CN101096722A - Dephosphorising agent for melted iron pretreatment by KR method - Google Patents
Dephosphorising agent for melted iron pretreatment by KR method Download PDFInfo
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- CN101096722A CN101096722A CNA2006100881156A CN200610088115A CN101096722A CN 101096722 A CN101096722 A CN 101096722A CN A2006100881156 A CNA2006100881156 A CN A2006100881156A CN 200610088115 A CN200610088115 A CN 200610088115A CN 101096722 A CN101096722 A CN 101096722A
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- iron pretreatment
- dephosphorization
- melted iron
- dephosphorising agent
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Abstract
The invention discloses a preprocessing dephosphorized agent of molten iron through KR stirring method, which comprises the following parts: 35-50wt% T, not less than 66.5% Fe, not more than 10.0% FeO, 30-45wt% active lime, 3-8wt% fluorescent stone, 0.5-5wt% blue powder and 0.5-8wt%BaCO3, wherein the materials are pressed into block to form the product with high-oxygen content to satisfy the need of KR technique to dephosphorize without providing auxiliary oxygen. The invention shortens the slag degrading time to protect environment, which makes the [P] less than 0.030% and removing rate not less than 65%.
Description
Technical field
The present invention relates to a kind of KR paddling process liquid iron pretreatment dephosphorizing agent, relate in particular to a kind of self oxygen level height, dephosphorized slag phosphate capacity height, and high utilization rate KR method Dephosphorising agent for melted iron pretreatment.
Background technology
Hot metal pretreatment is meant that molten iron enters that steel melting furnace (converter, electric furnace etc.) is preceding to carry out desiliconization, dephosphorization, desulfurization and handle, its objective is [Si] in the molten iron, [P], [S] are taken off alap level before going into converter, smelting excellent special steel, Clean Steel to satisfy, is indispensable operation in the ferrous metallurgy.
The pre-dephosphorization treatment method of molten iron, by feed way and alr mode can be divided into blowing process, the top adds flux mechanical mixing method (KR method) and the top adds flux nitrogen flushing paddling process etc.The KR method has equipment and takes up an area of little, less investment, and the desulfuration efficiency height obtains paying attention to.The dephosphorization thermodynamic condition requires oxygen to be bound to must be high as far as possible, but KR method hot metal pretreatment technology does not have spray gun and attached oxygen blowing apparatus, oxygen blast in addition, and oxygen source just seems particularly important in the dephosphorizing agent like this.Conventional dephosphorizing agent adopts iron scale, agglomerate or converter slag as oxygen source, oxygen source content is low in these raw materials, has oxygen reaction efficiency and utilization ratio problem in addition, is difficult to satisfy KR method dephosphorization the oxygen important and influential persons is asked, therefore conventional dephosphorizing agent dephosphorization effect in KR technology is bad, brings difficulty to dephosphorization.
During hot metal pretreatment, the dephosphorisation reaction owner will generate (CaOP by (CaO) under rich (O) condition
2O
5), and make [P] in the molten iron be removed (1), but because unstable (CaOP2O5) adds that [Si] preferential oxidation in the molten iron becomes (SiO
2), up to 3.0% above content [C], this is (CaOP of feasible generation again in the while molten iron
2O
5) rephosphorization reaction (2) easily takes place, the result is that phosphorus is got back in the molten iron again and gone, and therefore also can reduce dephosphorization effect, is difficult to reach lower [P] content.Concrete reaction as shown in the formula:
2[P]+5(O)+(CaO)＝(CaO·P
2O
5) (1)
(CaO·P
2O
5)+5[C]+(SiO
2)＝(CaO·SiO
2)+2[P]+5{CO} (2)
In KR method dephosphorization technology, if the top adds the powdery dephosphorizing agent, then in adition process, can be taken away by the dedusting vacuum fan in a large number, utilization ratio is very low, influences dephosphorization effect; If but add block dephosphorizing agent, though can avoid in adition process by dust-removal system take away unfavorable, after adding, can cause the dephosphorization thinner slag time long, react insufficient, dephosphorization rate also can obviously reduce.
The disclosed molten iron of Chinese patent CN1372009A, liquid steel dephosphorization agent are by 30%～60% ferric oxide (Fe
2O
3FeO), 30%～60% quickened lime (CaO), 5%～20% Calcium Fluoride (Fluorspan) (CaF
2), make the particulate state of 0.5-1mm.This dephosphorizing agent is because of being by top spray method or blowing the spray method and add, and because of competent oxygen source is arranged, thereby the composition of ferric oxide do not made qualification, and the oxygen source amount can not get stable the assurance in KR technology, adds easy generation rephosphorization and reacts, and does not reach the dephosphorization rate of high request; Secondly, its product particle is too little, uses in KR technology and will be siphoned away by dedusting wind in a large number, has reduced the utilization ratio of dephosphorizing agent.Therefore be unsuitable in KR method technology, using.
The disclosed high efficiency dephosphorating pellet for smelting of Chinese patent CN1290757A, by 40-70%CaO, 10-40%FeO, 8-15%CaF2, the 2-6% binding agent, die mould behind twice batch mixing burns in 150 ℃ of-200 ℃ of low temperature bakings, is incubated 24-48 hour.Because of its raw material all adopts FeO, oxygen level is low, and it is poor to be used for KR technology dephosphorization effect; Secondly, in the pressure ball process, add 3～15% water after 150 ℃ of-200 ℃ of low temperature bakings are burnt, can cause the inefficacy of CaO, dephosphorization effect reduces.So dephosphorization in the also inapplicable KR technology.
Chinese patent CN1524969 is disclosed to be the molten iron dephosphorization agent of raw material with the converter slag, is made up of converter slag 20～50, lime 15～28, ferriferous oxide 20～43, fluorite 0～3, soda 0～3, Wingdale 0～3.Raw material adopts up to 20～50% discarded converter slags, and the phosphorus of converter slag own, the higher (P of silicone content
2O
51-5%, SiO
210-30%), and also have more other composition, this certainly will influence the dephosphorization rate of dephosphorizing agent; Secondly, what ferriferous oxide adopted is agglomerate or steel rolling iron sheet, and oxygen source content is low, equally also is not suitable for dephosphorization in the KR technology.
Chinese patent CN1182799 is disclosed in top blast oxygen (oxygen supply intensity: 0.75-1.20N m
3/ min t) and the dephosphorizing agent that uses in the bottom blowing nitrogen technology, its A and/or B synthetic slag are formed, and are respectively synthetic slag A:CaO50-70%, ferriferous oxide 15-35%, fluorite CaF
25-15%; Synthetic slag B:CaO55-70%, ferriferous oxide 15-30%, fluorite CaF
24-10%, Na
2Co
34-9%.Same this dephosphorizing agent is not suitable for KR technology.
Above-mentioned dephosphorizing agent all is to use in supplemental oxygen technology is arranged, and self oxygen source content is low, is difficult to reach high dephosphorization requirement in the KR of no supplemental oxygen technology; Secondly, its dephosphorization slag phosphate capacity is little, and the rephosphorization reaction easily takes place, and also is difficult to reach the low-phosphorous requirement of molten iron; Besides, most of dephosphorizing agent all adopts powdery or fine particle formulation, is very easily taken away by the dedusting vacuum fan in KR technology, and utilization ratio is very low, is again a reason that causes dephosphorization effect bad.Therefore still having is worth improving.
Summary of the invention
The objective of the invention is to overcome the deficiency of above-mentioned prior art, provide a kind of self oxygen level height, dephosphorization slag phosphate capacity height, dephosphorizing agent utilization ratio height, the KR method Dephosphorising agent for melted iron pretreatment that dephosphorization effect is good.
Another object of the present invention is to provide a kind of KR method Dephosphorising agent for melted iron pretreatment that also has sweetening effectiveness at dephosphorization simultaneously.
KR method Dephosphorising agent for melted iron pretreatment of the present invention basic composition is: 35～50wt%T.Fe 〉=66.5%, (Fe
2O
3) and (Fe
3O
4) 〉=80% fine ore, 30～45wt% quickened lime, 3～8wt% fluorite, 0.5～5wt% bluestone powder, 0.5～8wt%BaCO
3, mix being pressed into block.
Wherein more excellent consisting of: 45～50wt% fine ore, 35～40wt% quickened lime, 5～8wt% fluorite, 1～3wt% bluestone powder, 2～5wt%BaCO
3
Above-mentioned component amount is the appropriate interval of optimizing of test, and it is not big especially departing from a small quantity influential effect, neither.
Among the present invention
Fine ore enriches ferric oxide though contain, and should select FeO content≤10%, contains the more Fe of polyoxy like this
2O
3And Fe
3O
4Content height, and (Fe
2O
3) and (Fe
3O
4) discharge oxygen than (FeO) easier reduction, can make dephosphorizing agent iron scale or agglomerate raw material usually, has higher oxygen source content, and easily discharge and phosphorus reaction, therefore in adding the KR technology of oxygen source, nothing can guarantee sufficient oxygen source, satisfy KR technology dephosphorization to the oxygen source demand, reach the ideal dephosphorization rate; Secondly, fine ore granularity little (generally below 200 orders), foreign matter content is few, reaction activity height, thereby dephosphorization effect is good.This is dephosphorizing agent one a big characteristic of the present invention.Wherein more preferably adopt SiO
2≤ 1.0%, the fine ore of S, P≤0.1% is placed restrictions on SiO
2, S, P content, can make dephosphorizing agent still less bring extra (SiO into
2), [P], [S], reach alap [Si], [P], [S] content.
Quickened lime, main effect be with molten iron in [P] form stable calcium phosphate, enter slag, this be a known technology, can add the quickened lime of common dephosphorizing agent use.Better adopt CaO 〉=92.0%, SiO among the present invention
2≤ 2.0%, the quickened lime of activity 〉=280ml helps increasing oxygen source amount in the dephosphorizing agent equally, and keeps low [Si] requirement, and high activity more helps reaction and carry out, and improves dephosphorization effect.
Fluorite can reduce the dephosphorizing agent fusing point, the accelerationization slag, and this also is a known technology, can add the fluorite that common dephosphorizing agent uses.The present invention is for avoiding SiO in the fluorite
2The negative effect of bringing better adopts CaF
2〉=87.0%, SiO
2≤ 5.0% fluorite.
Bluestone powder (claiming lime carbonate again) plays expander function in the present invention.Bluestone powder is evenly distributed in the dephosphorizing agent, makes that wherein bluestone powder is met high temperature and emitted CO rapid the decomposition after the block dephosphorizing agent adding hot metal ladle
2Produce gas expansion, can make block dephosphorizing agent moment be cracked into molecule, so fusing and fully with molten iron in [P] reaction, the shorteningizations slag time, sufficient reacting, the while, its expansion power also enlivened the molten bath, the realization high efficiency dephosphorating.For giving full play to its functional effect, the present invention better adopts CaCO
3〉=98.0% bluestone powder.
BaCO
3, find to add dephosphorizing agent one through test and can improve phosphate capacity in the dephosphorization slag, promptly can remove more phosphorus with the slag of amount; Two add molten iron can resolve into (BaO) and (CO
2), not only increase to stir power, and (BaO) generate than (CaOP with [P] reaction in the molten iron
2O
5) more stable (BaOP
2O
5), greatly reduce rephosphorization reaction generation (reaction formula: 2[P]+5 (O)+(BaO)=(BaOP
2O
5)), thereby significantly improve dephosphorization effect; In addition, it also has expander function, can quicken block dephosphorizing agent cracking and refinement, the shorteningization slag time, improves reaction effect.This is the another big characteristic of dephosphorizing agent of the present invention.In the dephosphorizing agent of the present invention, BaCO
3Better adopt the chemical pure level.
The present invention's second purpose realizes, is by adding 0.5～5wt%CaCl
2, CaCl more preferably wherein
21～3%.Add CaCl
2, make dephosphorizing agent in dephosphorization, subsidiary have stronger sweetening power, can adopt commercial goods calcium chloride.Chemical pure level CaCl is better adopted in negative impact for avoiding bringing into impurity among the present invention
2
In addition, the present invention is pressed into block, helps transportation, reinforced, and guarantees not siphoned away by dust-removal system in reinforced process, can improve dephosphorizing agent utilization ratio in KR technology; Use simultaneously more compliance with environmental protection requirements of pulvis.Described block, be meant obviously greater than fine particle, its size does not reach at least and is siphoned away by the dedusting air draught, geometrical shape is not limit, such as but not limited to spherical or oblate spheroid shape, its size is decided according to customer requirements, wherein with the oblate spheroid shape of 1.5-3.0cm * 3.0-6.0cm for well, this shape helps being delivered to high hopper by rotary conveyor.Briquetting better is to adopt not adding additives pressurization briquetting technology or raw material weight to add a small amount of paraffin (for example 1～5wt% paraffin) briquetting technology, can avoid bringing impurity into because of adding binding agent.The present invention preferably adopts the latter, and the paraffin room temperature is solid-state, a little the temperature (about 70 ℃ of fusing points) liquid state, and help at the low pressure compacted under, not only play binding agent (liquid phase bonding) effect, and it is few to have an oxious component than its binding agent, and do not have moisture and exist, can not influence (CaO) function.Powdery paraffin all can be mixed with other raw material during preparation, be heated to for example 70～90 ℃ of compound stalk formings of melted paraffin wax temperature, be cooled to room temperature holding type piece then rapidly.
Among the present invention, above-mentioned various raw materials all add with powder-form, and its globule size can have no special requirements, and can adopt commercial goods powdery or particulate state all size, but for improving dephosphorizing agent reaction efficiency in KR technology, better adopt the following fine powder of 100 orders.
KR method Dephosphorising agent for melted iron pretreatment of the present invention is owing to adopt height to contain Fe
2O
3And Fe
3O
4Fine ore, and add BaCO
3And make blocks, and and appropriate proportioning raw materials, existing dephosphorizing agent has: self oxygen level height, the KR technology dephosphorization that can satisfy no supplemental oxygen is to the oxygen source requirement; Significantly improved phosphate capacity in the slag, dephosphorization effect is significantly strengthened; Transportation, reinforced convenient is difficult for being siphoned away by dust suction wind, and the feature of environmental protection is good, and can be cracked into fine powder after adding fast, dephosphorizing agent utilization ratio height, it is short to change the slag time, sufficient reacting, dephosphorization effect is good, [P]＜0.030% behind the dephosphorization in KR method hot metal pretreatment, decreasing ratio 〉=65%.Add CaCl
2, make dephosphorizing agent in dephosphorization, subsidiary have a stronger sweetening power.Briquetting adopts paraffin wax binder, not only help low pressure molding, and scatter rapidly after also helping adding molten iron, and inclusion-free brings into, and technology is simple, and the production efficiency height can be boosted productivity 3-6 doubly than pellet forming process.
Owing to do not contain iron scale and pellet, agglomerate, converter slag in the dephosphorizing agent of the present invention, therefore make and do not contain the flake ferric oxide skin in the dephosphorizing agent, and being the agglomerate of melting solid or converter slag, pellet, this is product of the present invention and the maximum difference of other dephosphorizing agents check.
Below in conjunction with three optimization embodiments, further specify the present invention.
Embodiment
Embodiment: take by weighing raw material respectively by table 1, example 1,2 mixes, and heats to 80 ℃ of compound stalk formings, is cooled to room temperature rapidly; Example 3 is mixed in closed system, and through the 25-40Mpa compound stalk forming, briquetting is the oblate spheroid shape of 1.5-3.0cm * 3.0-6.0cm.
Table 1 embodiment dephosphorizing agent prescription (wt%)
| Raw material | Fine ore | Lime powder | Fluorite | Bluestone powder | BaCO 3 | CaCl 2 | Paraffin adds |
| Example 1 | 50.0 | 35.0 | 8.0 | 2.0 | 3.0 | 2.0 | 2 |
| Example 2 | 48.0 | 38.0 | 6.0 | 1.0 | 4.0 | 3.0 | 3.0 |
| Example 3 | 40.0 | 40.0 | 8.0 | 4.0 | 8.0 |
Illustrate: each material fineness 100 order, fine ore T.Fe 〉=66.5%, (Fe
2O
3) and (Fe
3O
4) 〉=80%, SiO
2≤ 1.0%, S, P≤0.1%; Lime powder CaO 〉=92.0%, SiO
2≤ 2.0%, activity 〉=280ml; Fluorite CaF
2〉=87.0%, SiO
2≤ 5.0%; Bluestone powder CaCO
3〉=98.0%; BaCO
3〉=98%; CaCl
2〉=98%.
Table 2 example 1 add-on 35kg/t uses the result
| Project | Si(％) | P(％) | S(％) | Temperature (℃) |
| Before the processing | 0.15 | 0.085 | 0.026 | 1295 |
| After the processing | 0 | 0.027 | 0.006 | 1210 |
| Efficient (%) | 100 | 68.2 | 76.9 | Descend 85 |
Table 3 example 2 add-on 33kg/t use the result
| Project | Si(％) | P(％) | S(％) | Temperature (℃) |
| Before the processing | 0.16 | 0.083 | 0.025 | 1318 |
| After the processing | 0.01 | 0.028 | 0.007 | 1240 |
| Efficient (%) | 93.8 | 66.3 | 72.0 | Descend 78 |
Table 4 example 3 add-on 36kg/t use the result
| Project | Si(％) | P(％) | S(％) | Temperature (℃) |
| Before the processing | 0.16 | 0.083 | 0.029 | 1312 |
| After the processing | 0.00 | 0.024 | 0.007 | 1236 |
| Efficient (%) | 100 | 71.1 | 75.9 | Descend 76 |
More than use the result to show, under KR technology, use dephosphorizing agent of the present invention, reached the effect of the pretreated molten iron of dephosphorization [P]＜0.030%.
Claims (9)
1, KR method Dephosphorising agent for melted iron pretreatment basic composition is: 35～50wt%T.Fe 〉=66.5%, (Fe
2O
3) and (Fe
3O
4) 〉=80% fine ore, 30～45wt% quickened lime, 3～8wt% fluorite, 0.5～5wt% bluestone powder, 0.5～8wt%BaCO
3, mix being pressed into block.
2, according to the described KR method of claim 1 Dephosphorising agent for melted iron pretreatment, it is characterized in that fine ore 45～50wt%, quickened lime 35～40wt%, fluorite 5～8wt%, bluestone powder 1～3wt%, BaCO
32～5wt%.
3, according to claim 1 or 2 described KR method Dephosphorising agent for melted iron pretreatment, it is characterized in that also being added with 0.5～5wt%CaCl
2
4, according to the described KR method of claim 3 Dephosphorising agent for melted iron pretreatment, it is characterized in that said CaCl
21～3wt%.
5, according to the described KR method of claim 3 Dephosphorising agent for melted iron pretreatment, it is characterized in that said fine ore SiO
2≤ 1.0%, S, P≤0.1%; Said quickened lime CaO 〉=92.0%, SiO
2≤ 2.0%, activity 〉=280ml; Said fluorite CaF
2〉=87.0%, SiO
2≤ 5.0%; Said bluestone powder CaCO
3〉=98.0%; Said CaCl
2And BaCO
3Content 〉=98%.
6,, it is characterized in that the outer dephosphorizing agent weight 1-5% paraffin binder that is added with according to claim 1 or 2 described KR method Dephosphorising agent for melted iron pretreatment.
7,, it is characterized in that the outer dephosphorizing agent weight 2-5% paraffin binder that is added with according to the described KR method of claim 3 Dephosphorising agent for melted iron pretreatment.
8, according to claim 1,2,4,5 or 7 described KR method Dephosphorising agent for melted iron pretreatment, it is characterized in that said block is the oblate spheroid shape.
9, described according to Claim 8 KR method Dephosphorising agent for melted iron pretreatment is characterized in that said oblate spheroid is 1.5-3.0cm * 3.0-6.0cm.
Priority Applications (1)
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|---|---|---|---|
| CNB2006100881156A CN100526480C (en) | 2006-06-28 | 2006-06-28 | Dephosphorising agent for melted iron pretreatment by KR method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100881156A CN100526480C (en) | 2006-06-28 | 2006-06-28 | Dephosphorising agent for melted iron pretreatment by KR method |
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| Publication Number | Publication Date |
|---|---|
| CN101096722A true CN101096722A (en) | 2008-01-02 |
| CN100526480C CN100526480C (en) | 2009-08-12 |
Family
ID=39010801
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|---|---|---|---|
| CNB2006100881156A Expired - Fee Related CN100526480C (en) | 2006-06-28 | 2006-06-28 | Dephosphorising agent for melted iron pretreatment by KR method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102776310A (en) * | 2011-05-09 | 2012-11-14 | 中国科学院过程工程研究所 | Pretreating dephosphorizing agent for molten iron containing metallic magnesium residues |
| EP2663660A2 (en) * | 2011-01-15 | 2013-11-20 | Almamet GmbH | Agent for treating molten metals, method for the production and use thereof |
| CN109252014A (en) * | 2018-10-09 | 2019-01-22 | 敬业钢铁有限公司 | A kind of Hot Metal Pretreatment desulfurization dephosphorization technique |
| CN110724790A (en) * | 2019-10-31 | 2020-01-24 | 辽宁科技学院 | Steelmaking dephosphorizing agent interface modifier and preparation and use methods of modified dephosphorizing agent |
| CN110885911A (en) * | 2019-10-18 | 2020-03-17 | 山西建龙实业有限公司 | Process for pretreating, desiliconizing and dephosphorizing KR molten iron |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4242328C2 (en) * | 1992-12-15 | 1995-06-08 | Alfred Dipl Ing Dr Freissmuth | Means for desulfurization, dephosphorization, desiliconization and denitrification of pig iron and cast iron melts |
| KR100504295B1 (en) * | 2000-06-14 | 2005-07-27 | 제이에프이 엔지니어링 가부시키가이샤 | Method and apparatus for producing desulfurizing agent for hot-metal |
-
2006
- 2006-06-28 CN CNB2006100881156A patent/CN100526480C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2663660A2 (en) * | 2011-01-15 | 2013-11-20 | Almamet GmbH | Agent for treating molten metals, method for the production and use thereof |
| CN102776310A (en) * | 2011-05-09 | 2012-11-14 | 中国科学院过程工程研究所 | Pretreating dephosphorizing agent for molten iron containing metallic magnesium residues |
| CN102776310B (en) * | 2011-05-09 | 2014-04-02 | 中国科学院过程工程研究所 | Pretreating dephosphorizing agent for molten iron containing metallic magnesium residues |
| CN109252014A (en) * | 2018-10-09 | 2019-01-22 | 敬业钢铁有限公司 | A kind of Hot Metal Pretreatment desulfurization dephosphorization technique |
| CN110885911A (en) * | 2019-10-18 | 2020-03-17 | 山西建龙实业有限公司 | Process for pretreating, desiliconizing and dephosphorizing KR molten iron |
| CN110724790A (en) * | 2019-10-31 | 2020-01-24 | 辽宁科技学院 | Steelmaking dephosphorizing agent interface modifier and preparation and use methods of modified dephosphorizing agent |
| CN110724790B (en) * | 2019-10-31 | 2021-04-13 | 辽宁科技学院 | Steelmaking dephosphorizing agent interface modifier and preparation and use methods of modified dephosphorizing agent |
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|---|---|
| CN100526480C (en) | 2009-08-12 |
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