CN102899451B - A kind of electrochemical decarburization pre-melted slag and preparation method thereof - Google Patents

A kind of electrochemical decarburization pre-melted slag and preparation method thereof Download PDF

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CN102899451B
CN102899451B CN201210408322.0A CN201210408322A CN102899451B CN 102899451 B CN102899451 B CN 102899451B CN 201210408322 A CN201210408322 A CN 201210408322A CN 102899451 B CN102899451 B CN 102899451B
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slag
decarburization
raw material
electrochemical
melted slag
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CN102899451A (en
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贾吉祥
廖相巍
赵刚
曹东
李广帮
郭庆涛
朱晓雷
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Angang Steel Co Ltd
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Angang Steel Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
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Abstract

The present invention discloses a kind of electrochemical decarburization pre-melted slag and preparation method thereof, and it forms CaO:30% ~ 45%, Al 2o 3: <3%, MgO:6% ~ 12%, SiO 2: <1%, FeO:1% ~ 10%, Fe 2o 3: 30% ~ 50%, BaO:0.1% ~ 5%, other is inevitable impurity.Raw material is granule lime, Quadratic aluminum dust, steel rolling iron scale, light dolomite and barium carbonate powder; Different raw materials is made granularity through fragmentation and is less than 100 object pulvis; Granule lime, 20% ~ 40%, Quadratic aluminum dust, <3%, steel rolling iron scale, 40% ~ 60%, light dolomite, 15% ~ 30%, barium carbonate powder, 0.2% ~ 6%; Put into mixer batch mixing 5 ~ 100min; 10 ~ 100min at being warming up to 1300 ~ 1500 DEG C in process furnace, air cooling is to room temperature; Be broken into the fritting clinker that granularity is 0.5 ~ 100mm.

Description

A kind of electrochemical decarburization pre-melted slag and preparation method thereof
Technical field
The invention belongs to process for making technical field, be specifically related to a kind of applicable electrochemical decarburization pre-melted slag and preparation method thereof.
Background technology
Along with the continuous progress of science and technology, ultra-low carbon cold-rolling thin plate ([C]≤30 × 10 -6) be widely used in automobile, household electrical appliances, electronic applications.As everyone knows, solid solution carbon has had a strong impact on the deep drawability of steel, in order to obtain surface quality and the good cold rolled sheet steel of processing characteristics, must reduce dissolved carbon content in steel.
Traditional decarbonization method is that oxygen is fed molten bath, by the oxidation of coal in iron carbon melt.In reaction process, the carbon in molten bath and oxygen react, and the CO gas of generation is discharged in the form of bubbles from molten bath.Decarburizing reaction process is generally made up of following link:
1) carbon by metal inside to metal/gas phase interface transmission;
2) at metal vapour phase interface generation chemical reaction;
3) gaseous product is moved to gas phase slag phase interface by metal vapour phase interface;
4) at gas phase slag phase interface generation chemical reaction;
5) transmission of ferriferous oxide in slag phase boundray layer;
6) ferriferous oxide is in slag middle transmission mutually.
After decarburization terminates, retain in molten steel and have excessive oxygen, therefore also need to add a large amount of reductors and deoxidation treatment is carried out to molten steel.This just brings a series of adverse influence, and such as use reductor to increase smelting cost, moreover deoxidation products can cause continous casting sprue to block, deoxidation products also can cause cold rolled sheet surface quality problems etc.So when requiring more and more higher to steel sublimate, be badly in need of finding that other is clean, pollution-free, decarbonization method at low cost.Therefore many workers are devoted to the research of the decarburization novel method of cleanly low cost.Its Research Thinking is mainly reflected in some documents, as document " electrochemical mechanism that Fe-C melt and slag react " and " reaction of iron carbon metallic particles and slag ", and application number is the Chinese invention patent of 201110077874.3, utilize electrochemical reaction mechanism, iron liquid, between molten steel and slag additional conductor or apply electric field, without the need to can realize the object of decarburization to oxygen supply in molten steel, also avoid molten steel peroxidation simultaneously, use reductor, pollute the problems such as molten steel.
For Applied Electrochemistry carbon rejection processes, selecting reasonable slag system, is one of key of whole technology, is related to the level that whether carbon in melt can be taken off expection.This just requires that slag has the features such as good oxygen ions migrate ability, good electroconductibility, suitable viscosity, suitable fusing point, uniform and stable chemical composition.
The slag system of current application is mainly CaO, SiO 2, Al 2o 3and FeO x, wherein CaO, SiO 2, Al 2o 3the ratio of mass percent be more fixing, and slag fusing point is higher, and viscosity is slightly large.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, what technical problem to be solved by this invention was to provide a kind of efficient pollution-free has applicable electrochemical decarburization pre-melted slag of the features such as good oxygen ions migrate ability, good electroconductibility, suitable viscosity, suitable fusing point, uniform and stable chemical composition and preparation method thereof.
The present invention seeks to be realized by technical scheme below:
During design slag system, the following factor of main consideration:
A, slag need have good oxygen ions migrate ability, if the travelling speed of oxonium ion under additional conductor or DC Electric Field is too slow in slag, this method of deoxidation does not just have the value of practical application.In addition oxonium ion in slag in zwitterion migration shared ratio be the bigger the better, namely the transport number of oxonium ion is the bigger the better, and it is related to the success or not of experiment.
B, slag need have good electroconductibility, select the slag system that conductive capability is strong, then slag intermediate ion is more, is conducive to the carrying out of electrochemical reaction.
C, select the slag system that positively charged ion electrolytic potential is higher, make the regulation range of extra electric field wider.
The vapour pressure of d, consideration slag composition, should not volatilize volatile or on a small quantity under experimental temperature; Otherwise volatilization causes the change of slag ingredient, affects deoxidation, is unfavorable for that practical operation is done simultaneously.
E, slag should have suitable viscosity, and viscosity is too large, and slag fluidity is bad, is not suitable for ion migration; The too little control being also unfavorable for decarburization of viscosity.
The composition of f, slag wants uniformity, ensures stable chemical nature.
1, carry out the exploitation of this pre-melted slag by above-mentioned mentality of designing, a kind of electrochemical decarburization pre-melted slag of the present invention, its composition is by mass percentage: CaO:30% ~ 45%, Al 2o 3: <3%, MgO:6% ~ 12%, SiO 2: <1%, FeO:1% ~ 10%, Fe 2o 3: 30% ~ 50%, BaO:0.1% ~ 5%, other is inevitable impurity, and above each constituent mass per-cent sum is 100%;
This pre-melted slag material granularity is 0.5 ~ 100mm.
2, prepare the method for above-mentioned electrochemical decarburization pre-melted slag, be made up of following steps:
(1) get the raw materials ready
The raw material that this pre-melted slag uses is granule lime, Quadratic aluminum dust, steel rolling iron scale, light dolomite and barium carbonate powder.
(2) raw material crushing
Different raw materials is made granularity through fragmentation and is less than 100 object pulvis.
(3) prepare burden
Prepared burden in following ratio by raw material, the mass percent of different material batching is:
Granule lime, 20% ~ 40%, Quadratic aluminum dust, <3%, steel rolling iron scale, 40% ~ 60%, light dolomite, 15% ~ 30%, barium carbonate powder, 0.2% ~ 6%.
(4) batch mixing
The raw material prepared in proportion is put into mixer batch mixing 5 ~ 100min, make it fully mix.
(5) heating and melting
Loaded by mixed raw material in process furnace, under being warming up to 1300 ~ 1500 DEG C of high temperature, and lasting 10 ~ 100min makes its complete melting, guarantees that slag composition is even, at hot lower slag air cooling to room temperature, obtains frit.
(6) broken
Frit is broken into the fritting clinker that granularity is 0.5 ~ 100mm.
Described granule lime, main component is CaO, 85% ~ 93%(mass percent), MgO, <5%(mass percent), P 2o 5, <0.05(mass percent), SiO 2, <1%(mass percent); Quadratic aluminum dust, main component is Al 2o 3, >92%(mass percent), metallic aluminium, <3%(mass percent), other impurity <6%(mass percent); Steel rolling iron scale, main component is Fe 2o 3, 85% ~ 93%(mass percent), FeO, 6% ~ 15%(mass percent), other impurity <1%(mass percent); Light dolomite, main component is CaO, 40% ~ 50%(mass percent), MgO, 35% ~ 45%(mass percent), other are impurity; Barium carbonate, main component is BaCO 3>99.5%(mass percent), other are impurity.
The uniform composition good stability of pre-melted slag of the present invention, has low melting point (1200 ~ 1300 DEG C), and viscosity is suitable for (0.1 ~ 2 PaS), good fluidity, and burn-off rate is fast, specific conductivity high.CaO, Fe suitable in slag 2o 3content, causes in Pre melting process the CaOFe generating low melting point 2o 3, 2CaOFe 2o 3and CaO2Fe 2o 3ensure that this pre-melted slag has lower fusing point and burn-off rate faster mutually, simultaneously due to Fe 2o 3existence, for slag provides a large amount of vacant electron site, increase slag electronic conductivity, add the FeO content that slag is suitable, thus make slag have good oxygen ionic conductivity; MgO appropriate in pre-melted slag, can improve the specific conductivity of slag, and can control the viscosity of slag; SiO 2belong to acidic oxide, in melting slag, main and oxonium ion forms silica radical ion, and this is disadvantageous to oxygen ions migrate, but a small amount of SiO 2can slag fluidity be improved, ensure that this pre-melted slag has suitable viscosity; In addition in slag also containing a certain amount of BaO, this kind of basic oxide add the specific conductivity that can improve pre-melted slag, sulfur capacity and the phosphate capacity of pre-melted slag can also be improved simultaneously, have some superiority to purification melt; This fritting slag charge is block (granularity: 0.5 ~ 100mm), and surface tension is little, and can moltenly be invaded by melt, to melt, no dust pollution in use procedure rapidly in use procedure, utilization ratio, recovery rate be high, have good energy saving standard effect.
This pre-melted slag is joined in Fe-C melt and carry out electrochemical decarburization, efficient pollution-free decarburization can be realized, can by carbon content in Fe-C melt by initial 4.3%(mass percent within 30min) take off to 0.5%(mass percent) below.This pre-melted slag is used to carry out electrochemical decarburization, easy to operate, with low cost, the decarburization object of environmental protection, efficient, low cost can be realized.
Accompanying drawing explanation
Fig. 1: embodiment 2 electrochemical decarburization pre-melted slag fusing point (hemisphere point) test pattern;
Fig. 2: the embodiment 2 electrochemical decarburization molten speed figure of pre-melted slag;
Fig. 3: embodiment 2 electrochemical decarburization pre-melted slag viscosity test pattern.
Embodiment
In conjunction with below the effect of method of the present invention and generation thereof is described with several specific embodiment.
Embodiment 1:
Granule lime, Quadratic aluminum dust, steel rolling iron scale, light dolomite and barium carbonate powder are first crushed to-100 orders on request, then the raw material granule lime after fragmentation is got, 20%, Quadratic aluminum dust, 1.5%, steel rolling iron scale, 58%, light dolomite, 15%, barium carbonate powder, 5.5%, put into mixer batch mixing 15min, then process furnace is put into by heating raw materials to 1310 DEG C fusing, slag composition is even to keep 60min to guarantee, by melting slag air cooling to room temperature, finally frit is broken into the pre-melted slag particle that granularity is 60 ~ 90mm.
Embodiment 2:
Granule lime, Quadratic aluminum dust, steel rolling iron scale, light dolomite and barium carbonate powder are first crushed to-150 orders on request, then the raw material granule lime after fragmentation is got, 28%, Quadratic aluminum dust, 2.5%, steel rolling iron scale, 47%, light dolomite, 19%, barium carbonate powder, 3.5%, put into mixer batch mixing 40min, then process furnace is put into by heating raw materials to 1400 DEG C fusing, slag composition is even to keep 30min to guarantee, by melting slag air cooling to room temperature, finally frit is broken into the pre-melted slag particle that granularity is 20 ~ 50mm.The mass percent composition of this electrochemical decarburization pre-melted slag sees the following form.
Embodiment 3:
Granule lime, Quadratic aluminum dust, steel rolling iron scale, light dolomite and barium carbonate powder are first crushed to-200 orders on request, then the raw material granule lime after fragmentation is got, 30%, Quadratic aluminum dust, 3%, steel rolling iron scale, 42%, light dolomite, 23%, barium carbonate powder, 2%, put into mixer batch mixing 80min, then process furnace is put into by heating raw materials to 1470 DEG C fusing, slag composition is even to keep 15min to guarantee, by melting slag air cooling to room temperature, finally frit is broken into the pre-melted slag particle that granularity is 3 ~ 20mm.
Table 1 is the final pre-melted slag composition of each embodiment.
The mass percent of table 1 electrochemical decarburization pre-melted slag composition and each composition
Apply this pre-melted slag and carry out electrochemical decarburization test, test and carry out on 500Kg multifunctional DC electric arc stove.Added by the pre-melted slag of the present embodiment gained in Fe-C melt, Heating temperature is 1600 DEG C; The DC electric field applied between pre-melted slag and Fe-C melt, decarburization the results are shown in Table 2.
Table 2 is applied pre-melted slag and is carried out electrochemical decarburization result

Claims (2)

1. an electrochemical decarburization pre-melted slag, its composition is by mass percentage: CaO:38.22% ~ 43.15%, Al 2o 3: <3%, MgO:6% ~ 12%, SiO 2: <1%, FeO:4.2% ~ 10%, Fe 2o 3: 30% ~ 39.33%, BaO:0.1% ~ 5%, other is inevitable impurity, and above each constituent mass per-cent sum is 100%.
2. a preparation method for electrochemical decarburization pre-melted slag according to claim 1, is characterized in that following steps:
(1) get the raw materials ready
Raw material is granule lime, Quadratic aluminum dust, steel rolling iron scale, light dolomite and barium carbonate powder;
(2) raw material crushing
Different raw materials is made granularity through fragmentation and is less than 100 object pulvis;
(3) prepare burden
Prepared burden in following ratio by raw material, the mass percent of different material batching is:
Granule lime, 20% ~ 40%, Quadratic aluminum dust, 2.5% ~ 3%, steel rolling iron scale, 40% ~ 60%, light dolomite, 15% ~ 30%, barium carbonate powder, 0.2% ~ 6%;
(4) batch mixing
The raw material prepared in proportion is put into mixer batch mixing 5 ~ 100min, make it fully mix;
(5) heating and melting
Loaded by mixed raw material in process furnace, under being warming up to 1300 ~ 1500 DEG C of high temperature, and lasting 10 ~ 100min makes its complete melting, at hot lower slag air cooling to room temperature, obtains frit;
(6) broken
Frit is broken into the fritting clinker that granularity is 0.5 ~ 100mm.
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CN102321784A (en) * 2011-08-22 2012-01-18 辽宁天和科技股份有限公司 Pre-molten conductive slag for electrochemical deoxidation and preparation method thereof
CN102399939A (en) * 2010-09-07 2012-04-04 鞍钢股份有限公司 Premelted slag for unpolluted deoxidization with externally applied voltage between metal and slag and preparation method thereof
CN102719617A (en) * 2011-03-29 2012-10-10 鞍钢股份有限公司 Electrochemical decarburization method for iron-carbon melts and apparatus thereof

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JPS5754215A (en) * 1980-09-19 1982-03-31 Nippon Steel Corp Method of refining with slag minimized by using combined flux
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Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
CN101245403A (en) * 2007-02-16 2008-08-20 宝山钢铁股份有限公司 Oxidized powder preparation for reinforcing liquid steel decarburization
CN102399939A (en) * 2010-09-07 2012-04-04 鞍钢股份有限公司 Premelted slag for unpolluted deoxidization with externally applied voltage between metal and slag and preparation method thereof
CN102719617A (en) * 2011-03-29 2012-10-10 鞍钢股份有限公司 Electrochemical decarburization method for iron-carbon melts and apparatus thereof
CN102321784A (en) * 2011-08-22 2012-01-18 辽宁天和科技股份有限公司 Pre-molten conductive slag for electrochemical deoxidation and preparation method thereof

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