CN115637305A - Method for acid leaching of iron element in iron ore or steel slag and application thereof - Google Patents
Method for acid leaching of iron element in iron ore or steel slag and application thereof Download PDFInfo
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- CN115637305A CN115637305A CN202211297981.1A CN202211297981A CN115637305A CN 115637305 A CN115637305 A CN 115637305A CN 202211297981 A CN202211297981 A CN 202211297981A CN 115637305 A CN115637305 A CN 115637305A
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- acid
- iron
- leaching
- steel slag
- iron ore
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 229
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 96
- 238000002386 leaching Methods 0.000 title claims abstract description 95
- 239000002253 acid Substances 0.000 title claims abstract description 92
- 239000002893 slag Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 65
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 49
- 239000010959 steel Substances 0.000 title claims abstract description 49
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000002699 waste material Substances 0.000 claims abstract description 54
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 24
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 22
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 22
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011737 fluorine Substances 0.000 claims abstract description 15
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- -1 hydrogen ions Chemical class 0.000 claims description 8
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 150000004673 fluoride salts Chemical class 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 25
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001448 ferrous ion Inorganic materials 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 18
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910052918 calcium silicate Inorganic materials 0.000 description 6
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 6
- 235000012241 calcium silicate Nutrition 0.000 description 6
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 235000019976 tricalcium silicate Nutrition 0.000 description 6
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 235000021110 pickles Nutrition 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003818 cinder Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 2
- 239000011028 pyrite Substances 0.000 description 2
- 229910052683 pyrite Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910001341 Crude steel Inorganic materials 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 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
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000003922 charged colloid Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910021646 siderite Inorganic materials 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- 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
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- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the technical field of environmental protection, and discloses a method for acid leaching of iron elements in iron ore or steel slag and application thereof. The method comprises the following steps: s1, grinding slag: taking ground waste residues of iron ores or steel slag for later use; s2, acid preparation: respectively mixing sulfuric acid, auxiliary acid and a proper amount of water to obtain mixed acid; the auxiliary acid is any one of hydrochloric acid, nitric acid, hydrofluoric acid and oxalic acid; s3, leaching: and (3) adding a part of the waste residue obtained in the step (S1) into the mixed acid obtained in the step (S2) while stirring, adding a fluorine-containing leaching aid, continuously adding the rest waste residue, and reacting under a preset condition to obtain a product. The technical scheme of the invention is simple and convenient, the flow is short, the problem that ferrous ions are adsorbed to silicic acid and cannot be filtered out in the acid leaching process can be effectively solved by preparing the mixed acid and assisting with the fluorine-containing leaching aid, and the leaching rate can finally reach 92-98%. Greatly improves the leaching rate of the iron ore or the steel slag to the metallic iron.
Description
Technical Field
The invention relates to the technical field of environmental protection, and particularly relates to a method for acid leaching of iron elements in iron ore or steel slag and application thereof.
Background
The steel slag is a product in steel production, and is a solid waste with the greatest resource utilization difficulty in the steel slag due to the reasons of poor stability, poor grindability, low activity, heavy metal content, unstable components and the like, the comprehensive utilization rate of the steel slag is less than 40 percent at present, china is a major country for steel production, the yield of crude steel reaches 10.65 hundred million in 2020, the produced steel slag is 1.6 hundred million t, a certain content of iron is stored in the steel slag, and the iron metal is leached out usually by an acid leaching technology. In addition, iron elements also exist in different iron ores, and further extraction of the iron elements can effectively utilize the iron elements in the nature.
The prior art discloses a method for extracting and separating iron from industrial waste sludge and preparing ferrous sulfate and iron oxide red. The technology comprises four steps: a dilute sulfuric acid leaching process of industrial waste iron mud; a process for preparing iron oxide red by adopting an organic solvent ammonium reaction and oxidizing and roasting precipitates; the process for preparing ammonium sulfate by evaporating and crystallizing the precipitation liquid. Wherein the iron in the pickle liquor is +3, and the iron in the pickle liquor is reduced to +2 under the action of a reducing agent.
The prior art discloses a method for recovering iron from iron-containing ores, strong acid, ammonium salt and water are mixed according to the mass ratio of (1) to (1) and the mixing temperature is 20 ℃ and 80 ℃, the mixing time is more than 5 minutes, a leaching agent solution is obtained, and the leaching agent solution and ground iron ore particles are mixed according to the mass ratio of (3): adding the liquid-solid ratio of 1 into a pressurized reaction kettle, carrying out pressurized acid leaching at the reaction temperature of 80 ℃ and 150 ℃ and under the pressurized pressure of 0.5 Mp for 50 minutes, carrying out solid-liquid separation to obtain slag and weak acid leachate, adjusting the pH value of the acid leachate to 4-6.5, reacting for more than 20min, and carrying out solid-liquid separation to obtain an iron salt solution. The strong acid comprises sulfuric acid or hydrochloric acid, the ammonium salt comprises ammonium sulfate or ammonium chloride, the iron-containing ore is iron-containing tailings with the iron content of more than 15%, and the iron-containing tailings are sulfuric acid residues obtained after roasting of pyrite, iron-containing tailings obtained after ore dressing of copper ore or iron-containing furnace slag obtained after smelting of copper.
The prior art discloses a method for preparing ferric oxide by using waste residues containing iron, and ferric oxide is prepared by using the waste residues containing ferric iron. Firstly, reacting pyrite slag with sulfuric acid to obtain pickle liquor, then reacting the pickle liquor with ammonia water or liquid ammonia, wherein the pH value of the reaction is 3-14, the hydrothermal reaction temperature is 100-350 ℃, reacting for 0.5-24 h, filtering, washing and drying a filter cake to obtain a crude product of ferric oxide, and then calcining to obtain the ferric oxide.
The prior art discloses a process for extracting iron from sulfuric acid cinder by aid of an aid-enhanced acid leaching method, wherein the sulfuric acid cinder and an aid are mixed and placed in a normal-pressure reaction kettle, and the aid is H 2 C 2 O 4 Or (NH) 4 ) 2 C 2 O 4 Adding 30-50% sulfuric acid solution, stirring, reacting at 60-100 deg.C under normal pressure for 2-8 hr, performing solid-liquid separation after acid leaching reaction, precipitating iron from acid leaching filtrate containing iron and oxalate particles, removing impurities from the iron-precipitated filter cake to obtain iron-containing product, wherein the filtrate contains (NH) 4 ) 2 C 2 O 4 And returning to the acid leaching process for recycling. Wherein the solid-liquid ratio of the sulfuric acid solution is 1-8, and the mass ratio of the auxiliary agent to the sulfuric acid cinder is 1. (5% to 20%)
The above are conventional technologies for extracting metallic iron by acid leaching, but the phase composition of steel slag/iron-containing ore is complex, contains 19% or more of silicon, such as tricalcium silicate, dicalcium silicate and transition state substances among the tricalcium silicate and the dicalcium silicate, and silicic acid is formed in the acid leaching process, and leached ferrous ions are easily adsorbed by silicic acid, so that the recovery rate of metallic iron is influenced by the conventional acid leaching technology.
Disclosure of Invention
The invention provides a method for acid leaching of iron elements in iron ores or steel slags, aiming at overcoming the defects that the iron elements in the iron ores or steel slags in the prior art are easy to attach to silicic acid and are filtered and removed, so that the recovery rate of metallic iron is low and the like.
The invention also aims to provide an application of the method for leaching the iron element in the iron ore or the steel slag by acid.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a method for acid leaching of iron elements in iron ore or steel slag comprises the following steps:
s1, grinding slag: taking ground waste residues of iron ores or steel slag for later use;
s2, acid preparation: respectively mixing sulfuric acid, auxiliary acid and a proper amount of water to obtain mixed acid; the auxiliary acid is any one or combination of more of hydrochloric acid, nitric acid, hydrofluoric acid and oxalic acid;
s3, leaching: and (3) adding a part of the waste residue obtained in the step (S1) into the mixed acid obtained in the step (S2) while stirring, adding a fluorine-containing leaching aid, continuously adding the rest waste residue, reacting under a preset condition, and filtering to obtain a product.
Wherein the waste residue is a product obtained by grinding iron ore or steel slag, and specifically, the iron ore is magnetite, hematite, maghemite, ilmenite, limonite or siderite. The steel slag is pulverized blast furnace ironmaking slag, converter steel slag, open-hearth steel slag or electric furnace steel slag. The steel slag mainly comprises dicalcium silicate, tricalcium silicate, dicalcium ferrite, a large amount of unstable free calcium oxide, ferrous oxide, ferric oxide, magnesium oxide and the like.
During the acid leaching process, tricalcium silicate, dicalcium silicate and transition state substances among tricalcium silicate and dicalcium silicate in iron ore or steel slag react with acid to generate silicic acid (silicon-containing colloid), and the reaction equations are respectively as follows:
dicalcium silicate (2 CaO. SiO) 2 )+2H 2 SO 4 (concentrated) = H 2 SiO 3 (colloid) +2CaSO 4 +H 2 O，
Tricalcium silicate (3 CaO. SiO) 2 )+3H 2 SO 4 (concentrated) = H 2 SiO 3 (colloid) +3CaSO 4 +2H 2 O。
Meanwhile, the metallic iron compound generates ferric sulfate and ferrous sulfate in the acid solution, and a large amount of Fe is separated out 3+ And Fe 2+ Among them, since silicic acid colloid is negatively charged colloid, it is easy to adsorb positively charged Fe 3+ And Fe 2+ If the desorption treatment is not carried out, the recovery rate of the iron metal is influenced. Moreover, the sulfuric acid has better extraction effect on ferrous iron, and is difficult to leach high-valent iron, so that the recovery rate of iron is not high, the required time is long, and if the sulfuric acid is directly leached by a sulfuric acid solution, the reaction effect is not enoughIdeally.
It should be noted that, compared with the traditional method of treating iron ore or steel slag by using single acid, the method uses mixed acid as acid leaching solution in the acid leaching process, and combines with fluorine-containing auxiliary leaching agent to remove Fe 3+ And Fe 2+ The silicon acid is desorbed into the liquid, and the leaching rate of the iron ore or the steel slag is further improved. Specifically, the reaction equation of a mixed acid such as sulfuric acid and hydrochloric acid with iron elements in iron ore or steel slag is:
Fe 2 O 3 +3H 2 SO 4 ＝Fe 2 (SO 4 ) 3 +3H 2 O；
FeO+H 2 SO 4 ＝FeSO 4 +H 2 O；
Fe 2 O 3 +6HC1＝2FeCl 3 +3H 2 O；
FeO+2HCl＝FeCl 2 +H 2 O。
the sulfuric acid has obvious effect of extracting ferrous iron, and has good leaching rate to high-valent iron through hydrochloric acid, nitric acid, hydrofluoric acid and oxalic acid, so that the mixed acid is adopted for heating, stirring and adding a cosolvent to promote the reaction, so that the leaching rate of iron is improved.
Preferably, the particle size of the slag in the step S1 is-0.074mm, 95% and above. Specifically, the original iron ore or steel slag is screened by a 200-mesh sieve to obtain waste slag, and the granularity of the waste slag is reduced, so that the reaction area between the waste slag and the mixed acid is increased.
Preferably, the amount of sulfuric acid and co-acid added in step S2 is the product of the amount of theoretical substance and the excess factor; the theoretical amount of hydrogen ions in the sulfuric acid is 60-80% of the amount of hydrogen ion substances required by total iron in the waste residue, the theoretical amount of hydrogen ions in the co-acid is the amount of the remaining hydrogen ion substances required by total iron in the waste residue, the excess coefficient of the sulfuric acid is 1-1.5, and the excess coefficient of the co-acid is 1-1.5.
Further preferably, the amount of the theoretical species of hydrogen ions in the sulfuric acid is 80% of the amount of the hydrogen ion species required for total iron in the slag, and the amount of the theoretical species of hydrogen ions in the co-acid is 20% of the amount of the hydrogen ion species required for total iron in the slag. The excess factor for both sulfuric acid and co-acid was 1.2.
Preferably, the solid-liquid ratio of the waste residue in the step S1 to the mixed acid in the step S2 is 1kg: (4-10) L.
Preferably, the fluorine-containing leaching aid in step S3 is any one or a combination of more of fluoride salt and hydrofluoric acid. In addition, the fluorine element and silicon and aluminum present in the slag form AlF 5 2- And SiF 6 2- The method prevents the generation of silicon-containing colloid and fine solid particles, thereby being beneficial to the forward progress of the reaction between the waste residue and the mixed acid and improving the leaching rate of the iron element.
Further preferably, the fluorine-containing leaching aid in the step S4 is ammonium bifluoride, so that the method is cheaper, the process cost is saved, and the economic benefit is improved.
Preferably, the mass ratio of the fluorine-containing leaching aid to the waste residue is 1-5%.
More preferably, the fluorine-containing leaching aid accounts for 3% by mass of the waste residue.
Preferably, a part of the waste residue added in step S3 accounts for 40-60% of the mass of the waste residue in step S1. It should be noted that, because the reaction between the iron element in the waste residue and the mixed acid is an exothermic reaction, a large amount of heat is released in the reaction process, so that the waste residue is added in batches, the temperature rise process in the reaction system can be slowed down, and accidents such as scalding and burning caused by overhigh temperature can be avoided.
Further preferably, a part of the slag added in step S3 first accounts for 40% by mass of the slag in step S1.
Preferably, the preset conditions in step S3 are: stirring for 0.5h or more at normal temperature, wherein the stirring speed is 300-500 r/min.
Further preferably, the preset conditions in step S4 are: stirring for 1.5h at normal temperature with a stirring speed of 300r/min.
The invention also provides an application of the method for acid leaching of iron element in iron ore or steel slag in acid leaching of iron element in iron ore or steel slag. It should be noted that the iron ore or steel slag in the method has a complex phase, has a high silicon content (19% or more), and is easy to form silicic acid in the leaching process.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
compared with the traditional process which only adopts a single acid, the invention can greatly improve the leaching rate of the waste residue by preparing mixed acid, mixing sulfuric acid and any one of hydrochloric acid, nitric acid, hydrofluoric acid and oxalic acid, and then assisting with a fluorine-containing leaching aid to leach the iron element in the waste residue, so that the original leaching rate of 40-45 percent in the waste residue is improved to 92-98 percent, the process is simple and convenient, the flow is short, and the leaching rate of iron metal in iron ore, blast furnace iron-smelting slag, converter waste residue, open hearth furnace waste residue or electric furnace waste residue is greatly improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the present application will be clearly and completely described below with reference to the embodiments of the present application. It should be apparent that the described embodiments are only some of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments without inventive effort, are within the scope of protection of the present application.
Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
A method for acid leaching of iron element in iron ore or steel slag comprises the following steps:
s1, grinding slag: selecting steel slag produced by Guangdong Shaosuan steel limited company of Baoku group, drying and grinding the steel slag, sieving the steel slag by a 200-mesh sieve to obtain ground waste slag, and detecting that the total iron content is 19 percent; the granularity of the waste residue is-0.074mm, 95 percent and above.
The total iron content is the total content of iron element determined by chemical analysis of the waste residue and is expressed by mass fraction.
S2, acid preparation: respectively taking 325.68g of 98% sulfuric acid and 169.68g of 35% hydrochloric acid according to a preset proportion (the amount of iron in the waste residue is calculated according to ferrous ions, the theoretical substance of hydrogen ions in the sulfuric acid is 80% of the amount of hydrogen ion substances required by total iron in the waste residue, the theoretical substance of hydrogen ions in the auxiliary acid is 20% of the amount of hydrogen ion substances required by total iron in the waste residue, and the excess coefficients of the sulfuric acid and the auxiliary acid are both 1.2), mixing, adding proper amount of water, and preparing into 6L of solution to obtain mixed acid.
S3, leaching: taking 1kg of waste residue, adding 40% of waste residue into mixed acid under normal temperature condition while stirring, adding 3% of ammonium bifluoride relative to the mass of the waste residue, finally adding the rest waste residue, stirring for 1.5h under normal temperature condition with the stirring speed of 400r/min, and filtering to obtain the final product of the iron-rich mother liquor.
Examples 2 to 7
The procedure of the leaching method of iron element of examples 2 to 7 is the same as that of example 1 except for the following process conditions, which are specifically shown in table 1. And detecting the final product iron-rich mother liquor obtained by leaching.
TABLE 1 Process conditions for examples 2 to 7
Comparative example 1
The raw material composition, process steps and process conditions of comparative example 1 were similar to those of example 1, except that mixed acid was not prepared and leaching was performed only with sulfuric acid in step S3.
Comparative example 2
The raw material composition, process steps and process conditions of comparative example 2 were similar to those of example 1, except that no mixed acid was prepared and only hydrochloric acid was used for leaching in step S3.
Comparative example 3
The composition of the raw materials, process steps and process conditions of comparative example 3 were similar to those of example 1, except that no mixed acid was prepared and only nitric acid was used for leaching in step S3.
Comparative example 4
The composition of the raw materials, the process steps and the process conditions of comparative example 4 were similar to those of example 1, except that the mixed acid was not prepared and only hydrofluoric acid was used for leaching in step S3.
Comparative example 5
The composition of the raw materials, process steps and process conditions of comparative example 5 were similar to those of example 1, except that mixed acid was not prepared and leaching was performed only with oxalic acid in step S3.
Comparative example 6
The composition of the raw materials, process steps and process conditions of comparative example 6 were similar to those of example 1, except that no fluorine-containing leaching aid was added in step S3.
Comparative examples 7 to 19
The raw material composition, process steps and process conditions of comparative examples 7 to 19 were similar to those of example 1 except as shown in tables 2.1 to 2.3:
TABLE 2.1 Process conditions for comparative examples 7 to 11
TABLE 2.2 Process conditions for comparative examples 12 to 16
TABLE 2.3 Process conditions for comparative examples 17 to 19
The leaching products of examples 1 to 7 and comparative examples 1 to 19 were detected by the method of "titration of potassium dichromate by reduction of titanium trichloride" for determining the total iron content of GB-T6730.65-2009 iron ore ", and the leaching rate results were obtained as follows.
Table 3 iron leaching rate from slag of examples 1 to 4 and comparative examples 1 to 20
As can be seen from Table 3, the recovery rate of iron in the waste residues of examples 1 to 7 is as high as more than 92%, and it can be seen that the leaching rate and leaching rate of iron metal in the waste residues can be greatly improved under simple process conditions by using the mixed acid leaching solution in combination with the fluorine-containing leaching aid in the technology of the present invention.
As can be seen from comparative example 1, when sulfuric acid alone is used, the leaching rate is only 48%, the leaching effect is very different, and high-valence iron such as ferric silicate in the waste residue is difficult to leach.
Analysis of comparative examples 2 to 3 shows that the leaching effect is slightly better than that of sulfuric acid when hydrochloric acid and nitric acid are used independently, namely 64 percent and 58 percent respectively, but the leaching effect is different from that of mixed acid, and the hydrochloric acid and the nitric acid are more expensive than the sulfuric acid, the using amount is large, and the economic efficiency is low.
As can be seen from comparative example 4, hydrofluoric acid is most effective in leaching iron element from waste residue with a single acid, but hydrofluoric acid is expensive and generally used for extracting precious metals, and is not economical.
As can be seen from comparative example 5, the leaching efficiency is only 45% and the leaching effect is poor when only oxalic acid is used for leaching compared with the same types of hydrochloric acid, sulfuric acid and hydrofluoric acid.
As can be seen from comparative example 6, the leaching rate was only 58% without using the fluorine-containing leaching aid, which suppressed silica gel formation and positively promoted leaching of iron element from the waste residue.
As can be seen from comparative examples 7 to 10, the usage amount of sulfuric acid in the mixed acid is in positive correlation with the leaching rate of iron element, and as the usage amount of sulfuric acid is gradually reduced, the leaching rate of iron element in the waste residue is gradually reduced.
As can be seen from comparative examples 11 to 14, the amount of co-acid used in the mixed acid was positively correlated with the leaching rate of iron, and as the amount of co-acid was gradually reduced, the leaching rate of iron in the slag was gradually reduced. And the effect is more obvious than that of sulfuric acid.
The solid-liquid mixture solutions of comparative examples 15 to 16 were too thick or too thin, which was not favorable for sufficient contact between the reaction materials, resulting in a decrease in leaching rate.
In comparative example 17, the reaction time was too short and the reaction was insufficient, resulting in a low final leaching rate.
Comparative examples 18 to 19 were unsatisfactory in the final leaching rate because the stirring speed was too slow and too fast, which resulted in insufficient contact of the materials or short contact time.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The method for acid leaching of the iron element in the iron ore or the steel slag is characterized by comprising the following steps of:
s1, grinding slag: taking ground waste residues of iron ore or steel slag for later use, wherein the total iron content in the waste residues is known;
s2, acid preparation: respectively mixing sulfuric acid, auxiliary acid and a proper amount of water to obtain mixed acid; the auxiliary acid is any one or combination of more of hydrochloric acid, nitric acid, hydrofluoric acid and oxalic acid;
s3, leaching: and (3) adding a part of the waste residue obtained in the step (S1) into the mixed acid obtained in the step (S2) while stirring, adding a fluorine-containing leaching aid, continuously adding the rest waste residue, reacting under a preset condition, and filtering to obtain a product.
2. The method for acid leaching of iron elements from iron ore or steel slag according to claim 1, wherein the grain size of the slag in step S1 is-0.074 mm,95% or more.
3. The method for acid leaching of iron element from iron ore or steel slag according to claim 1, wherein the amount of sulfuric acid and the co-acid added in step S2 is the product of the amount of theoretical material and the excess factor; the amount of the theoretical substance of the hydrogen ions in the sulfuric acid is 60-80% of the amount of the hydrogen ion substance required by the total iron in the waste residue, the amount of the theoretical substance of the hydrogen ions in the co-acid is the amount of the hydrogen ion substance required by the rest of the total iron in the waste residue, the excess coefficient of the sulfuric acid is 1-1.5, and the excess coefficient of the co-acid is 1-1.5.
4. The method for acid leaching of iron element in iron ore or steel slag according to claim 1, wherein the solid-to-liquid ratio of the waste slag in step S1 to the mixed acid in step S2 is 1kg: (4-10) L.
5. The method for acid leaching of iron element in iron ore or steel slag according to claim 1, wherein the fluoride-containing leaching aid in step S3 is any one or more of fluoride salt and hydrofluoric acid.
6. The method for acid leaching of iron element in iron ore or steel slag according to claim 1, wherein the fluorine-containing leaching aid in step S3 is 1-5% by weight of the waste slag.
7. The method for acid leaching of iron element in iron ore or steel slag according to claim 1, wherein the part of the waste slag added in step S3 accounts for 40-60% of the mass of the waste slag in step S1.
8. The method for acid leaching of iron element in iron ore or steel slag according to claim 1, wherein the preset conditions in step S3 are as follows: stirring for 0.5h or more at normal temperature, wherein the stirring speed is 300-500 r/min.
9. The method of claim 1, wherein prior to step S2, the ground slag of step S1 is taken to determine the total iron content thereof.
10. Use of the method of acid leaching of iron elements from iron ore or steel slag according to any one of claims 1 to 9 for acid leaching of iron elements from iron ore or steel slag.
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