CN116875769A - Barium calcium aluminate desulfurizer and its preparation method and steel preparation method - Google Patents
Barium calcium aluminate desulfurizer and its preparation method and steel preparation method Download PDFInfo
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- FQNGWRSKYZLJDK-UHFFFAOYSA-N [Ca].[Ba] Chemical compound [Ca].[Ba] FQNGWRSKYZLJDK-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 52
- 239000010959 steel Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 78
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 71
- 230000023556 desulfurization Effects 0.000 claims abstract description 71
- 238000002844 melting Methods 0.000 claims abstract description 41
- 230000008018 melting Effects 0.000 claims abstract description 41
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 88
- 239000000203 mixture Substances 0.000 claims description 72
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 68
- 239000000843 powder Substances 0.000 claims description 56
- 239000002245 particle Substances 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 37
- 239000000292 calcium oxide Substances 0.000 claims description 34
- 235000012255 calcium oxide Nutrition 0.000 claims description 34
- 229910052717 sulfur Inorganic materials 0.000 claims description 30
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 29
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 29
- 239000011593 sulfur Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 24
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- 229910052788 barium Inorganic materials 0.000 claims description 17
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 17
- 239000011575 calcium Substances 0.000 claims description 17
- 229910052791 calcium Inorganic materials 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 230000003009 desulfurizing effect Effects 0.000 claims description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 235000019738 Limestone Nutrition 0.000 claims description 6
- 239000006028 limestone Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 5
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 238000004904 shortening Methods 0.000 abstract description 3
- 239000012071 phase Substances 0.000 description 122
- 230000000052 comparative effect Effects 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 239000012535 impurity Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 229910052814 silicon oxide Inorganic materials 0.000 description 9
- 229910010413 TiO 2 Inorganic materials 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 238000000227 grinding Methods 0.000 description 7
- 239000002893 slag Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910000976 Electrical steel Inorganic materials 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 229910004261 CaF 2 Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical group 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/064—Dephosphorising; Desulfurising
- C21C7/0645—Agents used for dephosphorising or desulfurising
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/10—Handling in a vacuum
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
Abstract
本发明涉及一种铝酸钡钙脱硫剂及其制备方法和钢材的制备方法。铝酸钡钙脱硫剂包括3CaO·Al2O3相、12CaO·7Al2O3相、2BaO·6CaO·4SiO2相和BaO·Al2O3相；在铝酸钡钙脱硫剂中，3CaO·Al2O3相、12CaO·7Al2O3相、2BaO·6CaO·4SiO2相和BaO·Al2O3相的总质量占比≥50％。该铝酸钡钙脱硫剂能够显著降低铝酸钡钙脱硫剂的熔点，加快了脱硫剂的熔化速度，使其能够尽快完全液化而与钢水充分反应，从而提升了脱硫效率，缩短了脱硫时间，并在使用量相同的条件下获得更高的脱硫率。The invention relates to a barium calcium aluminate desulfurizer, a preparation method thereof and a preparation method of steel. Barium calcium aluminate desulfurizer includes 3CaO·Al 2 O 3 phase, 12CaO·7Al 2 O 3 phase, 2BaO·6CaO·4SiO 2 phase and BaO·Al 2 O 3 phase; in barium calcium aluminate desulfurizer, 3CaO· The total mass proportion of the Al 2 O 3 phase, 12CaO·7Al 2 O 3 phase, 2BaO·6CaO·4SiO 2 phase and BaO·Al 2 O 3 phase is ≥50%. The barium calcium aluminate desulfurizer can significantly reduce the melting point of the barium calcium aluminate desulfurizer, speed up the melting speed of the desulfurizer, and enable it to completely liquefy as quickly as possible and fully react with molten steel, thus improving the desulfurization efficiency and shortening the desulfurization time. And obtain higher desulfurization rate under the same usage amount.
Description
技术领域Technical field
本发明涉及炼钢的技术领域，特别是涉及一种铝酸钡钙脱硫剂及其制备方法和钢材的制备方法。The present invention relates to the technical field of steelmaking, and in particular to a barium calcium aluminate desulfurizer and a preparation method thereof and a preparation method of steel.
背景技术Background technique
硫是钢铁中的有害杂质，硫含量对硅钢产品的铁磁性影响较大，低硫硅钢的开发是提高硅钢产品的导磁性、降低铁损耗的重要方向。现代化的钢铁生产工艺流程主要由转炉-RH炉-连铸等工序组成，钢水的脱硫处理通常在RH炉精炼的中后期进行。然而，传统的RH炉用脱硫剂存在着使用量大、脱硫时间长和脱硫率低等问题，严重制约了硅钢产品的质量和产能。Sulfur is a harmful impurity in steel. The sulfur content has a great influence on the ferromagnetism of silicon steel products. The development of low-sulfur silicon steel is an important direction to improve the magnetic permeability of silicon steel products and reduce iron loss. The modern steel production process mainly consists of converter-RH furnace-continuous casting and other processes. The desulfurization treatment of molten steel is usually carried out in the middle and late stages of RH furnace refining. However, the traditional desulfurizer used in RH furnaces has problems such as large usage, long desulfurization time and low desulfurization rate, which seriously restricts the quality and production capacity of silicon steel products.
发明内容Contents of the invention
基于此，有必要提供一种铝酸钡钙脱硫剂及其制备方法和钢材的制备方法，以克服传统的RH炉用脱硫剂使用量大、脱硫时间长和脱硫率低等的问题。Based on this, it is necessary to provide a barium calcium aluminate desulfurizer and its preparation method and steel preparation method to overcome the problems of traditional RH furnace desulfurizer usage such as large usage, long desulfurization time and low desulfurization rate.
本发明的上述目的是通过如下技术方案进行实现的：The above objects of the present invention are achieved through the following technical solutions:
本发明第一方面，提供一种铝酸钡钙脱硫剂，包括3CaO·Al2O3相、12CaO·7Al2O3相、2BaO·6CaO·4SiO2相和BaO·Al2O3相；In a first aspect, the present invention provides a barium calcium aluminate desulfurizer, including a 3CaO·Al 2 O 3 phase, a 12CaO·7Al 2 O 3 phase, a 2BaO·6CaO·4SiO 2 phase and a BaO·Al 2 O 3 phase;
在所述铝酸钡钙脱硫剂中，所述3CaO·Al2O3相、所述12CaO·7Al2O3相、所述2BaO·6CaO·4SiO2相和所述BaO·Al2O3相的总质量占比≥50％。In the barium calcium aluminate desulfurizer, the 3CaO·Al 2 O 3 phase, the 12CaO·7Al 2 O 3 phase, the 2BaO·6CaO·4SiO 2 phase and the BaO·Al 2 O 3 phase The total mass proportion is ≥50%.
在其中一个实施例中，在所述铝酸钡钙脱硫剂中，所述2BaO·6CaO·4SiO2相和所述BaO·Al2O3相的总质量占比≥15％。In one embodiment, in the barium calcium aluminate desulfurizer, the total mass proportion of the 2BaO·6CaO·4SiO 2 phase and the BaO·Al 2 O 3 phase is ≥15%.
在其中一个实施例中，所述铝酸钡钙脱硫剂的熔点为1230℃～1300℃。In one embodiment, the melting point of the barium calcium aluminate desulfurizer is 1230°C to 1300°C.
在其中一个实施例中，所述铝酸钡钙脱硫剂满足以下条件中的一个或多个：In one embodiment, the barium calcium aluminate desulfurizer satisfies one or more of the following conditions:
1)粒径为3mm～50mm或≤1mm；1) The particle size is 3mm~50mm or ≤1mm;
2)于1450℃～1550℃下的对数硫容量为-2.4～-2.1；2) Logarithmic sulfur capacity at 1450℃～1550℃ is -2.4～-2.1;
3)包括如下质量占比的成分：CaO，40％～50％；BaO，8％～20％；Al2O3，30％～45％：SiO2，1％～8％。3) Including the following components by mass: CaO, 40% to 50%; BaO, 8% to 20%; Al 2 O 3 , 30% to 45%: SiO 2 , 1% to 8%.
本发明第二方面，提供一种上述所述的铝酸钡钙脱硫剂的制备方法，其包括以下步骤：In a second aspect, the present invention provides a method for preparing the above-mentioned barium calcium aluminate desulfurizer, which includes the following steps:
提供含有钙源、钡源、铝源和硅源的混合料；Providing mixtures containing calcium, barium, aluminum and silicon sources;
使所述混合料完全熔化，得液态混合料；The mixture is completely melted to obtain a liquid mixture;
通过梯度降温法使所述液态混合料冷却凝固，得铝酸钡钙脱硫剂。The liquid mixture is cooled and solidified through a gradient cooling method to obtain a barium calcium aluminate desulfurizer.
在其中一个实施例中，所述使所述混合料完全熔化包括以下步骤：In one embodiment, the complete melting of the mixture includes the following steps:
升温至1500℃～1550℃，并保温至少15min。Raise the temperature to 1500℃~1550℃ and keep it warm for at least 15 minutes.
在其中一个实施例中，所述使所述混合料完全熔化还包括气流搅拌的步骤。In one embodiment, the step of completely melting the mixture further includes the step of airflow stirring.
在其中一个实施例中，所述气流搅拌的气体为氮气和/或氩气。In one embodiment, the gas stirred by the gas flow is nitrogen and/or argon.
在其中一个实施例中，所述梯度降温法包括以下步骤：In one embodiment, the gradient cooling method includes the following steps:
使所述液态混合料在≥800℃的温度下保温≥24h；Keep the liquid mixture at a temperature of ≥800°C for ≥24h;
以≥150℃/h的降温速率，从800℃降温至500℃；Cool from 800℃ to 500℃ at a cooling rate of ≥150℃/h;
以≥80℃/h的降温速率，从500℃降温至300℃；Cool from 500℃ to 300℃ at a cooling rate of ≥80℃/h;
以≥40℃/h的降温速率，从500℃降温至室温。Cool down from 500℃ to room temperature at a cooling rate of ≥40℃/h.
在其中一个实施例中，满足以下条件中的一个或多个：In one embodiment, one or more of the following conditions are met:
1)所述钙源为生石灰粉和/或石灰石粉；1) The calcium source is quicklime powder and/or limestone powder;
2)所述钡源为氧化钡粉、氢氧化钡粉和碳酸钡粉中的一种或多种；2) The barium source is one or more of barium oxide powder, barium hydroxide powder and barium carbonate powder;
3)所述铝源为氧化铝粉；3) The aluminum source is alumina powder;
4)所述钙源、所述钡源和所述铝源的粒径各自独立地为50目～200目。4) The particle sizes of the calcium source, the barium source and the aluminum source are each independently 50 mesh to 200 mesh.
本发明第三方面，提供一种钢材的制备方法，其包括上述所述的铝酸钡钙脱硫剂对钢水进行脱硫处理的步骤。A third aspect of the present invention provides a method for preparing steel, which includes the step of desulfurizing molten steel using the barium calcium aluminate desulfurizer described above.
在其中一个实施例中，每吨钢水中，所述铝酸钡钙脱硫剂的加入量为3kg～15kg。In one embodiment, the amount of the barium calcium aluminate desulfurizer added per ton of molten steel is 3kg to 15kg.
本发明具有以下有益效果：The invention has the following beneficial effects:
本发明提供的铝酸钡钙脱硫剂中，2BaO·6CaO·4SiO2相和BaO·Al2O3相的熔点在1260℃～1290℃范围内，低于CaO-Al2O3体系的所有物相；3CaO·Al2O3相和12CaO·7Al2O3相可增强CaO的活度而促进脱硫。将3CaO·Al2O3相、12CaO·7Al2O3相、2BaO·6CaO·4SiO2相和BaO·Al2O3相的总质量占比控制在50％以上，可充分发挥出这四个物相之间的协同增强作用，显著降低铝酸钡钙脱硫剂的熔点，加快了脱硫剂的熔化速度，使其能够尽快完全液化而与钢水充分反应，从而提升了脱硫速率，缩短了脱硫时间。与CaO-Al2O3体系的脱硫剂相比，CaO-BaO-Al2O3体系的硫容量更高，可进一步增强铝酸钡钙脱硫剂的脱硫能力，从而使得该脱硫剂在使用量相同的条件下获得更高的脱硫率。In the barium calcium aluminate desulfurizer provided by the invention, the melting points of the 2BaO·6CaO·4SiO 2 phase and the BaO·Al 2 O 3 phase are in the range of 1260°C to 1290°C, which are lower than those of the CaO-Al 2 O 3 system. Phase; 3CaO·Al 2 O 3 phase and 12CaO·7Al 2 O 3 phase can enhance the activity of CaO and promote desulfurization. Controlling the total mass proportion of 3CaO·Al 2 O 3 phase, 12CaO·7Al 2 O 3 phase, 2BaO·6CaO·4SiO 2 phase and BaO·Al 2 O 3 phase to more than 50% can give full play to these four The synergistic enhancement effect between the phases significantly reduces the melting point of the barium calcium aluminate desulfurizer, speeds up the melting speed of the desulfurizer, and enables it to completely liquefy as quickly as possible and fully react with molten steel, thereby increasing the desulfurization rate and shortening the desulfurization time. . Compared with the desulfurizer of the CaO-Al 2 O 3 system, the CaO-BaO-Al 2 O 3 system has a higher sulfur capacity, which can further enhance the desulfurization ability of the calcium barium aluminate desulfurizer, thereby making the desulfurizer use less Obtain higher desulfurization rate under the same conditions.
具体实施方式Detailed ways
为使本发明的上述目的、特征和优点能够更加明显易懂，下面对本发明的具体实施方式做详细的说明。在下面的描述中阐述了很多具体细节以便于充分理解本发明。但是本发明能够以很多不同于在此描述的其它方式来实施，本领域技术人员可以在不违背本发明内涵的情况下做类似改进，因此本发明不受下面公开的具体实施例的限制。In order to make the above objects, features and advantages of the present invention more obvious and understandable, specific implementation modes of the present invention are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the invention. However, the present invention can be implemented in many other ways different from those described here. Those skilled in the art can make similar improvements without departing from the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.
此外，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括至少一个该特征。在本发明的描述中，“多个”的含义是至少两个，例如两个，三个等，除非另有明确具体的限定。In addition, the terms “first” and “second” are used for descriptive purposes only and cannot be understood as indicating or implying relative importance or implicitly indicating the quantity of indicated technical features. Therefore, features defined as "first" and "second" may explicitly or implicitly include at least one of these features. In the description of the present invention, "plurality" means at least two, such as two, three, etc., unless otherwise expressly and specifically limited.
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field to which the invention belongs. The terminology used herein in the description of the invention is for the purpose of describing specific embodiments only and is not intended to limit the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
术语及定义：Terms and definitions:
本发明中，粒径是指颗粒的大小，又称为粒度。具体地说，球形颗粒的粒径即为所测颗粒的直径，非球形颗粒的粒径通常用等效粒径来表示，即用一个与所测颗粒具有相同体积或相同投影面积的同质球形颗粒的粒径作为所测颗粒的粒径。In the present invention, particle size refers to the size of particles, also known as particle size. Specifically, the particle diameter of spherical particles is the diameter of the measured particle. The particle diameter of non-spherical particles is usually expressed by the equivalent particle diameter, that is, a homogeneous sphere with the same volume or the same projected area as the measured particle. The particle size of the particles is used as the particle size of the measured particles.
本发明中，硫容量(Sulfur Capacity,Cs)是冶金工艺过程中衡量脱硫剂的脱硫能力的重要指标，可以用FactSage等热力学软件计算得到，也可以通过实验方法测得。对数硫容量(lgCs)是将硫容量换算为10的对数，对数硫容量越大，脱硫剂的脱硫能力越强。In the present invention, sulfur capacity (Sulfur Capacity, Cs) is an important index to measure the desulfurization ability of the desulfurizer in the metallurgical process. It can be calculated using thermodynamic software such as FactSage or measured through experimental methods. Logarithmic sulfur capacity (lgCs) is the logarithm of sulfur capacity converted into 10. The greater the logarithmic sulfur capacity, the stronger the desulfurization ability of the desulfurizer.
本发明中，气流搅拌是指向液体或固液混合物中通入气流进行搅拌的方法。In the present invention, airflow stirring refers to a method of introducing airflow into a liquid or a solid-liquid mixture for stirring.
本发明中，室温是指室内温度、一般温度或常温，其范围通常为15℃～30℃。In the present invention, room temperature refers to indoor temperature, general temperature or normal temperature, and its range is usually 15°C to 30°C.
利用RH炉对钢水进行真空精炼是获得高质量钢材的关键技术，可有效地脱除钢水中的碳、氧、硫和磷等多种杂质元素。其中，脱硫处理在RH炉精炼的中后期进行，常用的脱硫剂主要有CaO-CaF2渣系和CaO-Al2O3渣系两种类型。Vacuum refining of molten steel using an RH furnace is a key technology for obtaining high-quality steel, which can effectively remove various impurity elements such as carbon, oxygen, sulfur and phosphorus from molten steel. Among them, desulfurization treatment is carried out in the middle and late stages of RH furnace refining. Commonly used desulfurization agents mainly include CaO-CaF 2 slag system and CaO-Al 2 O 3 slag system.
CaO-CaF2渣系是目前公认的硫容量最高的脱硫剂，但实际脱硫过程中，CaO-CaF2渣系的脱硫效果不理想、不稳定，氟化物还会严重侵蚀炼钢设备，造成环境污染。而CaO-Al2O3渣系熔点高，相对成渣速度减缓，导致脱硫效果不够理想，严重影响了硅钢等钢铁制品的产能和质量。The CaO-CaF 2 slag system is currently recognized as the desulfurizer with the highest sulfur capacity. However, in the actual desulfurization process, the desulfurization effect of the CaO-CaF 2 slag system is unsatisfactory and unstable. Fluoride can also seriously corrode steelmaking equipment and cause environmental problems. pollute. The CaO-Al 2 O 3 slag system has a high melting point and slows down the slag formation speed, resulting in unsatisfactory desulfurization effect and seriously affecting the production capacity and quality of silicon steel and other steel products.
这是由于脱硫处理时，RH炉用脱硫剂在真空室内停留时间很短，离开真空室后就不会起到脱硫作用。而在真空室内，CaO-Al2O3渣系的熔点高，与钢水接触时还未完全熔化，因此脱硫剂与钢水之间没有充分反应，在脱硫剂加入量较少时脱硫率很低。若想要提升脱硫率，通常需要增加脱硫剂使用量、延长脱硫时间，这会导致脱硫处理的成本大幅度提升。发明人进一步研究发现，脱硫剂中各物相的成分和含量会影响脱硫剂的熔点，进而对脱硫剂的使用量、脱硫时间、硫容量和脱硫率等性能产生较大的影响。This is because during the desulfurization process, the desulfurization agent used in the RH furnace stays in the vacuum chamber for a very short time and will not have a desulfurization effect after leaving the vacuum chamber. In the vacuum chamber, the CaO-Al 2 O 3 slag system has a high melting point and is not completely melted when it comes into contact with molten steel. Therefore, there is no sufficient reaction between the desulfurizer and the molten steel. When the amount of desulfurizer added is small, the desulfurization rate is very low. If you want to increase the desulfurization rate, you usually need to increase the amount of desulfurization agent used and extend the desulfurization time, which will significantly increase the cost of desulfurization treatment. The inventor further studied and found that the composition and content of each phase in the desulfurizer will affect the melting point of the desulfurizer, which will have a greater impact on the usage of the desulfurizer, desulfurization time, sulfur capacity, desulfurization rate and other properties.
基于此，本发明第一方面，提供一种铝酸钡钙脱硫剂，以克服传统的脱硫剂的使用量大、脱硫时间长和脱硫率低等的问题。Based on this, the first aspect of the present invention provides a barium calcium aluminate desulfurizer to overcome the problems of traditional desulfurizers such as large usage, long desulfurization time and low desulfurization rate.
在一些实施方式中，铝酸钡钙脱硫剂包括3CaO·Al2O3相、12CaO·7Al2O3相、2BaO·6CaO·4SiO2相和BaO·Al2O3相；In some embodiments, the barium calcium aluminate desulfurizer includes 3CaO·Al 2 O 3 phase, 12CaO·7Al 2 O 3 phase, 2BaO·6CaO·4SiO 2 phase and BaO·Al 2 O 3 phase;
在铝酸钡钙脱硫剂中，3CaO·Al2O3相、12CaO·7Al2O3相、2BaO·6CaO·4SiO2相和BaO·Al2O3相的总质量占比≥50％。In the barium calcium aluminate desulfurizer, the total mass proportion of 3CaO·Al 2 O 3 phase, 12CaO·7Al 2 O 3 phase, 2BaO·6CaO·4SiO 2 phase and BaO·Al 2 O 3 phase is ≥50%.
本发明提供的铝酸钡钙脱硫剂中，2BaO·6CaO·4SiO2相和BaO·Al2O3相的熔点在1260℃～1290℃范围内，低于CaO-Al2O3体系的所有物相；3CaO·Al2O3相和12CaO·7Al2O3相可增强CaO的活度而促进脱硫。将3CaO·Al2O3相、12CaO·7Al2O3相、2BaO·6CaO·4SiO2相和BaO·Al2O3相的总质量占比控制在50％以上，可充分发挥出这四个物相之间的协同增强作用，显著降低铝酸钡钙脱硫剂的熔点，加快了脱硫剂的熔化速度，使其能够尽快完全液化而与钢水充分反应，从而提升了脱硫速率，缩短了脱硫时间。与CaO-Al2O3体系的脱硫剂相比，CaO-BaO-Al2O3体系的硫容量更高，可进一步增强铝酸钡钙脱硫剂的脱硫能力，从而使得该脱硫剂在使用量相同的条件下获得更高的脱硫率。In the barium calcium aluminate desulfurizer provided by the invention, the melting points of the 2BaO·6CaO·4SiO 2 phase and the BaO·Al 2 O 3 phase are in the range of 1260°C to 1290°C, which are lower than those of the CaO-Al 2 O 3 system. Phase; 3CaO·Al 2 O 3 phase and 12CaO·7Al 2 O 3 phase can enhance the activity of CaO and promote desulfurization. Controlling the total mass proportion of 3CaO·Al 2 O 3 phase, 12CaO·7Al 2 O 3 phase, 2BaO·6CaO·4SiO 2 phase and BaO·Al 2 O 3 phase to more than 50% can give full play to these four The synergistic enhancement effect between the phases significantly reduces the melting point of the barium calcium aluminate desulfurizer, speeds up the melting speed of the desulfurizer, and enables it to completely liquefy as quickly as possible and fully react with molten steel, thereby increasing the desulfurization rate and shortening the desulfurization time. . Compared with the desulfurizer of the CaO-Al 2 O 3 system, the CaO-BaO-Al 2 O 3 system has a higher sulfur capacity, which can further enhance the desulfurization ability of the calcium barium aluminate desulfurizer, thereby making the desulfurizer use less Obtain higher desulfurization rate under the same conditions.
可选地，在铝酸钡钙脱硫剂中，3CaO·Al2O3相、12CaO·7Al2O3相、2BaO·6CaO·4SiO2相和BaO·Al2O3相的总质量占比为50％～95％，在一些具体的示例中，3CaO·Al2O3相、12CaO·7Al2O3相、2BaO·6CaO·4SiO2相和BaO·Al2O3相在铝酸钡钙脱硫剂中的总质量占比可以为50％、55％、60％、65％、70％、75％、80％、85％、90％或95％等。Alternatively, in the barium calcium aluminate desulfurizer, the total mass proportion of the 3CaO·Al 2 O 3 phase, 12CaO·7Al 2 O 3 phase, 2BaO·6CaO·4SiO 2 phase and BaO·Al 2 O 3 phase is 50% to 95%, in some specific examples, 3CaO·Al 2 O 3 phase, 12CaO·7Al 2 O 3 phase, 2BaO·6CaO·4SiO 2 phase and BaO·Al 2 O 3 phase in barium calcium aluminate desulfurization The total mass proportion in the agent can be 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95%, etc.
在一些实施方式中，在铝酸钡钙脱硫剂中，2BaO·6CaO·4SiO2相和BaO·Al2O3相的总质量占比≥15％。In some embodiments, in the barium calcium aluminate desulfurizer, the total mass proportion of the 2BaO·6CaO·4SiO 2 phase and the BaO·Al 2 O 3 phase is ≥15%.
可选地，在铝酸钡钙脱硫剂中，2BaO·6CaO·4SiO2相和BaO·Al2O3相的总质量占比为15％～35％，在一些具体的示例中，2BaO·6CaO·4SiO2相和BaO·Al2O3相在铝酸钡钙脱硫剂中的总质量占比可以为15％、20％、25％、30％或35％等。Optionally, in the barium calcium aluminate desulfurizer, the total mass proportion of the 2BaO·6CaO·4SiO 2 phase and the BaO·Al 2 O 3 phase is 15% to 35%. In some specific examples, 2BaO·6CaO The total mass proportion of ·4SiO 2 phase and BaO·Al 2 O 3 phase in the barium calcium aluminate desulfurizer can be 15%, 20%, 25%, 30% or 35%, etc.
2BaO·6CaO·4SiO2相和BaO·Al2O3相的熔点在1260℃～1290℃之间，且BaO的硫容量更高，尽可能增大这两个物相的总质量占比，能够进一步提升铝酸钡钙脱硫剂的脱硫能力。The melting points of the 2BaO·6CaO·4SiO 2 phase and the BaO·Al 2 O 3 phase are between 1260°C and 1290°C, and BaO has a higher sulfur capacity. Try to increase the total mass proportion of these two phases as much as possible to achieve Further improve the desulfurization ability of barium calcium aluminate desulfurizer.
在一些实施方式中，铝酸钡钙脱硫剂包括如下质量占比的成分：CaO，40％～50％；BaO，8％～20％；Al2O3，30％～45％；SiO2，1％～8％；余量为杂质。In some embodiments, the barium calcium aluminate desulfurizer includes the following components by mass: CaO, 40% to 50%; BaO, 8% to 20%; Al 2 O 3 , 30% to 45%; SiO 2 , 1% ~ 8%; the balance is impurities.
将铝酸钡钙脱硫剂中的CaO、BaO、Al2O3和SiO2等成分的质量占比控制在合适范围内，有利于在脱硫剂中形成3CaO·Al2O3相、12CaO·7Al2O3相、2BaO·6CaO·4SiO2相和BaO·Al2O3相等物相，并将上述物相的总含量控制在特定范围内。Controlling the mass proportions of CaO, BaO, Al 2 O 3 and SiO 2 in the barium calcium aluminate desulfurizer within an appropriate range is conducive to the formation of 3CaO·Al 2 O 3 phase and 12CaO·7Al in the desulfurizer. 2 O 3 phase, 2BaO·6CaO·4SiO 2 phase and BaO·Al 2 O 3 phase, and the total content of the above phases is controlled within a specific range.
进一步可选地，在铝酸钡钙脱硫剂中，杂质的成分的质量占比应满足以下条件：MgO≤8％；TiO2≤0.1％；C≤0.15％；S≤0.1％。Further optionally, in the barium calcium aluminate desulfurizer, the mass proportion of impurity components should meet the following conditions: MgO ≤ 8%; TiO 2 ≤ 0.1%; C ≤ 0.15%; S ≤ 0.1%.
控制铝酸钡钙脱硫剂中的杂质组分的上限值，能够避免杂质组分在脱硫过程中进入钢水中而影响钢水的洁净度，有利于提高产品质量。Controlling the upper limit of impurity components in barium calcium aluminate desulfurizer can prevent impurity components from entering the molten steel during the desulfurization process and affecting the cleanliness of the molten steel, which is beneficial to improving product quality.
在一些实施方式中，铝酸钡钙脱硫剂的熔点为1230℃～1300℃。在一些具体的示例中，铝酸钡钙脱硫剂的熔点可以为1230℃、1235℃、1240℃、1245℃、1250℃、1255℃、1260℃、1265℃、1270℃、1275℃、1280℃、1285℃、1290℃、1295℃或1300℃等。In some embodiments, the melting point of the barium calcium aluminate desulfurizer is 1230°C to 1300°C. In some specific examples, the melting point of the barium calcium aluminate desulfurizer can be 1230°C, 1235°C, 1240°C, 1245°C, 1250°C, 1255°C, 1260°C, 1265°C, 1270°C, 1275°C, 1280°C, 1285℃, 1290℃, 1295℃ or 1300℃, etc.
钢水冶炼的温度通常在1550℃～1600℃左右，而脱硫剂与钢水界面的温度通常在1500℃左右，铝酸钡钙脱硫剂的熔点在1230℃～1300℃，能够使其快速熔化而形成液相，液态脱硫剂与钢水之间发生充分的液相脱硫反应，脱硫速度快，脱硫剂利用率高，脱硫率得到大幅度提升。The temperature of molten steel smelting is usually around 1550°C ~ 1600°C, while the temperature of the interface between the desulfurizer and the molten steel is usually around 1500°C. The melting point of the barium calcium aluminate desulfurizer is 1230°C ~ 1300°C, which allows it to melt quickly to form a liquid. phase, a sufficient liquid phase desulfurization reaction occurs between the liquid desulfurizer and the molten steel, the desulfurization speed is fast, the desulfurization agent utilization rate is high, and the desulfurization rate is greatly improved.
在一些实施方式中，铝酸钡钙脱硫剂于1450℃～1550℃下的对数硫容量为-2.4～-2.1。在一些具体的示例中，铝酸钡钙脱硫剂于1450℃～1550℃下的对数硫容量可以为-2.40、-2.35、-2.30、-2.25、-2.20、-2.15或-2.10等。In some embodiments, the logarithmic sulfur capacity of the barium calcium aluminate desulfurizer at 1450°C to 1550°C is -2.4 to -2.1. In some specific examples, the logarithmic sulfur capacity of the barium calcium aluminate desulfurizer at 1450°C to 1550°C may be -2.40, -2.35, -2.30, -2.25, -2.20, -2.15 or -2.10, etc.
可选地，铝酸钡钙脱硫剂的粒径为3mm～50mm，在一些具体的示例中，铝酸钡钙脱硫剂的粒径可以为3mm、5mm、10mm、15mm、20mm、25mm、30mm、35mm、40mm、45mm或50mm等。Optionally, the particle size of the barium calcium aluminate desulfurizer is 3mm to 50mm. In some specific examples, the particle size of the barium calcium aluminate desulfurizer can be 3mm, 5mm, 10mm, 15mm, 20mm, 25mm, 30mm, 35mm, 40mm, 45mm or 50mm etc.
可选地，铝酸钡钙脱硫剂的粒径≤1mm，在一些具体的示例中，铝酸钡钙脱硫剂的粒径可以为0.01mm、0.02mm、0.05mm、0.08mm、0.1mm、0.2mm、0.3mm、0.4mm、0.5mm、0.6mm、0.7mm、0.8mm、0.9mm或1mm等。Optionally, the particle size of the barium calcium aluminate desulfurizer is ≤1mm. In some specific examples, the particle size of the barium calcium aluminate desulfurizer can be 0.01mm, 0.02mm, 0.05mm, 0.08mm, 0.1mm, 0.2 mm, 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm or 1mm, etc.
将铝酸钡钙脱硫剂的粒径控制在3mm～50mm范围内，一方面能够增大脱硫剂的比表面积，有利于在钢水中快速分散和反应，加快了脱硫速率，另一方面能够防止脱硫剂因粒径过小而易于飘散和损耗，并避免小粒径的加工成本过高的问题。控制铝酸钡钙脱硫剂的粒径≤1mm，适用于利用喷雾法对钢水进行脱硫处理，可极短时间内使脱硫剂的分散均匀，进一步提高了脱硫效果。Controlling the particle size of barium calcium aluminate desulfurizer within the range of 3mm to 50mm can increase the specific surface area of the desulfurizer, facilitate rapid dispersion and reaction in molten steel, speed up the desulfurization rate, and prevent desulfurization on the other hand. The agent is easy to scatter and lose due to the small particle size, and avoids the problem of high processing costs for small particle sizes. Controlling the particle size of the barium calcium aluminate desulfurizer to ≤1mm is suitable for desulfurizing molten steel using the spray method. The desulfurizer can be dispersed evenly in a very short time, further improving the desulfurization effect.
本发明第二方面，提供一种铝酸钡钙脱硫剂的制备方法，用于制备上述所述的铝酸钡钙脱硫剂。In a second aspect, the present invention provides a method for preparing a barium calcium aluminate desulfurizer, which is used to prepare the above-mentioned barium calcium aluminate desulfurizer.
在一些实施方式中，铝酸钡钙脱硫剂的制备方法包括以下步骤：In some embodiments, the preparation method of barium calcium aluminate desulfurizer includes the following steps:
提供含有钙源、钡源、铝源和硅源的混合料；Providing mixtures containing calcium, barium, aluminum and silicon sources;
使混合料完全熔化，得液态混合料；Completely melt the mixture to obtain a liquid mixture;
通过梯度降温法使液态混合料冷却凝固，得铝酸钡钙脱硫剂。The liquid mixture is cooled and solidified through gradient cooling method to obtain barium calcium aluminate desulfurizer.
本发明对混合料进行熔融处理，促使混合料中的钙源、钡源、铝源和硅源能够互相作用，并梯度降温过程形成低熔点的3CaO·Al2O3相、12CaO·7Al2O3相、2BaO·6CaO·4SiO2相和BaO·Al2O3相，降低铝酸钡钙脱硫剂的熔点，提高使用过程中的熔化速度，从而在相同脱硫剂投料量的条件下获得更高的脱硫率。The present invention melts the mixture so that the calcium source, barium source, aluminum source and silicon source in the mixture can interact with each other, and the low melting point 3CaO·Al 2 O 3 phase and 12CaO·7Al 2 O are formed during the gradient cooling process. 3 phases, 2BaO·6CaO·4SiO 2 phases and BaO·Al 2 O 3 phases, lower the melting point of barium calcium aluminate desulfurizer and increase the melting speed during use, thereby obtaining higher quality under the same desulfurizer input amount. desulfurization rate.
在一些实施方式中，提供含有钙源、钡源、铝源和硅源的混合料包括以下步骤：对钙源、钡源、铝源和硅源分别进行研磨处理，混合，得混合料。In some embodiments, providing a mixture containing a calcium source, a barium source, an aluminum source and a silicon source includes the following steps: grinding the calcium source, barium source, aluminum source and silicon source respectively and mixing them to obtain a mixture.
铝酸钡钙脱硫剂中的氧化硅含量仅为1％～8％，通常可不单独添加氧化硅粉等原料作为硅源，而是以杂质的形式存在于钙源、钡源和铝源中，即钙源、钡源和铝源中的一种或多种可同时作为硅源。若钙源、钡源和铝源的纯度很高，氧化硅的含量不足时，可额外添加少量的氧化硅粉作为硅源。The silicon oxide content in the barium calcium aluminate desulfurizer is only 1% to 8%. Usually, raw materials such as silicon oxide powder do not need to be added separately as the silicon source, but exist in the form of impurities in the calcium source, barium source and aluminum source. That is, one or more of the calcium source, barium source and aluminum source can be used as the silicon source at the same time. If the purity of the calcium source, barium source and aluminum source is very high and the content of silicon oxide is insufficient, a small amount of additional silicon oxide powder can be added as the silicon source.
可选地，钙源为生石灰粉和/或石灰石粉。Optionally, the calcium source is quicklime powder and/or limestone powder.
生石灰(CaO)粉满足《YB/T 042-2014冶金石灰》中的普通冶金石灰二级的质量要求，即各成分的质量分数为：CaO≥85％，MgO<5％，SiO2≤3.5％，S≤0.05％。石灰石(CaCO3)粉满足《YB/T 5279-2005石灰石》中的普通石灰石PS530的质量要求，即各成分的质量分数为：CaO≥53％，MgO≤3.0％，SiO2≤1.5％，S≤0.035％。Quicklime (CaO) powder meets the quality requirements of the second level of ordinary metallurgical lime in "YB/T 042-2014 Metallurgical Lime", that is, the mass fraction of each component is: CaO ≥ 85%, MgO < 5%, SiO 2 ≤ 3.5% , S≤0.05%. Limestone (CaCO 3 ) powder meets the quality requirements of ordinary limestone PS530 in "YB/T 5279-2005 Limestone", that is, the mass fraction of each component is: CaO ≥ 53%, MgO ≤ 3.0%, SiO 2 ≤ 1.5%, S ≤0.035%.
可选地，钡源为氧化钡粉、氢氧化钡粉和碳酸钡粉中的一种或多种。Optionally, the barium source is one or more of barium oxide powder, barium hydroxide powder and barium carbonate powder.
在氧化钡(BaO)粉中，BaO的质量分数≥90％，SiO2的质量分数可以为1％～10％。氢氧化钡(Ba(OH)2)粉符合HG/T 2566-2006《工业氢氧化钡》中的优等品的质量要求，即Ba(OH)2的质量分数≥98.0％。碳酸钡(BaCO3)粉满足GB/T 1614-2021《工业碳酸钡》中的优等品的质量要求，即BaCO3的质量分数≥99.2％。In barium oxide (BaO) powder, the mass fraction of BaO is ≥90%, and the mass fraction of SiO2 can be 1% to 10%. Barium hydroxide (Ba(OH) 2 ) powder meets the quality requirements for premium products in HG/T 2566-2006 "Industrial Barium Hydroxide", that is, the mass fraction of Ba(OH) 2 is ≥98.0%. Barium carbonate (BaCO 3 ) powder meets the quality requirements of superior products in GB/T 1614-2021 "Industrial Barium Carbonate", that is, the mass fraction of BaCO 3 is ≥99.2%.
可选地，铝源为氧化铝粉。Optionally, the aluminum source is alumina powder.
氧化铝(Al2O3)粉满足《YS/T 803-2012冶金级氧化铝》中的YAO-1、YAO-2和YAO-3中的至少一种牌号的质量要求，即各成分的质量分数为：Al2O3≥98.4％，SiO2≤0.06％。Alumina (Al 2 O 3 ) powder meets the quality requirements of at least one of YAO-1, YAO-2 and YAO-3 in "YS/T 803-2012 Metallurgical Grade Alumina", that is, the quality of each component The fractions are: Al 2 O 3 ≥98.4%, SiO 2 ≤0.06%.
可选地，研磨处理的方法为球磨法、机械研磨法和超声波研磨法中的一种或多种。Optionally, the grinding treatment method is one or more of ball milling, mechanical grinding and ultrasonic grinding.
可选地，钙源、钡源、铝源和硅源的粒径各自独立地为50目～200目(即74μm～280μm)。在一些具体的示例中，钙源、钡源、铝源和硅源的的粒径各自独立地可以为50目、60目、70目、80目、90目、100目、110目、120目、130目、140目、150目、160目、170目、180目、190目或200目等。Optionally, the particle sizes of the calcium source, barium source, aluminum source and silicon source are each independently 50 mesh to 200 mesh (ie, 74 μm to 280 μm). In some specific examples, the particle sizes of the calcium source, barium source, aluminum source and silicon source can each independently be 50 mesh, 60 mesh, 70 mesh, 80 mesh, 90 mesh, 100 mesh, 110 mesh, and 120 mesh. , 130 mesh, 140 mesh, 150 mesh, 160 mesh, 170 mesh, 180 mesh, 190 mesh or 200 mesh, etc.
通过对钙源、钡源、铝源和硅源的的粒径进行控制，保证原料具有较大的比表面积，有利于原料的快速熔融、扩散、分解和互相作用，并促进低熔点物相的形成。By controlling the particle size of the calcium source, barium source, aluminum source and silicon source, the raw materials are ensured to have a large specific surface area, which is conducive to the rapid melting, diffusion, decomposition and interaction of the raw materials, and promotes the formation of low melting point phases. form.
在一些实施方式中，使混合料完全熔化包括以下步骤：In some embodiments, completely melting the mixture includes the following steps:
升温至1500℃～1550℃，并保温至少15min。Raise the temperature to 1500℃~1550℃ and keep it warm for at least 15 minutes.
在一些具体的示例中，升温的目标温度可以为1500℃、1505℃、1510℃、1515℃、1520℃、1525℃、1530℃、1535℃、1540℃、1545℃或1550℃等；保温时间可以为15min、20min、25min、30min、35min、40min、45min、50min、55min、60min或120min等。In some specific examples, the target temperature of heating can be 1500℃, 1505℃, 1510℃, 1515℃, 1520℃, 1525℃, 1530℃, 1535℃, 1540℃, 1545℃ or 1550℃, etc.; the holding time can be It is 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min or 120min, etc.
升温至1500℃～1550℃，可使混合料完全熔化形成液态混合料。在1500℃～1550℃范围内保温至少15min，能够使液态混合料中的各物相分散均匀，保证铝酸钡钙脱硫剂的熔点较为稳定。Raising the temperature to 1500℃~1550℃ can completely melt the mixture to form a liquid mixture. Keeping the temperature in the range of 1500°C to 1550°C for at least 15 minutes can make the various phases in the liquid mixture disperse evenly and ensure that the melting point of the barium calcium aluminate desulfurizer is relatively stable.
可选地，使混合料完全熔化还包括气流搅拌的步骤。Optionally, completely melting the mixture also includes the step of airflow stirring.
气流搅拌的装置简单，无搅拌部件，适宜于高温液体或腐蚀性液体的搅拌，能够进一步提升液态混合料的分散均匀性。同时，气流搅拌还会带走原料中的挥发组分，例如碳酸盐分解产生的CO2，促进原料的分解和互相作用。The airflow stirring device is simple and has no stirring parts. It is suitable for stirring high-temperature liquids or corrosive liquids, and can further improve the uniformity of dispersion of liquid mixtures. At the same time, airflow stirring will also take away volatile components in the raw materials, such as CO 2 produced by the decomposition of carbonates, promoting the decomposition and interaction of the raw materials.
进一步可选地，气流搅拌的气体为氮气和/或氩气。Further optionally, the gas stirred by the gas flow is nitrogen and/or argon.
氮气和氩气为惰性气体，能够在熔融过程中保护混合料不受O2、CO2等具有反应活性的气体的影响，避免混合料中的杂质元素发生氧化，同时防止CaO、BaO等碱性氧化物与CO2反应形成碳酸盐产物，从而保证脱硫剂具有低熔点和高硫容量的优点。Nitrogen and argon are inert gases that can protect the mixture from reactive gases such as O 2 and CO 2 during the melting process, avoid oxidation of impurity elements in the mixture, and prevent alkaline properties such as CaO and BaO. The oxide reacts with CO2 to form a carbonate product, thus ensuring that the desulfurizer has the advantages of low melting point and high sulfur capacity.
在一些实施方式中，梯度降温法包括以下步骤：In some embodiments, the gradient cooling method includes the following steps:
使液态混合料在≥800℃的温度下保温≥24h；Keep the liquid mixture at a temperature of ≥800°C for ≥24h;
以≥150℃/h的降温速率，从800℃降温至500℃；Cool from 800℃ to 500℃ at a cooling rate of ≥150℃/h;
以≥80℃/h的降温速率，从500℃降温至300℃；Cool from 500℃ to 300℃ at a cooling rate of ≥80℃/h;
以≥40℃/h的降温速率，从500℃降温至室温。Cool down from 500℃ to room temperature at a cooling rate of ≥40℃/h.
通过上述梯度降温法，能够促使液态混合料能够在缓慢的温度变化下进行物相转化，避免温度变化过快而无法形成足够的3CaO·Al2O3相、12CaO·7Al2O3相、2BaO·6CaO·4SiO2相和BaO·Al2O3相。Through the above gradient cooling method, the liquid mixture can be promoted to undergo phase transformation under slow temperature changes, preventing the temperature from changing too quickly to form sufficient 3CaO·Al 2 O 3 phase, 12CaO·7Al 2 O 3 phase, and 2BaO ·6CaO·4SiO 2 phase and BaO·Al 2 O 3 phase.
可选地，使液态混合料在≥800℃的温度下保温≥24h包括以下步骤：Optionally, maintaining the liquid mixture at a temperature of ≥800°C for ≥24h includes the following steps:
将液态混合料置于铁质容器中，并采取加盖保温的方法进行保温。Place the liquid mixture in an iron container and cover it to keep it warm.
可选地，在≥800℃的温度下保温≥24h后，采取吹风冷却的方法梯度降温至室温，以获得块状的铝酸钡钙脱硫剂。Optionally, after holding at a temperature of ≥800°C for ≥24 hours, use a blowing cooling method to gradually cool down to room temperature to obtain a massive barium calcium aluminate desulfurizer.
可选地，使液态混合料冷却凝固之后还包括破碎的步骤。Optionally, a crushing step is further included after the liquid mixture is cooled and solidified.
进一步可选地，将梯度降温得到的块状铝酸钡钙脱硫剂依次进行人工破碎和机械破碎，得粒径为3mm～50mm的铝酸钡钙脱硫剂。Further optionally, the massive barium calcium aluminate desulfurizer obtained by gradient cooling is sequentially crushed manually and mechanically to obtain a barium calcium aluminate desulfurizer with a particle size of 3 mm to 50 mm.
可选地，使块状铝酸钡钙脱硫剂破碎之后还包括研磨的步骤。Optionally, the step of grinding is further included after crushing the massive barium calcium aluminate desulfurizer.
进一步可选地，将粒径为3mm～50mm的铝酸钡钙脱硫剂进行球磨、机械研磨或超声波研磨，得粒径为≤1mm的铝酸钡钙脱硫剂。Further optionally, the barium calcium aluminate desulfurizer with a particle size of 3 mm to 50 mm is subjected to ball milling, mechanical grinding or ultrasonic grinding to obtain a barium calcium aluminate desulfurizer with a particle size of ≤1 mm.
本发明第三方面，提供一种钢材的制备方法，其包括采用上述所述的铝酸钡钙脱硫剂对钢水进行脱硫处理的步骤。A third aspect of the present invention provides a method for preparing steel, which includes the step of desulfurizing molten steel using the barium calcium aluminate desulfurizer described above.
可选地，每吨钢水中，铝酸钡钙脱硫剂的加入量为3kg～15kg。Optionally, the amount of barium calcium aluminate desulfurizer added per ton of molten steel is 3kg to 15kg.
以下结合具体实施例对本发明作进一步详细的说明。以下实施例中所用的原料，如无特别说明，均为市售产品。The present invention will be described in further detail below with reference to specific examples. The raw materials used in the following examples are all commercially available products unless otherwise specified.
实施例1Example 1
将生石灰粉(含有氧化硅杂质)、碳酸钡粉和氧化铝粉分别球磨至粒径为50目～200目，然后将生石灰粉、碳酸钡粉和氧化铝粉加入混料仓中混合均匀，得混合料；将混合料置于电炉中，升温至1500℃使混合料完全熔化，保温30min，升温过程中及保温过程中通入氮气进行气流搅拌，得液态混合料；将液态混合料倒入铁质容器中，利用吹风机吹风，使液态混合料冷却至室温，得块状的铝酸钡钙脱硫剂；将块状的铝酸钡钙脱硫剂进行人工破碎，然后投入至颚式破碎机中进行机械破碎，得粒径为3mm～50mm的铝酸钡钙脱硫剂。Ball-mill the quicklime powder (containing silicon oxide impurities), barium carbonate powder and alumina powder respectively to a particle size of 50 mesh to 200 mesh, then add the quicklime powder, barium carbonate powder and alumina powder to the mixing bin and mix evenly to obtain Mixture; Place the mixture in an electric furnace, raise the temperature to 1500°C to completely melt the mixture, and keep it warm for 30 minutes. During the heating process and the heat preservation process, nitrogen gas is introduced for airflow stirring to obtain a liquid mixture; pour the liquid mixture into iron In the mass container, use a hair dryer to cool the liquid mixture to room temperature to obtain a block barium calcium aluminate desulfurizer; manually crush the block barium calcium aluminate desulfurizer and then put it into a jaw crusher for processing Mechanically crush it to obtain barium calcium aluminate desulfurizer with a particle size of 3 mm to 50 mm.
请参阅表1，该铝酸钡钙脱硫剂包括如下质量占比的成分：CaO，42％；BaO，19％；Al2O3，35％；SiO2，2％；MgO，1.8％；TiO2，0.03％；C，0.08％；S，0.04％。请参阅表2，该铝酸钡钙脱硫剂包括如下质量占比的物相：3CaO·Al2O3相，37.1％；12CaO·7Al2O3相，3.4％；2BaO·6CaO·4SiO2相，7.1％；BaO·Al2O3相，25.2％。在表2中，C3A代表3CaO·Al2O3相，C12A7代表12CaO·7Al2O3相，B2C6S4代表2BaO·6CaO·4SiO2相，BA代表BaO·Al2O3相。Please refer to Table 1. The barium calcium aluminate desulfurizer includes the following mass proportions: CaO, 42%; BaO, 19%; Al 2 O 3 , 35%; SiO 2 , 2%; MgO, 1.8%; TiO 2 , 0.03%; C, 0.08%; S, 0.04%. Please refer to Table 2. The barium calcium aluminate desulfurizer includes the following phases by mass: 3CaO·Al 2 O 3 phase, 37.1%; 12CaO·7Al 2 O 3 phase, 3.4%; 2BaO·6CaO·4SiO 2 phase , 7.1%; BaO·Al 2 O 3 phase, 25.2%. In Table 2, C 3 A represents the 3CaO·Al 2 O 3 phase, C 12 A 7 represents the 12CaO·7Al 2 O 3 phase, B 2 C 6 S 4 represents the 2BaO·6CaO·4SiO 2 phase, and BA represents the BaO·Al 2 O 3 phase.
实施例2Example 2
将生石灰粉(含有氧化硅杂质)、碳酸钡粉和氧化铝粉分别球磨至粒径为50目～200目，然后将生石灰粉、碳酸钡粉和氧化铝粉加入混料仓中混合均匀，得混合料；将混合料置于电炉中，升温至1525℃使混合料完全熔化，保温20min，升温过程中及保温过程中通入氩气进行气流搅拌，得液态混合料；将液态混合料倒入铁质容器中，利用吹风机吹风，使液态混合料冷却至室温，得块状的铝酸钡钙脱硫剂；将块状的铝酸钡钙脱硫剂进行人工破碎，然后投入至颚式破碎机中进行机械破碎，得粒径为3mm～50mm的铝酸钡钙脱硫剂。Ball-mill the quicklime powder (containing silicon oxide impurities), barium carbonate powder and alumina powder respectively to a particle size of 50 mesh to 200 mesh, then add the quicklime powder, barium carbonate powder and alumina powder to the mixing bin and mix evenly to obtain Mixture; place the mixture in an electric furnace, raise the temperature to 1525°C to completely melt the mixture, and keep it warm for 20 minutes. During the heating process and the heat preservation process, argon gas is introduced for air flow stirring to obtain a liquid mixture; pour the liquid mixture into In an iron container, use a hair dryer to cool the liquid mixture to room temperature to obtain a block barium calcium aluminate desulfurizer; manually crush the block barium calcium aluminate desulfurizer and then put it into the jaw crusher Mechanical crushing is carried out to obtain barium calcium aluminate desulfurizer with a particle size of 3 mm to 50 mm.
请参阅表1，该铝酸钡钙脱硫剂包括如下质量占比的成分：CaO，45％；BaO，15％；Al2O3，36％；SiO2，2％；MgO，1.6％；TiO2，0.04％；C，0.11％；S，0.06％。请参阅表2，该铝酸钡钙脱硫剂包括如下质量占比的物相：3CaO·Al2O3相，40.7％；12CaO·7Al2O3相，7.4％；2BaO·6CaO·4SiO2相，6.3％；BaO·Al2O3相，19.1％。Please refer to Table 1. The barium calcium aluminate desulfurizer includes the following mass proportions: CaO, 45%; BaO, 15%; Al 2 O 3 , 36%; SiO 2 , 2%; MgO, 1.6%; TiO 2 , 0.04%; C, 0.11%; S, 0.06%. Please refer to Table 2. The barium calcium aluminate desulfurizer includes the following phases by mass: 3CaO·Al 2 O 3 phase, 40.7%; 12CaO·7Al 2 O 3 phase, 7.4%; 2BaO·6CaO·4SiO 2 phase , 6.3%; BaO·Al 2 O 3 phase, 19.1%.
实施例3Example 3
将生石灰粉(含有氧化硅杂质)、碳酸钡粉和氧化铝粉分别球磨至粒径为50目～200目，然后将生石灰粉、碳酸钡粉和氧化铝粉加入混料仓中混合均匀，得混合料；将混合料置于电炉中，升温至1550℃使混合料完全熔化，保温15min，升温过程中及保温过程中通入氩气进行气流搅拌，得液态混合料；将液态混合料倒入铁质容器中，利用吹风机吹风，使液态混合料冷却至室温，得块状的铝酸钡钙脱硫剂；将块状的铝酸钡钙脱硫剂进行人工破碎，然后投入至颚式破碎机中进行机械破碎，得粒径为3mm～50mm的铝酸钡钙脱硫剂。Ball-mill the quicklime powder (containing silicon oxide impurities), barium carbonate powder and alumina powder respectively to a particle size of 50 mesh to 200 mesh, then add the quicklime powder, barium carbonate powder and alumina powder to the mixing bin and mix evenly to obtain Mixture; Place the mixture in an electric furnace, raise the temperature to 1550°C to completely melt the mixture, and keep it warm for 15 minutes. During the heating process and the heat preservation process, argon gas is introduced for air flow stirring to obtain a liquid mixture; pour the liquid mixture into In an iron container, use a hair dryer to cool the liquid mixture to room temperature to obtain a block barium calcium aluminate desulfurizer; manually crush the block barium calcium aluminate desulfurizer and then put it into the jaw crusher Mechanical crushing is carried out to obtain barium calcium aluminate desulfurizer with a particle size of 3 mm to 50 mm.
请参阅表1，该铝酸钡钙脱硫剂包括如下质量占比的成分：CaO，49％；BaO，9％；Al2O3，38％；SiO2，2％；MgO，1.7％；TiO2，0.06％；C，0.04％；S，0.05％。请参阅表2，该铝酸钡钙脱硫剂包括如下质量占比的物相：3CaO·Al2O3相，53.2％；12CaO·7Al2O3相，13.4％；2BaO·6CaO·4SiO2相，6.5％；BaO·Al2O3相，11.2％。Please refer to Table 1. The barium calcium aluminate desulfurizer includes the following components by mass: CaO, 49%; BaO, 9%; Al 2 O 3 , 38%; SiO 2 , 2%; MgO, 1.7%; TiO 2 , 0.06%; C, 0.04%; S, 0.05%. Please refer to Table 2. The barium calcium aluminate desulfurizer includes the following phases by mass: 3CaO·Al 2 O 3 phase, 53.2%; 12CaO·7Al 2 O 3 phase, 13.4%; 2BaO·6CaO·4SiO 2 phase , 6.5%; BaO·Al 2 O 3 phase, 11.2%.
对比例1Comparative example 1
本对比例的脱硫剂为不含BaO的铝酸钙脱硫剂，粒径为3mm～50mm。The desulfurizer in this comparative example is a BaO-free calcium aluminate desulfurizer with a particle size of 3 mm to 50 mm.
请参阅表1，该铝酸钙脱硫剂包括如下质量占比的成分：CaO，54％；Al2O3，42％；SiO2，2％；MgO，1.5％；TiO2，0.04％；C，0.07％；S，0.04％。请参阅表2，该铝酸钙脱硫剂包括如下质量占比的物相：3CaO·Al2O3相，32.0％；12CaO·7Al2O3相，43.0％。Please refer to Table 1. The calcium aluminate desulfurizer includes the following mass proportions: CaO, 54%; Al 2 O 3 , 42%; SiO 2 , 2%; MgO, 1.5%; TiO 2 , 0.04%; C , 0.07%; S, 0.04%. Please refer to Table 2. The calcium aluminate desulfurizer includes the following phases by mass: 3CaO·Al 2 O 3 phase, 32.0%; 12CaO·7Al 2 O 3 phase, 43.0%.
对比例2Comparative example 2
本对比例的铝酸钡钙脱硫剂在制备时熔融处理的温度低于1500℃。The barium calcium aluminate desulfurizer of this comparative example is melted at a temperature lower than 1500°C during preparation.
将生石灰粉(含有氧化硅杂质)、碳酸钡粉和氧化铝粉分别球磨至粒径为50目～200目，然后将生石灰粉、碳酸钡粉和氧化铝粉加入混料仓中混合均匀，得混合料；将混合料置于电炉中，升温至1250℃使混合料完全熔化，保温15min，升温过程中及保温过程中通入氩气进行气流搅拌，得液态混合料；将液态混合料倒入铁质容器中，利用吹风机吹风，使液态混合料冷却至室温，得块状的铝酸钡钙脱硫剂；将块状的铝酸钡钙脱硫剂进行人工破碎，然后投入至颚式破碎机中进行机械破碎，得粒径为3mm～50mm的铝酸钡钙脱硫剂。Ball-mill the quicklime powder (containing silicon oxide impurities), barium carbonate powder and alumina powder respectively to a particle size of 50 mesh to 200 mesh, then add the quicklime powder, barium carbonate powder and alumina powder to the mixing bin and mix evenly to obtain Mixture; Place the mixture in an electric furnace, raise the temperature to 1250°C to completely melt the mixture, and keep it warm for 15 minutes. During the heating process and the heat preservation process, argon gas is introduced for air flow stirring to obtain a liquid mixture; pour the liquid mixture into In an iron container, use a hair dryer to cool the liquid mixture to room temperature to obtain a block barium calcium aluminate desulfurizer; manually crush the block barium calcium aluminate desulfurizer and then put it into the jaw crusher Mechanical crushing is carried out to obtain barium calcium aluminate desulfurizer with a particle size of 3 mm to 50 mm.
请参阅表1，该铝酸钡钙脱硫剂包括如下质量占比的成分：CaO，49％；BaO，9％；Al2O3，38％；SiO2，2％；MgO，1.7％；TiO2，0.06％；C，0.04％；S，0.06％。请参阅表2，该铝酸钡钙脱硫剂包括如下质量占比的物相：3CaO·Al2O3相，21.0％；12CaO·7Al2O3相，10.4％；2BaO·6CaO·4SiO2相，0％；BaO·Al2O3相，4.2％。Please refer to Table 1. The barium calcium aluminate desulfurizer includes the following components by mass: CaO, 49%; BaO, 9%; Al 2 O 3 , 38%; SiO 2 , 2%; MgO, 1.7%; TiO 2 , 0.06%; C, 0.04%; S, 0.06%. Please refer to Table 2. The barium calcium aluminate desulfurizer includes the following phases by mass: 3CaO·Al 2 O 3 phase, 21.0%; 12CaO·7Al 2 O 3 phase, 10.4%; 2BaO·6CaO·4SiO 2 phase , 0%; BaO·Al 2 O 3 phase, 4.2%.
对比例3Comparative example 3
本对比例的铝酸钡钙脱硫剂未进行梯度降温。The barium calcium aluminate desulfurizer in this comparative example did not undergo gradient cooling.
将生石灰粉(含有氧化硅杂质)、碳酸钡粉和氧化铝粉分别球磨至粒径为50目～200目，然后将生石灰粉、碳酸钡粉和氧化铝粉加入混料仓中混合均匀，得混合料；将混合料置于电炉中，升温至1530℃使混合料完全熔化，保温15min，升温过程中及保温过程中通入氩气进行气流搅拌，得液态混合料；将液态混合料倒入铁质容器中，使液态混合料自然冷却3天至室温，得块状的铝酸钡钙脱硫剂；将块状的铝酸钡钙脱硫剂进行人工破碎，然后投入至颚式破碎机中进行机械破碎，得粒径为3mm～50mm的铝酸钡钙脱硫剂。Ball-mill the quicklime powder (containing silicon oxide impurities), barium carbonate powder and alumina powder respectively to a particle size of 50 mesh to 200 mesh, then add the quicklime powder, barium carbonate powder and alumina powder to the mixing bin and mix evenly to obtain Mixture; Place the mixture in an electric furnace, raise the temperature to 1530°C to completely melt the mixture, and keep it warm for 15 minutes. During the heating process and the heat preservation process, argon gas is introduced for airflow stirring to obtain a liquid mixture; pour the liquid mixture into In an iron container, the liquid mixture is naturally cooled to room temperature for 3 days to obtain a block barium calcium aluminate desulfurizer; the block barium calcium aluminate desulfurizer is manually crushed and then put into a jaw crusher for processing Mechanically crush it to obtain barium calcium aluminate desulfurizer with a particle size of 3 mm to 50 mm.
请参阅表1，该铝酸钡钙脱硫剂包括如下质量占比的成分：CaO，49％；BaO，9％；Al2O3，38％；SiO2，2％；MgO，1.7％；TiO2，0.06％；C，0.04％；S，0.06％。请参阅表2，该铝酸钡钙脱硫剂包括如下质量占比的物相：3CaO·Al2O3相，15.3％；12CaO·7Al2O3相，3.4％；2BaO·6CaO·4SiO2相，1.9％；BaO·Al2O3相，8.2％。Please refer to Table 1. The barium calcium aluminate desulfurizer includes the following components by mass: CaO, 49%; BaO, 9%; Al 2 O 3 , 38%; SiO 2 , 2%; MgO, 1.7%; TiO 2 , 0.06%; C, 0.04%; S, 0.06%. Please refer to Table 2. The barium calcium aluminate desulfurizer includes the following phases by mass: 3CaO·Al 2 O 3 phase, 15.3%; 12CaO·7Al 2 O 3 phase, 3.4%; 2BaO·6CaO·4SiO 2 phase , 1.9%; BaO·Al 2 O 3 phase, 8.2%.
测试例test case
采用X射线荧光光谱仪测试铝酸钡钙脱硫剂中的氧化物的含量，并参照《GB/T20123-2006钢铁总碳硫含量的测定高频感应炉燃烧后红外吸收法》测试铝酸钡钙脱硫剂中的碳含量和硫含量，结果如表1所示。将铝酸钡钙脱硫剂中的成分输入热力学软件FactSage中计算其物相、熔点和对数硫容量，铝酸钡钙脱硫剂的物相的质量占比如表2所示，熔点和对数硫容量如表3所示。An X-ray fluorescence spectrometer was used to test the oxide content in the barium calcium aluminate desulfurizer, and the barium calcium aluminate desulfurization was tested with reference to "GB/T20123-2006 Determination of total carbon and sulfur content in iron and steel by high-frequency induction furnace post-combustion infrared absorption method" The carbon content and sulfur content in the agent are shown in Table 1. Input the components in the calcium barium aluminate desulfurizer into the thermodynamic software FactSage to calculate its phase, melting point and logarithmic sulfur capacity. The mass proportion of the physical phase of the calcium barium aluminate desulfurizer is shown in Table 2, the melting point and logarithmic sulfur capacity. The capacity is shown in Table 3.
由表2可知，实施例1～3的铝酸钡钙脱硫剂的2BaO·6CaO·4SiO2相和BaO·Al2O3相的总质量占比为17.7％～32.3％，四种目标物相的总质量占比为73.5％～84.3％。对比例1的铝酸钙脱硫剂只含有3CaO·Al2O3相和12CaO·7Al2O3相两个物相；对比例2和对比例3的铝酸钙脱硫剂中没有形成足够的3CaO·Al2O3相、12CaO·7Al2O3相、2BaO·6CaO·4SiO2相和BaO·Al2O3相，四个目标物相的总质量占比低于50％，含BaO的物相的总质量占比低于15％。It can be seen from Table 2 that the total mass proportion of the 2BaO·6CaO·4SiO 2 phase and the BaO·Al 2 O 3 phase of the barium calcium aluminate desulfurizer of Examples 1 to 3 is 17.7% to 32.3%, and the four target phases The total mass proportion is 73.5%~84.3%. The calcium aluminate desulfurizer of Comparative Example 1 only contains two physical phases: 3CaO·Al 2 O 3 phase and 12CaO·7Al 2 O 3 phase; not enough 3CaO is formed in the calcium aluminate desulfurizer of Comparative Example 2 and Comparative Example 3. ·Al 2 O 3 phase, 12CaO · 7Al 2 O 3 phase, 2BaO · 6CaO · 4SiO 2 phase and BaO · Al 2 O 3 phase. The total mass proportion of the four target phases is less than 50%. BaO-containing substances The total mass proportion of phases is less than 15%.
由表3可知，实施例1的铝酸钡钙脱硫剂的熔点为1296℃，1550℃下的对数硫容量lgCs＝-2.18。于1550℃下，对33炉钢水进行脱硫处理，每炉钢水有150吨(t)钢水，每吨钢水中铝酸钡钙脱硫剂的加入量为4kg～9kg，平均值为7.1kg。经脱硫处理后，脱硫率均值为64.6％，方差为5.8％。It can be seen from Table 3 that the melting point of the barium calcium aluminate desulfurizer of Example 1 is 1296°C, and the logarithmic sulfur capacity at 1550°C is lgCs=-2.18. At 1550°C, 33 furnaces of molten steel were desulfurized. Each furnace had 150 tons (t) of molten steel. The amount of barium calcium aluminate desulfurizer added per ton of molten steel was 4kg to 9kg, with an average of 7.1kg. After desulfurization treatment, the average desulfurization rate is 64.6% and the variance is 5.8%.
实施例2的铝酸钡钙脱硫剂的熔点为1282℃，1550℃下的对数硫容量lgCs＝-2.24。于1550℃下，对23炉钢水进行脱硫处理，每炉钢水有150吨(t)钢水，每吨钢水中铝酸钡钙脱硫剂的加入量为5kg～8kg，平均值为7.12kg。经脱硫处理后，脱硫率均值为62.8％，方差为6.1％。The melting point of the barium calcium aluminate desulfurizer in Example 2 is 1282°C, and the logarithmic sulfur capacity at 1550°C is lgCs=-2.24. At 1550°C, 23 furnaces of molten steel were desulfurized. Each furnace had 150 tons (t) of molten steel. The amount of barium calcium aluminate desulfurizer added per ton of molten steel was 5kg to 8kg, with an average value of 7.12kg. After desulfurization treatment, the average desulfurization rate is 62.8% and the variance is 6.1%.
实施例3的铝酸钡钙脱硫剂的熔点为1263℃，1550℃下的对数硫容量lgCs＝-2.32。于1550℃下，对18炉钢水进行脱硫处理，每炉钢水有150吨(t)钢水，每吨钢水中铝酸钡钙脱硫剂的加入量为4kg～8kg，平均值为7.05kg。经脱硫处理后，脱硫率均值为56.3％，方差为6.7％。The melting point of the barium calcium aluminate desulfurizer in Example 3 is 1263°C, and the logarithmic sulfur capacity at 1550°C is lgCs=-2.32. At 1550°C, 18 furnaces of molten steel were desulfurized. Each furnace had 150 tons (t) of molten steel. The amount of barium calcium aluminate desulfurizer added to each ton of molten steel was 4kg to 8kg, with an average value of 7.05kg. After desulfurization treatment, the average desulfurization rate is 56.3% and the variance is 6.7%.
对比例1的铝酸钙脱硫剂熔点为1358℃，1550℃下的对数硫容量lgCs＝-2.52。于1550℃下，对88炉钢水进行脱硫处理，每炉钢水有150吨(t)钢水，每吨钢水中铝酸钙脱硫剂的加入量为4kg～9kg，平均值为7.15kg。经脱硫处理后，脱硫率均值为48.3％，方差为7.7％。The melting point of the calcium aluminate desulfurizer in Comparative Example 1 is 1358°C, and the logarithmic sulfur capacity at 1550°C is lgCs=-2.52. At 1550°C, 88 furnaces of molten steel were desulfurized. Each furnace had 150 tons (t) of molten steel. The amount of calcium aluminate desulfurizer added per ton of molten steel was 4kg to 9kg, with an average of 7.15kg. After desulfurization treatment, the average desulfurization rate is 48.3% and the variance is 7.7%.
对比例2的铝酸钡钙脱硫剂的熔点为1343℃，1550℃下的对数硫容量lgCs＝-2.32。于1550℃下，对14炉钢水进行脱硫处理，每炉钢水有150吨(t)钢水，每吨钢水中铝酸钡钙脱硫剂的加入量为5kg～9kg，平均值为7.08kg。经脱硫处理后，脱硫率均值为51.4％，方差为9.3％。The melting point of the barium calcium aluminate desulfurizer in Comparative Example 2 is 1343°C, and the logarithmic sulfur capacity at 1550°C is lgCs=-2.32. At 1550°C, 14 furnaces of molten steel were desulfurized. Each furnace had 150 tons (t) of molten steel. The amount of barium calcium aluminate desulfurizer added to each ton of molten steel was 5kg to 9kg, with an average value of 7.08kg. After desulfurization treatment, the average desulfurization rate is 51.4% and the variance is 9.3%.
对比例3的铝酸钡钙脱硫剂的熔点为1313℃，1550℃下的对数硫容量lgCs＝-2.32。于1550℃下，对17炉钢水进行脱硫处理，每炉钢水有150吨(t)钢水，每吨钢水中铝酸钡钙脱硫剂的加入量6kg～9kg，平均kg～7.25kg。经脱硫处理后，脱硫率均值为50.2％，方差为8.9％。The melting point of the barium calcium aluminate desulfurizer in Comparative Example 3 is 1313°C, and the logarithmic sulfur capacity at 1550°C is lgCs=-2.32. At 1550°C, 17 furnaces of molten steel were desulfurized. Each furnace had 150 tons (t) of molten steel. The amount of barium calcium aluminate desulfurizer added per ton of molten steel was 6kg to 9kg, with an average of kg to 7.25kg. After desulfurization treatment, the average desulfurization rate is 50.2% and the variance is 8.9%.
经对比，实施例1～3的铝酸钙脱硫剂的熔点在1230℃～1300℃范围内，在脱硫处理时熔化速度快，能够在脱硫剂使用量相同的条件下获得更高的对数硫容量和脱硫率，避免了脱硫剂使用量大、脱硫时间长和脱硫率低等问题。其中，实施例1的铝酸钙脱硫剂脱硫能力最强，且脱硫效果最稳定。By comparison, the melting points of the calcium aluminate desulfurizers in Examples 1 to 3 are in the range of 1230°C to 1300°C, the melting speed is fast during the desulfurization process, and higher logarithmic sulfur can be obtained under the same usage amount of desulfurizers. Capacity and desulfurization rate, avoiding problems such as large use of desulfurizer, long desulfurization time and low desulfurization rate. Among them, the calcium aluminate desulfurizer of Example 1 has the strongest desulfurization ability and the most stable desulfurization effect.
表1.脱硫剂的成分的质量占比(wt.％)Table 1. Mass proportion of desulfurizer components (wt.%)
表2.脱硫剂的物相的质量占比(wt.％)Table 2. Mass proportion of desulfurizer phase (wt.%)
表3.脱硫剂的性能对比Table 3. Performance comparison of desulfurizers
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。The technical features of the above embodiments can be combined in any way. To simplify the description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, All should be considered to be within the scope of this manual.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准，说明书可以用于解释权利要求的内容。The above-mentioned embodiments only express several implementation modes of the present invention. The descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the invention. It should be noted that, for those of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the scope of protection of the patent of the present invention should be determined by the appended claims, and the description can be used to interpret the content of the claims.
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