CN116445983A - Fe-Si/CaCO3 material, preparation method thereof and application thereof as molten steel refining agent - Google Patents
Fe-Si/CaCO3 material, preparation method thereof and application thereof as molten steel refining agent Download PDFInfo
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- CN116445983A CN116445983A CN202310404734.5A CN202310404734A CN116445983A CN 116445983 A CN116445983 A CN 116445983A CN 202310404734 A CN202310404734 A CN 202310404734A CN 116445983 A CN116445983 A CN 116445983A
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- waste residue
- caco
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 65
- 239000010959 steel Substances 0.000 title claims abstract description 65
- 229910017082 Fe-Si Inorganic materials 0.000 title claims abstract description 47
- 229910017133 Fe—Si Inorganic materials 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 21
- 238000007670 refining Methods 0.000 title claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 title description 3
- 235000010216 calcium carbonate Nutrition 0.000 title description 3
- 239000002699 waste material Substances 0.000 claims abstract description 41
- 150000003839 salts Chemical class 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 230000002195 synergetic effect Effects 0.000 claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000010703 silicon Substances 0.000 claims abstract description 4
- 239000002893 slag Substances 0.000 claims description 41
- 238000001035 drying Methods 0.000 claims description 19
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 11
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims 1
- 229910002091 carbon monoxide Inorganic materials 0.000 claims 1
- 230000006835 compression Effects 0.000 claims 1
- 238000007906 compression Methods 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
- 239000007789 gas Substances 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000001816 cooling Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- 238000000748 compression moulding Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 101100272279 Beauveria bassiana Beas gene Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910005347 FeSi Inorganic materials 0.000 description 1
- 244000299461 Theobroma cacao Species 0.000 description 1
- 235000005764 Theobroma cacao ssp. cacao Nutrition 0.000 description 1
- 235000005767 Theobroma cacao ssp. sphaerocarpum Nutrition 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 235000001046 cacaotero Nutrition 0.000 description 1
- 239000000404 calcium aluminium silicate Substances 0.000 description 1
- 235000012215 calcium aluminium silicate Nutrition 0.000 description 1
- WNCYAPRTYDMSFP-UHFFFAOYSA-N calcium aluminosilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O WNCYAPRTYDMSFP-UHFFFAOYSA-N 0.000 description 1
- 229940078583 calcium aluminosilicate Drugs 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- WETINTNJFLGREW-UHFFFAOYSA-N calcium;iron;tetrahydrate Chemical compound O.O.O.O.[Ca].[Fe].[Fe] WETINTNJFLGREW-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 oxygen ions Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000002490 spark plasma sintering Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/36—Alloys obtained by cathodic reduction of all their ions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/184—Preparation of calcium carbonate by carbonation of solutions based on non-aqueous solvents
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides a Fe-Si/CaCO 3 Material, preparation method and application as molten steel refining agent, and relates to the technical field of resource utilization. The CO provided by the invention 2 Preparation of Fe-Si/CaCO by synergistic waste residue 3 A method of material comprising the steps of: (1) The waste residue is fixed at one end of a metal rod after being pressed and molded; the waste residue contains iron element, silicon element and calcium element; (2) Immersing the waste residue in molten salt, using the metal rod as a cathode, using the molten salt as an electrolyte, using an inert electrode as an anode, and adding CO 2 Carrying out melting electrolysis on the waste residue in the gas atmosphere to obtain Fe-Si/CaCO on the cathode 3 A material. The invention uses molten salt electrolysis one-step method to electrolyze CO 2 The Fe-Si/CaCO is prepared by the synergistic treatment of the waste residues 3 Powder, realize CO 2 And the waste residue is utilized cooperatively with green, low-temperature and carbon-free waste residue.
Description
Technical Field
The invention relates to the technical field of resource utilization, in particular to a Fe-Si/CaCO 3 The material, the preparation method and the application as a molten steel refining agent.
Background
The steel production process generates a large amount of CO 2 Steel slag, 2022 CO 2 About 33.8 hundred million tons of discharged amount, the accumulation amount of steel slag reaches 18 hundred million tons, CO 2 The utilization of steel slag becomes a hot spot and difficult problem. The double carbon target brings forward a new requirement for green cyclic development to the steel industry in China.
Currently, CO 2 The synergistic steel slag resource utilization is mainly concentrated on carbonating carbon fixation to prepare building materials, and although a large amount of steel slag can be consumed, CO is caused by low free CaO concentration in the steel slag 2 The utilization rate is low. In addition, the treatment cannot extract valuable metals Fe and Si in the steel slag or prepare Fe-Si alloy by utilizing the steel slag.
At present, typical Fe-Si alloy preparation methods mainly comprise carbothermic reduction, powder metallurgy, mechanical alloying, spark plasma sintering and laser sintering. Most of the methods take Fe and Si metal powder as raw materials, and high temperature conditions are needed; the carbothermic reduction process can use oxides as raw materials, but the process does not meet the green, low carbon requirements in a two carbon context.
Disclosure of Invention
The invention aims to provide a Fe-Si/CaCO 3 Material, preparation method thereof and application as molten steel refining agent, and the invention adopts CO 2 Preparation of Fe-Si/CaCO by synergistic waste residue 3 Material, fe-Si/CaCO obtained 3 The material can beAs a molten steel refining agent for clean steel production, the method is an important direction for realizing green circulation in the steel industry, provides a new thought for green circulation and high-end steel production under the background of double carbon, has higher scientific research value, and generates great social and economic benefits.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a CO 2 Preparation of Fe-Si/CaCO by synergistic waste residue 3 A method of material comprising the steps of:
(1) The waste residue is fixed at one end of a metal rod after being pressed and molded; the waste residue contains iron element, silicon element and calcium element;
(2) Immersing the waste residue in molten salt, using the metal rod as a cathode, using the molten salt as an electrolyte, using an inert electrode as an anode, and adding CO 2 Carrying out melting electrolysis on the waste residue in the gas atmosphere to obtain Fe-Si/CaCO on the cathode 3 A material.
Unlike conventional CO 2 The invention discloses a method for utilizing synergistic steel slag and an application way, wherein the method adopts a fused salt electrolysis method to realize CO 2 One-step preparation of Fe-Si/CaCaO by using synergistic waste residues 3 New technology of materials. CO 2 In the process of introducing molten salt electrolysis, oxygen in cathode waste residue is continuously removed, and partial oxygen ions and dissolved CO are used 2 Forming carbonate ions, partially passing through molten salt and being discharged in the form of oxygen at the anode, and carbonating the carbonate ions with calcium ions at the cathode to form CaCO 3 Continuously removing oxygen from the waste residue on the cathode to form Fe-Si alloy, and finally obtaining the cathode product of Fe-Si/CaCO 3 A material.
The invention fixes the waste residue at one end of the metal rod after the waste residue is pressed and formed. In the invention, the waste residue contains iron element, silicon element and calcium element, and is particularly preferably steel slag or red mud. In the present invention, the slag is preferably derived from steel slag converter slag or refining slag; the waste residue preferably includes a plurality of calcium ferrite, calcium silicate, iron oxide, aluminum silicate, calcium aluminosilicate, and calcium silicate.
In the invention, the waste residue is preferably dried at high temperature before being subjected to compression molding; the high temperature drying temperature is preferably 200-500 ℃, more preferably 300-400 ℃; the time for the high-temperature drying is preferably 6 to 24 hours, more preferably 10 to 18 hours. The invention removes the water in the waste residue by high temperature drying. The invention preferably carries out ball milling on the obtained waste residue after the high-temperature drying to obtain waste residue powder; and (3) carrying out compression molding on the waste residue powder. In the present invention, the particle size of the waste residue powder is preferably 30 to 150. Mu.m, more preferably 60 to 80. Mu.m.
In the present invention, the pressure of the press molding is preferably 4 to 12MPa, more preferably 10MPa; the temperature is preferably 300 to 1000 ℃, more preferably 400 ℃; the holding time is preferably 15 to 60 seconds, more preferably 20 to 30 seconds. In the invention, the morphology of the waste residue after compression molding is preferably compact blocks of 1cm multiplied by 2 cm.
In the present invention, the fixing means for fixing the waste residue to one end of the metal rod after the compression molding is preferably fixing by using a metal wire. In the present invention, the metal rod is preferably made of iron, nickel or copper.
The invention is characterized in that the waste residue is soaked in molten salt, the metal rod is used as a cathode, the molten salt is used as an electrolyte, an inert electrode is used as an anode, and the metal rod contains CO 2 Carrying out melting electrolysis on the waste residue in the gas atmosphere to obtain Fe-Si/CaCO on the cathode 3 A material. In the present invention, the molten salt is preferably a salt containing one or more of lithium, sodium, potassium and calcium, more preferably a chloride salt containing one or more of lithium, sodium, potassium and calcium, particularly preferably one or more of potassium chloride, sodium chloride, lithium chloride and calcium chloride. In the present invention, the inert electrode preferably includes tin dioxide, nickel alloy or graphite sheet. In the present invention, the CO 2 The gas preferably originates from air or steel, from exhaust gases from the thermal, coal industry or from anode exhaust gases in aluminium electrolysis.
In the present invention, the catalyst contains CO 2 The atmosphere of the gas preferably also includes a shielding gas. The invention is introduced with protective gas to protect the reaction systemNot contaminated by oxygen, and adjust CO 2 Concentration of the gas. In the present invention, the CO 2 The flow rate of the gas is preferably 5 to 500mL/min, more preferably 10 to 300mL/min; the shielding gas preferably comprises argon or nitrogen; the flow rate of the shielding gas is preferably 300 to 1500mL/min, more preferably 500 to 1000mL/min.
In the present invention, the time of the melt electrolysis is preferably 0.5 to 10 hours; the voltage is preferably 2 to 3.3V, more preferably 2.8 to 3.2V; the temperature of the molten salt at the time of the melt electrolysis is preferably 600 to 900 ℃, more preferably 700 to 850 ℃. In the melting electrolysis process, the waste residue is formed in CO 2 Forming Fe-Si alloy and CO by electro-reduction on cathode under blowing action 2 CaO electrolytically dissociated from the waste residue forms CaCO on the cathode 3 The method comprises the steps of carrying out a first treatment on the surface of the The molten salt contains CaO which is partially dissolved, and the molten salt and CO 2 Carbonation to form CaCO 3 And other carbonates.
The invention preferably takes out the cathode after the melting electrolysis, cools the cathode under the protection of inert gas, cleans the cathode, and then carries out drying treatment to obtain Fe-Si/CaCO 3 A material. In the present invention, the inert gas is preferably argon; the washing liquid used for the washing is preferably deionized water. In the present invention, the drying treatment is preferably performed in a vacuum drying oven; the temperature of the drying treatment is preferably 100-300 ℃ and the time is preferably 0.5-3 h.
In the present invention, the molten salt after the molten electrolysis contains carbonate; in the invention, the molten salt containing carbonate is preferably cooled, washed and separated with water, and dried to recover carbonate. In the present invention, the carbonate preferably includes one or more of calcium carbonate, sodium carbonate, lithium carbonate, potassium carbonate and magnesium carbonate.
The invention provides the Fe-Si/CaCO prepared by the method 3 Materials, including Fe-Si alloys and CaCO 3 . In the present invention, the Fe-Si alloy and CaCO 3 The mass ratio of (2) is preferably 33 to 95:5 to 67, more preferably 33:67.
In a specific embodiment of the present invention, the Fe-Si alloy includes Fe 3 One or more of Si and FeSi.
The invention provides the Fe-Si/CaCO according to the technical proposal 3 The material is used as a molten steel refining agent. Aiming at the new requirements of green cyclic development proposed by the iron and steel industry, CO 2 The synergistic waste residue is utilized and returned to steel production as a new way to meet the requirement. The quality control of clean steel production process is a key link for controlling the quality of steel products. The addition of a refining agent in the steelmaking process is an important means for producing clean steel, and the components of the refining agent are critical to the production of the clean steel. The invention adopts CO 2 Fe-Si/CaCO (sodium chloride/sodium hydroxide) prepared by synergistic steel slag 3 The molten steel refining agent is used for clean steel production, is an important direction for realizing green circulation in the steel industry, provides a new thought for green circulation and high-end steel production under the background of double carbon, has higher scientific research value, and generates great social benefit and economic benefit.
Drawings
FIG. 1 shows the use of CO in an embodiment of the present invention 2 Fe-Si/CaCO (sodium chloride/sodium hydroxide) prepared by synergistic steel slag 3 A process flow diagram of the molten steel refining agent;
FIG. 2 is a block diagram of Fe-Si/CaCO prepared according to example 1 3 XRD pattern of the powder;
FIG. 3 is a block diagram of Fe-Si/CaCO prepared according to example 2 3 XRD pattern of the powder;
FIG. 4 is a block diagram of Fe-Si/CaCO prepared according to example 3 3 XRD pattern of the powder.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
According to the process shown in FIG. 1, CO is used 2 Synergistic steelPreparation of Fe-Si/CaCO from slag 3 Molten steel refining agent:
1) Placing the steel slag in a ceramic crucible, and drying the steel slag in a heating furnace at a high temperature of 400 ℃ for 6 hours;
2) Taking out the dried steel slag from the ceramic crucible, cooling and performing ball milling;
3) 1g of ball-milled steel slag (with the grain diameter of 60-80 mu m) is pressed and formed (the pressure is 10MPa, the temperature is 400 ℃, the heat preservation and pressure maintaining time is 30 s) and then fixed at one end of a nickel rod by a metal wire;
4) Immersing the steel slag in molten salt (sodium chloride and calcium chloride with the molar ratio of 1:1), wherein the nickel rod is used as a cathode, the molten salt is used as an electrolyte, the temperature is kept at 850 ℃, an inert electrode tin dioxide is used as an anode, and the flow rate of argon is 500mL/min and CO 2 Introducing mixed gas with the flow rate of 20mL/min, and carrying out fusion electrolysis on the steel slag for 10h, wherein the electrolysis voltage is 2.8V;
5) Taking out the cathode, cooling under the protection of argon, cleaning, and placing in a vacuum drying oven at 150 ℃ for drying for 1h to obtain Fe-Si/CaCO 3 A powder; containing CaCO 3 After cooling, washing and separating, and after drying, recovering CaCO 3 。
FIG. 2 is a block diagram of Fe-Si/CaCO prepared according to example 1 3 XRD pattern of the powder. As can be seen from FIG. 2, XRD detection of the main phase of the sample is Fe-Si alloy and CaCO 3 There is a small amount of Fe, si metal.
Example 2
According to the process shown in FIG. 1, CO is used 2 Fe-Si/CaCO (sodium chloride/sodium hydroxide) prepared by synergistic steel slag 3 Molten steel refining agent:
1) Placing the steel slag in a ceramic crucible, and drying the steel slag in a heating furnace at a high temperature of 400 ℃ for 6 hours;
2) Taking out the dried steel slag from the ceramic crucible, cooling and performing ball milling;
3) 1g of ball-milled steel slag (with the grain diameter of 60-80 mu m) is pressed and formed (the pressure is 10MPa, the temperature is 400 ℃, the heat preservation and pressure maintaining time is 30 s) and then fixed at one end of a nickel rod by a metal wire;
4) The steel slag is soaked in molten salt (sodium chloride and calcium chloride with the mol ratio of 1:1) Wherein the nickel rod is used as a cathode, the molten salt is used as an electrolyte, the temperature is kept at 850 ℃, the inert electrode tin dioxide is used as an anode, and the flow rate of argon is 500mL/min and CO 2 Introducing mixed gas with the flow rate of 20mL/min, and carrying out fusion electrolysis on the steel slag for 10h, wherein the electrolysis voltage is 3.0V;
5) Taking out the cathode, cooling under the protection of argon, cleaning, and placing in a vacuum drying oven at 150 ℃ for drying for 1h to obtain Fe-Si/CaCO 3 A powder; containing CaCO 3 After cooling, washing and separating, and after drying, recovering CaCO 3 。
FIG. 3 is a block diagram of Fe-Si/CaCO prepared according to example 2 3 XRD pattern of the powder. As can be seen from FIG. 3, XRD detection of the main phase of the sample is Fe-Si alloy and CaCO 3 There is a small amount of Fe, si metal.
Example 3
According to the process shown in FIG. 1, CO is used 2 Fe-Si/CaCO (sodium chloride/sodium hydroxide) prepared by synergistic steel slag 3 Molten steel refining agent:
1) Placing the steel slag in a ceramic crucible, and drying the steel slag in a heating furnace at a high temperature of 400 ℃ for 6 hours;
2) Taking out the dried steel slag from the ceramic crucible, cooling and performing ball milling;
3) 1g of ball-milled steel slag (with the grain diameter of 60-80 mu m) is pressed and formed (the pressure is 10MPa, the temperature is 400 ℃, the heat preservation and pressure maintaining time is 30 s) and then fixed at one end of a nickel rod by a metal wire;
4) Immersing the steel slag in molten salt (sodium chloride and calcium chloride with the molar ratio of 1:1), wherein the nickel rod is used as a cathode, the molten salt is used as an electrolyte, the temperature is kept at 850 ℃, an inert electrode tin dioxide is used as an anode, and the flow rate of argon is 500mL/min and CO 2 Introducing mixed gas with the flow rate of 20mL/min, and carrying out fusion electrolysis on the steel slag for 10h, wherein the electrolysis voltage is 3.2V;
5) Taking out the cathode, cooling under the protection of argon, cleaning, and placing in a vacuum drying oven at 150 ℃ for drying for 1h to obtain Fe-Si/CaCO 3 A powder; containing CaCO 3 After cooling, washing and separating, and after drying, recovering CaCO 3 。
FIG. 4 is a real viewExample 3 Fe-Si/CaCO 3 XRD pattern of the powder. As can be seen from FIG. 4, XRD detection of Fe-Si alloy and CaCO in the sample 3 。
The invention firstly uses the molten salt electrolysis one-step method to electrolyze CO 2 The Fe-Si/CaCO is prepared by the cooperative treatment of steel slag 3 Powder, realize CO 2 The green, low-temperature and carbon-free synergistic utilization of the steel slag is CO 2 Provides a new solving way and a new thought in coordination with the utilization of steel slag resources.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. CO (carbon monoxide) 2 Preparation of Fe-Si/CaCO by synergistic waste residue 3 A method of material comprising the steps of:
(1) The waste residue is fixed at one end of a metal rod after being pressed and molded; the waste residue contains iron element, silicon element and calcium element;
(2) Immersing the waste residue in molten salt, using the metal rod as a cathode, using the molten salt as an electrolyte, using an inert electrode as an anode, and adding CO 2 Carrying out melting electrolysis on the waste residue in the gas atmosphere to obtain Fe-Si/CaCO on the cathode 3 A material.
2. The method according to claim 1, wherein the waste residue is steel slag or red mud.
3. The method of claim 1, wherein the waste residue further comprises high temperature drying prior to compression forming; the high-temperature drying temperature is 200-500 ℃; the high-temperature drying time is 6-24 h.
4. The method according to claim 1, wherein the pressure of the press forming is 4 to 12MPa and the temperature is 300 to 1000 ℃; the heat preservation and pressure maintaining time is 15-60 s.
5. The method of claim 1, wherein the molten salt is a salt comprising one or more of lithium, sodium, potassium, and calcium.
6. The method of claim 1, wherein the inert electrode comprises tin dioxide, nickel alloy, or graphite flake.
7. The method according to claim 1, characterized in that the catalyst contains CO 2 The atmosphere of the gas also includes a shielding gas.
8. The method according to claim 1, wherein the time of the melt electrolysis is 0.5 to 10 hours and the voltage is 2 to 3.3V; the temperature of the molten salt is 600-900 ℃ during the melting electrolysis.
9. The Fe-Si/CaCO prepared by the method according to any one of claims 1-8 3 Materials, including Fe-Si alloys and CaCO 3 。
10. The Fe-Si/CaCO as set forth in claim 9 3 The material is used as a molten steel refining agent.
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| CN202310404734.5A CN116445983A (en) | 2023-04-17 | 2023-04-17 | Fe-Si/CaCO3 material, preparation method thereof and application thereof as molten steel refining agent |
| PCT/CN2023/097934 WO2024027322A2 (en) | 2023-04-17 | 2023-06-02 | Fe-si/caco3 material, and preparation method therefor and use thereof of as molten steel refining agent |
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| CN202310404734.5A CN116445983A (en) | 2023-04-17 | 2023-04-17 | Fe-Si/CaCO3 material, preparation method thereof and application thereof as molten steel refining agent |
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| SU1668487A1 (en) * | 1989-04-11 | 1991-08-07 | Днепродзержинский Индустриальный Институт Им.М.И.Арсеничева | Electrolyte for making alloy by electrolysis |
| NO20060806L (en) * | 2006-02-17 | 2007-08-20 | Norsk Titanium Metals As | Method and apparatus for metal production |
| JP4707036B2 (en) * | 2007-02-08 | 2011-06-22 | 国立大学法人豊橋技術科学大学 | Method for producing alloy ingot by molten salt electrolysis using ESR heating |
| CN101979715B (en) * | 2010-12-01 | 2012-09-05 | 武汉大学 | Method for preparing silicon-calcium alloy |
| CN102560538B (en) * | 2011-12-15 | 2014-11-12 | 沈阳化工大学 | Method for treating waste fused salt produced in production of TiCl4 |
| CN105624365B (en) * | 2016-03-29 | 2017-08-11 | 马鞍山市兴达冶金新材料有限公司 | A kind of alkaline earth oxide is combined molten steel refining agent and preparation method thereof |
| CN108360023B (en) * | 2018-02-13 | 2020-06-23 | 鞍钢股份有限公司 | Method and device for composite deoxidation alloying of aluminum and magnesium |
| CN110760890B (en) * | 2019-11-27 | 2022-01-11 | 东北大学 | Method for treating smelting slag by electrolytic reduction of aluminum molten salt |
| CN113322492A (en) * | 2021-05-28 | 2021-08-31 | 华北理工大学 | Method for preparing iron silicon from molten salt electro-deoxidation copper slag |
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