CN117604193A - Slag conglomeration agent containing rare earth oxide, preparation process and application thereof - Google Patents
Slag conglomeration agent containing rare earth oxide, preparation process and application thereof Download PDFInfo
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- CN117604193A CN117604193A CN202311539574.1A CN202311539574A CN117604193A CN 117604193 A CN117604193 A CN 117604193A CN 202311539574 A CN202311539574 A CN 202311539574A CN 117604193 A CN117604193 A CN 117604193A
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- slag
- rare earth
- powder
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- earth oxide
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- 239000002893 slag Substances 0.000 title claims abstract description 172
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 76
- 229910001404 rare earth metal oxide Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 42
- 239000010959 steel Substances 0.000 claims abstract description 42
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 34
- 229910052742 iron Inorganic materials 0.000 claims abstract description 25
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 23
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 20
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims description 116
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 57
- 239000011707 mineral Substances 0.000 claims description 57
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 53
- 150000002910 rare earth metals Chemical class 0.000 claims description 49
- 239000010451 perlite Substances 0.000 claims description 40
- 235000019362 perlite Nutrition 0.000 claims description 40
- 239000000463 material Substances 0.000 claims description 35
- 239000010459 dolomite Substances 0.000 claims description 29
- 229910000514 dolomite Inorganic materials 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 18
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 13
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 238000004220 aggregation Methods 0.000 claims description 10
- 230000002776 aggregation Effects 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000004806 packaging method and process Methods 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 16
- 239000011593 sulfur Substances 0.000 abstract description 16
- 239000011574 phosphorus Substances 0.000 abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 9
- 238000003723 Smelting Methods 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 27
- 239000000292 calcium oxide Substances 0.000 description 19
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 9
- 238000006477 desulfuration reaction Methods 0.000 description 7
- 230000023556 desulfurization Effects 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 230000003009 desulfurizing effect Effects 0.000 description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 5
- 235000011941 Tilia x europaea Nutrition 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000010440 gypsum Substances 0.000 description 5
- 229910052602 gypsum Inorganic materials 0.000 description 5
- 239000004571 lime Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910021426 porous silicon Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- -1 rare earth sulfur compound Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 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
- C21C7/06—Deoxidising, e.g. killing
-
- 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
- C21C7/0006—Adding metallic additives
-
- 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
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/076—Use of slags or fluxes as treating agents
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a slag conglomeration agent containing rare earth oxide, a preparation process and application thereof, and belongs to the technical field of metal smelting. The slag conglomeration agent containing rare earth oxide comprises the following main chemical components in percentage by mass: 7-23% of SiO 2 ：29‑45%、Al 2 O 3 :13-23%, caO:3-7%, mgO:2-5%, al:0.5-1.5%, loss of burning: 4-9% and the balance of unavoidable impurities. The invention provides a slag conglomeration agent containing rare earth oxide, which has the effects of rapid slag conglomeration, easy slag dragging, no negative influence on sulfur and phosphorus fixation performance of steel slag, and obvious iron loss reduction.
Description
Technical Field
The invention belongs to the technical field of metal smelting, and particularly relates to a slag conglomeration agent containing rare earth oxide, a preparation process and application thereof.
Background
In order to improve the quality of molten steel, a series of slag-forming materials are added into the molten steel, so that smelting tasks such as deoxidization, sulfur, phosphorus, adsorption inclusion and the like are realized. Especially, when the variety of steel has ultralow sulfur requirement and high alloy requirement, the addition amount of the slag former is often large, and after the smelting task is completed, slag skimming treatment is carried out on molten steel, and then casting is carried out.
In actual production, the following problems exist in the slag skimming process: slag is difficult to gather by the scraper of the slag removing machine, and the gathered slag blocks are fragile, so that the long slag removing operation time affects the production rhythm; the phenomenon of iron wrapping in slag is common, wherein molten iron wrapped in slag can be lost along with the slag skimming process, so that the iron loss is large, and the economic benefit is influenced.
Disclosure of Invention
In view of the above, the invention aims to solve the technical problems of providing a slag conglomeration agent containing rare earth oxide aiming at the defects of the prior art, which has the effects of rapid slag conglomeration, easy slag dragging, no negative influence on sulfur and phosphorus fixation performance of steel slag and obvious iron loss reduction.
In order to solve the technical problems, the invention adopts the following technical scheme:
the slag conglomeration agent containing rare earth oxide comprises the following main chemical components in percentage by mass: 7-23% of SiO 2 ：29-45％、Al 2 O 3 :13-23%, caO:3-7%, mgO:2-5%, al:0.5-1.5%, loss of burning: 4-9%, which isThe balance being unavoidable impurities.
Preferably, the REO is derived from rare earth mineral powder and is La 2 O 3 、CeO 2 、Nd 2 O 3 And Y 2 O 3 At least one of (a) and (b).
The slag conglomeration agent containing rare earth oxide comprises the following raw materials in parts by weight: 10-30 parts of rare earth mineral powder, 40-60 parts of light burned perlite, 10-20 parts of AD powder and 10-20 parts of dolomite powder.
Wherein: the components of the rare earth mineral powder contain REO which is more than or equal to 70 percent and is La 2 O 3 、CeO 2 、Nd 2 O 3 And Y 2 O 3 One or a combination of two or more of the components.
The light burned perlite is perlite ore heat treated at 400-500 ℃ and contains SiO in the components 2 ≥72％，Al 2 O 3 More than or equal to 12 percent and expansion multiple more than or equal to 10 (1350 ℃).
The AD powder component contains simple substance [ Al ]]≥5％，Al 2 O 3 ≥75％，S≤0.2％。
The dolomite powder component contains CaO more than or equal to 30 percent, mgO more than or equal to 20 percent and loss of burning more than or equal to 40 percent.
Preferably, the mesh number of the rare earth mineral powder is more than 100 meshes; the mesh number of the AD powder is more than 100 meshes; the mesh number of the dolomite powder is more than 150 meshes; the mesh number of the light burned perlite is more than 100 meshes.
Preferably, the rare earth mineral powder is one or a mixture of two of bastnaesite mineral powder and ionic rare earth mineral powder.
A preparation method of a slag conglomeration agent containing rare earth oxide comprises the following steps:
and (3) batching: raw materials are matched according to the mass percentage of the slag conglomeration agent containing rare earth oxide;
mixing and grinding: mixing and adding all the materials after accurate metering into a mixing mill, and mixing and milling for 10-20min to obtain a uniformly mixed material;
and (3) drying: and (3) putting the uniformly mixed and ground materials into a drying kiln, baking, cooling, packaging and warehousing when the water content of the finished product is less than 2%, thus obtaining the finished product.
Preferably, the baking treatment includes: baking at 100-200deg.C for 30-60 min.
The application of the slag conglomeration agent containing rare earth oxide in slag skimming operation comprises the following specific use methods: determining the adding amount according to the using amount of 0.3-0.6kg/t of slag conglomeration agent; directly adding the slag aggregation agent to the slag surface, and completing the mixing of the slag aggregation agent and the steel slag through argon bottom blowing stirring of a steel ladle or mechanical stirring of a slag skimming machine, and carrying out slag skimming operation after 3-5 minutes.
To solve the foregoing problems of the prior art, metallurgical workers have generally employed methods of adding slag-forming agents to alleviate them. The raw material of slag conglomeration agent is commonly SiO-containing 2 Broken glass, perlite and the like of the components, and the action principle is as follows: after the slag conglomeration agent is added to the surface of molten steel, the lower layer raw material which is in direct contact with the molten steel is heated and melted and mixed with the original steel slag to generate acidic long slag, so that the fragility is reduced; the upper layer raw materials are heated to generate volume expansion, so that the steel slag is gathered into large slag blocks, and the slag skimming operation is facilitated. The method solves the problem of difficult slag skimming, but the slag conglomeration agent is pure SiO-containing 2 After the component acid material is added into molten steel, the alkalinity of the steel slag is probably greatly reduced, so that the problems of 'sulfur recovery' and 'phosphorus recovery' of the steel slag are caused, and the quality of the molten steel is reduced.
The patent document with the publication number of CN112553409A provides a vanadium-titanium-containing molten iron slag conglomeration agent and a preparation method thereof, wherein the slag conglomeration agent comprises the following raw materials in parts by weight: 20-40 parts of calcium oxide, 20-40 parts of aluminum oxide, 10-30 parts of porous silicon dioxide and 10-20 parts of fibrous gypsum particles. The preparation method comprises the following steps: and uniformly mixing calcium oxide, aluminum oxide, porous silicon dioxide and fibrous gypsum particles according to parts by weight, and drying until the water content is less than 2% to obtain the slag conglomeration agent. The alkalinity of the desulfurization slag is improved through calcium oxide in the slag conglomeration agent, the slag-iron separation effect is promoted, and the iron loss is reduced; porous silicon dioxide and fiber gypsum particles promote the aggregation of thin slag and improve the slag skimming rate. The whole performance of the slag conglomeration agent product is optimized. But also has the following non-negligible problems: 1. 30-60 parts of calcium oxide and fibrous gypsum are added, while promoting the gathering effect of slag blocks,however, the slag system is alkaline, belongs to short slag in the metallurgical slag system, has the characteristics of narrow solidification interval and high fragmentation, and is not beneficial to slag skimming operation. 2. Fibrous gypsum used in the product contains [ SiO ] 4 2- ]Ions have negative effects on the sulfur content of the slag system, and when slag is stirred by a slag removing machine to change the thermal condition of the slag system during slag removing operation, hidden danger of 'back sulfur' and 'back phosphorus' exists. 3. According to the technical scheme, the aim of reducing the iron loss is mainly achieved by promoting the separation of slag-iron interfaces, and the problem of iron loss caused by the phenomenon of iron wrapping in slag during slag block aggregation is not solved.
The publication No. CN110117687A provides a KR desulfurizing agent and a desulfurizing method, wherein the KR desulfurizing agent comprises the following components in percentage by mass: aluminum ash is more than 0 and less than or equal to 6 percent, lime is more than or equal to 94 percent, and aluminum ash and lime are as follows: 100%; the aluminum ash comprises the following chemical components in percentage by mass: al:20-25%, al 2 O 3 ：30-40％，SiO 2 ：5-10％，Na 2 O:2-3%, mgO:2-3%, O is less than CaO and less than 2.00%, O is less than FeO+MnO is less than 1.0%. The desulfurization method of the KR desulfurizing agent comprises the following steps: controlling the entering temperature, the entering Si content and the entering S content of molten iron to be desulfurized; adding the KR desulfurizing agent into molten iron to be desulfurized, and carrying out KR stirring treatment; and after desulfurization is completed, carrying out slag skimming treatment. The technology has the following defects in actual production and use: 1. the desulfurization effect is based on lime which is nearly the complete mass percentage in the product, and the components of the desulfurization effect are CaO, so that molten steel slag system is in a high alkalinity state to improve the desulfurization effect; however, the high-alkalinity slag system is a fragile short slag accepted by the metallurgical industry, and the slag skimming operation difficulty is greatly increased; 2. in the technical scheme, the desulfurization product is CaS (s) If the difficulty of slag skimming operation is reduced, an acidic slag conglomeration agent product commonly used in the current industry is required to be added, and accordingly, the alkalinity of a slag system is reduced, and the obvious 'sulfur return' problem occurs.
Therefore, the applicant considers that a slag conglomeration agent product which is high in efficiency, easy to drag, free of negative influence on sulfur and phosphorus fixation performance of steel slag and capable of obviously reducing iron loss is needed.
The slag conglomeration agent product of the invention adopts perlite which is one of the raw materialsThe source is wide, the price is low, the volume expansion can be quickly generated after the heating, and the excellent effect of gathering slag blocks is generated. The REO component contained in rare earth ore powder is excellent desulfurizing and dephosphorizing carrier, and can be combined with sulfur in slag to produce RE with melting point above 2000 deg.C 2 O 2 S-type rare earth sulfur compound, RE 2 O 5 The P type rare earth phosphorus compound can stably exist in the steel slag, so as to counteract the problems of 'sulfur return' and 'phosphorus return' of the steel liquid caused by the reduction of the alkalinity of the steel slag due to the addition of slag-forming agent products; can also be combined with Al contained in steel slag 2 O 3 Component formation xreo 2 O 3 Class of compounds, reduction of Al 2 O 3 The activity in the steel slag increases the adsorption effect of the steel slag on inclusions in the molten steel. The AD powder of one of the raw materials contains a certain proportion of simple substance [ Al ]]The oxidation-reduction exothermic reaction can be carried out with oxides in the steel slag, so that the thermodynamic environment of a slag interface is optimized, and the mixing reaction among slag components is promoted; wherein Al is contained in 2 O 3 The components can increase the viscosity of the steel slag and promote the gathering effect of slag blocks. The dolomite of one of the raw materials contains CaCO 3 、MgCO 3 Can be decomposed into CaO and MgO components at 750-950 ℃ and is an excellent sulfur-fixing and phosphorus-fixing carrier; more critical is the decomposition of the released CO 2 The gas can thoroughly stir the inside of the steel slag, so that the small area of 'iron wrapping' in the steel slag is fundamentally broken, the steel (iron) liquid beads fall back into the molten steel under the action of self gravity, the metal recovery rate is directly improved, and the iron loss is reduced. In addition, the slag conglomeration agent of the invention contains MgO and Al with specific contents 2 O 3 The steel-slag separation device is a component in the steel slag, which can effectively improve the interfacial tension of steel-slag, has good steel-slag separation effect in the slag skimming process, and reduces iron loss.
Compared with the prior art, the invention has the following beneficial effects:
1. controlling the mass percentage of REO between 7 and 23 percent by utilizing rare earth oxide, wherein the rare earth oxide is derived from rare earth minerals and is La 2 O 3 、CeO 2 、Nd 2 O 3 And Y 2 O 3 At least one of (2) greatly increasing the slag contentSulfur capacity, strengthening sulfur fixation and phosphorus fixation effects.
2. In order to increase the viscosity of the steel slag, a proper amount of AD powder is added into the product to carry Al 2 O 3 The components are beneficial to slag skimming operation; meanwhile, the addition of rare earth elements can inhibit the generation of the rare earth elements due to Al 2 O 3 The problem of reduced curing effect of sulfur and phosphorus caused by the increase of the components.
3. The AD powder has a small amount of elemental aluminum, which can be mixed with Fe in slag 2+ 、Fe 3+ 、Si 2+ Further reaction, while increasing the metal recovery rate, the thermit reaction is a forward exothermic reaction, so that the thermodynamic power environment of the slag interface can be optimized, and the slag aggregation effect is further promoted.
4. Adding CaCO with a certain proportion 3 、MgCO 3 On the one hand, the component releases CO when heated 2 The gas has a micro-stirring effect on the slag interface, and breaks through the phenomenon of iron wrapping; on the other hand, caO and MgO residues after decomposition are excellent sulfur-fixing and phosphorus-fixing carriers; mgO can also increase the interfacial tension of steel-slag and promote the steel-slag separation effect in the slag skimming process.
5. The slag conglomeration agent product is mainly prepared from SiO-containing materials 2 The perlite with the components has wide sources and low price, and is easy to control the cost.
Detailed Description
For a better understanding of the present invention, the following examples are set forth to further illustrate the invention, but are not to be construed as limiting the invention. In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention. It will be apparent, however, to one skilled in the art that the invention may be practiced without one or more of these details.
In all examples shown and discussed herein, any specific values should be construed as merely illustrative, and not a limitation. Thus, other examples of the exemplary embodiments may have different values.
Unless otherwise indicated, all starting materials are from commercially available products and unless otherwise indicated, they do not contain other components not explicitly indicated except for unavoidable impurities.
In the present invention, the number average of the band% not specifically described means mass fraction.
The invention provides a slag conglomeration agent containing rare earth oxide, which adopts a slag conglomeration agent containing REO and SiO 2 、Al 2 O 3 Preparing materials of CaO, mgO and Al, wherein:
REO is derived from rare earth mineral powder, wherein the REO content in the rare earth mineral powder is more than or equal to 70%, and REO is La 2 O 3 、CeO 2 、Nd 2 O 3 And Y 2 O 3 At least one of (2); when REO is La 2 O 3 、CeO 2 、Nd 2 O 3 And Y 2 O 3 When two or more components are combined, la is added to 2 O 3 、CeO 2 、Nd 2 O 3 And Y 2 O 3 The content ratio of (c) is not particularly limited.
The rare earth mineral powder is selected from one or two of bastnaesite mineral powder and ionic rare earth mineral powder; when the rare earth mineral powder is selected from the mixture of bastnaesite mineral powder and ionic rare earth mineral powder, the weight ratio of the bastnaesite mineral powder to the ionic rare earth mineral powder is not particularly limited, and the rare earth mineral powder can be selected from (0.1% -99.9%): (0.1% -99.9%).
The light burned perlite is perlite ore heat treated at 400-500 deg.C, and the components contain SiO 2 ≥72％，Al 2 O 3 More than or equal to 12 percent, and the expansion multiple at 1350 ℃ is more than or equal to 10;
the AD powder contains simple substance [ Al ]]≥5％，Al 2 O 3 ≥75％，S≤0.2％；
The dolomite powder component contains CaO more than or equal to 30 percent, mgO more than or equal to 20 percent and loss of burning more than or equal to 40 percent.
The mesh number of the rare earth mineral powder is more than 100 meshes; the mesh number of the AD powder is more than 100 meshes; the mesh number of dolomite powder is more than 150 meshes; the mesh number of the light burned perlite is more than 100 meshes.
The following is a specific embodiment example:
example 1
The slag conglomeration agent containing rare earth oxide comprises the following main chemical components in percentage by mass: 7.0% of SiO 2 ：45.0％、Al 2 O 3 :18.5%, caO:4.5%, mgO:4.5%, al:0.8%, loss on ignition: 6.0% of unavoidable impurities in balance; raw materials are matched according to the mass percentages; then, 10 parts of rare earth mineral powder, 60 parts of light burned perlite, 15 parts of AD powder and 15 parts of dolomite powder are provided according to parts by weight, and the materials are mixed and added into a mixing mill for 10 minutes to obtain a uniformly mixed material; and (3) putting the uniformly mixed and ground materials into a drying kiln, baking at 200 ℃ for 30 minutes, cooling, packaging and warehousing when the moisture content of the finished product is less than 2%, thus obtaining the finished product.
In the embodiment, the rare earth mineral powder is selected from bastnaesite powder, the REO content in the components is more than or equal to 70%, and the REO is La 2 O 3 And CeO 2 ；
The light burned perlite is perlite ore heat treated at 400 deg.C, and contains SiO 2 ≥72％，Al 2 O 3 More than or equal to 12 percent, and the expansion multiple is more than or equal to 10 (1350 ℃);
the AD powder contains simple substance [ Al ]]≥5％，Al 2 O 3 ≥75％，S≤0.2％；
The dolomite powder component contains CaO more than or equal to 30 percent, mgO more than or equal to 20 percent and loss of burning more than or equal to 40 percent.
The mesh number of the rare earth mineral powder is 100 meshes; the mesh number of the AD powder is 100 meshes; the mesh number of dolomite powder is 150 meshes; the mesh number of the light burned perlite is 100 meshes.
Example 2
The slag conglomeration agent containing rare earth oxide comprises the following main chemical components in percentage by mass: 9.2% of SiO 2 ：34.0％、Al 2 O 3 :20.8%, caO:6.0%, mgO:4.0%, al:1.2%, loss on ignition: 8.2% of unavoidable impurities in balance; raw materials are matched according to the mass percentages; then, 13 parts of rare earth mineral powder, 47 parts of light burned perlite, 20 parts of AD powder and 20 parts of dolomite powder are provided according to parts by weight, and the materials are mixed and added into a mixing mill for 20 minutes to obtain a uniformly mixed material; and (3) putting the uniformly mixed and ground materials into a drying kiln, baking at 180 ℃ for 40 minutes, cooling, packaging and warehousing when the moisture content of the finished product is less than 2%, thus obtaining the finished product.
In the embodiment, the rare earth mineral powder is selected from the mixture of bastnaesite mineral powder and ionic rare earth mineral powder, and the REO is equal to or more than 70 percent and is La 2 O 3 、CeO 2 、Nd 2 O 3 And Y 2 O 3 ；
The light burned perlite is 450 ℃ heat treated perlite ore, and the components contain SiO 2 ≥72％，Al 2 O 3 More than or equal to 12 percent, and the expansion multiple is more than or equal to 10 (1350 ℃);
the AD powder contains simple substance [ Al ]]≥5％，Al 2 O 3 ≥75％，S≤0.2％；
The dolomite powder component contains CaO more than or equal to 30 percent, mgO more than or equal to 20 percent and loss of burning more than or equal to 40 percent.
The mesh number of the rare earth mineral powder is 100 meshes; the mesh number of the AD powder is 100 meshes; the mesh number of dolomite powder is 150 meshes; the mesh number of the light burned perlite is 100 meshes.
Example 3
The slag conglomeration agent containing rare earth oxide comprises the following main chemical components in percentage by mass: 13.1% of SiO 2 ：38.3％、Al 2 O 3 :14.3%, caO:5.8%, mgO:3.9%, al:0.6%, loss on ignition: 7.7% of unavoidable impurities in balance; raw materials are matched according to the mass percentages; then, according to the weight parts, 18 parts of rare earth mineral powder, 53 parts of light burned perlite, 10 parts of AD powder and 19 parts of dolomite powder are provided, the above materials are mixed and added into a mixing mill, and the mixing mill is carried out for 18 minutes to obtain a uniformly mixed material; and (3) putting the uniformly mixed and ground materials into a drying kiln, baking at 125 ℃ for 50 minutes, cooling, packaging and warehousing when the moisture content of the finished product is less than 2%, thus obtaining the finished product.
In the embodiment, the rare earth mineral powder is selected from the mixture of bastnaesite mineral powder and ionic rare earth mineral powder, the REO content in the components is more than or equal to 70 percent, and the REO is La 2 O 3 、CeO 2 、Nd 2 O 3 And Y 2 O 3 ；
The light burned perlite is 500 ℃ heat treated perlite ore, and the components contain SiO 2 ≥72％，Al 2 O 3 More than or equal to 12 percent, and the expansion multiple is more than or equal to 10 (1350 ℃);
the AD powder component contains single componentMass [ Al ]]≥5％，Al 2 O 3 ≥75％，S≤0.2％；
The dolomite powder component contains CaO more than or equal to 30 percent, mgO more than or equal to 20 percent and loss of burning more than or equal to 40 percent.
The mesh number of the rare earth mineral powder is 100 meshes; the mesh number of the AD powder is 100 meshes; the mesh number of dolomite powder is 150 meshes; the mesh number of the light burned perlite is 100 meshes.
Example 4
The slag conglomeration agent containing rare earth oxide comprises the following main chemical components in percentage by mass: 14.8% of SiO 2 ：40.3％、Al 2 O 3 :15.8%, caO:3.6%, mgO:2.4%, al:0.6%, loss on ignition: 4.8% of unavoidable impurities in balance; raw materials are matched according to the mass percentages; then, according to the weight parts, 20 parts of rare earth mineral powder, 56 parts of light burned perlite, 12 parts of AD powder and 12 parts of dolomite powder are provided, and the above materials are mixed and added into a mixing mill for 10 minutes to obtain a uniformly mixed material; and (3) putting the uniformly mixed and ground materials into a drying kiln, baking at 200 ℃ for 30 minutes, cooling, packaging and warehousing when the moisture content of the finished product is less than 2%, thus obtaining the finished product.
In the embodiment, the rare earth mineral powder is selected from the mixture of bastnaesite mineral powder and ionic rare earth mineral powder, the REO content in the components is more than or equal to 70 percent, and the REO is La 2 O 3 、CeO 2 、Nd 2 O 3 And Y 2 O 3 ；
The light burned perlite is 450 ℃ heat treated perlite ore, and the components contain SiO 2 ≥72％，Al 2 O 3 More than or equal to 12 percent, and the expansion multiple is more than or equal to 10 (1350 ℃);
the AD powder contains simple substance [ Al ]]≥5％，Al 2 O 3 ≥75％，S≤0.2％；
The dolomite powder component contains CaO more than or equal to 30 percent, mgO more than or equal to 20 percent and loss of burning more than or equal to 40 percent.
The mesh number of the rare earth mineral powder is 200 meshes; the mesh number of the AD powder is 200 meshes; the mesh number of dolomite powder is 200 meshes; the mesh number of the light burned perlite is 200 mesh.
Example 5
A slag conglomeration agent containing rare earth oxide comprises the main chemical componentsREO in mass percent: 20.7% of SiO 2 ：33.2％、Al 2 O 3 :18.3%, caO:3.1%, mgO:2.0%, al:1.0%, loss on ignition: 4.0% of unavoidable impurities in balance; raw materials are matched according to the mass percentages; then, 28 parts of rare earth mineral powder, 45 parts of light burned perlite, 17 parts of AD powder and 10 parts of dolomite powder are provided according to parts by weight, and the materials are mixed and added into a mixing mill for 20 minutes to obtain a uniformly mixed material; and (3) putting the uniformly mixed and ground materials into a drying kiln, baking at 100 ℃ for 60 minutes, cooling, packaging and warehousing when the moisture content of the finished product is less than 2%, thus obtaining the finished product.
In the embodiment, the rare earth mineral powder is selected from the mixture of bastnaesite mineral powder and ionic rare earth mineral powder, the REO content in the components is more than or equal to 70 percent, and the REO is La 2 O 3 、CeO 2 、Nd 2 O 3 And Y 2 O 3 ；
The light burned perlite is 450 ℃ heat treated perlite ore, and the components contain SiO 2 ≥72％，Al 2 O 3 More than or equal to 12 percent, and the expansion multiple is more than or equal to 10 (1350 ℃);
the AD powder contains simple substance [ Al ]]≥5％，Al 2 O 3 ≥75％，S≤0.2％；
The dolomite powder component contains CaO more than or equal to 30 percent, mgO more than or equal to 20 percent and loss of burning more than or equal to 40 percent.
The mesh number of the rare earth mineral powder is 300 meshes; the mesh number of the AD powder is 300 meshes; the mesh number of dolomite powder is 300 meshes; the mesh number of the light burned perlite is 300 meshes.
Example 6
The slag conglomeration agent containing rare earth oxide comprises the following main chemical components in percentage by mass: 21.2%, siO 2 ：29.1％、Al 2 O 3 :19.1%, caO:3.3%, mgO:2.2%, al:1.3%, loss on ignition: 6.4% of unavoidable impurities in balance; raw materials are matched according to the mass percentages; then, 30 parts of rare earth mineral powder, 40 parts of light burned perlite, 19 parts of AD powder and 11 parts of dolomite powder are provided according to parts by weight, and the materials are mixed and added into a mixing mill for mixing and grinding for 15 minutes to obtain a uniformly mixed material; feeding the uniformly mixed and ground materials into a drying kilnBaking at 150deg.C for 45 min, cooling when the water content of the final product is below 2%, packaging, and warehousing to obtain the final product.
In the embodiment, the rare earth mineral powder is selected from the mixture of bastnaesite mineral powder and ionic rare earth mineral powder, the REO content in the components is more than or equal to 70 percent, and the REO is La 2 O 3 、CeO 2 、Nd 2 O 3 And Y 2 O 3 ；
The light burned perlite is 450 ℃ heat treated perlite ore, and the components contain SiO 2 ≥72％，Al 2 O 3 More than or equal to 12 percent, and the expansion multiple is more than or equal to 10 (1350 ℃);
the AD powder contains simple substance [ Al ]]≥5％，Al 2 O 3 ≥75％，S≤0.2％；
The dolomite powder component contains CaO more than or equal to 30 percent, mgO more than or equal to 20 percent and loss of burning more than or equal to 40 percent.
The mesh number of the rare earth mineral powder is 100 meshes; the mesh number of the AD powder is 100 meshes; the mesh number of dolomite powder is 150 meshes; the mesh number of the light burned perlite is 100 meshes.
The using method comprises the following steps: the application of the slag conglomeration agent in slag skimming operation comprises the following specific use methods: determining the adding amount according to the using amount of 0.3-0.6kg/t of slag conglomeration agent; directly adding the slag aggregation agent to the slag surface, and completing the mixing of the slag aggregation agent and the steel slag through argon bottom blowing stirring of a steel ladle or mechanical stirring of a slag skimming machine, and carrying out slag skimming operation after 3-5 minutes.
The following is a comparative example illustration:
comparative example 1
This comparative example 1 differs from example 1 in that: REO is not contained in slag conglomeration agent components, rare earth minerals are omitted from corresponding preparation materials, and the slag conglomeration agent comprises the following concrete components:
a slag conglomeration agent comprises the main chemical components of SiO in percentage by mass 2 ：46.8％、Al 2 O 3 :19.05%, caO:6.0%, mgO:4.0%, al:0.75%, loss on ignition: 8.0% and the balance of unavoidable impurities; raw materials are matched according to the mass percentages; then, 65 parts of light burned perlite, 15 parts of AD powder and 20 parts of dolomite powder are provided according to the weight parts, the materials are mixed and added into a mixing mill, and the mixture is mixed and milled for 10 minutes to obtain a uniformly mixed materialThe method comprises the steps of carrying out a first treatment on the surface of the And (3) putting the uniformly mixed and ground materials into a drying kiln, baking at 200 ℃ for 30 minutes, cooling, packaging and warehousing when the moisture content of the finished product is less than 2%, thus obtaining the finished product.
Comparative example 2
This comparative example 2 differs from example 1 in that: the slag conglomeration agent contains no Al, and AD powder is omitted from corresponding preparation materials, specifically:
the slag conglomeration agent comprises the following main chemical components in percentage by mass: 7.0% of SiO 2 ：43.2％、Al 2 O 3 :7.2%, caO:9.0%, mgO:6.0%, loss on ignition: 12.2% and the balance of unavoidable impurities; raw materials are matched according to the mass percentages; then, 10 parts of rare earth mineral powder, 60 parts of light burned perlite and 30 parts of dolomite powder are provided according to parts by weight, and the materials are mixed and added into a mixing mill for 10 minutes to obtain a uniformly mixed material; and (3) putting the uniformly mixed and ground materials into a drying kiln, baking at 200 ℃ for 30 minutes, cooling, packaging and warehousing when the moisture content of the finished product is less than 2%, thus obtaining the finished product.
Comparative example 3
Slag conglomeration agent (refer to example 1 disclosed in CN 104894324A) comprising chemical components in mass percent of SiO 2 65％，CaCO 3 18％，MgCO 3 14％，Al 2 O 3 3％。
Comparative example 4
A slag conglomeration agent (refer to example 1 disclosed in CN110317925 a) consisting of the following components in mass percent: 30wt% of CaO, 30wt% of SiC and 15wt% of Fe 2 O 3 10wt% of MgO and 15wt% of yttrium-based rare earth alloy; the components are measured according to the formula and added into a mixing device, and are mixed for 20min in a centrifugal mixing mode.
Comparative example 5
Slag conglomeration agent (refer to example 1 disclosed in CN110117687 a) consists of the following components in percentage by weight: the aluminum ash is 6% and the lime is 94%. The aluminum ash comprises the following chemical components in percentage by weight: al:25%, al 2 O 3 ：40％，SiO 2 ：10％，Na 2 O：3％，MgO：3％，CaO:2.00%, feO+MnO:1.0%. The CaO in the lime is 95 percent by weight.
Next, the content of the evaluation test will be described.
The slag conglomeration agent prepared in the examples 1-3 and the comparative examples 1-5 is used in slag skimming operation of steel smelting in a certain steel plant, and the adding amount is determined according to the using amount of 0.5kg/t of the slag conglomeration agent; directly adding the slag conglomeration agent onto the slag surface, completing the mixing of the slag conglomeration agent and the steel slag through stirring of argon bottom blowing of a steel ladle, and carrying out slag skimming operation after 5 minutes.
The following evaluation was completed during the use of the slag conglomeration agent:
(1) Measuring and recording the sulfur content in molten iron before the slag conglomeration agent is used and after slag skimming;
(2) Recording slag skimming time and slag skimming quantity, and calculating slag skimming and removing efficiency;
(3) Iron losses were measured and recorded.
The above measurement results are shown in the following table:
the results show that the slag conglomeration agent has good sulfur fixing effect and is not easy to generate the problem of 'sulfur recovery'; the skimming removal rate is up to more than 85%, which indicates that slag aggregation is fast, and slag blocks are easy to drag; meanwhile, the iron loss can be obviously reduced, and compared with the existing method, the iron loss reduction is more than 50%, and the method has obvious progress.
In addition, it should be understood by those skilled in the art that although many problems exist in the prior art, each embodiment or technical solution of the present invention may be modified in only one or several respects, without having to solve all technical problems listed in the prior art or the background art at the same time. Those skilled in the art will understand that nothing in one claim should be taken as a limitation on that claim.
Finally, it is noted that the above-mentioned embodiments are merely for illustrating the technical solution of the present invention, and that other modifications and equivalents thereof by those skilled in the art should be included in the scope of the claims of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. A slag conglomeration agent containing rare earth oxide is characterized in that: the main chemical components of the coating comprise REO in percentage by mass: 7-23% of SiO 2 ：29-45%、Al 2 O 3 :13-23%, caO:3-7%, mgO:2-5%, al:0.5-1.5%, loss of burning: 4-9% and the balance of unavoidable impurities.
2. A rare earth oxide-containing slag conglomeration agent according to claim 1, characterized in that: the REO is derived from rare earth mineral powder and is La 2 O 3 、CeO 2 、Nd 2 O 3 And Y 2 O 3 At least one of (a) and (b).
3. A rare earth oxide-containing slag conglomeration agent as claimed in claim 2, characterized in that: the raw materials of the composition are as follows in parts by weight: 10-30 parts of rare earth mineral powder, 40-60 parts of light burned perlite, 10-20 parts of AD powder and 10-20 parts of dolomite powder.
4. A rare earth oxide-containing slag conglomeration agent as claimed in claim 3, characterized in that: the components of the rare earth mineral powder contain REO which is more than or equal to 70 percent and is La 2 O 3 、CeO 2 、Nd 2 O 3 And Y 2 O 3 One or a combination of two or more of the components;
the light burned perlite is perlite ore heat treated at 400-500 ℃ and contains SiO in the components 2 ≥72%，Al 2 O 3 More than or equal to 12 percent, and the expansion multiple is more than or equal to 10 (1350 ℃);
the AD powder component contains simple substance [ Al ]]≥5%，Al 2 O 3 ≥75%，S≤0.2%；
The dolomite powder component contains CaO more than or equal to 30 percent, mgO more than or equal to 20 percent and loss of burning more than or equal to 40 percent.
5. A rare earth oxide-containing slag conglomeration agent as claimed in claim 3, characterized in that: the mesh number of the rare earth mineral powder is more than 100 meshes; the mesh number of the AD powder is more than 100 meshes; the mesh number of the dolomite powder is more than 150 meshes; the mesh number of the light burned perlite is more than 100 meshes.
6. A rare earth oxide-containing slag conglomeration agent as claimed in claim 3, characterized in that: the rare earth mineral powder is one or a mixture of two of bastnaesite mineral powder and ionic rare earth mineral powder.
7. A method for producing the rare earth oxide-containing slag conglomeration agent as defined in any one of claims 1 to 6, characterized in that: the method comprises the following steps:
and (3) batching: raw materials are matched according to the mass percentage of the slag conglomeration agent containing rare earth oxide;
mixing and grinding: mixing and adding all the materials after accurate metering into a mixing mill, and mixing and milling for 10-20min to obtain a uniformly mixed material;
and (3) drying: and (3) putting the uniformly mixed and ground materials into a drying kiln, baking, cooling, packaging and warehousing when the water content of the finished product is less than 2%, thus obtaining the finished product.
8. The method for preparing the slag conglomeration agent containing rare earth oxide according to claim 7, which is characterized in that: the baking treatment process conditions comprise: baking at 100-200deg.C for 30-60 min.
9. Use of the slag conglomeration agent according to any one of claims 1 to 6 or the slag conglomeration agent obtained by the preparation method according to claim 7 or 8 in slag skimming operations.
10. Use of the slag conglomeration agent according to claim 9 in slag skimming operations, characterized in that: the application method comprises the following steps: determining the adding amount according to the using amount of 0.3-0.6kg/t steel (iron) liquid of the slag conglomeration agent; directly adding the slag aggregation agent to the slag surface, and completing the mixing of the slag aggregation agent and the steel slag through argon bottom blowing stirring of a steel ladle or mechanical stirring of a slag skimming machine, and carrying out slag skimming operation after 3-5 minutes.
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