CN112624070B - Full utilization method of steel slag - Google Patents
Full utilization method of steel slag Download PDFInfo
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- CN112624070B CN112624070B CN202011405557.5A CN202011405557A CN112624070B CN 112624070 B CN112624070 B CN 112624070B CN 202011405557 A CN202011405557 A CN 202011405557A CN 112624070 B CN112624070 B CN 112624070B
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- 239000002893 slag Substances 0.000 title claims abstract description 146
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 128
- 239000010959 steel Substances 0.000 title claims abstract description 128
- 238000000034 method Methods 0.000 title claims abstract description 44
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 163
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 84
- 239000011574 phosphorus Substances 0.000 claims abstract description 83
- 229910052742 iron Inorganic materials 0.000 claims abstract description 79
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 67
- 239000011593 sulfur Substances 0.000 claims abstract description 67
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 58
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 52
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000007789 gas Substances 0.000 claims abstract description 40
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 26
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 18
- 230000009467 reduction Effects 0.000 claims abstract description 18
- 238000004064 recycling Methods 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 238000009628 steelmaking Methods 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims description 23
- 238000007254 oxidation reaction Methods 0.000 claims description 23
- 235000013980 iron oxide Nutrition 0.000 claims description 18
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 239000002918 waste heat Substances 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 239000000571 coke Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 238000009270 solid waste treatment Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 13
- 229910052593 corundum Inorganic materials 0.000 description 11
- 239000010431 corundum Substances 0.000 description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 9
- 239000000292 calcium oxide Substances 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000000889 atomisation Methods 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 238000012921 fluorescence analysis Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- WETINTNJFLGREW-UHFFFAOYSA-N calcium;iron;tetrahydrate Chemical compound O.O.O.O.[Ca].[Fe].[Fe] WETINTNJFLGREW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 238000007885 magnetic separation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 208000017667 Chronic Disease Diseases 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- RDXARWSSOJYNLI-UHFFFAOYSA-N [P].[K] Chemical compound [P].[K] RDXARWSSOJYNLI-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003570 air 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/12—Oxides of phosphorus
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B3/00—General features in the manufacture of pig-iron
- C21B3/04—Recovery of by-products, e.g. slag
- C21B3/06—Treatment of liquid slag
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2400/00—Treatment of slags originating from iron or steel processes
- C21B2400/02—Physical or chemical treatment of slags
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2400/00—Treatment of slags originating from iron or steel processes
- C21B2400/02—Physical or chemical treatment of slags
- C21B2400/03—Removing sulfur
-
- 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
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Carbon Steel Or Casting Steel Manufacturing (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a full utilization method of steel slag, belongs to the technical field of metallurgical solid waste treatment, solves the problems of large steel slag generation amount and low utilization rate in the prior art, and avoids steel slag stockpiling. The invention provides a full utilization method of steel slag, which comprises the following steps: introducing air or oxygen into the steel slag to convert sulfur in the steel slag into sulfur dioxide to be removed, thereby obtaining desulfurized steel slag; adding carbonaceous reducing agent into desulfurized steel slag to carry out carbothermic reduction, and using P as part of phosphorus in the steel slag after reduction2Removing the steam to obtain high-phosphorus high-carbon molten iron and low-sulfur low-phosphorus molten slag, and returning the low-sulfur low-phosphorus molten slag to the steelmaking environment for recycling; atomizing and oxidizing the high-phosphorus high-carbon molten iron, and removing carbon, sulfur and phosphorus impurities in the molten iron in a gaseous oxide form to obtain high-purity iron oxide powder; and (3) mixing and oxidizing all the obtained gases containing carbon, sulfur and phosphorus, cooling the sulfur and phosphorus in the gases to respectively prepare sulfuric acid and recover phosphorus pentoxide. The full utilization of sulfur, phosphorus, iron and slag in the steel slag is realized.
Description
Technical Field
The invention relates to the technical field of metallurgical solid waste treatment, in particular to a full utilization method of steel slag.
Background
About 150kg of steel slag is generated when one ton of steel is produced, the steel slag stacking amount in China currently exceeds 10 hundred million tons, and the utilization rate is only 10-20%. The process flow of steel slag treatment and utilization is shown in fig. 1, and generally, steel slag needs to be subjected to treatments such as granulation and magnetic separation and then is utilized in a grading manner. The granulating mode of the steel slag comprises a hot stuffy method, a disc splashing method, an air quenching method, a water quenching method, a roller method and a granulating wheel method, water is essentially used as a coolant, and besides the air quenching method can recover a small amount of heat, the heat energy of the steel slag in other methods is wasted and a large amount of water resources are consumed. And secondly, the magnetic separation powder steel has low iron grade and high phosphorus content, and can cause phosphorus enrichment in molten iron when used as sintering ingredients, reduce the iron grade of sintered ores and improve the treatment cost of the molten iron. In addition, the steel slag has high alkalinity, even though the slag is granulated and digested, the tailings still contain certain content of free CaO and MgO, and calcium silicate is in a metastable phase after quenching, so that the structure stability of the tailings is poor, and the tailings need to be stacked to achieve stabilization when being directly used as backfill or paving materials, so that the time consumption is long. If the tailings are ground and magnetically separated for recycling, the tailings are compact, hard and poor in grindability, so that the ore grinding cost for preparing the steel slag micro powder is high, the utilization economy is reduced, the water absorption is strong when the tailings are used as an additive of cement or concrete, the hardening time is shortened, the iron content is high, the addition amount is generally controlled within 30%, and the use amount is limited. Therefore, the utilization rate of tailings after magnetic separation of the steel slag is extremely low at present, and the steel slag is mainly subjected to stacking treatment and becomes a chronic disease for steel enterprises.
At present, the steel slag is treated by a reduction method and is concerned. The hot steel slag is first reduced by carbon heat, iron oxide and most of phosphorus in the steel slag are reduced to enter molten iron, the high-phosphorus molten iron is dephosphorized by potassium carbonate to obtain potassium phosphate which is used for preparing the phosphorus-potassium compound fertilizer, and the dephosphorized molten iron is returned to steel making. Meanwhile, the reduced low-phosphorus steel slag is used as a sintering flux or a cement raw material. The process has the advantages that iron and phosphorus in the steel slag are recovered, and meanwhile, the reduced tailings do not contain iron, so that the ore grinding cost of the steel slag is reduced, the addition amount of the steel slag in cement is increased, and the utilization of the steel slag is well promoted. However, the yield of the steel slag does not realize source reduction, the terminal utilization value is limited by the market environment of cement, and although the steel slag can be used as a sintering flux for sintering the flux consumption of the link, the effective flux content of the steel slag is far lower than that of lime, so that the grade of sintering ore and the slag amount in the blast furnace smelting process are reduced.
Most ideally, the steel slag is returned to the steel-making environment for recycling after recovering phosphorus and iron, so that the addition amount of the flux can be greatly reduced, and the slagging time is shortened. However, sulfur still exists in the steel slag in the form of CaS during the carbothermic reduction process of the steel slag, and the desulfurization effect of the steel slag is reduced after recycling and enrichment. In addition, potassium carbonate is consumed for dephosphorization of high-phosphorus molten iron, the potassium carbonate is high in price and easy to decompose and volatilize at high temperature, the loss in the high-temperature dephosphorization process is large, and meanwhile, the carbon content in the molten iron is high, and the molten iron needs to be returned to the steelmaking process for blowing again.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a method for utilizing steel slag in full quantity, which solves at least one of the following technical problems: (1) the iron, the sulfur and the phosphorus in the steel slag can not be fully utilized; (2) a large amount of alkaline flux is consumed in the steel-making process; (3) the environmental pollution problem caused by the piling of a large amount of tailings.
The invention provides a full utilization method of steel slag, which removes and recovers sulfur and phosphorus in the steel slag treatment process to obtain high-purity iron oxide powder and low-sulfur low-phosphorus molten slag, and does not generate tailings in full utilization, and comprises the following steps:
step 1, introducing air or oxygen into the steel slag to convert sulfur in the steel slag into sulfur dioxide to remove, thereby obtaining desulfurized steel slag;
step 2, adding a carbonaceous reducing agent into the desulfurized steel slag to carry out carbothermic reduction, and reducing the phosphorus in the steel slag partially by P2Removing the steam to obtain high-phosphorus high-carbon molten iron and low-sulfur low-phosphorus molten slag, and returning the low-sulfur low-phosphorus molten slag to the steelmaking environment for recycling;
step 3, atomizing and oxidizing the high-phosphorus high-carbon molten iron, and removing carbon, sulfur and phosphorus impurities in the molten iron in a gaseous oxide form to obtain high-purity iron oxide powder;
and 4, mixing and oxidizing all the gases containing carbon, sulfur and phosphorus obtained in the steps 1, 2 and 3, cooling the sulfur and phosphorus in the gases to respectively prepare sulfuric acid and recover phosphorus pentoxide.
Further, the high-purity iron oxide powder obtained in the step 3 is reduced to prepare high-purity iron.
Further, the gas after mixed oxidation in the step 4 is cooled to below 200 ℃ by the recovery of waste heat of a waste heat boiler, and P is deposited and recovered from gas phase in a solid form2O5Deposit and recover P2O5Spraying water to the gas, SO3And converting into industrial sulfuric acid.
Further, in the step 1, the ratio of the introduced oxygen to the amount of the metallic iron in the steel slag is 0.45:1 to 0.9: 1.
Further, in the step 1, the temperature of the steel slag is increased to 1650-1750 ℃, and the temperature is kept for 1h to 1.5 h.
Further, in the step 1, the flow rate of the introduced oxygen is 1.8L/min to 2L/min.
Further, in the step 1, the blowing time of the oxygen is 30min to 60 min.
Further, in the step 2, the phosphorus content in the high-phosphorus high-carbon molten iron is 2.3% -2.4%, and the carbon content is 4.3% -4.6%.
Further, in the step 2, the low-sulfur and low-phosphorus molten slag contains 0.041-0.047% of phosphorus and 0.008-0.013% of sulfur.
Further, the carbon reducing agent in the step 2 is a low-sulfur carbonaceous reducing agent, the low-sulfur carbonaceous reducing agent is semi-coke or graphite powder, and the amount ratio of carbon in the added carbonaceous reducing agent to the amount of oxygen atoms in iron oxides in the desulfurized steel slag is 1.5-1.8: 1.
Further, the step 2 is carbothermic reduced at 1700 ℃ to 1800 ℃ for 40min to 60 min.
Further, in the step 3, high-pressure air is used for atomizing and oxidizing the high-phosphorus high-carbon molten iron, and the oxidizing time is 30-50 min.
Further, in the step 3, the high-pressure air flow atomizes and oxidizes the high-phosphorus high-carbon molten iron, and the oxidation temperature is 1500-1600 ℃.
Further, in the step 3, the flow rate of the air is 2L/min to 2.8L/min.
Further, the gaseous oxide in the step 3 is carbon dioxide, sulfur trioxide and phosphorus pentoxide.
Further, in the step 4, the temperature of the oxidation is 1000 ℃ to 1100 ℃.
Compared with the prior art, the invention can realize at least one of the following beneficial effects:
(1) according to the invention, air or oxygen is firstly introduced into the steel slag for oxidation, the impurity sulfur in the steel slag is firstly converted into sulfur dioxide for removal, calcium sulfide is converted into calcium oxide in the oxidation process and combined with ferric oxide after iron oxidation to form calcium ferrite, the impurity sulfur in the steel slag is removed first, and the influence of the retention of the sulfur in the steel slag after the treatment in the prior art on the desulfurization effect of the steel slag in the recycling process in the steel-making link is avoided.
(2) Compared with the prior art, the desulfurized steel slag is subjected to carbothermic reduction, phosphorus in the slag is almost completely reduced, part of phosphorus is combined with metallic iron and enters molten iron to obtain high-phosphorus high-carbon molten iron, the other part of phosphorus is removed in the form of phosphorus vapor and enters a gas phase, and the obtained molten slag contains almost no sulfur and phosphorus, so that the influence of the molten slag on the dephosphorization effect during the recycling in the steelmaking link is avoided.
(3) The high-phosphorus high-carbon molten iron is atomized and cooled by high-pressure air, and sulfur and phosphorus in the molten iron are almost completely oxidized and removed to obtain high-purity iron oxide powder which can be used as a raw material for preparing high-purity iron, so that the additional value of the product is improved.
(4) Mixing the gas generated in the desulfurization oxidation stage, the carbon-heat reduction stage and the atomization oxidation stage of the high-phosphorus high-carbon molten iron of the steel slag, and mixing the SO generated in the desulfurization oxidation stage and the SO generated in the atomization oxidation stage of the steel slag2CO gas and P produced in carbon thermal reduction stage of gas and desulfurized slag2Steam, residual O in the gas produced in the oxidation stage by atomising high-phosphorus and high-carbon molten iron2Oxidizing, finally mixing the oxidized gas into SO3、CO2、P2O5，SO3For the preparation of sulfuric acid, P2O5Directly recycling. Compared with the prior art, in the process of treating and utilizing the steel slag, various substances in the steel slag are fully utilized, no treated tailings are generated, the full utilization of the steel slag is realized, and the problem of steel slag stockpiling at present is solved.
(5) According to the steel slag full utilization method provided by the invention, sulfur and phosphorus in the steel slag are removed and recovered in the steel slag treatment process, so that high-purity iron oxide powder and low-sulfur and low-phosphorus molten slag are obtained, and no tailings are generated in full utilization.
In the invention, the technical schemes can be combined with each other to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout.
FIG. 1 is a process for treating and utilizing steel slag of the prior art;
FIG. 2 is a flow chart of multi-stage oxidation-reduction treatment and total utilization of steel slag.
Detailed Description
The steel slag mainly comprises iron, magnesium, calcium, silicon and aluminum, and also comprises a part of phosphorus and sulfur impurities. Wherein, sulfur is the main raw material and the core element for preparing sulfuric acid, and phosphorus is the main raw material and the core element for preparing various phosphoric acid compounds, phosphate compounds, red phosphorus and white phosphorus. Therefore, for the full utilization of the steel slag, the extraction of sulfur and phosphorus impurities in the steel slag needs to be realized, and the impurities are converted into available related chemical raw materials; in addition, the recycling of the main component iron and slag in the steel slag is also required. Because sulfur and phosphorus in the steel slag are easy to enter molten steel again in the recycling process of the steel-making link to cause pollution to the molten steel, the sulfur and the phosphorus in the steel slag can be returned to the steel-making link for recycling after being removed. In addition, carbon, sulfur and phosphorus easily enter molten iron in the reduction process, so that the sulfur and phosphorus contents of the molten iron exceed the standard, and the molten iron needs to be further processed to improve the quality.
In this regard, in the method of utilizing the entire amount of steel slag, it is necessary to separate elemental sulfur from the steel slag at first. The thermal state steel slag reacts with iron, ferrous oxide and calcium sulfide in the steel slag through air or pure oxygen to form calcium ferrite and sulfur dioxide, so that the removal of sulfur is realized. Through research, the molar ratio of the introduced amount of oxygen to the metallic iron in the steel slag is controlled to be 0.45-0.9, and the sulfur content in the steel slag is reduced to be below 0.02 percent:
3O2(g)+CaS+2Fe＝SO2(g)+CaO·Fe2O3
2O2(g)+CaS+2FeO＝SO2(g)+CaO·Fe2O3
3O2(g)+CaO+4Fe＝2CaO·Fe2O3
O2(g)+2CaO+4FeO＝2CaO·Fe2O3
under the action of oxygen, sulfur is oxidized into sulfur dioxide gas to be separated from a system, and iron is oxidized at the same time and combined with calcium oxide into calcium ferrite.
The steel slag after sulfur removal finds that all elements can not be further separated because the elements are oxidized into high oxidation states by oxygen, so that a reducing agent, including low-sulfur carbonaceous reducing agents such as semi-coke or graphite powder, is added. Although a large amount of reducing agents can be used, since the use of other reducing agents introduces new impurity elements into steel slag, the reducing agents are based on existing elements in the existing system, and low-sulfur carbonaceous reducing agents such as semi coke and graphite powder are selected in consideration of their strong reducing ability, low price, and general use in steel production.
Based on the method, the steel slag after sulfur removal is sprayed into low-sulfur carbonaceous reducing agents such as semi-coke or graphite powder for direct reduction, most of phosphorus is reduced into molten iron, and a small part of phosphorus is reduced by P2Into the gas phase while part of the carbon is dissolved into the molten iron. Through research, the reduced molten slag has iron content lower than 2% and phosphorus content lower than 0.05%, and can be returned to the steelmaking link for recycling:
Ca3(PO4)2+5C＝3CaO+5CO+P2
3C+CaO·Fe2O3＝3CaO+5CO+Fe
the iron oxide is reduced into molten iron by carbon, and carbon which is not completely reacted and phosphorus reduced by carbon are dissolved in the molten iron to form high-phosphorus high-carbon molten iron. The high-phosphorus and high-carbon molten iron is atomized into small iron beads through an air high-pressure nozzle, and meanwhile, iron is oxidized into iron oxide in different forms. Researches show that carbon, sulfur and phosphorus in the iron oxide powder are all oxidized into gas to enter a gas phase, and the sum of the contents of the carbon, the sulfur and the phosphorus in the iron oxide powder is less than 0.01%:
FeS+2O2＝2FeO+SO2
C+O2＝CO2
4Fe3P+11O2＝12FeO+2P2O5
2Fe+O2＝2FeO
6FeO+O2＝2Fe3O4
4Fe3O4+O2＝6Fe2O3
after the molten iron is atomized and oxidized by air, iron is oxidized into iron oxide powder, phosphorus is oxidized into phosphorus pentoxide gas, and carbon is oxidized into carbon dioxide gas, so that the iron oxide powder can be smoothly separated from the phosphorus pentoxide gas and the carbon dioxide gas. It is additionally noted that in this step, a small amount of the impurity sulfur is also oxidized by air to sulfur dioxide, which is separated from the iron oxide powder in the gas phase along with phosphorus pentoxide and carbon dioxide.
Meanwhile, the gas generated in the steel slag oxidation stage and the desulfurized steel slag carbothermic reduction stage is mixed with the gas generated in the molten iron atomization oxidation stage, and because the molten iron atomization oxidation stage takes excess air as an oxidant, residual oxygen exists in the gas, and SO generated in the steel slag oxidation stage2And CO and P generated in the carbon thermal reduction stage of the desulfurized steel slag2Is completely oxidized.
2SO2+O2＝2SO3
2CO+O2＝2CO2
2P2+5O2＝2P2O5
The mixed oxidized gas comprises P2O5、CO2、SO3、O2And N2Five main components, namely recovering waste heat of the mixed gas through a waste heat boiler, and reducing the temperature to below 200 ℃ to obtain P2O5Separating and recovering from vapor deposition with solid powder, and absorbing SO with gas after removing phosphorus by water spray3The sulfuric acid is prepared, the sulfur is removed, and the residual gas reaches the standard and is discharged.
SO3+H2O＝H2SO4
Thereby realizing the full utilization of the steel slag.
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate preferred embodiments of the invention and together with the description, serve to explain the principles of the invention and not to limit the scope of the invention.
Example one
The invention discloses a full utilization method of steel slag, which is shown in figure 2.
The converter steel slag composition is shown in Table 1, and the content of TFe is 17.3%, the content of S is 0.09%, and the content of P is2O5The content was 1.42%.
TABLE 1 main chemical composition of converter slag
| Composition (I) | SiO2 | MFe | Al2O3 | FeO | MgO | S | P2O5 | CaO |
| Mass fraction% | 7.8 | 6.3 | 1.37 | 14.1 | 4.64 | 0.09 | 1.42 | 51.02 |
1kg of steel slag is placed in an induction furnace, the induction furnace takes a graphite crucible as a heating element, and magnesia is taken as a refractory material in the graphite crucible to prevent carburization. Heating to 1650 deg.C, maintaining for 1h to ensure that steel slag is fully melted, blowing compressed air into molten slag via a corundum tube at flow rate of 2L/min for 30min, and introducing O2The molar ratio of the iron powder to the metal iron in the steel slag is 0.45. And cooling the slag sample, crushing and grinding the slag sample to powder with the granularity of less than 0.074mm (200 meshes), and determining the sulfur content in the steel slag to be 0.018% by using a carbon-sulfur analyzer.
And (3) determining the contents of ferric oxide, ferroferric oxide and ferrous oxide in the desulfurized steel slag through chemical titration analysis, adding graphite powder according to the content of the ferric oxide in the steel slag, controlling the C/O to be 1.2, and respectively preserving the uniformly mixed samples in a resistance furnace at 1700 ℃ for 40min for reduction. And after the reduction sample is cooled, respectively measuring the phosphorus content of the molten iron and the molten iron through fluorescence analysis, and measuring the carbon content and the sulfur content of the molten iron through a carbon-sulfur analyzer. At this time, the contents of phosphorus and sulfur in the molten slag are 0.047% and 0.013%, and the contents of phosphorus, sulfur and carbon in the molten iron are 2.33%, 0.04% and 4.34%, respectively.
The molten iron obtained by reduction is cooled and crushed into fine metallic iron particles, 40g of the fine metallic iron particles are weighed and put into a corundum dish, and the corundum dish is heated to 1600 ℃ in a tubular resistance furnace, and air is introduced at the flow rate of 2L/min for oxidation for 30 min. And (4) measuring the contents of carbon and sulfur in the cooled oxidized sample by a carbon-sulfur analyzer, and measuring the content of phosphorus by fluorescence analysis. In this case, the carbon content was 0.005%, the sulfur content was 0.001%, and the phosphorus content was 0.003%.
Placing white phosphorus solid in corundum dish, placing corundum dish at two endsIn the tubular resistance furnace with air vent, introducing CO from one end of the tube2、SO2And air, and the resistance furnace is heated to 1000 ℃ from room temperature to simulate the mixed oxidation process. The gas discharged from the outlet end of the tube furnace enters an externally water-spraying cooled closed steel cylinder for cooling, and granular P is separated2O5The gas discharged from the cylinder enters a closed plastic bucket for containing water to absorb SO3The analysis of the residual gas by an infrared gas analyzer shows that SO is contained3Is completely absorbed and converted into sulfuric acid.
Example two
The invention discloses a method for treating and utilizing the total amount of steel slag.
1kg of steel slag which is the same as that in the first embodiment is selected and placed in an induction furnace, the temperature is raised to 1750 ℃, heat preservation is carried out for 1.5h, the steel slag is ensured to be fully melted, compressed air is blown into the steel slag through a corundum tube at the flow rate of 1.8L/min, the blowing time is 60min, and O is introduced at the moment2The molar ratio of the iron powder to the metal iron in the steel slag is 0.9. And cooling the slag sample, crushing and grinding the slag sample to powder with the granularity of less than 0.074mm (200 meshes), and determining the sulfur content in the steel slag to be 0.004% by a carbon-sulfur analyzer.
And determining the contents of ferric oxide, ferroferric oxide and ferrous oxide in the desulfurized steel slag through chemical titration analysis, adding graphite powder according to the content of the iron oxide in the steel slag, controlling the C/O to be 1.5, and respectively preserving the uniformly mixed samples in a resistance furnace at 1800 ℃ for 60min for reduction. And after the reduction sample is cooled, respectively measuring the phosphorus content of the molten iron and the molten iron through fluorescence analysis, and measuring the carbon content and the sulfur content of the molten iron through a carbon-sulfur analyzer. At the moment, the phosphorus and sulfur contents of the melt separation slag are 0.041 percent and 0.008 percent, and the phosphorus, sulfur and carbon contents of the molten iron are 2.38 percent, 0.043 percent and 4.51 percent respectively.
The molten iron obtained by reduction is cooled and crushed into fine metallic iron particles, 40g of the fine metallic iron particles are weighed and put into a corundum dish, and the corundum dish is heated to 1500 ℃ in a tubular resistance furnace, and air is introduced at the flow rate of 2.8L/min for oxidation, wherein the oxidation time is 50 min. And (4) measuring the contents of carbon and sulfur in the cooled oxidized sample by a carbon-sulfur analyzer, and measuring the content of phosphorus by fluorescence analysis. In this case, the carbon content was 0.002%, the sulfur content was 0.001%, and the phosphorus content was 0.001%.
White phosphorus solid is placed in a corundum dish, the corundum dish is placed in a tubular resistance furnace with air vents at two ends, and CO is introduced from one end of the tube2、SO2And air, and the resistance furnace is heated to 1100 ℃ from room temperature, so that the mixed oxidation process is simulated. The gas discharged from the outlet end of the tube furnace enters an externally water-spraying cooled closed steel cylinder for cooling, and granular P is separated2O5The gas discharged from the cylinder enters a closed plastic bucket for containing water to absorb SO3Is converted into sulfuric acid. The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. The full utilization method of the steel slag is characterized by comprising the following steps:
step 1, introducing air or oxygen into the steel slag to convert sulfur in the steel slag into sulfur dioxide to remove, thereby obtaining desulfurized steel slag;
step 2, adding a carbonaceous reducing agent into the desulfurized steel slag to carry out carbothermic reduction, and reducing the phosphorus in the steel slag partially by P2Removing the steam to obtain high-phosphorus high-carbon molten iron and low-sulfur low-phosphorus molten slag, and returning the low-sulfur low-phosphorus molten slag to the steelmaking environment for recycling;
step 3, atomizing and oxidizing the high-phosphorus high-carbon molten iron, and removing carbon, sulfur and phosphorus impurities in the molten iron in a gaseous oxide form to obtain high-purity iron oxide powder;
and 4, mixing and oxidizing all the gases containing carbon, sulfur and phosphorus obtained in the steps 1, 2 and 3, cooling the sulfur and phosphorus in the gases to respectively prepare sulfuric acid and recover phosphorus pentoxide.
2. The method for utilizing the steel slag in full quantity according to claim 1, wherein the high-purity iron oxide powder obtained in the step 3 is reduced to prepare high-purity iron.
3. The method for utilizing the steel slag in full according to claim 1, wherein the gas after the mixed oxidation in the step 4 is cooled to below 200 ℃ by the recovery of waste heat of a waste heat boiler, and P is deposited and recovered from a gas phase in a solid form2O5Deposit and recover P2O5Spraying water to the gas, SO3And converting into industrial sulfuric acid.
4. The method for utilizing the steel slag in full according to claim 1, wherein the ratio of the oxygen gas introduced in step 1 to the amount of the metallic iron in the steel slag is 0.45:1 to 0.9: 1.
5. The method for utilizing the steel slag in full quantity according to claim 1, wherein the carbon reducing agent in the step 2 is a low-sulfur carbonaceous reducing agent, the low-sulfur carbonaceous reducing agent is semi-coke or graphite powder, and the quantity ratio of carbon in the added carbonaceous reducing agent to the quantity of oxygen atoms in iron oxides in the desulfurized steel slag is 1.5-1.8: 1.
6. The method for utilizing the steel slag in full quantity according to claim 1, wherein the step 2 is carried out by carbothermic reduction at 1700 ℃ to 1800 ℃ for 40min to 60 min.
7. The method for utilizing the steel slag in full quantity according to claim 1, wherein in the step 3, high-pressure air is used for atomizing and oxidizing the high-phosphorus high-carbon molten iron for 30-40 min.
8. The method for utilizing the steel slag in full quantity according to claim 7, wherein the high-pressure air flow is used for atomizing and oxidizing the high-phosphorus high-carbon molten iron, and the oxidation temperature is 1500-1600 ℃.
9. The method for utilizing the steel slag in full quantity according to claim 1, wherein the gaseous oxide in the step 3 is carbon dioxide, sulfur trioxide, phosphorus pentoxide.
10. The method for utilizing the steel slag in full quantity according to claim 1, wherein the temperature for oxidizing in the step 4 is 1000 ℃ to 1100 ℃.
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