CN116875769A - Barium calcium aluminate desulfurizing agent and preparation method thereof, and preparation method of steel - Google Patents
Barium calcium aluminate desulfurizing agent and preparation method thereof, and preparation method of steel Download PDFInfo
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- calcium aluminate
- barium
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- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 145
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 142
- FQNGWRSKYZLJDK-UHFFFAOYSA-N [Ca].[Ba] Chemical compound [Ca].[Ba] FQNGWRSKYZLJDK-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 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 60
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 55
- 230000023556 desulfurization Effects 0.000 claims abstract description 55
- 238000002844 melting Methods 0.000 claims abstract description 44
- 230000008018 melting Effects 0.000 claims abstract description 44
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 120
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 74
- 239000000203 mixture Substances 0.000 claims description 66
- 235000012255 calcium oxide Nutrition 0.000 claims description 60
- 239000000292 calcium oxide Substances 0.000 claims description 60
- 239000000843 powder Substances 0.000 claims description 56
- 239000007788 liquid Substances 0.000 claims description 36
- 238000001816 cooling Methods 0.000 claims description 33
- 239000002245 particle Substances 0.000 claims description 33
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 28
- 229910052717 sulfur Inorganic materials 0.000 claims description 26
- 239000011593 sulfur Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 19
- 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
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 235000019738 Limestone Nutrition 0.000 claims description 6
- 239000006028 limestone Substances 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 5
- 239000000463 material Substances 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 238000004904 shortening Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 118
- 230000000052 comparative effect Effects 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 238000003756 stirring Methods 0.000 description 13
- 239000012535 impurity Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 9
- 229910052814 silicon oxide Inorganic materials 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- 238000000498 ball milling Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 239000002893 slag Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910000976 Electrical steel Inorganic materials 0.000 description 5
- 238000007664 blowing Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000004321 preservation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910004261 CaF 2 Inorganic materials 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 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
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005259 measurement Methods 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
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 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
The invention relates to a barium calcium aluminate desulfurizing agent, a preparation method thereof and a preparation method of steel. The barium calcium aluminate desulfurizing agent comprises 3 CaO.Al 2 O 3 Phase, 12 CaO.7Al 2 O 3 Phase, 2BaO.6CaO.4SiO 2 Phase and BaO.Al 2 O 3 A phase; in the barium calcium aluminate desulfurizing agent, 3CaO.Al 2 O 3 Phase, 12 CaO.7Al 2 O 3 Phase, 2BaO.6CaO.4SiO 2 Phase and BaO.Al 2 O 3 The total mass ratio of the phases is more than or equal to 50 percent. The barium calcium aluminate desulfurizer can obviously reduce the melting point of the barium calcium aluminate desulfurizer, quicken the melting speed of the desulfurizer, and ensure that the desulfurizer can be completely liquefied as soon as possible and fully react with molten steel, thereby improving the desulfurization efficiency, shortening the desulfurization time and obtaining higher desulfurization rate under the condition of the same usage amount.
Description
Technical Field
The invention relates to the technical field of steelmaking, in particular to a barium calcium aluminate desulfurizing agent and a preparation method thereof as well as a preparation method of steel.
Background
Sulfur is a harmful impurity in steel, the influence of sulfur content on ferromagnetism of a silicon steel product is large, and development of low-sulfur silicon steel is an important direction for improving magnetic permeability of the silicon steel product and reducing iron loss. The modern steel production process flow mainly comprises the working procedures of converter-RH furnace-continuous casting and the like, and the desulfurization treatment of molten steel is usually carried out at the middle and later stages of refining in the RH furnace. However, the conventional desulfurizing agent for RH furnaces has the problems of large usage amount, long desulfurization time, low desulfurization rate and the like, and severely restricts the quality and productivity of silicon steel products.
Disclosure of Invention
Based on the above, it is necessary to provide a barium calcium aluminate desulfurizer, a preparation method thereof and a preparation method of steel, so as to solve the problems of large usage amount, long desulfurization time, low desulfurization rate and the like of the traditional desulfurizer for RH furnaces.
The above object of the present invention is achieved by the following technical solutions:
in a first aspect, the invention provides a barium calcium aluminate desulfurizer comprising 3 CaO.Al 2 O 3 Phase, 12 CaO.7Al 2 O 3 Phase, 2BaO.6CaO.4SiO 2 Phase and BaO.Al 2 O 3 A phase;
in the barium calcium aluminate desulfurizing agent, the 3 CaO.Al 2 O 3 Phase, 12 CaO.7Al 2 O 3 Phase, the 2BaO.6CaO.4SiO 2 Phase and the BaO.Al 2 O 3 The total mass ratio of the phases is more than or equal to 50 percent.
In one embodiment, in the barium calcium aluminate desulfurizer, the 2 BaO.6CaO.4SiO 2 Phase and the BaO.Al 2 O 3 The total mass ratio of the phases is more than or equal to 15 percent.
In one embodiment, the melting point of the barium calcium aluminate desulfurizer is 1230-1300 ℃.
In one embodiment, the barium calcium aluminate desulphurisation agent satisfies one or more of the following conditions:
1) The grain diameter is 3 mm-50 mm or less than or equal to 1mm;
2) The logarithmic sulfur capacity at 1450-1550 ℃ is-2.4 to-2.1;
3) Including for exampleThe following components in percentage by mass: caO,40% -50%; baO,8% -20%; al (Al) 2 O 3 ，30％～45％：SiO 2 ，1％～8％。
In a second aspect of the present invention, there is provided a method for preparing the barium calcium aluminate desulfurizing agent, comprising the steps of:
providing a mixture containing a calcium source, a barium source, an aluminum source and a silicon source;
completely melting the mixture to obtain a liquid mixture;
and cooling and solidifying the liquid mixture by a gradient cooling method to obtain the barium calcium aluminate desulfurizing agent.
In one embodiment, the completely melting the mixture comprises the steps of:
heating to 1500-1550 deg.C, and preserving heat for at least 15min.
In one embodiment, the step of completely melting the mixture further comprises a step of air stirring.
In one embodiment, the gas stream stirred gas is nitrogen and/or argon.
In one embodiment, the gradient cooling method comprises the following steps:
keeping the temperature of the liquid mixture at not less than 800 ℃ for not less than 24 hours;
cooling from 800 ℃ to 500 ℃ at a cooling rate of more than or equal to 150 ℃/h;
cooling from 500 ℃ to 300 ℃ at a cooling rate of more than or equal to 80 ℃/h;
cooling from 500 ℃ to room temperature at a cooling rate of more than or equal to 40 ℃/h.
In one embodiment, one or more of the following conditions are met:
1) The calcium source is quicklime powder and/or limestone powder;
2) The barium source is one or more of barium oxide powder, barium hydroxide powder and barium carbonate powder;
3) The aluminum source is alumina powder;
4) The particle size of the calcium source, the barium source and the aluminum source is respectively 50-200 meshes.
In a third aspect of the present invention, there is provided a method for producing a steel material comprising the step of desulfurizing molten steel with the barium calcium aluminate desulfurizing agent described above.
In one embodiment, the adding amount of the barium calcium aluminate desulfurizing agent is 3 kg-15 kg in each ton of molten steel.
The invention has the following beneficial effects:
in the barium calcium aluminate desulfurizing agent provided by the invention, 2BaO.6CaO.4SiO 2 Phase and BaO.Al 2 O 3 The melting point of the phase is within 1260-1290 ℃ and lower than CaO-Al 2 O 3 A system property phase; 3 CaO. Al 2 O 3 Phase and 12 CaO.7Al 2 O 3 The phase can enhance the activity of CaO to promote desulfurization. 3 CaO.Al 2 O 3 Phase, 12 CaO.7Al 2 O 3 Phase, 2BaO.6CaO.4SiO 2 Phase and BaO.Al 2 O 3 The total mass ratio of the phases is controlled to be more than 50%, the synergistic enhancement effect among the four phases can be fully exerted, the melting point of the barium calcium aluminate desulfurizing agent is obviously reduced, the melting speed of the desulfurizing agent is accelerated, and the desulfurizing agent can be completely liquefied as soon as possible and fully reacts with molten steel, so that the desulfurizing rate is improved, and the desulfurizing time is shortened. With CaO-Al 2 O 3 CaO-BaO-Al compared with the desulfurizing agent of the system 2 O 3 The sulfur capacity of the system is higher, and the desulfurization capability of the barium calcium aluminate desulfurizing agent can be further enhanced, so that the desulfurizing agent can obtain higher desulfurization rate under the condition of the same usage amount.
Detailed Description
The following detailed description of the present invention will provide further details in order to make the above-mentioned objects, features and advantages of the present invention more comprehensible. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, whereby the invention is not limited to the specific embodiments disclosed below.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Terminology and definition:
in the present invention, particle size refers to the size of particles, also known as particle size. Specifically, the particle diameter of the spherical particles is the diameter of the measured particles, and the particle diameter of the non-spherical particles is usually expressed by the equivalent particle diameter, that is, the particle diameter of a homogeneous spherical particle having the same volume or the same projected area as the measured particles is used as the particle diameter of the measured particles.
In the invention, the Sulfur Capacity (Cs) is an important index for measuring the desulfurization Capacity of the desulfurizing agent in the metallurgical process, and can be obtained by calculation by thermodynamic software such as FactSage and the like, and also can be measured by an experimental method. The logarithmic sulfur capacity (lgCs) is a logarithm of 10 in terms of sulfur capacity, and the greater the logarithmic sulfur capacity, the greater the desulfurization ability of the desulfurizing agent.
In the present invention, the air flow stirring is a method of stirring by introducing air flow into liquid or solid-liquid mixture.
In the present invention, room temperature means an indoor temperature, a general temperature or a normal temperature, and the range thereof is usually 15 to 30 ℃.
The vacuum refining of molten steel by using an RH furnace is a key technology for obtaining high-quality steel, and can effectively remove carbon, carbon and carbon in the molten steel,Oxygen, sulfur, phosphorus, and the like. Wherein the desulfurization treatment is carried out in the middle and later stages of RH furnace refining, and the common desulfurizing agent mainly comprises CaO-CaF 2 Slag system and CaO-Al 2 O 3 Slag is of two types.
CaO-CaF 2 The slag system is the currently accepted desulfurizing agent with the highest sulfur capacity, but in the actual desulfurization process, caO-CaF 2 The desulfurization effect of the slag system is not ideal and stable, and fluoride can seriously erode steelmaking equipment to cause environmental pollution. Whereas CaO-Al 2 O 3 The slag system has high melting point and slow relative slag forming speed, so that the desulfurization effect is not ideal, and the productivity and quality of steel products such as silicon steel and the like are seriously affected.
This is because the desulfurizing agent for RH furnace has a short residence time in the vacuum chamber during the desulfurization treatment, and does not play a role in desulfurization after leaving the vacuum chamber. In the vacuum chamber, caO-Al 2 O 3 The slag system has a high melting point and does not completely melt when in contact with molten steel, so that there is insufficient reaction between the desulfurizing agent and molten steel, and the desulfurizing rate is low when the amount of the desulfurizing agent added is small. If the desulfurization rate is to be increased, it is generally necessary to increase the amount of the desulfurizing agent and to lengthen the desulfurization time, which leads to a significant increase in the cost of the desulfurization treatment. The inventor further researches and discovers that the components and the content of each phase in the desulfurizing agent can influence the melting point of the desulfurizing agent, and further greatly influence the use amount, the desulfurizing time, the sulfur capacity, the desulfurizing rate and other performances of the desulfurizing agent.
Based on the above, the first aspect of the invention provides a barium calcium aluminate desulfurizer to solve the problems of large usage amount, long desulfurization time, low desulfurization rate and the like of the traditional desulfurizer.
In some embodiments, the barium calcium aluminate desulphurisation agent comprises 3cao.al 2 O 3 Phase, 12 CaO.7Al 2 O 3 Phase, 2BaO.6CaO.4SiO 2 Phase and BaO.Al 2 O 3 A phase;
in the barium calcium aluminate desulfurizing agent, 3CaO.Al 2 O 3 Phase, 12 CaO.7Al 2 O 3 Phase, 2BaO.6CaO.4SiO 2 Phase and BaO.Al 2 O 3 The total mass ratio of the phases is more than or equal to 50 percent.
In the barium calcium aluminate desulfurizing agent provided by the invention, 2BaO.6CaO.4SiO 2 Phase and BaO.Al 2 O 3 The melting point of the phase is within 1260-1290 ℃ and lower than CaO-Al 2 O 3 A system property phase; 3 CaO. Al 2 O 3 Phase and 12 CaO.7Al 2 O 3 The phase can enhance the activity of CaO to promote desulfurization. 3 CaO.Al 2 O 3 Phase, 12 CaO.7Al 2 O 3 Phase, 2BaO.6CaO.4SiO 2 Phase and BaO.Al 2 O 3 The total mass ratio of the phases is controlled to be more than 50%, the synergistic enhancement effect among the four phases can be fully exerted, the melting point of the barium calcium aluminate desulfurizing agent is obviously reduced, the melting speed of the desulfurizing agent is accelerated, and the desulfurizing agent can be completely liquefied as soon as possible and fully reacts with molten steel, so that the desulfurizing rate is improved, and the desulfurizing time is shortened. With CaO-Al 2 O 3 CaO-BaO-Al compared with the desulfurizing agent of the system 2 O 3 The sulfur capacity of the system is higher, and the desulfurization capability of the barium calcium aluminate desulfurizing agent can be further enhanced, so that the desulfurizing agent can obtain higher desulfurization rate under the condition of the same usage amount.
Optionally, in the barium calcium aluminate desulfurizing agent, 3CaO.Al 2 O 3 Phase, 12 CaO.7Al 2 O 3 Phase, 2BaO.6CaO.4SiO 2 Phase and BaO.Al 2 O 3 The total mass ratio of the phases is 50-95%, in some specific examples, 3CaO.Al 2 O 3 Phase, 12 CaO.7Al 2 O 3 Phase, 2BaO.6CaO.4SiO 2 Phase and BaO.Al 2 O 3 The total mass ratio of the phases in the barium calcium aluminate desulfurizing agent can be 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95%, etc.
In some embodiments, in the barium calcium aluminate desulphurizer, 2BaO.6CaO.4SiO 2 Phase and BaO.Al 2 O 3 The total mass ratio of the phases is more than or equal to 15 percent.
Optionally, in the barium calcium aluminate desulfurizing agent, 2BaO.6CaO.4SiO 2 Phase and BaO.Al 2 O 3 The total mass ratio of the phases is 15% to 35%, in some specific examples，2BaO·6CaO·4SiO 2 Phase and BaO.Al 2 O 3 The total mass ratio of the phases in the barium calcium aluminate desulfurizing agent can be 15%, 20%, 25%, 30% or 35% and the like.
2BaO·6CaO·4SiO 2 Phase and BaO.Al 2 O 3 The melting point of the phases is between 1260 ℃ and 1290 ℃, the sulfur capacity of BaO is higher, the total mass ratio of the two phases is increased as much as possible, and the desulfurization capacity of the barium calcium aluminate desulfurizing agent can be further improved.
In some embodiments, the barium calcium aluminate desulphurisation agent comprises the following components in mass ratio: caO,40% -50%; baO,8% -20%; al (Al) 2 O 3 ，30％～45％；SiO 2 1% -8%; the balance being impurities.
CaO, baO, al in the barium calcium aluminate desulfurizing agent 2 O 3 And SiO 2 The mass ratio of the components is controlled in a proper range, which is favorable for forming 3 CaO.Al in the desulfurizing agent 2 O 3 Phase, 12 CaO.7Al 2 O 3 Phase, 2BaO.6CaO.4SiO 2 Phase and BaO.Al 2 O 3 And (3) equaling the phases and controlling the total content of the phases within a specific range.
Further alternatively, in the barium calcium aluminate desulfurizing agent, the mass ratio of the components of the impurities should satisfy the following conditions: mgO is less than or equal to 8 percent; tiO (titanium dioxide) 2 ≤0.1％；C≤0.15％；S≤0.1％。
The upper limit value of the impurity component in the barium calcium aluminate desulfurizer is controlled, so that the impurity component can be prevented from entering molten steel in the desulfurization process to influence the cleanliness of the molten steel, and the product quality is improved.
In some embodiments, the barium calcium aluminate desulfurization agent has a melting point of 1230 ℃ to 1300 ℃. In some specific examples, the barium calcium aluminate desulfurizing agent may have a melting point of 1230 ℃, 1235 ℃, 1240 ℃, 1245 ℃, 1250 ℃, 1255 ℃, 1260 ℃, 1265 ℃, 1270 ℃, 1275 ℃, 1280 ℃, 1285 ℃, 1290 ℃, 1295 ℃, 1300 ℃, or the like.
The smelting temperature of molten steel is about 1550-1600 ℃, the interface temperature of desulfurizing agent and molten steel is about 1500 ℃, the melting point of barium calcium aluminate desulfurizing agent is 1230-1300 ℃, the desulfurizing agent and molten steel can be quickly melted to form liquid phase, sufficient liquid phase desulfurizing reaction occurs between the liquid desulfurizing agent and molten steel, the desulfurizing speed is high, the desulfurizing agent utilization rate is high, and the desulfurizing rate is greatly improved.
In some embodiments, the barium calcium aluminate desulfurization agent has a logarithmic sulfur capacity of-2.4 to-2.1 at 1450 ℃ to 1550 ℃. In some specific examples, the barium calcium aluminate desulphurisation agent may have a logarithmic sulphur capacity of-2.40, -2.35, -2.30, -2.25, -2.20, -2.15 or-2.10, etc. at 1450-1550 ℃.
Alternatively, the particle size of the barium calcium aluminate desulphurisation agent is from 3mm to 50mm, in some specific examples the particle size of the barium calcium aluminate desulphurisation agent may be 3mm, 5mm, 10mm, 15mm, 20mm, 25mm, 30mm, 35mm, 40mm, 45mm or 50mm etc.
Alternatively, the particle size of the barium calcium aluminate desulfurizer is less than or equal to 1mm, and in some specific examples, the particle size of the barium calcium aluminate desulfurizer may be 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, 1mm, or the like.
The particle size of the barium calcium aluminate desulfurizer is controlled within the range of 3-50 mm, so that on one hand, the specific surface area of the desulfurizer can be increased, the desulfurizer is beneficial to being rapidly dispersed and reacted in molten steel, the desulfurization rate is accelerated, on the other hand, the desulfurizer can be prevented from being easy to fly and lose due to the too small particle size, and the problem of too high processing cost of the small particle size is avoided. The particle size of the barium calcium aluminate desulfurizer is controlled to be less than or equal to 1mm, the desulfurizer is suitable for desulfurizing molten steel by a spray method, the desulfurizer can be uniformly dispersed in a very short time, and the desulfurization effect is further improved.
In a second aspect of the invention, a method for preparing a barium calcium aluminate desulfurizing agent is provided, which is used for preparing the barium calcium aluminate desulfurizing agent.
In some embodiments, the method of preparing the barium calcium aluminate desulfurization agent comprises the steps of:
providing a mixture containing a calcium source, a barium source, an aluminum source and a silicon source;
completely melting the mixture to obtain a liquid mixture;
and cooling and solidifying the liquid mixture by a gradient cooling method to obtain the barium calcium aluminate desulfurizing agent.
The invention carries out melting treatment on the mixture, promotes the calcium source, the barium source, the aluminum source and the silicon source in the mixture to interact, and forms 3 CaO-Al with low melting point in the gradient cooling process 2 O 3 Phase, 12 CaO.7Al 2 O 3 Phase, 2BaO.6CaO.4SiO 2 Phase and BaO.Al 2 O 3 The melting point of the barium calcium aluminate desulfurizer is reduced, and the melting speed in the use process is increased, so that higher desulfurization rate is obtained under the condition of the same feeding amount of the desulfurizer.
In some embodiments, providing a mixture comprising a calcium source, a barium source, an aluminum source, and a silicon source includes the steps of: and respectively grinding a calcium source, a barium source, an aluminum source and a silicon source, and mixing to obtain a mixture.
The silicon oxide content in the barium calcium aluminate desulfurizing agent is only 1% -8%, and the raw materials such as silicon oxide powder and the like can be generally not independently added as a silicon source, but exist in the form of impurities in a calcium source, a barium source and an aluminum source, namely one or more of the calcium source, the barium source and the aluminum source can be simultaneously used as the silicon source. If the purity of the calcium source, the barium source and the aluminum source is high, a small amount of silicon oxide powder can be additionally added as a silicon source when the content of silicon oxide is insufficient.
Optionally, the calcium source is quicklime powder and/or limestone powder.
The quicklime (CaO) powder meets the quality requirement of the second level of common metallurgical lime in YB/T042-2014 metallurgical lime, namely, the mass fractions of the components are as follows: caO is more than or equal to 85 percent, mgO<5％，SiO 2 Less than or equal to 3.5 percent and S less than or equal to 0.05 percent. Limestone (CaCO) 3 ) The powder meets the quality requirement of the common limestone PS530 in YB/T5279-2005 limestone, namely the mass fractions of the components are as follows: caO is more than or equal to 53 percent, mgO is less than or equal to 3.0 percent, siO 2 ≤1.5％，S≤0.035％。
Optionally, the barium source is one or more of barium oxide powder, barium hydroxide powder, and barium carbonate powder.
In the barium oxide (BaO) powder, the mass fraction of BaO is more than or equal to 90 percent, siO 2 Can be 1% to 1% by mass10%. Barium hydroxide (Ba (OH) 2 ) The powder meets the quality requirements of superior products in HG/T2566-2006 industrial barium hydroxide, namely Ba (OH) 2 The mass fraction of (2) is more than or equal to 98.0%. Barium carbonate (BaCO) 3 ) The powder meets the quality requirement of superior products in GB/T1614-2021 industrial barium carbonate, namely BaCO 3 The mass fraction of (2) is more than or equal to 99.2%.
Optionally, the aluminum source is alumina powder.
Alumina (Al) 2 O 3 ) The powder meets the quality requirement of at least one brand of YAO-1, YAO-2 and YAO-3 in YS/T803-2012 metallurgical grade alumina, namely the mass fraction of each component is as follows: al (Al) 2 O 3 ≥98.4％，SiO 2 ≤0.06％。
Optionally, the method of grinding treatment is one or more of ball milling, mechanical grinding and ultrasonic grinding.
Alternatively, the particle size of the calcium source, barium source, aluminum source, and silicon source are each independently 50 mesh to 200 mesh (i.e., 74 μm to 280 μm). In some specific examples, the particle sizes of the calcium source, the barium source, the aluminum source, and the silicon source may each independently be 50 mesh, 60 mesh, 70 mesh, 80 mesh, 90 mesh, 100 mesh, 110 mesh, 120 mesh, 130 mesh, 140 mesh, 150 mesh, 160 mesh, 170 mesh, 180 mesh, 190 mesh, 200 mesh, or the like.
By controlling the particle sizes of the calcium source, the barium source, the aluminum source and the silicon source, the raw materials are ensured to have larger specific surface area, the rapid melting, diffusion, decomposition and interaction of the raw materials are facilitated, and the formation of a low-melting-point phase is promoted.
In some embodiments, completely melting the mix comprises the steps of:
heating to 1500-1550 deg.C, and preserving heat for at least 15min.
In some specific examples, the target temperature of the elevated temperature may be 1500 ℃, 1505 ℃, 1510 ℃, 1515 ℃, 1520 ℃, 1525 ℃, 1530 ℃, 1535 ℃, 1540 ℃, 1545 ℃,1550 ℃, or the like; the incubation time may be 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min, 120min, etc.
The temperature is raised to 1500 ℃ to 1550 ℃ to enable the mixture to be completely melted to form liquid mixture. The temperature is kept for at least 15min within the range of 1500-1550 ℃, so that each phase in the liquid mixture can be uniformly dispersed, and the melting point of the barium calcium aluminate desulfurizing agent is ensured to be stable.
Optionally, the step of completely melting the mixture further comprises a step of air stirring.
The device for stirring the air flow is simple, has no stirring component, is suitable for stirring high-temperature liquid or corrosive liquid, and can further improve the dispersion uniformity of the liquid mixture. At the same time, the gas flow stirring also takes away volatile components in the raw materials, such as CO generated by carbonate decomposition 2 Promote the decomposition and interaction of the raw materials.
Further optionally, the gas stream stirred gas is nitrogen and/or argon.
The nitrogen and the argon are inert gases, and can protect the mixture from O in the melting process 2 、CO 2 The influence of reactive gases, etc., to avoid oxidation of impurity elements in the mixture and to prevent alkaline oxides such as CaO, baO, etc. and CO 2 The reaction forms carbonate products, thereby ensuring the advantages of low melting point and high sulfur capacity of the desulfurizing agent.
In some embodiments, the gradient cooling method comprises the steps of:
keeping the temperature of the liquid mixture at not less than 800 ℃ for not less than 24 hours;
cooling from 800 ℃ to 500 ℃ at a cooling rate of more than or equal to 150 ℃/h;
cooling from 500 ℃ to 300 ℃ at a cooling rate of more than or equal to 80 ℃/h;
cooling from 500 ℃ to room temperature at a cooling rate of more than or equal to 40 ℃/h.
By the gradient cooling method, the liquid mixture can be promoted to perform phase transformation under slow temperature change, and the phenomenon that enough 3CaO and Al cannot be formed due to too fast temperature change is avoided 2 O 3 Phase, 12 CaO.7Al 2 O 3 Phase, 2BaO.6CaO.4SiO 2 Phase and BaO.Al 2 O 3 And (3) phase (C).
Optionally, keeping the liquid mixture at a temperature of not less than 800 ℃ for not less than 24 hours comprises the following steps:
the liquid mixture is placed in an iron container, and the heat preservation is carried out by adopting a capping heat preservation method.
Optionally, after heat preservation is carried out for more than or equal to 24 hours at the temperature of more than or equal to 800 ℃, the temperature is reduced to room temperature in a gradient way by adopting a blowing cooling method, so that the blocky barium calcium aluminate desulfurizing agent is obtained.
Optionally, the liquid mixture is cooled and solidified and then crushed.
Further alternatively, the bulk barium calcium aluminate desulfurizer obtained by gradient cooling is subjected to manual crushing and mechanical crushing in sequence to obtain the barium calcium aluminate desulfurizer with the particle size of 3-50 mm.
Optionally, the step of grinding is further included after crushing the bulk barium calcium aluminate desulphurisation agent.
Further alternatively, ball milling, mechanical grinding or ultrasonic grinding are carried out on the barium calcium aluminate desulfurizing agent with the particle size of 3-50 mm, so as to obtain the barium calcium aluminate desulfurizing agent with the particle size of less than or equal to 1 mm.
In a third aspect of the present invention, there is provided a method for producing a steel material comprising the step of desulfurizing molten steel by using the above-mentioned barium calcium aluminate desulfurizing agent.
Optionally, the adding amount of the barium calcium aluminate desulfurizing agent in each ton of molten steel is 3 kg-15 kg.
The present invention will be described in further detail with reference to specific examples. The raw materials used in the following examples are all commercially available products unless otherwise specified.
Example 1
Ball milling quicklime powder (containing silicon oxide impurities), barium carbonate powder and alumina powder respectively to a particle size of 50-200 meshes, and then adding the quicklime powder, the barium carbonate powder and the alumina powder into a mixing bin for uniform mixing to obtain a mixture; placing the mixture into an electric furnace, heating to 1500 ℃ to enable the mixture to be completely melted, preserving heat for 30min, introducing nitrogen during heating and heat preserving, and stirring by air flow to obtain a liquid mixture; pouring the liquid mixture into an iron container, and blowing by using a blower to cool the liquid mixture to room temperature to obtain a blocky barium calcium aluminate desulfurizing agent; the blocky barium calcium aluminate desulfurizing agent is crushed manually and then is put into a jaw crusher for mechanical crushing, and the barium calcium aluminate desulfurizing agent with the grain diameter of 3 mm-50 mm is obtained.
Referring to Table 1, the barium calcium aluminate desulfurizing agent comprises the following components in percentage by mass: caO,42%; baO,19%; al (Al) 2 O 3 ，35％；SiO 2 ，2％；MgO，1.8％；TiO 2 0.03%; c,0.08%; s,0.04%. Referring to Table 2, the barium calcium aluminate desulfurizing agent comprises the following phases in percentage by mass: 3 CaO. Al 2 O 3 Phase, 37.1%;12 CaO.7Al 2 O 3 Phase, 3.4%;2 BaO.6CaO.4SiO 2 Phase, 7.1%; baO.Al 2 O 3 Phase, 25.2%. In Table 2, C 3 A represents 3 CaO. Al 2 O 3 Phase C 12 A 7 Represents 12 CaO.7Al 2 O 3 Phase B 2 C 6 S 4 Represents 2BaO.6CaO.4SiO 2 Phase, BA represents BaO.Al 2 O 3 And (3) phase (C).
Example 2
Ball milling quicklime powder (containing silicon oxide impurities), barium carbonate powder and alumina powder respectively to a particle size of 50-200 meshes, and then adding the quicklime powder, the barium carbonate powder and the alumina powder into a mixing bin for uniform mixing to obtain a mixture; placing the mixture in an electric furnace, heating to 1525 ℃ to enable the mixture to be completely melted, preserving heat for 20min, introducing argon gas during heating and heat preservation, and stirring by air flow to obtain a liquid mixture; pouring the liquid mixture into an iron container, and blowing by using a blower to cool the liquid mixture to room temperature to obtain a blocky barium calcium aluminate desulfurizing agent; the blocky barium calcium aluminate desulfurizing agent is crushed manually and then is put into a jaw crusher for mechanical crushing, and the barium calcium aluminate desulfurizing agent with the grain diameter of 3 mm-50 mm is obtained.
Referring to Table 1, the barium calcium aluminate desulfurizing agent comprises the following components in percentage by mass: caO,45%; baO,15%; al (Al) 2 O 3 ，36％；SiO 2 ，2％；MgO，1.6％；TiO 2 ，0.04％；C，0.11％；S，0.06％。Referring to Table 2, the barium calcium aluminate desulfurizing agent comprises the following phases in percentage by mass: 3 CaO. Al 2 O 3 Phase, 40.7%;12 CaO.7Al 2 O 3 Phase, 7.4%;2 BaO.6CaO.4SiO 2 Phase, 6.3%; baO.Al 2 O 3 Phase, 19.1%.
Example 3
Ball milling quicklime powder (containing silicon oxide impurities), barium carbonate powder and alumina powder respectively to a particle size of 50-200 meshes, and then adding the quicklime powder, the barium carbonate powder and the alumina powder into a mixing bin for uniform mixing to obtain a mixture; placing the mixture in an electric furnace, heating to 1550 ℃ to enable the mixture to be completely melted, preserving heat for 15min, introducing argon gas during heating and heat preserving to carry out air flow stirring, and obtaining a liquid mixture; pouring the liquid mixture into an iron container, and blowing by using a blower to cool the liquid mixture to room temperature to obtain a blocky barium calcium aluminate desulfurizing agent; the blocky barium calcium aluminate desulfurizing agent is crushed manually and then is put into a jaw crusher for mechanical crushing, and the barium calcium aluminate desulfurizing agent with the grain diameter of 3 mm-50 mm is obtained.
Referring to Table 1, the barium calcium aluminate desulfurizing agent comprises the following components in percentage by mass: caO,49%; baO,9%; al (Al) 2 O 3 ，38％；SiO 2 ，2％；MgO，1.7％；TiO 2 0.06%; c,0.04%; s,0.05%. Referring to Table 2, the barium calcium aluminate desulfurizing agent comprises the following phases in percentage by mass: 3 CaO. Al 2 O 3 Phase, 53.2%;12 CaO.7Al 2 O 3 Phase, 13.4%;2 BaO.6CaO.4SiO 2 Phase, 6.5%; baO.Al 2 O 3 11.2% of phase.
Comparative example 1
The desulfurizing agent of the comparative example is a BaO-free calcium aluminate desulfurizing agent, and the particle size is 3-50 mm.
Referring to Table 1, the calcium aluminate desulfurizing agent comprises the following components in percentage by mass: caO,54%; al (Al) 2 O 3 ，42％；SiO 2 ，2％；MgO，1.5％；TiO 2 0.04%; c,0.07%; s,0.04%. Please refer toReading table 2, the calcium aluminate desulfurizing agent comprises the following phases in percentage by mass: 3 CaO. Al 2 O 3 Phase, 32.0%;12 CaO.7Al 2 O 3 Phase, 43.0%.
Comparative example 2
The temperature of the melting treatment of the barium calcium aluminate desulfurizing agent in the comparative example is lower than 1500 ℃.
Ball milling quicklime powder (containing silicon oxide impurities), barium carbonate powder and alumina powder respectively to a particle size of 50-200 meshes, and then adding the quicklime powder, the barium carbonate powder and the alumina powder into a mixing bin for uniform mixing to obtain a mixture; placing the mixture in an electric furnace, heating to 1250 ℃ to enable the mixture to be completely melted, preserving heat for 15min, introducing argon gas during heating and heat preserving to carry out airflow stirring, and obtaining a liquid mixture; pouring the liquid mixture into an iron container, and blowing by using a blower to cool the liquid mixture to room temperature to obtain a blocky barium calcium aluminate desulfurizing agent; the blocky barium calcium aluminate desulfurizing agent is crushed manually and then is put into a jaw crusher for mechanical crushing, and the barium calcium aluminate desulfurizing agent with the grain diameter of 3 mm-50 mm is obtained.
Referring to Table 1, the barium calcium aluminate desulfurizing agent comprises the following components in percentage by mass: caO,49%; baO,9%; al (Al) 2 O 3 ，38％；SiO 2 ，2％；MgO，1.7％；TiO 2 0.06%; c,0.04%; s,0.06%. Referring to Table 2, the barium calcium aluminate desulfurizing agent comprises the following phases in percentage by mass: 3 CaO. Al 2 O 3 Phase, 21.0%;12 CaO.7Al 2 O 3 Phase, 10.4%;2 BaO.6CaO.4SiO 2 Phase, 0%; baO.Al 2 O 3 Phase, 4.2%.
Comparative example 3
The barium calcium aluminate desulfurizing agent of the comparative example was not subjected to gradient cooling.
Ball milling quicklime powder (containing silicon oxide impurities), barium carbonate powder and alumina powder respectively to a particle size of 50-200 meshes, and then adding the quicklime powder, the barium carbonate powder and the alumina powder into a mixing bin for uniform mixing to obtain a mixture; placing the mixture in an electric furnace, heating to 1530 ℃ to enable the mixture to be completely melted, preserving heat for 15min, introducing argon gas during heating and heat preserving to perform air flow stirring to obtain a liquid mixture; pouring the liquid mixture into an iron container, and naturally cooling the liquid mixture for 3 days to room temperature to obtain a blocky barium calcium aluminate desulfurizing agent; the blocky barium calcium aluminate desulfurizing agent is crushed manually and then is put into a jaw crusher for mechanical crushing, and the barium calcium aluminate desulfurizing agent with the grain diameter of 3 mm-50 mm is obtained.
Referring to Table 1, the barium calcium aluminate desulfurizing agent comprises the following components in percentage by mass: caO,49%; baO,9%; al (Al) 2 O 3 ，38％；SiO 2 ，2％；MgO，1.7％；TiO 2 0.06%; c,0.04%; s,0.06%. Referring to Table 2, the barium calcium aluminate desulfurizing agent comprises the following phases in percentage by mass: 3 CaO. Al 2 O 3 15.3% of phase; 12 CaO.7Al 2 O 3 Phase, 3.4%;2 BaO.6CaO.4SiO 2 Phase, 1.9%; baO.Al 2 O 3 8.2% of phase.
Test case
The content of oxides in the barium calcium aluminate desulfurizer was tested by an X-ray fluorescence spectrometer, and the carbon content and the sulfur content in the barium calcium aluminate desulfurizer were tested by referring to the high-frequency induction furnace infrared absorption method after combustion, which is a measurement of the total carbon and sulfur content of iron and steel, GB/T20123-2006, and the results are shown in Table 1. The components in the barium calcium aluminate desulfurizer are input into thermodynamic software FactSage to calculate the phase, melting point and logarithmic sulfur capacity, wherein the mass ratio of the phase of the barium calcium aluminate desulfurizer is shown in table 2, and the melting point and the logarithmic sulfur capacity are shown in table 3.
As is clear from Table 2, the barium calcium aluminate desulfurizing agents of examples 1 to 3 were 2BaO.6CaO.4SiO 2 Phase and BaO.Al 2 O 3 The total mass ratio of the phases is 17.7-32.3%, and the total mass ratio of the four target phases is 73.5-84.3%. The calcium aluminate desulfurizing agent of comparative example 1 contains only 3CaO.Al 2 O 3 Phase and 12 CaO.7Al 2 O 3 Two phases; the calcium aluminate desulphurants of comparative example 2 and comparative example 3 did not form enough 3 CaO-ai 2 O 3 Phase, 12 CaO.7Al 2 O 3 Phase, 2BaO.6CaO.4SiO 2 Phase and BaO.Al 2 O 3 The total mass ratio of the four target phases is lower than 50%, and the total mass ratio of the phase containing BaO is lower than 15%.
As can be seen from table 3, the melting point of the barium calcium aluminate desulfurizing agent of example 1 is 1296 ℃ and logarithmic sulfur capacity lgcs= -2.18 at 1550 ℃. At 1550 ℃, the 33-furnace molten steel is desulfurized, 150 tons (t) of molten steel are contained in each furnace of molten steel, the adding amount of the barium calcium aluminate desulfurizing agent in each ton of molten steel is 4 kg-9 kg, and the average value is 7.1kg. After desulfurization treatment, the mean value of desulfurization rate was 64.6% and the variance was 5.8%.
The melting point of the barium calcium aluminate desulphurisation agent of example 2 is 1282 ℃, logarithmic sulphur capacity lgcs= -2.24 at 1550 ℃. Desulfurizing 23 molten steel at 1550 deg.c, with 150 tons of molten steel, and adding barium calcium aluminate desulfurizing agent in 5-8 kg and average value of 7.12kg. After desulfurization treatment, the mean value of desulfurization rate was 62.8% and the variance was 6.1%.
The melting point of the barium calcium aluminate desulphurisation agent of example 3 is 1263 ℃, logarithmic sulphur capacity lgcs= -2.32 at 1550 ℃. Desulfurizing 18 molten steel at 1550 deg.c, with 150 tons of molten steel, and adding barium calcium aluminate desulfurizing agent in the amount of 4-8 kg and average value of 7.05kg. After desulfurization treatment, the mean value of desulfurization rate was 56.3% and the variance was 6.7%.
The melting point of the calcium aluminate desulfurizing agent of comparative example 1 is 1358 ℃, and the logarithmic sulfur capacity lgcs= -2.52 at 1550 ℃. Desulfurizing 88 molten steel at 1550 deg.c, with 150 tons of molten steel, the amount of calcium aluminate desulfurizing agent added in each ton of molten steel being 4-9 kg and average value being 7.15kg. After desulfurization treatment, the mean value of desulfurization rate was 48.3% and the variance was 7.7%.
The melting point of the barium calcium aluminate desulfurizing agent of comparative example 2 is 1343 ℃, and logarithmic sulfur capacity lgcs= -2.32 at 1550 ℃. Desulfurizing 14 molten steel at 1550 deg.c, with 150 tons of molten steel, and adding barium calcium aluminate desulfurizing agent in 5-9 kg and average value of 7.08kg. After desulfurization treatment, the mean value of desulfurization rate was 51.4% and the variance was 9.3%.
The melting point of the barium calcium aluminate desulfurizing agent of comparative example 3 is 1313 ℃, and logarithmic sulfur capacity lgcs= -2.32 at 1550 ℃. Desulfurizing 17 molten steel at 1550 deg.c, with 150 tons of molten steel, and adding 6-9 kg of barium calcium aluminate desulfurizing agent in each ton of molten steel, and average kg-7.25 kg. After desulfurization treatment, the mean value of desulfurization rate was 50.2% and the variance was 8.9%.
By contrast, the melting point of the calcium aluminate desulfurizing agent of examples 1-3 is in the range of 1230-1300 ℃, the melting speed is high during desulfurization treatment, higher logarithmic sulfur capacity and desulfurization rate can be obtained under the condition that the using amount of the desulfurizing agent is the same, and the problems of large using amount of the desulfurizing agent, long desulfurization time, low desulfurization rate and the like are avoided. Among them, the calcium aluminate desulfurizing agent of example 1 had the strongest desulfurizing ability and the most stable desulfurizing effect.
TABLE 1 mass ratio of components of desulfurizing agent (wt.%)
| CaO | BaO | Al 2 O 3 | SiO 2 | MgO | TiO 2 | C | S | |
| Example 1 | 42 | 19 | 35 | 2 | 1.8 | 0.03 | 0.08 | 0.04 |
| Example 2 | 45 | 15 | 36 | 2 | 1.6 | 0.04 | 0.11 | 0.06 |
| Example 3 | 49 | 9 | 38 | 2 | 1.7 | 0.06 | 0.04 | 0.05 |
| Comparative example 1 | 54 | / | 42 | 2 | 1.5 | 0.04 | 0.07 | 0.04 |
| Comparative example 2 | 49 | 9 | 38 | 2 | 1.7 | 0.06 | 0.08 | 0.06 |
| Comparative example 3 | 49 | 9 | 38 | 2 | 1.7 | 0.05 | 0.05 | 0.04 |
Table 2. Mass ratio of phases of desulfurizing agent (wt.%)
| C 3 A | C 12 A 7 | B 2 C 6 S 4 | BA | BaO-containing phase | Four object phases | |
| Example 1 | 37.1 | 3.4 | 7.1 | 25.2 | 32.3 | 72.8 |
| Example 2 | 40.7 | 7.4 | 6.3 | 19.1 | 25.4 | 73.5 |
| Example 3 | 53.2 | 13.4 | 6.5 | 11.2 | 17.7 | 84.3 |
| Comparative example 1 | 32.0 | 43.0 | / | / | / | 75.0 |
| Comparative example 2 | 21.0 | 10.4 | 0 | 4.2 | 4.2 | 35.6 |
| Comparative example 3 | 15.3 | 3.4 | 1.9 | 8.2 | 10.1 | 28.8 |
TABLE 3 comparison of the Performance of desulfurizing Agents
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. The scope of the invention is, therefore, indicated by the appended claims, and the description may be intended to interpret the contents of the claims.
Claims (12)
1. A barium calcium aluminate desulfurizing agent is characterized by comprising 3 CaO.Al 2 O 3 Phase, 12 CaO.7Al 2 O 3 Phase, 2BaO.6CaO.4SiO 2 Phase and BaO.Al 2 O 3 A phase;
in the barium calcium aluminate desulfurizing agent, the 3 CaO.Al 2 O 3 Phase, 12 CaO.7Al 2 O 3 Phase, the 2BaO.6CaO.4SiO 2 Phase and the BaO.Al 2 O 3 The total mass ratio of the phases is more than or equal to 50 percent.
2. The barium calcium aluminate desulfurizing agent according to claim 1, wherein in the barium calcium aluminate desulfurizing agent, the 2bao.6cao.4sio 2 Phase and the BaO.Al 2 O 3 The total mass ratio of the phases is more than or equal to 15 percent.
3. The barium calcium aluminate desulfurization agent according to claim 2, wherein the melting point of the barium calcium aluminate desulfurization agent is 1230 ℃ to 1300 ℃.
4. A barium calcium aluminate desulphurisation agent according to any one of claims 1 to 3, wherein the barium calcium aluminate desulphurisation agent meets one or more of the following conditions:
1) The grain diameter is 3 mm-50 mm or less than or equal to 1mm;
2) The logarithmic sulfur capacity at 1450-1550 ℃ is-2.4 to-2.1;
3) Comprises the following components in percentage by mass: caO,40% -50%; baO,8% -20%; al (Al) 2 O 3 ，30％～45％；SiO 2 ，1％～8％。
5. A method for preparing the barium calcium aluminate desulfurizing agent according to any one of claims 1 to 4, comprising the steps of:
providing a mixture containing a calcium source, a barium source, an aluminum source and a silicon source;
completely melting the mixture to obtain a liquid mixture;
and cooling and solidifying the liquid mixture by a gradient cooling method to obtain the barium calcium aluminate desulfurizing agent.
6. The method for preparing a barium calcium aluminate desulfurizing agent according to claim 5, wherein said completely melting said mixture comprises the steps of:
heating to 1500-1550 deg.C, and preserving heat for at least 15min.
7. The method of preparing a barium calcium aluminate desulfurization agent according to claim 6, wherein the step of completely melting the mixture further comprises a step of air-flow agitation.
8. The method for preparing a barium calcium aluminate desulfurizing agent according to claim 7, wherein the gas stirred by the gas flow is nitrogen and/or argon.
9. The method for preparing a barium calcium aluminate desulfurizing agent according to claim 5, wherein the gradient cooling method comprises the steps of:
keeping the temperature of the liquid mixture at not less than 800 ℃ for not less than 24 hours;
cooling from 800 ℃ to 500 ℃ at a cooling rate of more than or equal to 150 ℃/h;
cooling from 500 ℃ to 300 ℃ at a cooling rate of more than or equal to 80 ℃/h;
cooling from 500 ℃ to room temperature at a cooling rate of more than or equal to 40 ℃/h.
10. The method of preparing a barium calcium aluminate desulfurization agent according to claim 5, wherein one or more of the following conditions are satisfied:
1) The calcium source is quicklime powder and/or limestone powder;
2) The barium source is one or more of barium oxide powder, barium hydroxide powder and barium carbonate powder;
3) The aluminum source is alumina powder;
4) The particle size of the calcium source, the barium source and the aluminum source is respectively 50-200 meshes.
11. A method for producing a steel material, comprising the step of desulfurizing molten steel with the barium calcium aluminate desulfurizing agent according to any one of claims 1 to 4.
12. The method for producing steel according to claim 11, wherein the amount of the barium calcium aluminate desulfurizing agent added is 3kg to 15kg per ton of molten steel.
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| CN117732460A (en) * | 2023-12-18 | 2024-03-22 | 湖北禾谷环保有限公司 | Chlorine-resistant COS hydrolysis catalyst and preparation method and application thereof |
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