon liquid have certain impact capacity, are conducive to eliminating vacuum suction, blast argon gas, magnesium
Excessive foamed slag caused by vapor egress, can also break through the slag blanket scull (skull) that molten bath top in stove easily occurs, and improve
The mobility of silicon molten iron bath.
Chrome ore typically has point of lump ore and fine ore, and lump ore is adapted to Ferrous Metallurgy technique to refine chrome-bearing alloy, but lump ore is got over
Come more rare, price is higher, increasing chrome ore is the form of fine ore, be all powder after particularly low-grade Chromium ore beneficiation
Ore deposit, will typically first pass through sintering, pelletizing and briquetting artificial lump ore is made to use, though so in steel and iron industry chromite ore fine
Right supply is higher than lump ore, but needs, by complicated pretreatment, to be often out of favour, and processing cost is higher.In this hair
In bright, the remaining ferrosilicon of melting after refining magnesium directly can enter ferrosilicon molten bath by chromite ore fine, carry out the alloying of chromium, be contained
Ferrochrome or chrome-bearing alloy steel, if using the method for jet metaurgy, reaction rate is very high, and the unfavorable conditions of fine ore becomes
Advantage.
In embodiments, with the poor ferrosilicon liquid after refining magnesium, the reduction DIRECT ALLOYING of chrome ore is carried out, chromium system is smelted not
The molten steel that becomes rusty is preferred scheme.
The General Implementing process of the present invention is as follows, is explained with reference to Fig. 4.
A. furnace charge prepares
A01：High temperature silicon iron liquid 102 is melted after mineral hot furnace is tapped a blast furnace, into the ferrosilicon bag with insulation cover, refining magnesium is transported to
Stove feed location, for example with 65% ferrosilicon liquid, and the amount of ferrosilicon liquid finishes 2 times of the quantity of slag for refining magnesium, substantially in ferrosilicon
Silicon content is 10-15 times of theoretical silicon demand；
A02：Dolomite is white as forging after being calcined in rotary kiln, that is, magnesium ore deposit 101, and magnesium refining furnace 20 is transported to while hot and is added
Discharge position, can be in tolerance range in equipment for energy-conservation, and the cooling of magnesium ore deposit is more few better, such as 800-1000 DEG C；
A03：Prepare a certain amount of calcined bauxite, fluorite etc. in addition as fluxing agent and dolime and collectively constitute refining magnesium
Raw material 101, to be finished according to refining magnesium 15% of clinker obtained by 80% oxidation magnesium-reduced be aluminum oxide, 5% is that calcirm-fluoride carries out dispensing,
It is transported to the feed location of magnesium refining furnace 20.
B. furnace charge is mixed
B01：Pushed up from magnesium refining furnace stove 20 and a part of magnesium ore deposit, fluxing agent 101 are added in stove, while from top by ferrosilicon liquid
102 are slowly injected into stove, keep ferrosilicon liquid is long-term constantly to be injected from top；
B02：In smelting process, with the rhythm and quantity matched with ferrosilicon liquid phase, it will intermittently or constantly contain magnesium
Furnace charge 101 is added in stove, and causes ferrosilicon liquid to fall into close proximity in stove with furnace charge.
C. silicon heat refining magnesium
C01：Can using resistance, electroslag, sensing, plasma or with the electric arc heated mode for stablizing arcing device,
The power transmission of molten bath in stove 100 is heated, maintains to be evacuated to vavuum pump 13 in 1400-1700 DEG C of bath temperature in stove, stove
800-50000Pa, while argon bottom-blowing, the outer magnetic stirrer of startup stove so that furnace charge containing magnesium 101 fills with liquid-state silicon iron liquid 102
Divide mixing, strong agitation, while the lasting furnace charge supply at the top of keeping；
C02：Magnesium vapor is generated, and escapes furnace chamber, into condenser 11, be condensed collection, and remaining furnace gas passes through deduster 12,
Taken away by vavuum pump 13.
D. tap a blast furnace slag tap, slag gold separation
D01：Smelt to a certain extent, such as magnesium vapor is no longer produced when either yield is decreased obviously or according to operation
After the empirically determined duration of heat, Gas Stirring and function composite by electromagnetic stirring are reduced, is changed to uniformly be blown into indifferent gas from furnace bottom
Body so that ferrosilicon bath flowing weakens, and progressively separates clear and definite slag blanket and ferrosilicon liquid layer；
D02：Air pressure in regulating stove, to stove inside and outside air pressure balance or stove in malleation, progress taps a blast furnace tapping operation, can be with slag
Iron is mixed out, also can bottom first tap a blast furnace and then slag tap again, can also only be slagged tap from higher position and stay in ferrosilicon in stove, then in stove
Slag gold separation is carried out in ladle outside interior or stove, can both take skimming to operate, can also bottom tap a blast furnace so that slag, silicon
Iron liquid is divided in two containers, and slag, which is removed, is used as other purposes.
E. ferrosilicon liquid is returned
E01：Judge whether ferrosilicon liquid reaches poor silicon concentration, it is assumed that be defined as 30%, according to ferrosilicon liquid initial concentration and always
Amount, magnesium ore deposit amount and magnesium content, magnesium-reduced rate with reference to addition can substantially obtain ferrosilicon liquid concentration, can also take more
Advanced on-line quick detection or the magnesium yield in magnesium condenser carry out automatic identification, protracted experience and fixed operation
Also it would know that silicon concentration.If silicon concentration is more than poor silicon concentration, A01 operational sequences are returned to, are again introduced into stove, it is and new
A collection of magnesium ore deposit secondary response again, until D02 processes, then judge whether to reach poor silicon concentration again；
E02：At any moment during this period, certain density ferrosilicon liquid or silicon-iron block can be supplemented, to supplement silicon
Consumption, supplement ferrosilicon or do not supplement ferrosilicon, do not influence normal operation, and supplement ferrosilicon can make it that silicon molten iron bath is unlikely
It is too fast in volume decline, because the continuous consumption of silicon and the abundance zone of iron carry out the lifting of the liquid-tight degree of ferrosilicon.
F is poor, and ferrosilicon liquid is transported to ferrochrome stove
F01：After the recoverable refining magnesium operation of multiple ferrosilicon liquid, ferrosilicon liquid is come out of the stove again, and current ferrosilicon liquid has reached poor
Silicon concentration 30%, after being separated with slag, is not returned to magnesium refining furnace 10, and is conveyed to the feed location of ferrochrome stove 20；
F02：Poor silicon ferrosilicon liquid 202 forges white etc. help with the feed way similar with magnesium refining furnace with chrome ore, lime, dolomite
Flux 201 is added in ferrochrome stove together, and to maintain good melting bath stirring, solid charge can by stages and in groups or continuously add
Enter, ferrosilicon bath remains unchanged, and centre can divide tapping operation several times, then add solid charge, can also be by chrome ore and stone
Ash etc. is pre- to be melt into slag, disposable or be added portionwise and mixed with ferrosilicon liquid；
G smelts ferrochrome
G01：Mode, reinforcing mixing are integrally shaken etc. by bottom blown gas, top-blown gas jet, electromagnetic agitation, ferrochrome stove
Process so that iron, chromium are entered in metal bath 200 by Si reduction in chrome ore, generation silica and alkaline calcium oxide, oxidation
Magnesium etc. is combined in slag phase；
G02：Silicothermic reduction chromium, iron sheet can typically not need outside heat supply, can also suitably use as exothermic reaction
The mode supplementary heatings such as electrical heating, oxygen, combustion gas, iron scale, other chemical heat sources, can vacuumize can also be without vacuum
Environment；
G03：It is continuously added into or is added portionwise solid charge or fritting melt cinder to bathe to ferrosilicon, until Silicon in Ferrosilicon consumption
Totally, or close to a relatively low concentration, such as 0.5~3%, the chrome ore in furnace charge more thoroughly to be reduced, then
It is appropriate to be passed through oxidizing gas or add the oxidants such as iron scale, while suitable lime etc. is incorporated, by the silicon in ferrochrome
Thoroughly removing.
H ferrochrome is refined
H01：Ferrochrome liquid can be directly smelted into containing the chromium stainless steel mother liquors such as chromium 13%, 20%, 25%, or supplying
Nickel turns into nickel chromium stainless steel mother liquor, be either incorporated nickel, manganese turn into nickel chromium triangle manganese systems mother liquor of stainless steel or smelt into containing chromium 40~
50% and the ferrochrome of more high chrome contents.If smelting product chromium content is told somebody what one's real intentions are, iron ore is used in refining ferrochrome link increase
Ratio so that the more ferriferous oxides of Si reduction；
H02：According to the content of impurity in furnace charge, ferrochrome liquid or mother liquor of stainless steel can be refined, further to carry
Rise quality.
First embodiment：
A is from the 65% of mine heat furnace smelting 48 tons of ferrosilicon liquid, 1600 DEG C of keeping temperature, while it is 40% to prepare containing MgO
Dolomite forges white 20 tons, keeps 800 DEG C of temperature, gets 1.3 tons of 3.5 tons of bauxite, the fluorite of calcining ready as fluxing agent.
B ferrosilicon liquid is blended into the liquid material container 102 above magnesium refining furnace, from the batch (-type) of liquid material container 102 injection magnesium refining furnace,
Forge white 101 to be also added in stove from from batch (-type) above furnace roof, and the ferrosilicon liquid in stove is well mixed with forging white, fluxing agent.
C adds half while when solid-state furnace charge also adds half, start power transmission in stove, be evacuated to simultaneously in ferrosilicon liquid
3000Pa, is passed through argon gas and carries out bottom blowing stirring, begins with magnesium vapor and enters condensation chamber 11, maintains molten bath and charge-temperature not low
In 1600 DEG C.Start to cool down magnesium vapor in condensation chamber so that magnesium is condensed.It is synchronous successively to add all remaining stoves
Material, and continue power transmission, vacuumize smelting.All furnace charges enter after stove, continue to smelt 10 minutes.
D reduces the flow of argon bottom-blowing so that is filled with argon gas to pressure-fired in molten metal, slag layering, stove in molten bath, beats
Blow-on bottom liquid outlet, ferrosilicon liquid is first flowed out, and then slag, which is then flowed out, comes, and is covered in above ferrosilicon liquid, manually or skimming
Device excludes slag.
E delivers to ferrosilicon liquid above magnesium refining furnace again, the step of restarting A-D.It is repeated 4 times after totally 5 smeltings, surveys
Ferrosilicon liquid total amount is determined for 36 tons, silicon concentration is 53%, add 15 tons of 65% ferrosilicon liquid, ferrosilicon liquid total amount is 51 tons, siliceous to be
56.8%, the step of continuing to repeat A-D, then carry out 9 smeltings, last 3 adjustment vacuum to 1000Pa, final residual silicon
Iron liquid total amount is 29.7 tons, silicon content 26%.
29.7 tons siliceous 26% of ferrosilicon liquid is transported to ferrochrome stove charge door by F, gets out 35 tons of chromite, iron scale
15 tons, 35 tons of lime, dolomite forges white 2 tons, after being well mixed, and ferrochrome stove is added several times, pulls down reducing slag before charging every time,
Then mixture charge is added.
G reducing and smeltings are finished, and pull down reducing slag, tapping, 43 tons of Molten Ferroalloys are obtained, wherein containing chromium 20.1%, C, P, S
Respectively 0.1%, 0.008%, 0.004%, it can be used as mother liquor of stainless steel.
35 tons of magnesium metal, average power consumption 7200kwh per ton are obtained altogether.
In first embodiment, the smelting principle and chromium of Si reduction chromium, the source whereabouts of ferro element are as shown in Figure 5.
Second embodiment：
Raw material prepares essentially identical with first embodiment, when being smelted per stove, is added in ferrosilicon liquid and contains aluminium 20%, siliceous
2 tons of 40% Alsimin, remaining operation is constant.The preferential Si reduction magnesium of aluminium, enters in slag as aluminum oxide.Reducing agent alloy
Liquid still is able to steady production magnesium metal, ferrochrome liquid.In second embodiment, aluminium, the smelting principle of Si reduction chromium and chromium, iron
The source whereabouts of element is as shown in Figure 6.
3rd embodiment：
Initial feed uses 48 tons of the ferrosilicon liquid containing nickel, wherein siliceous is still 65%, nickeliferous 7%, remaining is iron, middle
Ferrosilicon is not added, other operations are constant.Reducing agent aluminium alloy still is able to steady production magnesium metal, and 35 tons are dropped in ferrosilicon total amount
After below, it is changed to every stove dolime and halves addition, fluxing agent auxiliary material also halves addition in proportion, the alloy at siliceous 30%
Liquid quality is 24 tons, turns nickel during going to smelt ferrochrome, supplying chrome ore and iron scale, refining chromium and stays in aluminium alloy, finally obtains
Chromium 20%, nickeliferous 8.6% 36 tons of mother liquor of stainless steel must be contained.In 3rd embodiment, the smelting principle and chromium of Si reduction chromium,
Nickel, ferro element source whereabouts it is as shown in Figure 7.
Fourth embodiment：
The present embodiment will contain magnesia melting refining chromium slag as refining magnesium raw material, that is, ferrosilicon using " reverse recoverable "
102 be to be introduced into magnesium refining furnace 10, and refining magnesium, which is finished, enters refining chromium stove 20 after poor silicon, but the magnesium ore deposit containing magnesia is first as refining chromium
The part of raw material 201, which enters, refines chromium stove 20, and the slag -2 for then refining the chromium depleted rich magnesium of poor iron after chromium is finished is re-used as refining magnesium original
Material 101 enters magnesium refining furnace 10, ferrosilicon liquid as shown in Figure 8, the technique glide path of magnesia mineral aggregate.
Dolime and chrome ore, lime and fluxing agent etc. are mixed in advance, the raw material 201 of refining chromium stove 20 is formed, point
Refining chromium stove 20 is repeatedly added to, and is sufficiently mixed with 30% ferrosilicon liquid 202, keeps the ratio between ferrosilicon liquid and every batch of mineral aggregate to be far above
Silicon amount needed for chemical reaction, every batch of mineral aggregate after completion of the reaction, discharges the hot slag containing magnesia, is used as refining magnesium raw material 101
" reverse " enters magnesium refining furnace 10, and the ferrosilicon liquid 102 with siliceous 65% is sufficiently mixed, and carries out refining magnesium, the whole reduction that refining magnesium is finished
Slag is discharged, and then proceedes to that the high silicon silicon that furnace charge is used as in 101 and magnesium refining furnace that melts for containing magnesia that chromium stove is newly discharged will be refined
Iron liquid 101 is mixed, and carries out refining magnesium.
In aforementioned four embodiment, refining magnesium after poor silicon ferrosilicon liquid smelt chromium stainless steel mother liquor when, except Fig. 5,
Main alloy element chromium, nickel shown in Fig. 6, Fig. 7, iron source are outer, molten stainless steel also need to the relatively low carbon of control ratio, phosphorus, sulphur,
The constituent contents such as oxygen, hydrogen, nitrogen.
Chromium stainless steel liquid in of the invention and embodiment is carbon containing relatively low, because, the solubility of original carbon in ferrosilicon
It is smaller, as shown in figure 9, so resulting in the mother liquor of stainless steel of low-carbon.
Emphasized once dephosphorization.In stainless steel smelting process, dephosphorization is a vital task.General Ferrous Metallurgy is used
Dephosphorization under oxidizing atmosphere means, but in smelting stainless steel, because chromium can be oxidized prior to phosphorus and cause alloying element chromium in stainless steel
Loss, so the stainless steel capital is in early oxidation dephosphorization, once into the later stage, dephosphorization is just relatively difficult.But the present invention is carried
The method of confession so that there are two big advantages to realize the dephosphorization of smelting stainless steel.This two big advantage is to be evaporated in vacuo dephosphorization, reduction respectively
Dephosphorization.
Phosphorus is Volatile Elements, and boiling point only has 280 DEG C, completely can be by the dephosphorization that volatilizees, and its vapour pressure is even above magnesium
Such volatile metal.But in steel and iron industry, phosphorus is combined into relatively stable Fe in molten steel with iron2P、Fe3P, is reduced
The activity of phosphorus, thus be difficult in steel and iron industry to slough phosphorus in molten steel with the method for evaporation.
But phosphorus with iron in the case where not combined, gas phase is easily accessible, using this feature, the electric furnace manufacture-yellow of phosphorous chemical industry
Phosphorus is able to large-scale production, also higher come deep phosphorous removal using phosphorous vapor pressure in the Physical purification of polysilicon.In electric furnace manufacture-yellow
In phosphorus industrial production, as long as being added without steel cuttings in furnace charge, it becomes possible to realize that the phosphorus that reduction is obtained largely is entered with phosphorous vapor
Gas phase, condensation collection obtains yellow phosphorus, and the ferrophosphorus of by-product only has the 10-20% of yellow phosphorus, phosphorous rate 18-26%, it is seen that phosphorus not with
If iron is combined, obtained phosphorus at least 95% is reduced at 1400-1600 DEG C and evaporates into gas phase.But if adding steel in furnace charge
Bits, then the phosphorus 80% or so that reduction is obtained is entered in ferrophosphorus, and gas phase is entered within only 20%, so that as with ferrophosphorus
For major product, the condensed thick phosphorus of phosphorous vapor is byproduct.
When Physical purifies photovoltaic crystal silicon material, also using the method for being evaporated in vacuo dephosphorization.By the pure silicon material of melting true
Several hours are stood in the air, and phosphorus content can be removed to several ppm magnitudes.
In ferrosilicon liquid, because silicon and iron generate stable FeSi etc. so that phosphorus can not be combined with iron, thus be possessed
The condition of dephosphorization is evaporated in vacuo, typically in more than silicone content 20-30%, phosphorus just can largely be removed using vacuum vapor deposition method.
Ferrosilicon refine magnesium link, vacuum suction, blast argon gas stirring, magnesium vapor generate and is pumped, these three vacuum imitate
It should be superimposed, be very beneficial for the removing of phosphorus.
Except being evaporated in vacuo dephosphorization, dephosphorization under reducing atmosphere is also important dephosphorization means.For refining the forging containing CaO, MgO of magnesium
Calcined dolomite is added in ferrosilicon liquid and is sufficiently mixed, and has a small amount of calcium also to generate while magnesium is largely produced, and possesses strong reduction bar
Part, both metals can generate Ca with phosphorus3P2、Mg3P2Into slag phase, i.e., so-called dephosphorization under reducing atmosphere, such as formula (4), (5) institute
Show.In conventional stainless steel smelting, because the vapour pressure of calcium, magnesium metal is very high, when adding molten stainless steel dephosphorizing, most of calcium,
Magnesium evaporation loss, is only combined with phosphorus on a small quantity, so dephosphorization metal utilizing status is not ideal enough.And the present invention in the first purpose just
It is largely to produce magnesium vapor, thus in the absence of the situation that dephosphorization evaporation of metal loses.
3Ca+2 [P]={ Ca3P2} (4)
3Mg+2 [P]={ Mg3P2} (5)
It should also be noted that the phosphorus content of poor silicon ferrosilicon is relatively low, but in refining ferrochrome link, it is necessary to take precautions against chrome ore and lime
It is not so high Deng the phosphorus content in fluxing agent.
If the phosphorus of magnesium refining furnace material is very high, then can have certain Ca in smelting magnesium slag3P2、Mg3P2, it should be noted that this
The protection against the tide of slag, can not directly be contacted with water or vapor, to prevent the PH of generation severe toxicity3, endanger the health of people, it should moistureproof and
Phosphate is oxidized to as early as possible under isolation air conditions.
Desulfurization is also the approach similar to dephosphorization, but more easy.In stainless steel smelting, the higher slag charge of alkalescence is added,
Desulfurization can be achieved.Present invention refining magnesium link, the magnesium ore deposit of addition forged for the dolomite of strong basicity it is white, being capable of effectively desulfurization.In addition,
The evaporation desulfurized effect similar to evaporation dephosphorization can also be superimposed, and obtain excellent desulfurized effect.
Deoxidation effect.Using poor silicon ferrosilicon liquid smelting stainless steel, wherein because silicone content is high, oxygen content is very low, reaches good
Good deoxidation effect.
Degasifying effect.Refine magnesium link in, vacuum suction, argon gas stirring, magnesium vapor take away, can by the H in ferrosilicon liquid,
N etc. is removed to relatively low level.
In addition to the advantages indicated above, it can be made full use of as the DIRECT ALLOYING for carrying out chrome ore using poor silicon ferrosilicon liquid
Large number of, cheap chromite ore fine.The chrome ore of nature about 75% is chromite ore fine, and only 25% is chrome ore block.Using ore deposit heat
During ferrochrome needed for stove smelting stainless steel, the gas permeability operated for mineral hot furnace, it is necessary to the expensive lump ore of selection, or will
The advance briquetting of cheap fine ore, pelletizing or sintering become bulk material, cause complex process, energy consumption to improve, cost increases, and
In the present invention poor silicon ferrosilicon liquid still when magnesium is refined in the way of, using poor silicon ferrosilicon liquid as continuous phase, chromite ore fine is as scattered
Both be sufficiently mixed mutually is carried out, the granularity of chromite ore fine is relatively thin to be conducive to refining chromium process on the contrary, can obtain good chromium
DIRECT ALLOYING so that inexpensive can utilize in liberal supply, cheap chromite ore fine.
In fourth embodiment, using " recoverable " the melting refining chromium slag containing magnesia as magnesium raw material is refined, three are at least brought
Further optimization.Content of magnesia is very high in chrome ore, generally reaches 10-22%, particularly after refining chromium, oxygen in remaining slag
Change magnesium higher, it is such as unfavorable to be used for refining magnesium, it is the larger wasting of resources.Further, refining magnesium process needs the heat energy of extraneous input larger,
And refine chromium process energy consumption for negative value or remain basically stable, so refining chromium stove will be introduced into after dolomite calcination, exist equivalent to by magnesium ore deposit
Melted in advance in refining chromium stove, reduce the thermic load of refining magnesium link, while refining the small amounts chromium that chromium link fails fully to reduce
Reduce, entered in ferrosilicon liquid in high silicon iron liquid in magnesium refining furnace, it is final to have flowed to refining chromium stove again, therefore the synthesis of chromium is received
Rate obtains further lifting.
Advantage of the technical solution of the present invention of table 2 in refining magnesium field
The technical solution of the present invention of table 3 is smelting the advantage in chrome stainless steel field
In summary, it these are only presently preferred embodiments of the present invention, the scope of the present invention should not be limited with this, i.e., it is all
It is the simple equivalent changes and modifications made according to claims of the present invention and description, all should still belongs to patent of the present invention
In the range of covering.
Claims (13)
1. the method that ferrosilicon bath step reduces magnesium-smelting silicothermic process coproduction liquid containing ferrochrome, it is characterised in that include following technique：
A., the molten alloy liquid for being at least 25-70% containing silicon, two kinds of elements of iron and initial siliceous mass percent is provided, it is described
Molten alloy liquid is placed in vacuum in firing magnesium-smelting furnace, the firing magnesium-smelting furnace and is maintained at 350-50000Pa, and temperature is maintained at
1200—1800℃；
B. the molten alloy liquid and a collection of material containing magnesia are mixed, keeps the molten alloy liquid quality to be consistently greater than
Unreacted and reaction after multivariant oxide constitute the quality of slag phase, and keep the siliceous quality of molten alloy liquid be always silicon also
Magnesium chemical theory needs 10-15 times of siliceous amount in former slag phase, and Si reduction magnesia, generation magnesium vapor escapes the molten alloy liquid
And the collection that is condensed, and the slag phase formed after reaction is isolated into the firing magnesium-smelting furnace；
C. when the silicon concentration in a collection of reacted molten alloy liquid of magnesia is more than a poor silicon concentration, iterative process
B；When the silicon concentration in molten alloy liquid is equal to or less than the poor silicon concentration, poor silicon molten alloy liquid is formed, will be described
Poor silicon molten alloy liquid is placed in refining chromium reduction furnace, the poor silicon concentration refer to siliceous mass percent in molten alloy liquid between
Between 15% -50% and less than a concentration of the initial siliceous mass percent of the molten alloy liquid；
D. the poor silicon molten alloy liquid and a collection of material containing chromium oxide of refining chromium reduction furnace, Si reduction oxidation are placed in described in mixing
Chromium, generation crome metal is dissolved in the poor silicon molten alloy liquid, obtains liquid containing ferrochrome.
2. the method that ferrosilicon bath step as claimed in claim 1 reduces magnesium-smelting silicothermic process coproduction liquid containing ferrochrome, its feature
Be, the molten alloy liquid in the technique A is stirred in firing magnesium-smelting furnace by argon gas, electromagnetic force stirring or mechanical agitation in
One or more of stirrings.
3. the method that ferrosilicon bath step as claimed in claim 1 reduces magnesium-smelting silicothermic process coproduction liquid containing ferrochrome, its feature
It is, also containing the aluminium element that mass percent is 1-30% in the molten alloy liquid in the technique A.
4. the method that ferrosilicon bath step as claimed in claim 1 reduces magnesium-smelting silicothermic process coproduction liquid containing ferrochrome, its feature
It is, also containing the nickel element that mass percent is 0.5-20% in the molten alloy liquid in the technique A.
5. the method that ferrosilicon bath step as claimed in claim 1 reduces magnesium-smelting silicothermic process coproduction liquid containing ferrochrome, its feature
Be, in the technique B material containing magnesia for calcining after dolomite, calcining after magnesite, magnesia it is waste and old
One or more in refractory material, the metallurgical slag containing magnesia or the slag melted containing magnesia.
6. the method that ferrosilicon bath step as claimed in claim 1 reduces magnesium-smelting silicothermic process coproduction liquid containing ferrochrome, its feature
It is, after a collection of magnesia in the technique B at least 50% reacts, will just reacts the slag phase formed and refine magnesium also from described
Former stove is separated.
7. the method that ferrosilicon bath step as claimed in claim 1 reduces magnesium-smelting silicothermic process coproduction liquid containing ferrochrome, its feature
It is, the technique B also includes adding ferrosilicon into the molten alloy liquid, keeps the molten alloy liquid quality to be consistently greater than
Unreacted and reaction after multivariant oxide constitute the quality of slag phase, and keep the siliceous quality of molten alloy liquid be always silicon also
Magnesium chemical theory needs 1.5-200 times of siliceous amount in former slag phase.
8. the method that ferrosilicon bath step as claimed in claim 1 reduces magnesium-smelting silicothermic process coproduction liquid containing ferrochrome, its feature
It is, the mode for separating the slag phase for reacting formation from the firing magnesium-smelting furnace in the technique B is included the melting
Aluminium alloy and slag phase are discharged after the firing magnesium-smelting furnace again by molten alloy liquid recharge to the firing magnesium-smelting furnace, Huo Zhezhi together
Connect and separate slag phase from the firing magnesium-smelting furnace.
9. the method that ferrosilicon bath step as claimed in claim 1 reduces magnesium-smelting silicothermic process coproduction liquid containing ferrochrome, its feature
It is, is added in the molten alloy liquid in the technique B and contain aluminum oxide and/or contain the material of calcirm-fluoride as slag former.
10. the method that ferrosilicon bath step as claimed in claim 1 reduces magnesium-smelting silicothermic process coproduction liquid containing ferrochrome, its feature
Be, the liquid containing ferrochrome in the technique D for smelt chromium stainless steel mother liquor, the liquid containing ferrochrome contain chromium matter
It is 10-50% to measure percentage.
11. the method that ferrosilicon bath step as claimed in claim 1 reduces magnesium-smelting silicothermic process coproduction liquid containing ferrochrome, its feature
It is, calcined limestone, dolomite is added in the technique D and forges white powder, the material containing calcium oxide or the thing containing magnesia
One or more in matter are used as slag former.
12. the method that ferrosilicon bath step reduces magnesium-smelting silicothermic process coproduction chromium stainless steel liquid, it is characterised in that include following work
Skill：
A., molten alloy liquid at least containing silicon, two kinds of elements of iron and initial siliceous mass percent 25-70% is provided, it is described molten
Melt aluminium alloy and be placed in firing magnesium-smelting furnace, the firing magnesium-smelting furnace keeps 350-50000Pa vacuum condition and 1200-1800 to take the photograph
The temperature conditionss of family name's degree；
B. the molten alloy liquid and a collection of material containing magnesia are mixed, the material containing magnesia is step D institutes
The reduction slag of discharge, keeps the molten alloy liquid quality to be consistently greater than multivariant oxide after unreacted and reaction and constitutes slag
The quality of phase, and keep the 10- that the siliceous quality of molten alloy liquid is always the siliceous amount of magnesium chemical theory need in Si reduction slag phase
15 times, Si reduction magnesia, generation magnesium vapor escapes the molten alloy liquid and the collection that is condensed, and will react the slag phase formed
Isolate the firing magnesium-smelting furnace；
C. when the silicon concentration in a collection of reacted molten alloy liquid of magnesia is more than a poor silicon concentration, iterative process
B；When the silicon concentration in molten alloy liquid is equal to or less than the poor silicon concentration, poor silicon molten alloy liquid is formed, will be described
Poor silicon molten alloy liquid is placed in refining chromium reduction furnace, the poor silicon concentration refer to siliceous mass percent in molten alloy liquid between
Between 15% -50% and less than a concentration of the initial siliceous mass percent of the molten alloy liquid；
D. the poor silicon molten alloy liquid and a collection of thing at least containing chromium oxide, magnesia of refining chromium reduction furnace are placed in described in mixing
Matter, Si reduction chromium oxide, generation crome metal is dissolved in the poor silicon molten alloy liquid, chromium stainless steel liquid is obtained, containing aerobic
The reduction slag of change magnesium returns to step B as the melting furnace charge of refining magnesium after being separated with the chromium stainless steel liquid.
13. method of the ferrosilicon bath step reduction magnesium-smelting silicothermic process coproduction containing manganese, containing molybdenum, containing vanadium or tungsten-containing alloy steel liquid, its feature
It is, includes following technique：
A., molten alloy liquid at least containing silicon, two kinds of elements of iron and initial siliceous mass percent 25-70% is provided, it is described molten
Melt aluminium alloy and be placed in firing magnesium-smelting furnace, the firing magnesium-smelting furnace keeps 350-50000Pa vacuum condition and 1200-1800 to take the photograph
The temperature conditionss of family name's degree；
B. the molten alloy liquid and a collection of material containing magnesia are mixed, keeps the molten alloy liquid quality to be consistently greater than
Unreacted and reaction after multivariant oxide constitute the quality of slag phase, and keep the siliceous quality of molten alloy liquid be always silicon also
Magnesium chemical theory needs 10-15 times of siliceous amount in former slag phase, and Si reduction magnesia, generation magnesium vapor escapes the molten alloy liquid
And the collection that is condensed, and the slag phase for reacting formation is isolated into the firing magnesium-smelting furnace；
C. when the silicon concentration in a collection of reacted molten alloy liquid of magnesia is more than a poor silicon concentration, iterative process
B；When the silicon concentration in molten alloy liquid is equal to or less than the poor silicon concentration, poor silicon molten alloy liquid is formed, will be described
Poor silicon molten alloy liquid is placed in refining manganese, refining molybdenum, refining vanadium or refining tungsten reduction furnace, and the poor silicon concentration refers to containing in molten alloy liquid
One between 15% -50% and less than the initial siliceous mass percent of the molten alloy liquid of silicon mass percent is dense
Degree；
D. mix the poor silicon molten alloy liquid for being placed in refining manganese, refining molybdenum, refining vanadium or refining tungsten reduction furnace and it is a collection of containing manganese oxide,
The material of molybdenum oxide, vanadium oxide or tungsten oxide, Si reduction manganese oxide, molybdenum oxide, vanadium oxide or tungsten oxide, generation manganese metal, molybdenum,
Vanadium or tungsten are dissolved in the poor silicon molten alloy liquid, are obtained containing manganese, containing molybdenum, containing vanadium or tungsten-containing alloy steel liquid.
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| CN111321310B (en) * | 2020-02-10 | 2024-03-19 | 中国恩菲工程技术有限公司 | Method and system for preparing magnesium metal |
| CN112501434B (en) * | 2020-10-19 | 2023-04-14 | 北京中冶设备研究设计总院有限公司 | Liquid magnesium smelting reducing agent and application thereof |
| CN112853121B (en) * | 2020-12-30 | 2022-07-12 | 北京中冶设备研究设计总院有限公司 | Method for producing metal magnesium |
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| KR100793591B1 (en) * | 2006-12-28 | 2008-01-14 | 주식회사 포스코 | Method for reduction of metallic chromium from slag containing chromium oxide |
| CN100485071C (en) * | 2007-06-09 | 2009-05-06 | 山西太钢不锈钢股份有限公司 | Electric furnace smelting recovery method for chronium-nickel alloy element in stainless steel dedusting ash |
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