CN102399941B - Calcium aluminate for desulfurization of ultralow titanium and carbon steel and preparation method thereof - Google Patents
Calcium aluminate for desulfurization of ultralow titanium and carbon steel and preparation method thereof Download PDFInfo
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- CN102399941B CN102399941B CN201010276441.6A CN201010276441A CN102399941B CN 102399941 B CN102399941 B CN 102399941B CN 201010276441 A CN201010276441 A CN 201010276441A CN 102399941 B CN102399941 B CN 102399941B
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Abstract
The invention relates to calcium aluminate for desulfurization of ultralow titanium and carbon steel and a preparation method thereof. The calcium aluminate comprises more than or equal to 94% of Ca12Al14O33, less than or equal to 2% of Ca3Al2O6, less than or equal to 2% of Ca2SiO4, less than or equal to 1.5% of MgO, less than or equal to 0.01% of pure Ti and less than or equal to 0.02% of pure carbon. The preparation method comprises the following steps of: (1) preparing materials according to the following proportions: 60-65% of CaO and 35-40% of Al; (2) mixing the proportioned raw material particles in a material mixer; (3) adding the mixed materials into a smelting furnace, and blowing fuel to heat the furnace to make furnace temperature achieve 950-1050 DEG C; (4) blowing oxygen into the furnace, heating the furnace body to 1450-1500 DEG C; and (5) cooling and crushing premelted slag into 5-30 mm blocks. The desulfurizing agent provided by the invention has the advantages of low production cost, easy for storage, low melting point, high slag melting speed, high desulfurization effect and small corrosion to refractory materials, and the carbon increase amount and the titanium increase amount of liquid steel can be effectively controlled.
Description
Technical field
The invention belongs to steel-making refining techniques, relate in particular to ultralow titanium, ultra low-carbon steel desulfurization preliminary melting type calcium aluminate sweetening agent and preparation method thereof.
Background technology
Along with the development of engineering, more and more higher to the use properties requirement of steel, in steel, sulphur is harmful element conventionally, as it effectively not removed in fusion process, will seriously restrict the use properties of steel.Therefore, in industrial production, conventionally in liquid steel refining process, add a certain amount of sweetening agent by removal of sulphur at present.
The kind of sweetening agent is a lot, and because calcium aluminate has, fusing point is low, sulfur capacity is high, be easy to preservation, thereby calcium aluminate is widely used in STEELMAKING PRODUCTION as sweetening agent.But for the extremely low steel grade of titanium, carbon content in ask for something steel, if use the calcium aluminate without strict control titanium and carbon content, very easily cause that molten steel titanium, carbon content exceed standard.
Chinese patent CN1188154 discloses a kind of formula and manufacture method thereof of low silicon content aluminium-calcium slag.Its formula comprises: aluminium vanadine, and calcium stone, coke, manufacture method is: select low levels SiO
2aluminium vanadine ore, calcium stone, be broken into bulk, get aluminium vanadine: 25～29%, calcium stone: 43～47%, coke: 25～29% batching, be weight percentage.Select cupola furnace melting batch in the time of 1385 ℃, after coming out of the stove calcium aluminate.This calcium aluminate has rational chemical constitution, and fusing point is low, without free calcium oxide, has good mobility, is conducive to absorb sulphur in steel.But titanium, the carbon content of the calcium aluminate of this kind of method production are higher.In raw material, adopted coke, sweetening process easily causes molten steel carburetting, has also adopted aluminium vanadine in raw material simultaneously, because titanium oxide is common and bauxitic clay is natural associated minerals, therefore the titanium oxide content in the calcium aluminate of this kind of method production is higher, and sweetening process easily causes that molten steel increases titanium.< < preliminary melting type calcium aluminate for ultra-clean steel and preparation method thereof > > patent (application number 200810035054.6) discloses a kind of calcium aluminate and preparation method thereof, this sweetening agent composition is: CaO:48～56%, Al
2o
3: 40～50%, SiO
2: 0.5～3%, MgO:0.5～1.5%, and be not more than 0.02% C, be not more than 0.02% S, be not more than 0.02 TiO
2, be not more than 0.02% S; Be weight percentage.When prepared by above-mentioned calcium aluminate, in order to reduce titanium in calcium aluminate and the content of carbon, the Wingdale that raw material is high-quality and high-purity Al
2o
3powder, but full titanium is not explained, because the titanium of all valence states and form may be all titanium by the aluminium reducing in steel in sweetening agent, thereby causes that in steel, titanium content exceeds standard.Simultaneously because raw material adopts industrial Al
2o
3, because titanium oxide is difficult to from industrial Al
2o
3in thoroughly remove, therefore equally easily cause that molten steel increases titanium smelting the extremely low steel grade of titanium content.< < low-titanium calcium aluminate and preparation method thereof > > patent (application number 200310125135.2) discloses a kind of calcium aluminate and preparation method thereof, it is raw material that raw material is used commercial alumina and byproduct, calcite or Wingdale, fluorite and feldspar, through pulverizing, mixed melting, cooling, crush and screen and form.It is raw material that this calcium aluminate has adopted commercial alumina and byproduct thereof equally, thereby also the content of titanium oxide can not be down to utmost point low value.
As mentioned above, existing calcium aluminate sweetening agent can not meet the requirement of ultralow titanium, carbon steel desulfurization, can cause carburetting, the increasing titanium phenomenon of molten steel in use procedure.The present invention proposes a kind of sweetening agent that is applicable to ultralow titanium, carbon steel desulfurization.
Summary of the invention
The object of the invention is to overcome the existing deficiency of above prior art, a kind of ultralow titanium, ultra low-carbon steel of being specially adapted to is provided, in sweetening process, can make molten steel recarburization and increase titanium to be all controlled at below 5ppm calcium aluminate sweetening agent that slagging speed is fast, desulfurization degree is high and preparation method thereof.
Basic thought of the present invention is to prepare raw material choose aluminium and the calcium oxide of sweetening agent, avoids raw material to bring impurity element into, as titanium and carbon.In production process, by fritting, aluminium and calcium oxide are prepared into low melting point calcium aluminate, this sweetening agent is guaranteeing that molten steel increases titanium amount below 5ppm, and carbon increasing amount has that slagging speed is fast, desulfurization degree is high, the resistance to material of vacuum trough body is corroded to little feature in below 5ppm.
Calcium aluminate composition of the present invention is (weight percent): Ca
12al
14o
33>=94%, Ca
3al
2o
6≤ 2%, Ca
2siO
4≤ 2%, MgO≤1.5%, full Ti≤0.01%, full C≤0.02%.Above-mentioned full Ti refers to the content of whole Ti in calcium aluminate; Full C refers to the content of whole C in calcium aluminate.
The preparation method of calcium aluminate of the present invention is as follows.
(1) by following weight percent batching: CaO:60～65%, Al:35～40%.The granularity of described CaO and Al is 0-10mm, and to improve reaction homogeneity and Reaction time shorten, both proportionings are in order to generate Ca after reacting with oxygen
12al
14o
33, this calcium aluminate fusing point is low, and sulfur capacity is high, and sweetening effectiveness is good, is the main component of sweetening agent of the present invention.
(2) feed particles preparing being put into mixer mixes.The mixing time of raw material is more than 2 hours, fully mixes guaranteeing; Mixing time is no more than 4 hours, to avoid manpower and material resources consumption.
(3) compound is added in smelting furnace, winding-up fuel oil heats, furnace temperature 950-1050 ℃.Described smelting furnace is oil oven, should avoid adopting electric furnace and cupola furnace, and furnace equipment investment is large, and adopts electrode to heat up, and the carbon content in product is greater than 0.5%; It is fuel that cupola furnace adopts coke, and the carbon content in its fritting product is also greater than 0.5%, and silicon-dioxide is greater than 2.5%.The fuel oil of oil oven should select calorific value to be greater than 41840 kilojoules, the low sulphur heavy oil that the weight percent of sulphur content is less than 1.3%.
(4) to the oxygen of jetting in stove, make melt be warming up to 1450-1500 ℃.Winding-up oxygen object is; Guarantee on the one hand O
2react with Al and generate Al
2o
3, Al then
2o
3react with CaO and generate calcium aluminate, the material of desulfurization when calcium aluminate is steel-making.On the other hand, utilize O
2react a large amount of heat of emitting with Al, make melt be warming up to 1450-1500 ℃, temperature is greater than 1450 ℃ can guarantee that slag fully melts, and temperature is less than 1500 ℃, can effectively avoid other as Ca
3al
2o
6deng the generation of high-melting-point substances, take and guarantee the Ca that the primary product after pre-melted slag cooled and solidified is low melting point
12al
14o
33.In addition, also can capable of saving fuel oil and the consumption of oxygen.
(5) cooling, the bulk that is broken into 5-30mm of pre-melted slag.The pre-melted slag of coming out of the stove when more than 1400 ℃, should not adopt the cooling modes such as water-cooled cooling, should adopt slow cooling mode cooling, speed of cooling be controlled at 5 ℃/below min, guarantee that cooled product is with Ca
12al
14o
33be main.
By effective control smelting temperature and speed of cooling, Ca in the calcium aluminate that employing present method is produced
12al
14o
33component concentration is high, can be up to more than 94%, and be unfavorable for the Ca of desulfurization
3al
2o
6and Ca
2siO
4be less than 2%, owing to selecting high quality raw material, the content of MgO is also lower than 1.5%, and full Ti content is lower than 0.01%, and full C is lower than 0.02%.And Ca
12al
14o
33have fusing point low, sulfur capacity is high, the feature that sweetening effectiveness is good, and therefore sweetening agent of the present invention has stronger sweetening power.
The sweetening agent of the present invention not only content of titanium and carbon is extremely low, and has rodent dioxide-containing silica also extremely low to refractory brick.In process of production, make full use of O
2react the feature of emitting large calorimetric with Al, saved fuel oil, reduced production cost.With the sweetening agent that this method is produced, be not only easy to preserve, fusing point is low, changes slag speed fast, and desulfuration efficiency is high, little to resistance to material erosion, and can effectively control the carbon increasing amount of molten steel and increase titanium amount.
Embodiment
The present invention is further described by the following embodiment.
Embodiment 1
(1) by following weight percent, add raw material: CaO:61%, Al:39%.The granularity of CaO is 0-10mm, and the granularity of Al is 0-10mm.
(2) feed particles is carried out in mixer to mechanically mixing, mixing time is 2 hours.
(3) compound is added in smelting furnace, the fuel oil of then jetting heats.Fuel oil calorific value is 41900 kilojoules, and the weight percent of sulphur content is less than 1.2%, and furnace temperature is risen to 980 ℃.
(4) to the oxygen of jetting in stove, carry out melting.Make melt be warming up to 1470 ℃.
(5) come out of the stove, stand-by after cooling, broken.When more than 1400 ℃, controlling speed of cooling is 4 ℃/min.Trimmed size is 5-10mm.
By aforesaid operations, gained calcium aluminate composition is (weight percent %): Ca
12al
14o
33: 95.11%, Ca
3al
2o
6: 1.82%, Ca
2siO
4: 1.96%, MgO:1.08%, full Ti:0.007%, full C:0.02%.
Embodiment 2:
(1) by following weight percent, add following raw material: CaO:63%, Al:37%.The granularity of CaO is 0-7mm, and the granularity of Al is 0-7mm.
(2) feed particles is carried out in mixer to mechanically mixing, mixing time is 2.5 hours.
(3) compound is added the fuel oil of then jetting in smelting furnace heat.Fuel oil calorific value is 42200 kilojoules, and the weight percent of sulphur content is less than 1.2%, and furnace temperature is risen to 1005 ℃.
(4) to the oxygen of jetting in stove, carry out melting.Make melt be warming up to 1480 ℃.
(5) come out of the stove, stand-by after cooling, broken.When more than 1400 ℃, controlling speed of cooling is 3 ℃/min.Trimmed size is 5-15mm.
By aforesaid operations, gained calcium aluminate composition is (weight percent %): Ca
12al
14o
33: 95.39%, Ca
3al
2o
6: 1.62%, Ca
2siO
4: 1.86%, MgO:1.11%, full Ti:0.01%, full C:0.01%.
Embodiment 3:
(1) by following weight percent, add following raw material: CaO:64%, Al:36%.The granularity of CaO is 0-5mm, and the granularity of Al is 0-5mm.
(2) feed particles is carried out in mixer to mechanically mixing, mixing time is 3.5 hours.
(3) compound is added the fuel oil of then jetting in smelting furnace heat.Fuel oil calorific value is 43210 kilojoules, and the weight percent of sulphur content is less than 1.1%, and furnace temperature is risen to 1010 ℃.
(4) to the oxygen of jetting in stove, carry out melting.Make melt be warming up to 1490 ℃.
(5) come out of the stove, stand-by after cooling, broken.When more than 1400 ℃, controlling speed of cooling is 3 ℃/min.Trimmed size is 5-25mm.
By aforesaid operations, gained calcium aluminate composition is (weight percent %): Ca
12al
14o
33: 96.67%, Ca
3al
2o
6: 0.73%, Ca
2siO
4: 1.27%, MgO:1.31%, full Ti:0.009%, full C:0.012%.
The sweetening agent of above-described embodiment is added in molten steel and carries out desulfurization, and desulfurization the results are shown in Table 1.
Table 1 adopts the molten steel desulfurizing effect (wt%) of embodiment of the present invention sweetening agent
From table 1, adopt the desulfurization degree of sweetening agent of the present invention all more than 50%, and the molten steel recarburization in whole sweetening process and increasing titanium all can be controlled at below 5ppm again simultaneously.
Claims (4)
1. a preparation method for ultralow titanium, carbon steel calcium aluminate for desulfurization, is characterized in that comprising the following steps: 1. by following weight percent batching: CaO:60～65%, Al:35～40%; 2. the feed particles preparing being put into mixer mixes; 3. compound is added in smelting furnace, winding-up fuel oil heats, furnace temperature 950-1050 ℃; 4. to the oxygen of jetting in stove, make melt be warming up to 1450-1500 ℃; 5. cooling, the bulk that is broken into 5-30mm of pre-melted slag; Described pre-melted slag is cooling with the speed of cooling of≤5 ℃/min in when more than 1400 ℃; Described calcium aluminate composition weight percent is: Ca
12al
14o
33>=94%, Ca
3al
2o
6≤ 2%, Ca
2siO
4≤ 2%, MgO≤1.5%, full Ti≤0.01%, full C≤0.02%.
2. the preparation method of calcium aluminate according to claim 1, is characterized in that described CaO and the granularity of Al are 0-10mm.
3. the preparation method of calcium aluminate according to claim 1, the mixing time that it is characterized in that described raw material is 2～4h.
4. the preparation method of calcium aluminate according to claim 1, is characterized in that described smelting furnace is oil oven, and described fuel oil is that calorific value is greater than the low sulphur heavy oil that the weight percent of 41840 kilojoules, sulphur content is less than 1.3%.
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|---|---|---|---|---|
| CN1804055A (en) * | 2005-01-12 | 2006-07-19 | 宝山钢铁股份有限公司 | Premelting slag for RH vacuum treatment deep desulfurization of ultra low carbon steel |
| CN101168787A (en) * | 2007-11-28 | 2008-04-30 | 孙中强 | Calcium-calcium aluminate core-spun yarn for steel smelting |
| CN101244835A (en) * | 2008-03-25 | 2008-08-20 | 上海彭浦冶金辅料有限公司 | Preliminary melting type calcium aluminate for ultra-clean steel and method of manufacturing the same |
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| JP2004263285A (en) * | 2003-03-04 | 2004-09-24 | Nippon Steel Corp | Agent and method for desulfurizing molten steel and method for producing calcium aluminate source |
| JP3824605B2 (en) * | 2003-12-01 | 2006-09-20 | 電気化学工業株式会社 | Steel additive |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1804055A (en) * | 2005-01-12 | 2006-07-19 | 宝山钢铁股份有限公司 | Premelting slag for RH vacuum treatment deep desulfurization of ultra low carbon steel |
| CN101168787A (en) * | 2007-11-28 | 2008-04-30 | 孙中强 | Calcium-calcium aluminate core-spun yarn for steel smelting |
| CN101244835A (en) * | 2008-03-25 | 2008-08-20 | 上海彭浦冶金辅料有限公司 | Preliminary melting type calcium aluminate for ultra-clean steel and method of manufacturing the same |
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| JP特开2004-263285A 2004.09.24 |
| JP特开2005-163073A 2005.06.23 |
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