CN101736123B - Boron-containing alloy smelting process with high yield - Google Patents
Boron-containing alloy smelting process with high yield Download PDFInfo
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Abstract
The invention discloses a boron-containing alloy smelting process with high yield. The process is characterized in that firstly boron-containing alloy is smelted in an electric furnace, when the temperature of the alloy is 180-230 DEG C higher than liquidus temperature, 0.2-0.5 % of calcium-silicon is added for preliminary deoxygenation, then 0.12-0.18% of aluminium is added for final deoxygenation, and then 0.2-0.3% of ferrotitanium is added for fixing nitrogen in metal solution, and finally ferrotitanium and ferroboron tightly wrapped by an aluminium plate are added into metal liquid together, when the temperature of boron-containing alloy is 200-260 DEG C higher than the liquidus temperature, boron-containing alloy liquid is discharged and can be used for pouring of cast or cast ingot. The invention is adopted to smelt boron-containing alloy, yield of boron element is over 90%, consumption of boron element can be obviously reduced, and boron-containing alloy production cost can be reduced, thus the invention has better economic and social benefits.
Description
Technical field
The present invention is a kind of smelting process of boron-containing alloy, and the boron-containing alloy smelting process that particularly a kind of boron recovery rate is high belongs to the Metal smelting technical field.
Technical background
Boron adds in the ferrous materials, and the part of boron solid solution can improve the hardenability and the hardening capacity of matrix in matrix, part of boron combines the iron boron compound that generates high rigidity with iron, therefore, boron adds in the ferrous materials can increase substantially the hardness of ferrous materials, and improves wear resistance.But boron is active very strong element, and the scaling loss amount is big in the adding ferrous materials, and recovery rate is lower, causes the huge waste of resource.In order to improve the recovery rate of boron in the boron-containing alloy smelting process, Chinese invention patent CN1600884 discloses the method for the direct smelting boron steel of a kind of pig iron containing boron, with the pig iron containing boron of paigeite after blast furnace separates is raw material, through pretreatment desulfurizing, selecting yellow soda ash base, lime base or calcium carbide base or their compound base for use is sweetening agent earlier; Adopt converter smelting then, processing step is: (1) charging: the molten iron after the desulfurization is 50%～70% adding by weight, and all the other are steel scrap and iron ore; (2) slag making: selecting slag former for use is CaO and small amounts iron sheet, magnesium oxide, when furnace temperature reaches 1400 ℃, and keeps under 1400 ℃ of conditions of furnace temperature, adds slag former; (3) oxygen blast: oxygen supply time is 20～25mi n, and oxygen supply intensity is: 2.5～3.5Nm
3/ t.mi n; (4) terminal point control: tapping temperature is 1550～1580 ℃, and adds manganeseirom or silicomanganese, makes Mn in the steel 〉=0.6%, and boron content is B:0.001～0.006% (weight) in the final boron steel.The boron steel smelting cost of this invention is low, and boron is evenly distributed in steel, and the stable performance of steel has been opened up new way for paigeite blast furnace separated product further fully utilizes.Chinese invention patent CN1718829 also discloses a kind of film austenic toughened martensite wear resistant cast steel, it specifically consists of: C:0.25～0.34wt%, Si:1.45～2.05wt%, Mn:0.90～1.20wt%, Cr:1.80～2.50wt%, B:0.0005～0.005wt%, Ti:0.01～0.06wt%, RE:0.015～0.08wt%, Al:0.015～0.06wt%, S≤0.035wt%, P≤0.035wt%, surplus is Fe.Its manufacturing step comprises molten steel melting and thermal treatment, after conventional process for making is finished, successively adds TiFe alloy, RESiFe alloy and BFe alloy melting, handles through high temperature normalizing, insulation, shrend and low-temperaturetempering then.But, aforesaid method is unconformable when being applied to that the higher boron-containing alloy of boron content is smelted, this is because of in the higher boron-containing alloy smelting process of boron content, need to add more ferro-boron, if adopt aforesaid method that ferro-boron is added in the alloy, to cause alloy temperature sharply to descend, and alloying constituent is inhomogeneous.Therefore, in the higher boron-containing alloy smelting process of boron-containing quantity, all be at present in the alloy melting later stage, directly ferro-boron is added in the smelting furnace, come out of the stove into casting ladle after being heated to the tapping temperature of requirement then, pour into foundry goods or ingot casting at last.There is the serious deficiency of boron recovery rate low (less than 80%) and boron waste, causes the boron-containing alloy cost to raise.In order to alleviate the scaling loss of boron, improve its recovery rate, Chinese invention patent CN101250659 also discloses the method that a kind of vacuum metling boron-containing steel improves and stablize the boron rate of recovery, it is characterized in that, carry out boron alloyization before the molten steel vacuum-treat.After the molten steel vacuum-treat, get the analysis of molten steel sample, the boron rate of recovery is stabilized in more than 90%.Can realize producing same boracic steel grade, smelting component boron content deviation is less than 2ppm (promptly 0.0002%) between stove and the stove.Carry out boron alloyization after having solved the molten steel vacuum-treat, boron rate of recovery instability and boron alloy process can cause the secondary pollution problem to molten steel.Chinese invention patent CN101451209 also discloses the adding method of ferro-boron in a kind of steel smelting procedure, described steel smelting procedure comprises furnace melting, refining, vacuum-treat, and oxygen level is not more than 20ppm in the molten steel after present method control refining, aluminium content is not less than 0.010%; Feeding aluminium aluminium percentage composition to the molten steel is 0.080-0.120% before the vacuum, adds ferro-boron then, carries out vacuum-treat, and the big Argon for the treatment of processes stirs.After adopting this inventive method, the rate of recovery of smelting back boron can reach more than 90%.But, adopting the high boron alloy of vacuum method melting, complex process, apparatus expensive cause the material produce cost to increase.
Summary of the invention
The objective of the invention is to solve in the existing boron-containing alloy smelting process and have the low deficiency of boron recovery rate, provide and smelted the boron-containing alloy novel process under the atmospheric condition.
For achieving the above object, the present invention's later stage of boron-containing alloy melting in the prior art, add the silicocalcium pre-deoxidation earlier, add the aluminium final deoxygenation again, add the nitrogen in the titanium fixing metal solution then, at last ferro-boron is added in the metal liquid.For oxidation and the scaling loss that prevents boron, earlier ferro-boron is preheated to 250～350 ℃, in ferro-boron, add the ferrotianium that accounts for metal liquid total amount 0.3%～0.6% then, the ferrotianium granularity is controlled at 6～12mm.And with the aluminium sheet of thickness 2～4mm that ferro-boron and ferrotianium parcel is tight, add together in the electric furnace, coming out of the stove at last promptly can be used for the cast of foundry goods or ingot casting.
The object of the invention can realize by following measure:
Smelting metal alloy material in electric furnace at first, when the temperature of metal alloy compositions is higher than it more than liquidus temperature 180～230 ℃ the time, add the silicocalcium pre-deoxidation that accounts for alloy liquid quality 0.2%～0.5% in the stove, add the aluminium final deoxygenation that accounts for alloy liquid quality 0.12%～0.18% in the stove again, add the nitrogen in the ferrotianium fixing metal solution that accounts for alloy liquid quality 0.2%～0.3% in the stove then; Ferro-boron is preheated to 250～350 ℃, and adds the ferrotianium that accounts for alloy liquid quality 0.3%～0.6% in the stove in ferro-boron, the ferrotianium granularity is controlled at 6～12mm; Aluminium sheet with thickness 2～4mm is tight with ferro-boron and ferrotianium parcel, to wrap up tight ferro-boron and ferrotianium adds in the metal liquid together with aluminium sheet at last, when the temperature of boron-containing alloy is higher than it more than liquidus temperature 200～260 ℃ the time, boron-containing alloy liquid is come out of the stove and promptly be can be used for the cast of foundry goods or ingot casting.
The mass percent of above-mentioned silicocalcium is: Ca 〉=28%, C＜0.8%, Fe＜5.0%, Al＜2.4%, P＜0.04%, S＜0.06%, surplus Si.
The mass percent of above-mentioned ferrotianium is: 28-32%Ti, Al＜5%, Si＜5%, Mn＜2.5%, C＜0.15%, P＜0.06%, S＜0.04%, Cu＜0.4%, surplus Fe.
The mass percent of above-mentioned ferro-boron is: 20-25%B, C＜0.1%, Si＜3.0%, Al＜4.0%, S＜0.02%, P＜0.03%, Cu＜0.1%, surplus Fe.
The present invention earlier with 0.2%～0.5% silicocalcium pre-deoxidation, adds 0.12%～0.18% aluminium final deoxygenation again in the boron-containing alloy smelting process, can reduce the oxygen level in the molten metal, prevents that ferro-boron from adding the oxidization burning loss of fashionable boron.In addition, boron and nitrogen also have higher avidity, therefore, before adding ferro-boron, also in metal liquid, add 0.2%～0.3% ferrotianium, utilize the reaction of titanium and nitrogen to form Ti N, nitrogen in can the fixing metal liquation prevents the reaction of boron and nitrogen, helps improving the recovery rate of boron.In addition, ferro-boron adds before the metal liquid, carries out thermal pretreatment at 250～350 ℃, can prevent that ferro-boron from adding after, the metal liquid temperature phenomenon that sharply descends appears, can shorten the heat, alleviate the oxidization burning loss of boron.In addition, ferro-boron adds in the metal liquid, and is tight with the aluminium sheet parcel of thickness 2～4mm, utilizes the good desoxydatoin of aluminium, can further reduce the oxidization burning loss of boron, improves the recovery rate of boron.In addition, add the ferrotianium that accounts for metal liquid total amount 0.3%～0.6% in ferro-boron, the ferrotianium granularity is controlled at 6～12mm, mainly contains two effects: one makes ferrotianium further play azotification; Its two, the tiny TiN and the TiC that utilize the reaction of titanium and nitrogen, carbon to form can rise and solidify central role, it is tiny to help foundry goods or ingot structure that boron-containing alloy pours into a mould subsequently, improves its mechanical property and hot workability.
The present invention compared with prior art has the following advantages:
1, melting boron-containing alloy of the present invention, the boron recovery rate reaches 93%～96%, and the recovery rate of boron is suitable during with the vacuum melting boron-containing alloy, but the melting cost is starkly lower than the vacuum melting boron-containing alloy;
2, the present invention adopts and smelts the boracic cooperation under the conventional atmospheric condition, easy and simple to handle, the present invention has overcome the low deficiency of boron recovery rate under the conventional smelting condition, the boron recovery rate only is 75%～80% under the conventional smelting condition, can obviously save the boron resource, reduce the boron-containing alloy production cost;
3, adopt the boron-containing alloy of melting of the present invention to pour into foundry goods or ingot casting, organize tinyly, can improve its mechanical property and hot workability.
Embodiment
Below in conjunction with embodiment the present invention is further described.
Embodiment 1:
Adopt 500 kilograms of medium-frequency induction furnace melting boron content to surpass 0.5% boracic high-speed steel material, concrete processing step is as follows:
(1) in electric furnace, adds starting material such as steel scrap, ferrochrome, molybdenum-iron, ferrotungsten, the pig iron and vanadium iron, send electric smelting then, when the temperature of alloy is higher than more than the liquidus temperature 183 ℃, (mass percent of silicocalcium is: 29.37%Ca in the silicocalcium pre-deoxidation of adding 0.2%, 0.30%C, 1.16%Fe, 0.73%Al, surplus Si), add 0.18% aluminium final deoxygenation again, (mass percent of ferrotianium is: 30.69%Ti, 0.72%Al, 1.18%Si to add 0.3% ferrotianium then, 0.63%Mn, 0.06%C, 0.11%Cu, surplus Fe.) nitrogen in the fixing metal liquation.
(2) (mass percent of ferro-boron is: 22.07%B, 0.04%C, 1.08%Si, 1.25%Al, 0.03%Cu, surplus Fe with ferro-boron.) be preheated to 350 ℃, in ferro-boron, add the ferrotianium that accounts for metal liquid total amount 0.3%, the ferrotianium granularity is controlled at 6～12mm, and with the aluminium sheet of thickness 4mm that ferro-boron and ferrotianium parcel is tight.
(3) will wrap up tight ferro-boron and ferrotianium adds in the metal liquid together with aluminium sheet at last, when the temperature of boron-containing alloy was higher than more than the liquidus temperature 202 ℃, boron-containing alloy liquid was come out of the stove and is poured into roll.Adopt the mass percent of the boracic high-speed steel material of aforesaid method smelting to be: 1.38%B, 0.95%C, 5.77%Cr, 1.06%W, 2.45%Mo, 1.93%V, 0.08%Ti, surplus Fe, the recovery rate of boron reaches 95.3%.
Embodiment 2:
Adopt 750 kilograms of medium-frequency induction furnace melting boron content to surpass 0.5% boracic wear-resistant steel alloy, concrete processing step is as follows:
(1) in electric furnace, adds starting material such as steel scrap, the pig iron, ferrochrome, ferrosilicon and ferromanganese, send electric smelting then, when the temperature of alloy is higher than more than the liquidus temperature 229 ℃, (mass percent of silicocalcium is: 29.37%Ca in the silicocalcium pre-deoxidation of adding 0.5%, 0.30%C, 1.16%Fe, 0.73%Al, surplus Si), add 0.12% aluminium final deoxygenation again, (mass percent of ferrotianium is: 30.69%Ti, 0.72%Al, 1.18%Si to add 0.2% ferrotianium then, 0.63%Mn, 0.06%C, 0.11%Cu, surplus Fe.) nitrogen in the fixing metal liquation.
(2) (mass percent of ferro-boron is: 22.07%B, 0.04%C, 1.08%Si, 1.25%Al, 0.03%Cu, surplus Fe with ferro-boron.) be preheated to 250 ℃, in ferro-boron, add the ferrotianium that accounts for metal liquid total amount 0.6%, the ferrotianium granularity is controlled at 6～12mm, and with the aluminium sheet of thickness 2mm that ferro-boron and ferrotianium parcel is tight.
(3) will wrap up tight ferro-boron and ferrotianium adds in the metal liquid together with aluminium sheet at last, when the temperature of boron-containing alloy was higher than more than the liquidus temperature 255 ℃, boron-containing alloy liquid was come out of the stove and is poured into grinder hammerhead.Adopt the mass percent of the boracic abrasion-resistant cast steel material of aforesaid method smelting to be: 1.62%B, 0.38%C, 2.39%Cr, 1.21%Mn, 0.88%Si, 0.11%Ti, surplus Fe, the recovery rate of boron reaches 94.8%.
Embodiment 3:
Adopt 500 kilograms of medium-frequency induction furnace melting boron content to be lower than 0.5% boracic cast steel material, concrete processing step is as follows:
(1) in electric furnace, adds starting material such as steel scrap, ferrochrome, molybdenum-iron, the pig iron, nickel plate, ferrosilicon and ferromanganese, send electric smelting then, when the temperature of alloy is higher than more than the liquidus temperature 217 ℃, (mass percent of silicocalcium is: 29.37%Ca in the silicocalcium pre-deoxidation of adding 0.4%, 0.30%C, 1.16%Fe, 0.73%Al, surplus Si), add 0.15% aluminium final deoxygenation again, (mass percent of ferrotianium is: 30.69%Ti, 0.72%Al, 1.18%Si to add 0.2% ferrotianium then, 0.63%Mn, 0.06%C, 0.11%Cu, surplus Fe.) nitrogen in the fixing metal liquation.
(2) (mass percent of ferro-boron is: 22.07%B, 0.04%C, 1.08%Si, 1.25%Al, 0.03%Cu, surplus Fe with ferro-boron.) be preheated to 300 ℃, in ferro-boron, add the ferrotianium that accounts for metal liquid total amount 0.4%, the ferrotianium granularity is controlled at 6～12mm, and with the aluminium sheet of thickness 3mm that ferro-boron and ferrotianium parcel is tight.
(3) will wrap up tight ferro-boron and ferrotianium adds in the metal liquid together with aluminium sheet at last, when the temperature of boron-containing alloy was higher than more than the liquidus temperature 227 ℃, boron-containing alloy liquid was come out of the stove and is poured into excavator bucket teeth.Adopt the mass percent of the boracic cast steel material of aforesaid method smelting to be: 0.004%B, 0.33%C, 1.52%Cr, 0.47%Mo, 0.70%Ni, 1.26%Si, 0.56%Mn, 0.09%Ti, surplus Fe, the recovery rate of boron reaches 93.1%.
Adopt melting boron-containing alloy material of the present invention, boron loses less, the recovery rate height.The foundry goods that adopts the present invention to pour into a mould in addition, dense structure, result of use is good.Use melting boron-containing alloy material of the present invention, can reduce the alloy production cost, have good economic benefits.
Claims (1)
1. the smelting process of the boron-containing alloy that a boron recovery rate is high is characterized in that, may further comprise the steps:
Smelting metal alloy material in electric furnace at first, when the temperature of metal alloy compositions is higher than it more than liquidus temperature 180～230 ℃ the time, add the silicocalcium pre-deoxidation that accounts for alloy liquid quality 0.2%～0.5% in the stove, add the aluminium final deoxygenation account for alloy liquid quality 0.12%～0.18% in the stove again, add the fixing nitrogen in the alloy liquid of ferrotianium that accounts for alloy liquid quality 0.2%～0.3% in the stove then; Ferro-boron is preheated to 250～350 ℃, and adds the ferrotianium that accounts for alloy liquid total mass 0.3%～0.6% in the stove in ferro-boron, the ferrotianium granularity is controlled at 6～12mm; Aluminium sheet with thickness 2～4mm is tight with ferro-boron and ferrotianium parcel, to wrap up tight ferro-boron and ferrotianium with aluminium sheet at last adds in the stove in the alloy liquid together, when the temperature of boron-containing alloy is higher than it more than liquidus temperature 200～260 ℃ the time, boron-containing alloy liquid is come out of the stove and promptly be can be used for the cast of foundry goods or ingot casting;
The mass percent of silicocalcium is: Ca 〉=28%, C＜0.8%, Fe＜5.0%, Al＜2.4%, P＜0.04%, S＜0.06%, surplus Si;
The mass percent of ferrotianium is: 28-32%Ti, Al＜5%, Si＜5%, Mn＜2.5%, C＜0.15%, P＜0.06%, S＜0.04%, Cu＜0.4%, surplus Fe;
The mass percent of ferro-boron is: 20-25%B, C＜0.1%, Si＜3.0%, Al＜4.0%, S＜0.02%, P＜0.03%, Cu＜0.1%, surplus Fe.
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| CN102719724B (en) * | 2011-03-29 | 2014-07-30 | 鞍钢股份有限公司 | Method for improving and stabilizing boron yield in smelting boron-containing steel |
| CN102181602B (en) * | 2011-04-28 | 2012-07-11 | 抚顺新钢铁有限责任公司 | Method for adding oxidizable alloy in molten steel |
| CN111020103A (en) * | 2019-11-22 | 2020-04-17 | 舞阳钢铁有限责任公司 | Ferroboron adding method and ferroboron adding device for improving acid-soluble boron proportion |
| CN115121787B (en) * | 2021-10-20 | 2024-04-19 | 杭州屹通新材料股份有限公司 | Water atomization ferroboron powder and preparation method thereof |
| CN114703337A (en) * | 2022-04-06 | 2022-07-05 | 成都先进金属材料产业技术研究院股份有限公司 | Smelting method for 10Cr11Co3W3NiMoVNbNB heat-resistant steel |
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