CN103014327A - Chrome-manganese ore composite pellets for argon oxygen refinement furnace, and preparation method thereof - Google Patents
Chrome-manganese ore composite pellets for argon oxygen refinement furnace, and preparation method thereof Download PDFInfo
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- CN103014327A CN103014327A CN2011102804598A CN201110280459A CN103014327A CN 103014327 A CN103014327 A CN 103014327A CN 2011102804598 A CN2011102804598 A CN 2011102804598A CN 201110280459 A CN201110280459 A CN 201110280459A CN 103014327 A CN103014327 A CN 103014327A
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Abstract
The present invention discloses chrome-manganese ore composite pellets for an argon oxygen refinement furnace, and a preparation method thereof. The composite pellets comprise the following components, by weight, 28-43% of chrome ore, 11-22% of manganese ore, 25-45% of graphite, 5-10% of ferrosilicon, and 5-7% of a binder. The preparation method comprises: respectively grinding the chrome ore, the manganese ore, the graphite and the ferrosilicon into fine powders with a particle size of not more than 1 mm, mixing the powders, adding the binder to the mixed powder, uniformly stirring to prepare pellets with a diameter of 20-50 mm, drying for 8-10 h at a temperature of 80-250 DEG C, naturally cooling, and carrying out sealed storage. With the chrome-manganese ore composite pellets for the argon oxygen refinement furnace, a chrome-manganese element yield in pellets during a decarbonization process can be improved, and slag desulfurization capacity is increased.
Description
Technical field
The present invention relates to a kind of supplementary material for ferrous metallurgy, particularly a kind of argon oxygen decarburizing furnace chromium manganese ore composite pellet and preparation method thereof that carries out chrome-manganese alloy for stainless steel smelting process.
Background technology
Chromium (Cr), manganese (Mn) are indispensable elements in the stainless steel, and they also are one of main alloy element in the stainless steel.The material that carries out at present chrome-manganese alloy in the argon oxygen decarburizing furnace steelmaking process is that chromium is that iron alloy, manganese are iron alloy, these two kinds of alloys are to be become to contain manganese, contained ferrochrome by chrome ore, Smelting Plant, big for environment pollution in whole production process, energy consumption and production cost are higher.And when argon oxygen decarburizing furnace is smelted, after reduction finishes, for preventing the later stage molten steel recarburization, join in the argon oxygen decarburizing furnace stove with the form of metal ferromanganese, cause the further rising of production cost.
Along with the development of steel-smelting technology, employing chrome ore, manganese ore have occurred and directly carried out alloying in converter and electric furnace.But problem is the chromium in the chrome ore mainly is to exist with picrochromite, chromohercynite form, fusing point is high in the liquid phase slag, and solubleness is very little, and reductive condition is subjected to the impact of carbon in the mother liquor of stainless steel, chromium content larger, carbon content is lower, chromium content is higher, and the beginning reduction temperature is higher.And manganese element is the element of very easily oxidation, increase along with oxidizing atmosphere, to be difficult to satisfy the demand of Reduction of manganese ore condition, therefore in whole argon oxygen decarburizing furnace smelting process, the recovery rate of chromium, manganese unstable (before the reduction phase), difficulty is applied in the increase that has caused the reduction process ferrosilicon to consume.
Summary of the invention
The object of the present invention is to provide a kind of argon oxygen decarburizing furnace with chromium manganese ore composite pellet and preparation method thereof, improve the recovery rate of chromium, manganese in the whole argon oxygen decarburizing furnace smelting process, thereby reduce ferrochrome, ferromanganese add-on; And can the promotionization slag, improve the desulfuration ability of slag.
Another object of the present invention provides the preparation method that a kind of argon oxygen decarburizing furnace is used chromium manganese ore composite pellet.
For achieving the above object, argon oxygen decarburizing furnace of the present invention chromium manganese ore composite pellet, its weight percentages of components is:
Chrome ore: 28～43%;
Manganese ore: 11～22%;
Graphite: 25～45%;
Ferrosilicon: 5～10%;
Binding agent: 5～7%.
Cr in the above-mentioned chrome ore
2O
3Weight percentage be 45.0～50.0%;
The weight percentage of MnO is 25～38% in the above-mentioned manganese ore, and manganese ore can be manganese raw ore, manganese sinter or rich manganese ore;
The weight percentage of carbon in the above-mentioned graphite: 78.0～86.0%;
Ferrosilicon is take coke, steel cuttings, quartz (or silica) as raw material, the iron silicon alloy made from electrosmelting.The weight percentage of above-mentioned Silicon in Ferrosilicon is 72.0～80.0%;
Above-mentioned binding agent can be the general binding agent in this area, Xylo-Mucine, methylcellulose gum, Vltra tears or amylan etc.
Above-mentioned argon oxygen decarburizing furnace can adopt following method to be prepared from chromium manganese ore composite pellet, chrome ore, manganese ore, graphite, ferrosilicon are ground to form respectively the fine powder that granularity is not more than 1mm, mix, adding binding agent stirs again, make the pelletizing that diameter is 20～50mm, again this pelletizing is dried 8～10 hours, naturally cooling under 80～250 ℃ of temperature, sealing is preserved.
The Main Function of various materials among the present invention:
Chrome ore, wherein the chromium element is the principal element of stainless steel product;
Manganese ore, wherein manganese element is the principal element of stainless steel product, allocate certain proportion into after, accelerate the lime dissolving, promote the converting process slag, improve the desulfuration ability of slag.
Graphite is again a kind of reductive agent of less expensive as heating element simultaneously;
Ferrosilicon is strong heating element, is again stronger reductive agent simultaneously.
The present invention adopts the theoretical foundation of chrome ore, manganese ore, graphite and ferrosilicon as follows:
1) effect of chrome ore
In argon oxygen decarburizing furnace is smelted, there is the process that oxidation and reduction are carried out simultaneously in the chromium element in the mother liquor of stainless steel, utilize the argon oxygen decarburizing furnace Primary period, mother liquor of stainless steel has the characteristics (entering stove mother liquor carbon content greater than 1.50%) of high temperature (entering stove mother liquor temperature greater than 1450 ℃), high-carbon, to contain chromite ore fine directly packs in the argon oxygen decarburizing furnace stove, with the graphite in the composite pellet, ferrosilicon with the chrome ore melting, and the part chromium element reduction in the chrome ore out (seen reaction equation 1,2), enter the purpose that molten steel reaches alloying.
In the argon oxygen decarburizing furnace reduction process, adopt ferrosilicon to make reductive agent, the noble metal element Cr in the reduced blast furnace will partly form the chromite ore fine Cr of slag
2O
3, be reduced into chromium metal (seeing reaction equation 2).
By the reduction of above-mentioned two processes, the recovery rate of the chromium of chromite ore fine can reach more than 85%, and this method takes full advantage of cheap chromium powder ore resource, has reduced production cost and has smelted energy consumption.
(Cr
2O
3)+3[C]=2[Cr]+3CO reaction equation 1
2 (Cr
2O
3)+3[Si]=4[Cr]+3SiO
2Reaction equation 2
2) effect of manganese ore
At the argon oxygen decarburizing furnace blowing initial stage, increase the MnO content in the slag, generate low-melting tephroite, fully dwindle Ca
2SiO
4, Ca
3SiO
4Phase region, make slag keep evenly liquid in very wide temperature range.Studies show that the slag that contains 1%MnO, open and blow 3.5min and will emerge in multitude dystectic Ca
2S, Ca
3S, and contain the slag of 15%MnO Ca occurs after blowing 6～7min opening
2S, Ca
3S, therefore high MnO slag can delay Ca
2S, Ca
3The generation of S, raisingization slag speed promotes picrochromite in the chrome ore, chromohercynite fusing.
The increase of MnO content in the slag can improve the partition ratio of sulphur (S), and Mn increases in the slag, makes O content in the steel, promote that desulphurization reaction carries out to positive dirction, so MnO content improves in the slag, is conducive to the argon oxygen decarburizing furnace slag desulfurization.
Manganese element also is the principal element of stainless steel product simultaneously, utilize argon oxygen decarburizing furnace stove Primary period, mother liquor of stainless steel has the characteristics of high temperature, high-carbon, the manganese ore powder is directly packed in the argon oxygen decarburizing furnace stove, with the graphite in the composite pellet, ferrosilicon with the manganese ore melting, and the part manganese element in the manganese ore restored (seeing reaction equation 3,4), enter the purpose that molten steel reaches alloying.
In the argon oxygen decarburizing furnace reduction process, adopt ferrosilicon to make reductive agent, noble metal element M n in the reduced blast furnace, part has been formed the MnO of slag, be reduced into manganese metal (seeing reaction equation 4), by the reduction of above-mentioned two processes, the recovery rate of the manganese of manganese ore powder can reach more than 85%.
(MnO)+[C]=[Mn]+CO reaction equation 3
2 (MnO)+[Si]=2[Mn]+SiO
2Reaction equation 4
3) effect of graphite, ferrosilicon
When argon oxygen decarburizing furnace blew, the C content of mother liquor of stainless steel reduced gradually, and the Cr content of mother liquor of stainless steel own is higher, therefore in the chrome ore reduction ratio of chromium along with the reduction of C content, and reduce gradually (see reaction equation 1, reactant C content, reaction is carried out to opposite direction).So only rely on carbon in the molten iron to realize that the chrome ore DIRECT ALLOYING is difficulty relatively, must additional reducing agent, namely need extra solid carbon and solid silicon to reduce Cr
2O
3Therefore chrome ore will add in the stove by a certain percentage simultaneously with graphite, ferrosilicon in the actual production, carries out smoothly with the DIRECT ALLOYING that promotes steel.
Graphite, ferrosilicon are to the effect of manganese ore, and is identical with chrome ore.
4) requirement of chrome ore, manganese ore, graphite, ferrosilicon granularity
Under 1560 ℃ reduction temperature, the reducing material granularity is less, and reduction rate is larger.The reduction rate of chrome ore is faster, chromium in the chrome ore will enter molten steel as early as possible, because the characteristics of argon oxygen decarburizing furnace, be lower than 1560 ℃ at liquid steel temperature, there are the process of simultaneous oxidation in chromium in the molten steel, carbon, when liquid steel temperature rises to more than 1560 ℃, with the carbon in the preferential oxidation molten steel, chrome ore will be difficult to be reduced along with the reduction of carbon content in the molten steel this moment.And from blowing, reach 1560 ℃ to liquid steel temperature, and only need the short several minutes time, so the reduction rate of chrome ore is faster, with regard to more favourable being reduced, the recovery rate of chrome ore is higher.
Because suitability for industrialized production, chromite ore fine, manganese ore powder, graphite, ferrosilicon are made the particle less than 0.09mm, to produce, cost all brings disadvantageous effect, composite factor is considered chromite ore fine, manganese ore powder, graphite, that the ferrosilicon granularity is decided to be 0.09～0.20mm is comparatively suitable.
Argon oxygen decarburizing furnace of the present invention in the argon oxygen decarburizing furnace smelting process, utilizes carbon, element silicon reduction chromium, manganese element in the pellet with chromium manganese ore composite pellet, uses simultaneously manganese oxide reduction chrome ore fusing point in the pelletizing, and the helpization slag reduces the splash of converting process metal.Adopt argon oxygen decarburizing furnace of the present invention with chromium manganese ore composite pellet, can improve in the pelletizing chromium manganese element in the recovery rate of carbon rejection process, and improved the sweetening power of slag.
Embodiment
After the argon oxygen decarburizing furnace stove is packed mother liquor of stainless steel into, open in igniting and to add chromium manganese ore composite pellet of the present invention by furnace top bin before blowing, utilize the mother liquor of stainless steel temperature, pelletizing is melted as early as possible.
Chromium manganese ore composite pellet embodiment composition of the present invention is referring to table 1:
Table 1: each component proportion table (weight percent) of chromium manganese ore composite pellet
| Embodiment | Chrome ore (%) | Manganese ore (%) | Graphite (%) | Ferrosilicon (%) | Binding agent (%) |
| 1 | 43.0 | 15.0 | 30.0 | 6.0 | 6.0 |
| 2 | 41.5 | 19.0 | 26.0 | 6.5 | 7.0 |
| 3 | 40.0 | 20.5 | 25.0 | 8.5 | 6.0 |
| 4 | 38.5 | 11.0 | 38.5 | 6.5 | 5.5 |
| 5 | 34.0 | 15.0 | 34.5 | 10.0 | 6.5 |
| 6 | 33.5 | 17.5 | 39.0 | 5.0 | 5.0 |
| 7 | 31.0 | 22.0 | 35.0 | 5.5 | 6.5 |
| 8 | 28.0 | 14.0 | 45.0 | 7.5 | 5.5 |
| 9 | 38.5 | 11.0 | 38.5 | 6.5 | 5.5 |
| 10 | 38.5 | 11.0 | 38.5 | 6.5 | 5.5 |
Each embodiment in the his-and-hers watches 1 describes:
Embodiment 1:
Take by weighing each component by the described formula table corresponding data of table 1.
Wherein, Cr in the described chrome ore
2O
3Weight percentage be 45%, the weight percentage of MnO is 38% in the described manganese ore, the weight percentage of carbon is 78% in the described graphite, the weight percentage of described Silicon in Ferrosilicon is 80%, described binding agent is Xylo-Mucine.
Chrome ore, manganese ore, graphite, ferrosilicon are ground to form respectively the fine powder that granularity is 0.09mm, mix, add binding agent again and stir, make the pelletizing that diameter is 30mm, again this pelletizing is dried 9 hours, naturally cooling under 150 ℃ of temperature, sealing is preserved.
Embodiment 2:
Take by weighing each component by the described formula table corresponding data of table 1.
Wherein, Cr in the described chrome ore
2O
3Weight percentage be 45.5%, the weight percentage of MnO is 36% in the described manganese ore, the weight percentage of carbon is 79% in the described graphite, the weight percentage of described Silicon in Ferrosilicon is 79%, described binding agent is methylcellulose gum.
Chrome ore, manganese ore, graphite, ferrosilicon are ground to form respectively the fine powder that granularity is 0.12mm, mix, add binding agent again and stir, make the pelletizing that diameter is 20mm, again this pelletizing is dried 8 hours, naturally cooling under 200 ℃ of temperature, sealing is preserved.
Embodiment 3:
Take by weighing each component by the described formula table corresponding data of table 1.
Wherein, Cr in the described chrome ore
2O
3Weight percentage be 46%, the weight percentage of MnO is 34% in the described manganese ore, the weight percentage of carbon is 80% in the described graphite, the weight percentage of described Silicon in Ferrosilicon is 78%, described binding agent is Vltra tears.
Chrome ore, manganese ore, graphite, ferrosilicon are ground to form respectively the fine powder that granularity is 0.13mm, mix, add binding agent again and stir, make the pelletizing that diameter is 25mm, again this pelletizing is dried 10 hours, naturally cooling under 80 ℃ of temperature, sealing is preserved.
Embodiment 4:
Take by weighing each component by the described formula table corresponding data of table 1.
Wherein, Cr in the described chrome ore
2O
3Weight percentage be 47%, the weight percentage of MnO is 32% in the described manganese ore, the weight percentage of carbon is 81% in the described graphite, the weight percentage of described Silicon in Ferrosilicon is 77%, described binding agent is amylan.
Chrome ore, manganese ore, graphite, ferrosilicon are ground to form respectively the fine powder that granularity is 0.15mm, mix, add binding agent again and stir, make the pelletizing that diameter is 35mm, again this pelletizing is dried 8.5 hours, naturally cooling under 250 ℃ of temperature, sealing is preserved.
Embodiment 5:
Take by weighing each component by the described formula table corresponding data of table 1.
Wherein, Cr in the described chrome ore
2O
3Weight percentage be 48%, the weight percentage of MnO is 30% in the described manganese ore, the weight percentage of carbon is 82% in the described graphite, the weight percentage of described Silicon in Ferrosilicon is 76%, described binding agent is Xylo-Mucine.
Chrome ore, manganese ore, graphite, ferrosilicon are ground to form respectively the fine powder that granularity is 0.16mm, mix, add binding agent again and stir, make the pelletizing that diameter is 33mm, again this pelletizing is dried 9.5 hours, naturally cooling under 100 ℃ of temperature, sealing is preserved.
Embodiment 6:
Take by weighing each component by the described formula table corresponding data of table 1.
Wherein, Cr in the described chrome ore
2O
3Weight percentage be 48.5%, the weight percentage of MnO is 28% in the described manganese ore, the weight percentage of carbon is 83% in the described graphite, the weight percentage of described Silicon in Ferrosilicon is 75%, described binding agent is amylan.
Chrome ore, manganese ore, graphite, ferrosilicon are ground to form respectively the fine powder that granularity is 0.17mm, mix, add binding agent again and stir, make the pelletizing that diameter is 40mm, again this pelletizing is dried 10 hours, naturally cooling under 120 ℃ of temperature, sealing is preserved.
Embodiment 7:
Take by weighing each component by the described formula table corresponding data of table 1.
Wherein, Cr in the described chrome ore
2O
3Weight percentage be 49%, the weight percentage of MnO is 26% in the described manganese ore, the weight percentage of carbon is 84.0% in the described graphite, the weight percentage of described Silicon in Ferrosilicon is 74%, described binding agent is methylcellulose gum.
Chrome ore, manganese ore, graphite, ferrosilicon are ground to form respectively the fine powder that granularity is 0.19mm, mix, add binding agent again and stir, make the pelletizing that diameter is 45mm, again this pelletizing is dried 9 hours, naturally cooling under 180 ℃ of temperature, sealing is preserved.
Embodiment 8:
Take by weighing each component by the described formula table corresponding data of table 1.
Wherein, Cr in the described chrome ore
2O
3Weight percentage be 50%, the weight percentage of MnO is 25% in the described manganese ore, the weight percentage of carbon is 86% in the described graphite, the weight percentage of described Silicon in Ferrosilicon is 72%, described binding agent is Vltra tears.
Chrome ore, manganese ore, graphite, ferrosilicon are ground to form respectively the fine powder that granularity is 0.20mm, mix, add binding agent again and stir, make the pelletizing that diameter is 50mm, again this pelletizing is dried 8 hours, naturally cooling under 220 ℃ of temperature, sealing is preserved.
Embodiment 9:
Adopt prescription and the preparation method identical with embodiment 4, difference is that chrome ore, manganese ore, graphite, ferrosilicon are ground to form respectively the fine powder that granularity is 0.60mm.
Embodiment 10:
Adopt prescription and the preparation method identical with embodiment 4, difference is that chrome ore, manganese ore, graphite, ferrosilicon are ground to form respectively the fine powder that granularity is 1.00mm.
Comparative Examples:
Be that most of alloys are added by furnace top bin on 120 tons of argon oxygen decarburizing furnaces at nominal capacity, at the blowing initial stage with high carbon ferro-chrome with addition of the lower limit that requires to composition Cr, the high carbon ferro-chrome add-on is about 10 tons.After entering the molten steel reduction period, with the composition Cr of low carbon ferrochromium fine setting molten steel, and composition Mn be by manganese metal with addition of, the manganese metal add-on is about 1.5 tons.
Embodiment 1～10th, is on 120 tons of argon oxygen decarburizing furnaces at nominal capacity, adds 2.5～3.5 tons/stove of chromium manganese ore composite pellet of the present invention, and test result sees Table 2.
Table 2:
As can be seen from Table 2, reduction silicon consumption before and after enforcement the present invention, the not increase of reduction Cr content.
It is fine powder below the 1mm that chrome ore, manganese ore, graphite, ferrosilicon are ground to form respectively granularity, and the recovery rate of chromium, manganese can reach more than 85% and 82% respectively in the chromium manganese ore composite pellet.
And chrome ore, manganese ore, graphite, ferrosilicon are ground to form respectively the fine powder that granularity is 0.09～0.20mm, and the recovery rate of chromium, manganese can reach respectively more than 90% and 87% in the chromium manganese ore composite pellet, and desulfurization degree can obviously improve.
Claims (7)
1. an argon oxygen decarburizing furnace is with chromium manganese ore composite pellet, and its weight percentages of components is:
Chrome ore: 28～43%;
Manganese ore: 11～22%;
Graphite: 25～45%;
Ferrosilicon: 5～10%;
Binding agent: 5～7%.
2. argon oxygen decarburizing furnace as claimed in claim 1 is characterized in that Cr in the described chrome ore with chromium manganese ore composite pellet
2O
3Weight percentage be 45.0～50.0%.
3. argon oxygen decarburizing furnace as claimed in claim 1 is characterized in that with chromium manganese ore composite pellet the weight percentage of MnO is 25～38% in the described manganese ore.
4. argon oxygen decarburizing furnace as claimed in claim 1 is characterized in that the weight percentage of carbon in the described graphite: 78.0～86.0% with chromium manganese ore composite pellet.
5. argon oxygen decarburizing furnace as claimed in claim 1 is characterized in that with chromium manganese ore composite pellet the weight percentage of described Silicon in Ferrosilicon is 72.0～80.0%.
One kind such as each described argon oxygen decarburizing furnace in the claim 1～5 with the preparation method of chromium manganese ore composite pellet, it is characterized in that, chrome ore, manganese ore, graphite, ferrosilicon are ground to form respectively the fine powder that granularity is not more than 1mm, mix, adding binding agent stirs again, make the pelletizing that diameter is 20～50mm, again this pelletizing is dried 8～10 hours, naturally cooling under 80～250 ℃ of temperature, sealing is preserved.
7. argon oxygen decarburizing furnace as claimed in claim 6 is characterized in that with the preparation method of chromium manganese ore composite pellet the granularity of described fine powder is 0.09～0.20mm.
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| CN201110280459.8A CN103014327B (en) | 2011-09-21 | 2011-09-21 | Chrome-manganese ore composite pellets for argon oxygen refinement furnace, and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015092138A1 (en) * | 2013-12-17 | 2015-06-25 | Outotec (Finland) Oy | Method for producing manganese containing ferroalloy |
| CN105506271A (en) * | 2014-09-24 | 2016-04-20 | 宝钢不锈钢有限公司 | Chromium ore composite pellet used for reduction in argon-oxygen refining furnace, production method and application thereof |
| WO2018011467A1 (en) * | 2016-07-11 | 2018-01-18 | Outotec (Finland) Oy | Process for manufacturing ferrochromium alloy with desired content of manganese, nickel and molybdenum |
| CN115505677A (en) * | 2021-06-23 | 2022-12-23 | 宝山钢铁股份有限公司 | Low-silicon niobium-manganese ball and preparation method and application thereof |
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| CN1066295A (en) * | 1991-04-28 | 1992-11-18 | 北京科技大学 | Reclaim the metal in the argon/oxygen furnace |
| CN1415766A (en) * | 2002-10-10 | 2003-05-07 | 吴光亮 | Composite ball rolls of manganese and its preparation method |
| CN1928137A (en) * | 2005-09-05 | 2007-03-14 | 湖南华菱涟源钢铁有限公司 | Mn-Fe alloy production process |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066295A (en) * | 1991-04-28 | 1992-11-18 | 北京科技大学 | Reclaim the metal in the argon/oxygen furnace |
| CN1415766A (en) * | 2002-10-10 | 2003-05-07 | 吴光亮 | Composite ball rolls of manganese and its preparation method |
| CN1928137A (en) * | 2005-09-05 | 2007-03-14 | 湖南华菱涟源钢铁有限公司 | Mn-Fe alloy production process |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015092138A1 (en) * | 2013-12-17 | 2015-06-25 | Outotec (Finland) Oy | Method for producing manganese containing ferroalloy |
| US10125413B2 (en) | 2013-12-17 | 2018-11-13 | Outotec (Finland) Oy | Method for producing manganese containing ferroalloy |
| EA031206B1 (en) * | 2013-12-17 | 2018-11-30 | Оутотек (Финлэнд) Ой | Method for producing manganese containing ferroalloy |
| CN105506271A (en) * | 2014-09-24 | 2016-04-20 | 宝钢不锈钢有限公司 | Chromium ore composite pellet used for reduction in argon-oxygen refining furnace, production method and application thereof |
| WO2018011467A1 (en) * | 2016-07-11 | 2018-01-18 | Outotec (Finland) Oy | Process for manufacturing ferrochromium alloy with desired content of manganese, nickel and molybdenum |
| CN115505677A (en) * | 2021-06-23 | 2022-12-23 | 宝山钢铁股份有限公司 | Low-silicon niobium-manganese ball and preparation method and application thereof |
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