CN102382927B - Molten iron smelting method and vanadium-containing molten iron smelting method - Google Patents
Molten iron smelting method and vanadium-containing molten iron smelting method Download PDFInfo
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Abstract
The invention provides a molten iron smelting method, which includes that first slag formers are added into desulfurized molten iron in a converter to realize first-time blowing slag forming under the condition of oxygen blowing, and second slag formers are added into the converter to realize second-time blowing slag forming under the condition of oxygen blowing after 50-70wt.% of total slag is removed. The invention further provides a vanadium-containing molten iron smelting method. The smelting methods solve the problems of insufficiency of heat sources for steelmaking with molten iron and difficulty in slag forming and dephosphorization, so that the process is smooth, equipment investment is less, production cost is low, and simultaneously capacities and production rhythms of front and back procedures can be matched in aftereffect.
Description
Technical field
The present invention relates to a kind of molten iron smelting method and utilize the smelting process of the vanadium-bearing hot metal of this method.
Background technology
Phosphorus is detrimental impurity in the steel, easily at grain boundary segregation, causes steel " cold short ", significantly reduces the low-temperature impact toughness of steel.Some aviations, nuclear power, corrosion-resistant pipeline require finished product phosphorus to be lower than 0.005 weight % with steel.
Sulphur also is one of harmful element in the steel, is surface active element, often assembles in segregation on the steel crystal boundary or on the out-phase interface with the form of MnS, and sulphur is cause steel hot-short to the harm of steel maximum.Some X70 and above rank oil pipeline steel and high-level automobile steel etc. require finished product sulphur to be lower than 0.005 weight %.
In China, part iron factory adopts v-bearing titanomagnetite smelting, and the P content of smelting in the back acquisition molten iron is 0.060-0.080 weight %, and S content is 0.055-0.100 weight %, and Si content is 0.10-0.30 weight %, and V content is 0.20-0.35 weight %; In order to guarantee effective extraction and the utilization of vanadium resource, vanadium extraction and desulfurization production before converter steelmaking, have been carried out; The thick vanadium slag that obtains after the vanadium extraction is convenient to back step operation water law vanadium extraction (requiring CaO in the thick vanadium slag≤3.0 weight %), but can't carry out pre-dephosphorization, and therefore, steel-making converter is born whole dephosphorization tasks.Carbonaceous amount percentage composition is 3.4-4.0 weight % in the molten iron that obtains after the vanadium extraction, and silicon, manganese heating slagging constituent content are trace in the molten iron.Therefore, vanadium-bearing hot metal is produced the restricted link that there is the following aspects in ultralow phosphorus low-sulfur steel:
(1) existence of vanadium-bearing hot metal S height (exceeding 0.030-0.040 percentage point of common molten iron S content), temperature low (than low 40-50 ℃ of common molten iron temperature) and Ti, V element has influenced the mass transfer of S in molten iron, is unfavorable for desulfurization.
(2) in order to guarantee that vanadium resource effectively extracts, can't carry out pre-dephosphorization during vanadium extraction.
(3) molten iron-steelmaking after the vanadium extraction, heat source insufficiency, slag making dephosphorization difficulty.
In prior art, technology and the method for common molten iron production ultra-low phosphoretic steel or ultralow-sulfur steel have certain document and patent report, but, in the converter steelmaking industrial production, be not the production method that raw material production P content and S content all are lower than the ultralow phosphorus low-sulfur steel of 0.005 weight % with the vanadium-bearing hot metal also.
Summary of the invention
The objective of the invention is provides a kind of molten iron smelting method in order to obtain better dephosphorization effect in blowing technology.
Another object of the present invention is in order to overcome when smelting with vanadium-bearing hot metal, and the problem of the molten iron slag making dephosphorization difficulty after the desulfurization vanadium extraction provides a kind of smelting process of vanadium-bearing hot metal.
The invention provides a kind of molten iron smelting method, this method comprises: in converter, add first slag former in the molten iron under the oxygen blast condition after the desulfurization and carry out the slag making of blowing the first time, after the 50-70 weight % of slag total amount got rid of, under the oxygen blast condition, add second slag former in the converter again and carry out the slag making of blowing the second time.
The present invention also provides a kind of smelting process of vanadium-bearing hot metal, and this method may further comprise the steps: vanadium-bearing hot metal is carried out desulfurization, the molten iron after the desulfurization is carried out vanadium extraction, the molten iron after the desulfurization vanadium extraction is smelted according to above-mentioned molten iron smelting method.
Molten iron smelting method provided by the invention effectively dephosphorization in convertor steelmaking process reduces the phosphorus content in the molten steel, and the converter dephosphorization rate is reached more than 94%.
The smelting process of vanadium-bearing hot metal provided by the invention not only guarantees effective utilization and the extraction of vanadium resource, effectively dephosphorization in vanadium extraction from hot metal and molten iron converter steelmaking simultaneously, the energy stably desulphurizing, and solved the problem of the molten iron-steelmaking heat source insufficiency after the vanadium extraction, slag making dephosphorization difficulty, make the technology direct motion, facility investment is little, production cost is low, simultaneously can aftereffect coupling front and back operation production capacity and rhythm of production.Produce the high-level high added value steel of ultralow phosphorus low-sulfur for vanadium-bearing hot metal the important channel is provided.Can in the converter steelmaking industrial production, obtain the ultralow phosphorus low-sulfur steel that P content and S content all are lower than 0.005 weight % by smelting process of the present invention.
Embodiment
The invention provides a kind of molten iron smelting method, this method comprises: in converter, add first slag former in the molten iron under the oxygen blast condition after the desulfurization and carry out the slag making of blowing the first time, after the 50-70 weight % eliminating with the slag total amount, converter is returned zero-bit, under the oxygen blast condition, add second slag former again in the converter and carry out the slag making of blowing the second time.
Above-mentioned first slag former is lime powder, high magnesium lime, composite slag and steel-smelting sewage sludge.Under the preferable case, the condition of slag making of blowing the described first time is: with respect to the molten iron after 1 ton of described desulfurization, the add-on of active lime powder is that the add-on of 25-30 kilogram, high magnesium lime is that the add-on of 14-18 kilogram, composite slag is that the add-on of 14-18 kilogram, steel-smelting sewage sludge is the 3-5 kilogram, oxygen blow duration is 360-480 second, with respect to the molten iron after 1 ton of described desulfurization, blowing oxygen quantity is 20-25Nm
3Described second slag former is lime powder, high magnesium lime and composite slag.Under the preferable case, the condition of slag making of blowing the described second time is: with respect to the molten iron after 1 ton of described desulfurization, the add-on of active lime powder is that the add-on of 18-25 kilogram, high magnesium lime is that the add-on of 5-10 kilogram, composite slag is the 5-8 kilogram, oxygen blow duration is 420-540 second, with respect to the molten iron after 1 ton of described desulfurization, blowing oxygen quantity is 25-30Nm
3
In the present invention, be benchmark with the gross weight of described active lime powder, the CaO content in the described active lime powder is 85-90 weight %; Gross weight with described high magnesium lime is benchmark, and the MgO content in the described high magnesium lime is 30-40 weight %, and the CaO content in the described high magnesium lime is 48-55 weight %; Contain SiO in the described composite slag
2, MnO and TFe, be benchmark with the gross weight of described composite slag, the SiO in the composite slag
2Content is 45-55 weight %, and MnO content is 5-10 weight %, and TFe content is 15-20 weight %.
In the present invention, TFe refers to full iron, and comprising metallic iron and ferriferous oxide, the oxide compound of described iron mainly comprises FeO and Fe
2O
3In the present invention, described sludge ball of steel smelting is to suppress after the dedusting ash drying of will make steel to form, and contains ferriferous oxide, CaO, SiO
2, multiple constituent element such as MgO.
The present invention also provides a kind of smelting process of vanadium-bearing hot metal, and this method may further comprise the steps: vanadium-bearing hot metal is carried out desulfurization, the molten iron after the desulfurization is carried out vanadium extraction, the molten iron after the desulfurization vanadium extraction is smelted according to above-mentioned molten iron smelting method.
The above-mentioned method that vanadium-bearing hot metal is carried out desulfurization comprises: vanadium-bearing hot metal is contacted with sweetening agent carry out composite blowing, the condition of composite blowing reaches more than 94% desulfurization degree, S content in the molten iron after the desulfurization≤0.005 weight %.Wherein, total amount with described vanadium-bearing hot metal is benchmark, and the C content of described vanadium-bearing hot metal is that 4.0-4.6 weight %, V content are that 0.20-0.35 weight %, Mn content are that 0.20-0.30 weight %, S content are that 0.055-0.100 weight %, P content are that 0.060-0.080 weight %, Si content are that 0.10-0.30 weight %, Ti content are that 0.10-0.35 weight %, Fe content are more than the 94 weight %.
In the present invention, described sweetening agent can use passive lime powder and deactivating magnesium powder, can also use calcium carbide (CaC
2) with mixture and the deactivating magnesium powder of passive lime powder, preferably use passive lime powder and deactivating magnesium powder.Under the preferable case, the condition of described composite blowing is: with respect to 1 ton of described vanadium-bearing hot metal, the consumption of described passive lime powder is the 3.5-5.5 kilogram, and the consumption of described deactivating magnesium powder is the 0.9-1.2 kilogram; The time of described composite blowing is 18-35 minute, and the granularity of described passive lime powder and deactivating magnesium powder is all in 140 orders.Total amount with described passive lime powder is benchmark, and the CaO content in the described passive lime powder is 89-95 weight %; Total amount with described deactivating magnesium powder is benchmark, and the Mg content in the described deactivating magnesium powder is greater than 93 weight %.
The above-mentioned method that molten iron after the desulfurization is carried out vanadium extraction comprises: in converter, with the molten iron after the desulfurization with after dephosphorizing agent mixes, carry out oxygen supply and blow vanadium and pre-dephosphorization, in 3 minutes of beginning oxygen supply, add refrigerant, beginning 4.5-6 minute of oxygen supply, add slag supplying agent, obtain molten iron and vanadium slag after the desulfurization vanadium extraction, in the molten iron after described desulfurization vanadium extraction, C content is 3.6-4.0 weight %, S content is≤0.005 weight %, P content is≤0.040 weight %, and with respect to the molten iron after 1 ton of described desulfurization, blowing oxygen quantity is 9-13Nm
3The method of the molten iron after the desulfurization being carried out vanadium extraction among the present invention can guarantee effective extraction of 85% above vanadium resource.
Molten iron after the desulfurization is being carried out in the method for vanadium extraction, with respect to the molten iron after 1 ton of described desulfurization, the consumption of described dephosphorizing agent is preferably the 10-25 kilogram, and the consumption of described refrigerant is preferably the 3-10 kilogram, and the consumption of described slag supplying agent is preferably the 1-3 kilogram.
In order not influence the purpose that vanadium slag quality can reach dephosphorization simultaneously, employed dephosphorizing agent is preferably the sodium salt dephosphorizing agent in the present invention, more preferably uses yellow soda ash.Described refrigerant can use iron scale and/or cooled agglomerated pellet.Fe in the described iron scale
2O
3Content be that the content of 30.4 weight %, FeO is 62.7 weight %.Described slag supplying agent can use carbonaceous material and/or magnesian, preferably uses hard coal, class graphite or magnesia, more preferably uses magnesia.
In the present invention, with vanadium-bearing hot metal carry out desulfurization, vanadium extraction, blow for the first time slag making and the slag making of blowing for the second time, obtain C content and be 0.04-0.06%, P content less than 0.003% and the molten steel of S content after less than 0.008% desulfurization vanadium extraction.Wherein, blow for the first time slag making basicity (CaO and SiO in the slag
2Quality percentage composition ratio) be 2.0-3.0, slag making terminal point slag (CaO and SiO in the slag blow for the second time
2Quality percentage composition ratio) be 5.0-7.0, the slag making deslagging temperature that blows for the first time is 1350-1450 ℃, and the slag making endpoint molten steel temperature that blows for the second time is 1620-1650 ℃.
The smelting process of vanadium-bearing hot metal of the present invention can also comprise, after the molten iron after the desulfurization vanadium extraction is smelted according to above-mentioned molten iron smelting method, molten steel after smelting is carried out the pushing off the slag tapping, in molten steel, add low-phosphorous low sulfur metal, low-phosphorous low-sulfur alloy and carburelant, make molten steel phosphorization total amount in 0.001 weight %.
Employed carburelant is carburelant known in those skilled in the art among the present invention, is preferably in pitch coke, hard coal and the carbon dust one or more.In the present invention, described low-phosphorous low sulfur metal can use manganese metal, and the P content in the described manganese metal is＜0.04 weight %, and S content is＜0.05 weight %, Mn content 〉=97.0 weight %; Described low-phosphorous low-sulfur alloy is ferro-silicon, and the P content in the described ferro-silicon is＜0.03 weight %, and S content is＜0.06 weight %, and Si content is 75-80 weight %, and Fe content is 20-25 weight %.In the present invention, there is no particular limitation to the add-on of carburelant, low-phosphorous low sulfur metal and low-phosphorous low-sulfur alloy, can select suitable add-on according to the steel grade of smelting.
In order to reduce ladle slag rephosphorization behind the converter smelting, the smelting process of vanadium-bearing hot metal of the present invention also comprises and reduces under the converter tapping quantity of slag and add refining slag in ladle, makes in the ladle slag rephosphorization total amount in 0.001 weight %.
The quantity of slag realizes in the following manner under the described minimizing converter tapping, namely, before molten steel after described will the smelting carries out the pushing off the slag tapping, with respect to the molten steel after 1 ton of described smelting, the high magnesium lime that adds the 3-5 kilogram in the molten steel after the described smelting carries out dry slag, increasing the viscosity of slag, the speed control of simultaneously molten steel being tapped in 400 Kilograms Per Seconds, make under the converter tapping quantity of slag with respect to 1 ton of tapping molten steel smaller or equal to 6 kilograms.Wherein, be benchmark with the gross weight of described high magnesium lime, the MgO content in the described high magnesium lime is 30-40 weight %, the CaO content in the described high magnesium lime is 48-55 weight %.
Above-mentioned to add refining slag in the ladle be with respect to the molten steel after 1 ton of described smelting, adds the refining slag of 4-6 kilogram in tapping process in the ladle.Gross weight with described refining slag is benchmark, and described refining slag contains the active lime powder of 60-80 weight % and the fluorite of 20-40 weight %.Gross weight with described active lime powder is benchmark, and the CaO content in the described active lime powder is 85-90 weight %.
The smelting process of vanadium-bearing hot metal of the present invention can also comprise, the molten steel that adds behind low-phosphorous low sulfur metal, low-phosphorous low-sulfur alloy and the carburelant is made the white slag reduction at the LF refining furnace, obtain P content smaller or equal to 0.005 weight %, the S content ultralow phosphorus ultralow-sulfur steel smaller or equal to 0.005 weight %.The described method of making the white slag reduction is included in the LF refining furnace and adds aluminum shot, with respect to the molten steel behind 1 ton of adding low-phosphorous low sulfur metal, low-phosphorous low-sulfur alloy and carburelant, add 0.6-0.8 kilogram aluminum shot, and the gross weight percentage composition of the FeO in the ladle slag and MnO is controlled in 2.0 weight %.In the smelting process of vanadium-bearing hot metal of the present invention, when making the white slag reduction, also carry out the fine setting of LF refining furnace heat temperature raising and molten steel composition.
The smelting process of vanadium-bearing hot metal of the present invention can also comprise casts the LF molten steel after refining, and described casting is carried out according to ordinary method.
In order to understand the present invention better, further specify below in conjunction with the present invention of embodiment.
Embodiment 1
What present embodiment was smelted is the high-level low-phosphorous sulphur pipe line steel of 27CrMoV.
(1) be that raw material carries out the dark desulfurization of composite blowing with the vanadium-bearing hot metal, its winding-up time is 18.33 minutes, with respect to 1 ton of vanadium-bearing hot metal, use 3.53 kilograms passive lime powder (content of CaO is 93.2 weight %), 0.91 the deactivating magnesium powder (metal M g content is 93.4 weight %) of kilogram, the molten iron after the acquisition desulfurization.In vanadium-bearing hot metal, the content of C by weight percentage, V, Mn, S, P, Si, Ti, Fe is as shown in table 1.In the molten iron after the gained desulfurization, the content of C by weight percentage, V, Mn, S, P, Si, Ti, Fe is as shown in table 2.
(2) molten iron after the desulfurization of adding 140t in climbing the converter of steel 120t blowing vanadium extracting, the sodium salt (NaCO that contains 86.8 weight % of adding 1.5t
3), and to adopt 339 oxygen rifles to carry out oxygen supply and blow vanadium and pre-dephosphorization, in the beginning oxygen supply 0-3 minute adds 1.4t iron scale (Fe in stove
2O
3Content be that the content of 30.4 weight %, FeO is 62.7 weight %), after 4.8 minutes of the beginning oxygen supply, add in the stove after 250 kilograms of magnesia (content of MgO is 77.3 weight %) carry out residue adjustment, the pushing off the slag tapping was carried out in oxygen supply in 38 seconds again, obtain molten iron and vanadium slag after the desulfurization vanadium extraction, the blow end point temperature is 1423 ℃.In the molten iron after gained desulfurization vanadium extraction, the content of C by weight percentage, V, Mn, S, P, Si, Ti and Fe is as shown in table 3.In vanadium slag, CaO by weight percentage, Na
2O, V
2O
5, SiO
2, MgO, TFe, P and S content as shown in table 4.With respect to the molten iron after 1 ton of desulfurization, blowing oxygen quantity is 10.1Nm
3
(3) climbing blow again molten iron after the desulfurization vanadium extraction that adds 140t in the steel converter of steel 120t, and adopting 536 oxygen rifles to carry out the oxygen supply first time, with respect to the molten iron after 1 ton of desulfurization vanadium extraction, blowing oxygen quantity is 22Nm
3In the beginning oxygen supply, with respect to the molten iron after 1 ton of desulfurization vanadium extraction, the active lime powder, 18 kilograms composite slag, 18 kilograms high magnesium lime and 3.0 kilograms the sludge ball of steel smelting that add 29.5 kilograms continuously, and add in 5 minutes in the beginning oxygen supply, oxygen supply time stops oxygen supply and promotes the oxygen rifle in the time of 460 seconds, and stove is got rid of slag.Behind the 50 weight % of slag eliminating total amount converter is returned zero-bit and carry out the oxygen supply second time, with respect to the molten iron after 1 ton of desulfurization vanadium extraction, blowing oxygen quantity is 26Nm
3In the beginning oxygen supply, with respect to the molten iron after 1 ton of desulfurization vanadium extraction, the active lime powder, 5 kilograms composite slag and 5 kilograms the high magnesium lime that add 18 kilograms continuously, and add in 6.5 minutes beginning for the second time oxygen supply, oxygen supply time stops oxygen supply and promotes the oxygen rifle in the time of 525 seconds, the acquisition temperature is 1626 ℃ low-phosphorous low-sulfur molten steel, and in the low-phosphorous low-sulfur molten steel of gained, the content of C by weight percentage, Mn, P and S is as shown in table 5; Then with respect to 1 ton of low-phosphorous low-sulfur molten steel, stirring 2.5 minutes is blown in the high magnesium lime utilization that adds 3.0 kilograms again, again with respect to 1 ton of low-phosphorous low-sulfur molten steel, (content of active lime powder is 60.8 weight % to add 6 kilograms refining slag in ladle, the content of fluorite is 39.2 weight %), carry out the pushing off the slag tapping, during tapping, molten steel is tapped speed control in 400 Kilograms Per Seconds, make under the converter tapping quantity of slag with respect to 1 ton of tapping molten steel smaller or equal to 6 kilograms; In tapping process, add manganese metal (P＜0.04 weight %, S＜0.05 weight %, Mn content is 97.0 weight %), ferro-silicon (P＜0.03 weight %, P＜0.06 weight %, Si content are 75.3 weight %, and Fe content is 24.61 weight %) and pitch coke (C content is 76 weight %), in the molten steel after adding low-phosphorous low sulfur metal, low-phosphorous low-sulfur alloy and carburelant, the content of C by weight percentage, Si, Mn, P and S is as shown in table 6.
(4) molten steel that will add behind low-phosphorous low sulfur metal, low-phosphorous low-sulfur alloy and the carburelant is handled by the electrically heated of LF stove and trimming, when handling, add aluminum shot in the ladle and make the white slag reduction, with respect to the molten steel behind 1 ton of adding low-phosphorous low sulfur metal, low-phosphorous low-sulfur alloy and carburelant, the aluminum shot add-on is 0.8 kilogram, making the white slag recovery time is 36.8 minutes, obtains ultralow phosphorus super low sulfur molten steel.FeO is 1.16 weight % in the ladle slag of LF stove processing back, and MnO is 0.39 weight % in the ladle slag of processing back.In ultralow phosphorus super low sulfur molten steel, the content of C by weight percentage, Si, Mn, P and S is as shown in table 8.
(5) this molten steel is namely obtained ultralow phosphorus low-sulfur strand product by continuous casting protection casting.
In the present embodiment, by weight percentage, the CaO content in the active lime powder, the MgO content in the high magnesium lime and CaO content, the SiO in the composite slag
2Content, MnO content, TFe content, the ferriferous oxide content in the sludge ball of steel smelting, CaO content, SiO
2Content, MgO content are as shown in table 7.
Embodiment 2
What present embodiment was smelted is the low-phosphorous sulphur pipe line steel of 27CrMoNbV.
(1) be that raw material carries out the dark desulfurization of composite blowing with the vanadium-bearing hot metal, its winding-up time is 34.6 minutes, with respect to 1 ton of vanadium-bearing hot metal, use 5.2 kilograms passive lime powder (content of CaO is 93.2 weight %), 1.11 the deactivating magnesium powder (metal M g content is 93.4 weight %) of kilogram, the molten iron after the acquisition desulfurization.In vanadium-bearing hot metal, the content of C by weight percentage, V, Mn, S, P, Si, Ti, Fe is as shown in table 1.In the molten iron after the gained desulfurization, the content of C by weight percentage, V, Mn, S, P, Si, Ti, Fe is as shown in table 2.
(2) molten iron after the desulfurization of adding 140t in climbing the converter of steel 120t blowing vanadium extracting, the sodium salt (NaCO that contains 86.8 weight % of adding 3.2t
3), and to adopt 339 oxygen rifles to carry out oxygen supply and blow vanadium and dephosphorization, in the beginning oxygen supply 1-3 minute adds 500 kilograms of iron scale (Fe in stove
2O
3Content be that the content of 30.4 weight %, FeO is 62.7 weight %), after 5.5 minutes of the beginning oxygen supply, add in the stove after 250 kilograms of magnesia (content of MgO is 77.3 weight %) carry out residue adjustment, the pushing off the slag tapping was carried out in oxygen supply in 30 seconds again, obtain molten iron and vanadium slag after the desulfurization vanadium extraction, the blow end point temperature is 1386 ℃.In the molten iron after gained desulfurization vanadium extraction, the content of C by weight percentage, V, Mn, S, P, Si, Ti and Fe is as shown in table 3.In vanadium slag, CaO by weight percentage, Na
2O, V
2O
5, SiO
2, MgO, TFe, P and S content as shown in table 4.With respect to the molten iron after 1 ton of desulfurization, blowing oxygen quantity is 11.4Nm
3
(3) climbing blow again molten iron after the desulfurization vanadium extraction that adds 140t in the steel converter of steel 120t, and adopting 536 oxygen rifles to carry out the oxygen supply first time, with respect to the molten iron after 1 ton of desulfurization vanadium extraction, blowing oxygen quantity is 24.3Nm
3In the oxygen blown while of beginning, with respect to the molten iron after 1 ton of desulfurization vanadium extraction, add 25 kilograms active lime powder, 14 kilograms composite slag, 14 kilograms high magnesium lime and 5 kilograms sludge ball of steel smelting continuously, and blow oxygen supply and add in 5 minutes opening; Oxygen supply time stops oxygen supply and promotes the oxygen rifle in the time of 370 seconds, and stove is got rid of slag.Behind the 70 weight % of slag eliminating total amount converter is returned zero-bit and carry out the oxygen supply second time, with respect to the molten iron after 1 ton of desulfurization vanadium extraction, blowing oxygen quantity is 26.5Nm
3In the beginning oxygen supply, with respect to the molten iron after 1 ton of desulfurization vanadium extraction, adds 25 kilograms active lime powder, 8 kilograms composite slag and 10 kilograms high magnesium lime, and begin oxygen supply in the second time and add in 6.5 minutes; Oxygen supply time stops oxygen supply and promotes the oxygen rifle in the time of 435 seconds, the acquisition temperature is 1638 ℃ low-phosphorous low-sulfur molten steel, and in the low-phosphorous low-sulfur molten steel of gained, the content of C by weight percentage, Mn, P and S is as shown in table 5; Then with respect to 1 ton of low-phosphorous low-sulfur molten steel, add 5.0 kilograms high magnesium lime utilization and blow again and stirred 2.5 minutes, again with respect to 1 ton of low-phosphorous low-sulfur molten steel, (content of active lime powder is 69.8 weight %, fluorite (CaF to add 4.0 kilograms refining slag
2) content be 30.2 weight %), carry out pushing off the slag tapping, during tapping, molten steel is tapped speed control in 400 Kilograms Per Seconds, make under the converter tapping quantity of slag with respect to 1 ton of tapping molten steel less than 6 kilograms; In tapping process, add manganese metal (P＜0.04 weight %, S＜0.05 weight %, Mn content is 97.0 weight %), ferro-silicon (P＜0.03 weight %, P＜0.06 weight %, Si content are 75.2 weight %, and Fe content is 24.71 weight %) and pitch coke (C content is 76 weight %), in the molten steel after adding low-phosphorous low sulfur metal, low-phosphorous low-sulfur alloy and carburelant, the content of C by weight percentage, Si, Mn, P and S is as shown in table 6.
(4) molten steel that will add behind low-phosphorous low sulfur metal, low-phosphorous low-sulfur alloy and the carburelant is handled by the electrically heated of LF stove and trimming, when handling, add aluminum shot in the ladle and make the white slag reduction, with respect to the molten steel behind 1 ton of adding low-phosphorous low sulfur metal, low-phosphorous low-sulfur alloy and carburelant, the aluminum shot add-on is 0.6 kilogram, making the white slag recovery time is 28.4 minutes, obtains ultralow phosphorus super low sulfur molten steel.The LF stove is handled FeO 1.03 weight % in the ladle slag of back, and MnO is 0.24 weight % in the ladle slag of processing back.In ultralow phosphorus super low sulfur molten steel, the content of C by weight percentage, Si, Mn, P and S is as shown in table 8.
(5) this molten steel is namely obtained ultralow phosphorus low-sulfur strand product by continuous casting protection casting.
In the present embodiment, by weight percentage, the SiO in the CaO content in the active lime powder, the MgO content in the high magnesium lime and CaO content, the composite slag
2Content, MnO content, TFe content, the ferriferous oxide content in the sludge ball of steel smelting, CaO content, SiO
2Content, MgO content are as shown in table 7.
Embodiment 3
What present embodiment was smelted is the P72LX cord steel.
(1) be that raw material carries out the dark desulfurization of composite blowing with the vanadium-bearing hot metal, its winding-up time is 24.2 minutes, with respect to 1 ton of vanadium-bearing hot metal, use 4.7 kilograms passive lime powder (content of CaO is 93.2 weight %), 1.03 the deactivating magnesium powder (metal M g content is 93.4 weight %) of kilogram, the molten iron after the acquisition desulfurization.In vanadium-bearing hot metal, the content of C by weight percentage, V, Mn, S, P, Si, Ti, Fe is as shown in table 1.In the molten iron after the gained desulfurization, the content of C by weight percentage, V, Mn, S, P, Si, Ti, Fe is as shown in table 2.
(2) molten iron after the desulfurization of adding 140t in climbing the converter of steel 120t blowing vanadium extracting, the sodium salt (NaCO that contains 86.8 weight % of adding 2.8t
3), and to adopt 339 oxygen rifles to carry out oxygen supply and blow vanadium and dephosphorization, in the beginning oxygen supply 1-3 minute adds 1t iron scale (Fe in stove
2O
3Content be that the content of 30.4 weight %, FeO is 62.7 weight %), after 5.2 minutes of the beginning oxygen supply, add in the stove after 250 kilograms of magnesia (content of MgO is 77.3 weight %) carry out residue adjustment, the pushing off the slag tapping was carried out in oxygen supply in 40 seconds again, obtain molten iron and vanadium slag after the desulfurization vanadium extraction, the blow end point temperature is 1401 ℃.In the molten iron after gained desulfurization vanadium extraction, the content of C by weight percentage, V, Mn, S, P, Si, Ti and Fe is as shown in table 3.In vanadium slag, CaO by weight percentage, Na
2O, V
2O
5, SiO
2, MgO, TFe, P and S content as shown in table 4.With respect to the molten iron after 1 ton of desulfurization, blowing oxygen quantity is 11Nm
3
(3) climbing blow again molten iron after the desulfurization vanadium extraction that adds 140t in the steel converter of steel 120t, and adopting 536 oxygen rifles to carry out the oxygen supply first time, with respect to the molten iron after 1 ton of desulfurization vanadium extraction, blowing oxygen quantity is 21.6Nm
3In the oxygen blown while of beginning, with respect to the molten iron after 1 ton of desulfurization vanadium extraction, add 28 kilograms active lime powder, 15 kilograms composite slag, 16 kilograms high magnesium lime and 5 kilograms sludge ball of steel smelting, and blow oxygen supply and add in 5 minutes opening; Oxygen supply time stops oxygen supply and promotes the oxygen rifle in the time of 430 seconds, and stove is got rid of slag.Behind the 60 weight % of slag eliminating total amount converter is returned zero-bit and carry out the oxygen supply second time, with respect to the molten iron after 1 ton of desulfurization vanadium extraction, blowing oxygen quantity is 28.4Nm
3When beginning oxygen supply for the second time, with respect to the molten iron after 1 ton of desulfurization vanadium extraction, add 20 kilograms active lime powder, 6 kilograms composite slag and 8 kilograms high magnesium lime, and add in 6.5 minutes beginning for the second time oxygen supply, oxygen supply time stops oxygen supply and promotes the oxygen rifle in the time of 445 seconds, the acquisition temperature is 1644 ℃ the low-phosphorous low-sulfur molten steel of molten steel, and in the low-phosphorous low-sulfur molten steel of gained, the content of C by weight percentage, Mn, P and S is as shown in table 5; Then with respect to 1 ton of low-phosphorous low-sulfur molten steel, stirring 2.5 minutes is blown in the high magnesium lime utilization that adds 5.0 kilograms again, again with respect to 1 ton of low-phosphorous low-sulfur molten steel, (content of active lime powder is 78.8 weight % to add 5.0 kilograms refining slag, the content of fluorite is 21.2 weight %), carry out the pushing off the slag tapping, during tapping, molten steel is tapped speed control in 400 Kilograms Per Seconds, make under the converter tapping quantity of slag with respect to 1 ton of tapping molten steel smaller or equal to 6 kilograms; In tapping process, add manganese metal (P＜0.04 weight %, S＜0.05 weight %, Mn content is 97.0 weight %), ferro-silicon (P＜0.03 weight %, P＜0.06 weight %, Si content are 75.15 weight %, and Fe content is 24.76 weight %) and pitch coke (C content is 76 weight %), in the molten steel after adding low-phosphorous low sulfur metal, low-phosphorous low-sulfur alloy and carburelant, the content of C by weight percentage, Si, Mn, P and S is as shown in table 6.
(4) molten steel that will add behind low-phosphorous low sulfur metal, low-phosphorous low-sulfur alloy and the carburelant is handled by the electrically heated of LF stove and trimming, when handling, add aluminum shot in the ladle and make the white slag reduction, with respect to the molten steel behind 1 ton of adding low-phosphorous low sulfur metal, low-phosphorous low-sulfur alloy and carburelant, the aluminum shot add-on is 0.7 kilogram, making the white slag recovery time is 31.2 minutes, obtains ultralow phosphorus super low sulfur molten steel.FeO is 1.26 weight % in the ladle slag of LF stove processing back, and MnO is 0.52 weight % in the ladle slag of processing back.In ultralow phosphorus super low sulfur molten steel, the content of C by weight percentage, Si, Mn, P and S is as shown in table 8.
(5) this molten steel is namely obtained ultralow phosphorus low-sulfur strand product by continuous casting protection casting.
In the present embodiment, by weight percentage, the SiO in the CaO content in the active lime powder, the MgO content in the high magnesium lime and CaO content, the composite slag
2Content, MnO content, TFe content, the ferriferous oxide content in the sludge ball of steel smelting, CaO content, SiO
2Content, MgO content are as shown in table 7.
Table 1
| C | V | Mn | S | P | Si | Ti | Fe | |
| Embodiment 1 | 4.39 | 0.299 | 0.20 | 0.061 | 0.067 | 0.18 | 0.16 | Surplus is Fe |
| Embodiment 2 | 4.56 | 0.301 | 0.25 | 0.098 | 0.079 | 0.23 | 0.32 | Surplus is Fe |
| Embodiment 3 | 4.52 | 0.288 | 0.22 | 0.071 | 0.071 | 0.17 | 0.23 | Surplus is Fe |
Table 2
| C | V | Mn | S | P | Si | Ti | Fe | |
| Embodiment 1 | 4.37 | 0.292 | 0.22 | 0.0042 | 0.067 | 0.16 | 0.17 | Surplus is Fe |
| Embodiment 2 | 4.48 | 0.298 | 0.27 | 0.0027 | 0.078 | 0.20 | 0.307 | Surplus is Fe |
| Embodiment 3 | 4.44 | 0.284 | 0.23 | 0.0035 | 0.072 | 0.15 | 0.21 | Surplus is Fe |
Table 3
| C | V | Mn | S | P | Si | Ti | Fe | |
| Embodiment 1 | 3.83 | 0.036 | 0.04 | 0.0041 | 0.038 | Trace | Trace | Surplus is Fe |
| Embodiment 2 | 3.96 | 0.032 | 0.04 | 0.0028 | 0.021 | Trace | Trace | Surplus is Fe |
| Embodiment 3 | 3.74 | 0.041 | 0.05 | 0.0033 | 0.034 | Trace | Trace | Surplus is Fe |
Table 4
| CaO | NaO | V 2O 5 | SiO 2 | MgO | TFe | P | S | |
| Embodiment 1 | 2.85 | 14.23 | 15.42 | 14.27 | 6.01 | 27.41 | 0.91 | 0.167 |
| Embodiment 2 | 1.93 | 27.64 | 16.21 | 15.14 | 5.18 | 26.73 | 1.29 | 0.132 |
| Embodiment 3 | 2.16 | 21.43 | 15.84 | 12.28 | 5.87 | 26.94 | 1.14 | 0.11 |
Table 5
| C | Mn | P | S | |
| Embodiment 1 | 0.041 | 0.033 | 0.0021 | 0.0071 |
| Embodiment 2 | 0.056 | 0.038 | 0.0027 | 0.0052 |
| Embodiment 3 | 0.051 | 0.041 | 0.0029 | 0.0061 |
Table 6
| C | Si | Mn | P | S | |
| Embodiment 1 | 0.25 | 0.27 | 0.41 | 0.0033 | 0.0077 |
| Embodiment 2 | 0.27 | 0.29 | 0.42 | 0.0039 | 0.0056 |
| Embodiment 3 | 0.71 | 0.23 | 0.49 | 0.0041 | 0.0073 |
Table 7
Table 8
| C | Si | Mn | P | S | |
| Embodiment 1 | 0.27 | 0.31 | 0.42 | 0.0038 | 0.0031 |
| Embodiment 2 | 0.28 | 0.30 | 0.41 | 0.0044 | 0.0023 |
| Embodiment 3 | 0.72 | 0.25 | 0.52 | 0.0047 | 0.0042 |
As can be known from the results of Table 8, can in the converter steelmaking industrial production, obtain the ultralow phosphorus low-sulfur steel that P content and S content all are lower than 0.005 weight % by smelting process of the present invention.
Claims (16)
1. the smelting process of a vanadium-bearing hot metal, this method may further comprise the steps: vanadium-bearing hot metal is carried out desulfurization, molten iron after the desulfurization is carried out vanadium extraction, molten iron after the desulfurization vanadium extraction is smelted in accordance with the following methods: in converter, add first slag former in the molten iron under the oxygen blast condition after the desulfurization and carry out the slag making of blowing the first time, after the 50-70 weight % of slag total amount got rid of, under the oxygen blast condition, add second slag former in the converter again and carry out the slag making of blowing the second time
Wherein, described first slag former is lime powder, high magnesium lime, composite slag and steel-smelting sewage sludge, and described second slag former is lime powder, high magnesium lime and composite slag;
The condition of slag making of blowing the described first time is: with respect to the molten iron after 1 ton of described desulfurization, the add-on of active lime powder is that the add-on of 25-30 kilogram, high magnesium lime is that the add-on of 14-18 kilogram, composite slag is that the add-on of 14-18 kilogram, steel-smelting sewage sludge is the 3-5 kilogram, oxygen blow duration is 360-480 second, with respect to the molten iron after 1 ton of described desulfurization, blowing oxygen quantity is 20-25Nm
3
The condition of slag making of blowing the described second time is: with respect to the molten iron after 1 ton of described desulfurization, the add-on of active lime powder is that the add-on of 18-25 kilogram, high magnesium lime is that the add-on of 5-10 kilogram, composite slag is the 5-8 kilogram, oxygen blow duration is 420-540 second, with respect to the molten iron after 1 ton of described desulfurization, blowing oxygen quantity is 25-30Nm
3
2. method according to claim 1 wherein, is benchmark with the gross weight of described active lime powder, and the CaO content in the described active lime powder is 85-90 weight %; Gross weight with described high magnesium lime is benchmark, and the MgO content in the described high magnesium lime is 30-40 weight %, and the CaO content in the described high magnesium lime is 48-55 weight %; Contain SiO in the described composite slag
2, MnO and TFe, be benchmark with the gross weight of described composite slag, the SiO in the composite slag
2Content is 45-55 weight %, and MnO content is 5-10 weight %, and TFe content is 15-20 weight %.
3. the smelting process of vanadium-bearing hot metal according to claim 1, wherein, the described method that vanadium-bearing hot metal is carried out desulfurization comprises: vanadium-bearing hot metal is contacted with sweetening agent carry out composite blowing, the condition of composite blowing makes S content≤0.005 weight % in the molten iron after the desulfurization.
4. the smelting process of vanadium-bearing hot metal according to claim 3, wherein, described sweetening agent is passive lime powder and deactivating magnesium powder, the condition of described composite blowing is: with respect to 1 ton of described vanadium-bearing hot metal, the consumption of described passive lime powder is the 3.5-5.5 kilogram, the consumption of described deactivating magnesium powder is the 0.9-1.2 kilogram, and the time of described composite blowing is 18-35 minute; Total amount with described passive lime powder is benchmark, and the CaO content in the described passive lime powder is 89-95 weight %; Total amount with described deactivating magnesium powder is benchmark, and the Mg content in the described deactivating magnesium powder is greater than 93 weight %.
5. according to the smelting process of claim 1 or 4 described vanadium-bearing hot metals, wherein, total amount with described vanadium-bearing hot metal is benchmark, and the C content of described vanadium-bearing hot metal is that 4.0-4.6 weight %, V content are that 0.20-0.35 weight %, Mn content are that 0.20-0.30 weight %, S content are that 0.055-0.100 weight %, P content are that 0.060-0.080 weight %, Si content are that 0.10-0.30 weight %, Ti content are that 0.10-0.35 weight %, Fe content are more than the 94 weight %.
6. the smelting process of vanadium-bearing hot metal according to claim 1, wherein, the described method that molten iron after the desulfurization is carried out vanadium extraction comprises: in converter, with the molten iron after the desulfurization with after dephosphorizing agent mixes, carry out oxygen supply and blow vanadium and pre-dephosphorization, in beginning 3 minutes of oxygen supply, add refrigerant, 4.5-6 minute of beginning oxygen supply, add slag supplying agent, obtain molten iron and vanadium slag after the desulfurization vanadium extraction, in the molten iron after described desulfurization vanadium extraction, C content is 3.6-4.0 weight %, S content is≤0.005 weight %, P content is≤0.040 weight %, and with respect to the molten iron after 1 ton of described desulfurization, blowing oxygen quantity is 9-13Nm
3
7. the smelting process of vanadium-bearing hot metal according to claim 6, wherein, with respect to the molten iron after 1 ton of described desulfurization, the consumption of described dephosphorizing agent is the 10-25 kilogram, and the consumption of described refrigerant is the 3-10 kilogram, and the consumption of described slag supplying agent is the 1-3 kilogram.
8. according to the smelting process of claim 6 or 7 described vanadium-bearing hot metals, wherein, described dephosphorizing agent is the sodium salt dephosphorizing agent, and described refrigerant is iron scale and/or cooled agglomerated pellet, and described slag supplying agent is carbonaceous material and/or magnesian.
9. the smelting process of vanadium-bearing hot metal according to claim 8, wherein, described sodium salt is yellow soda ash.
10. the smelting process of vanadium-bearing hot metal according to claim 1, wherein, the smelting process of described vanadium-bearing hot metal also comprises, after the slag making of blowing for the second time, molten steel after smelting is carried out the pushing off the slag tapping, and in tapping process, in molten steel, add low-phosphorous low sulfur metal, low-phosphorous low-sulfur alloy and carburelant, make molten steel phosphorization total amount in 0.001 weight %.
11. the smelting process of vanadium-bearing hot metal according to claim 10, wherein, described carburelant is to be selected from pitch coke, hard coal and the carbon dust one or more, described low-phosphorous low sulfur metal is manganese metal, P content in the described manganese metal is＜0.04 weight %, S content is＜0.05 weight %, Mn content 〉=97.0 weight %; Described low-phosphorous low-sulfur alloy is ferro-silicon, and the P content in the described ferro-silicon is＜0.03 weight %, and S content is＜0.06 weight %, and Si content is 75-80 weight %, and Fe content is 20-25 weight %.
12. the smelting process of vanadium-bearing hot metal according to claim 10, wherein, the smelting process of described vanadium-bearing hot metal also comprises, before molten steel after described will the smelting carries out the pushing off the slag tapping, with respect to the molten steel after 1 ton of described smelting, the high magnesium lime that adds the 3-5 kilogram in the molten steel after the described smelting, the molten steel that has added high magnesium lime is tapped in the ladle, the refining slag that in described tapping process, adds the 4-6 kilogram in the ladle, and make tapping speed in 400 Kilograms Per Seconds, the quantity of slag smaller or equal to 6 kilograms, makes ladle slag rephosphorization total amount with respect to 1 ton of tapping molten steel in 0.001 weight % under the converter tapping.
13. the smelting process of vanadium-bearing hot metal according to claim 12 wherein, is benchmark with the gross weight of described high magnesium lime, the MgO content in the described high magnesium lime is 30-40 weight %, and the CaO content in the described high magnesium lime is 48-55 weight %.
14. the smelting process of vanadium-bearing hot metal according to claim 12 wherein, is benchmark with the gross weight of described refining slag, described refining slag contains the active lime powder of 60-80 weight % and the fluorite of 20-40 weight %; Gross weight with described active lime powder is benchmark, and the CaO content in the described active lime powder is 85-90 weight %.
15. the smelting process of vanadium-bearing hot metal according to claim 10, wherein, the smelting process of described vanadium-bearing hot metal also comprises, the molten steel that adds behind low-phosphorous low sulfur metal, low-phosphorous low-sulfur alloy and the carburelant is made the white slag reduction at the LF refining furnace, obtain P content smaller or equal to 0.005 weight %, the S content ultralow phosphorus ultralow-sulfur steel smaller or equal to 0.005 weight %.
16. the smelting process of vanadium-bearing hot metal according to claim 15, wherein, the described method of making the white slag reduction is included in the LF refining furnace and adds aluminum shot, with respect to the molten steel behind 1 ton of adding low-phosphorous low sulfur metal, low-phosphorous low-sulfur alloy and carburelant, add 0.6-0.8 kilogram aluminum shot, and the gross weight percentage composition of the FeO in the ladle slag and MnO is controlled in 2.0 weight %.
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| CN103540703B (en) * | 2012-07-11 | 2016-01-20 | 攀钢集团研究院有限公司 | The method of a kind of converter Dephosphorization vanadium extraction |
| CN103540704B (en) * | 2012-07-11 | 2015-03-04 | 攀钢集团研究院有限公司 | Method for extracting vanadium by using converter |
| CN102912069B (en) * | 2012-10-31 | 2014-10-01 | 攀钢集团研究院有限公司 | Low-cost slag splashing protection method of vanadium extraction converter |
| CN103014224B (en) * | 2012-12-11 | 2014-12-17 | 攀钢集团攀枝花钢铁研究院有限公司 | Splashed slag furnace protection method for vanadium extraction converter |
| CN103320566B (en) * | 2013-06-26 | 2015-09-09 | 攀钢集团攀枝花钢铁研究院有限公司 | Double slag process smelts the method for half steel |
| CN103409595B (en) * | 2013-07-24 | 2015-02-18 | 攀钢集团攀枝花钢铁研究院有限公司 | Dephosphorization and steel-making method of vanadium-containing molten iron |
| CN103966424B (en) * | 2014-05-23 | 2016-01-20 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of method of blank vanadium slag sintering vanadium extraction |
| CN106216645B (en) * | 2016-08-30 | 2018-12-28 | 成都工业学院 | The method of ferrocolumbium casting dealuminzation |
| CN107557534A (en) * | 2017-10-31 | 2018-01-09 | 攀钢集团攀枝花钢铁研究院有限公司 | The production method of extremely low phosphoretic steel |
| CN107723415B (en) * | 2017-10-31 | 2019-05-10 | 攀钢集团攀枝花钢铁研究院有限公司 | The production method of the ultralow phosphorus ultra-low-carbon steel of super-low sulfur |
| CN107746907B (en) * | 2017-10-31 | 2019-11-08 | 攀钢集团攀枝花钢铁研究院有限公司 | The production method of clean steel |
| CN108285946B (en) * | 2018-03-15 | 2020-02-11 | 成渝钒钛科技有限公司 | Vanadium extraction method by using vanadium-containing pig iron and steel-making process by using vanadium-containing pig iron |
| CN108486454B (en) * | 2018-03-30 | 2020-05-19 | 攀钢集团攀枝花钢钒有限公司 | Smelting method of ultra-low phosphorus steel |
| CN110055371A (en) * | 2019-05-14 | 2019-07-26 | 成都先进金属材料产业技术研究院有限公司 | The method that molten iron production vanadium slag containing sodium directly leaches vanadium extraction |
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| CN101691623A (en) * | 2009-11-02 | 2010-04-07 | 攀钢集团攀枝花钢铁研究院有限公司 | Process for smelting vanadium-containing molten iron converter |
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| CN101691623A (en) * | 2009-11-02 | 2010-04-07 | 攀钢集团攀枝花钢铁研究院有限公司 | Process for smelting vanadium-containing molten iron converter |
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