CN115637305B - Method for leaching iron element in iron ore or steel slag by acid and application thereof - Google Patents
Method for leaching iron element in iron ore or steel slag by acid and application thereof Download PDFInfo
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- CN115637305B CN115637305B CN202211297981.1A CN202211297981A CN115637305B CN 115637305 B CN115637305 B CN 115637305B CN 202211297981 A CN202211297981 A CN 202211297981A CN 115637305 B CN115637305 B CN 115637305B
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- acid
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- iron
- steel slag
- waste residue
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 211
- 238000002386 leaching Methods 0.000 title claims abstract description 91
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 89
- 239000002253 acid Substances 0.000 title claims abstract description 83
- 239000002893 slag Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 59
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 44
- 239000010959 steel Substances 0.000 title claims abstract description 44
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000002699 waste material Substances 0.000 claims abstract description 64
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 23
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 22
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011737 fluorine Substances 0.000 claims abstract description 16
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 8
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 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 17
- 239000007788 liquid Substances 0.000 claims description 10
- 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
- 150000004673 fluoride salts Chemical class 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 26
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract description 8
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 229910001448 ferrous ion Inorganic materials 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 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 14
- 239000000243 solution Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 229910052918 calcium silicate Inorganic materials 0.000 description 5
- 235000012241 calcium silicate Nutrition 0.000 description 5
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 235000019976 tricalcium silicate Nutrition 0.000 description 5
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 239000000084 colloidal system Substances 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
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 4
- 239000011028 pyrite Substances 0.000 description 4
- 229910052683 pyrite Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 239000003818 cinder Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 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
- 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
- 230000015572 biosynthetic process 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
- 230000002596 correlated effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 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
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 235000021110 pickles Nutrition 0.000 description 2
- 238000005554 pickling Methods 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
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 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
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 206010053615 Thermal burn Diseases 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
- 230000009286 beneficial effect 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
- 239000003795 chemical substances by application Substances 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
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 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
- 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-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
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001105 regulatory effect 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
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid 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
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- 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 leaching iron element acid in iron ore or steel slag and application thereof. The method comprises the following steps: s1, grinding slag: taking the ground waste residue in the iron ore or steel slag for standby; 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: adding a part of waste residues in the step S1 into the mixed acid in the step S2 while stirring, adding the fluorine-containing leaching aid, continuously adding the rest waste residues, and reacting under preset conditions to obtain a product. The method has the advantages of simple and convenient technical scheme and short flow, and can effectively solve the problem that ferrous ions are adsorbed on silicic acid and cannot be filtered out in the acid leaching process by preparing the mixed acid and assisting with the fluorine-containing leaching aid, and finally the leaching rate can reach 92-98%. Greatly improves the leaching rate of the iron ore or steel slag to the metal iron.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to a method for leaching iron element acid in iron ore or steel slag and application thereof.
Background
The steel slag is a product in steel production, is a solid waste with the largest recycling difficulty in 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%, the steel slag is produced in China, the crude steel yield in 2020 reaches 10.65 hundred million, 1.6 hundred million of steel slag is produced, and iron with a certain content is stored in the steel slag, and iron metal is leached out by an acid leaching technology generally. 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 mud and preparing ferrous sulfate and iron oxide red. The technology design comprises four steps: a dilute sulfuric acid leaching process of industrial waste iron mud; adopting an organic solvent ammonium reaction and a precipitate oxidizing roasting process to prepare iron oxide red; and (3) preparing ammonium sulfate by evaporating and crystallizing the precipitate. Wherein the iron in the pickling solution is +3 valent, and the iron in the pickling solution is reduced to +2 valent under the action of the reducing agent.
The prior art discloses a method for recovering iron from iron-containing ore, which comprises the steps of mixing strong acid, ammonium salt and water according to the mass ratio of (1 3): (1 3): (1) 15, wherein the mixing temperature is 20 ℃ and 80 ℃, the mixing time is more than 5 minutes, obtaining a leaching agent solution, and grinding iron ore particles according to the mass ratio of (3) 10: 1, the reaction temperature is 150 ℃ and the pressurizing pressure is 0.5 Mp, after 50 minutes of pressurizing and acid leaching, slag and weak acid leaching liquid are obtained through solid-liquid separation, the pH value of the acid leaching liquid is regulated to be 4-6.5, the reaction is carried out for more than 20 minutes, and ferric salt solution is obtained through solid-liquid separation. 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 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 dressing of copper ore or iron-containing slag obtained after smelting of copper.
The prior art discloses a method for preparing ferric oxide from ferric waste residues. 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 of the reaction is 3-14, the hydrothermal reaction temperature is 100-350 ℃, the reaction time is 0.5-24 h, filtering, washing and drying a filter cake to obtain a crude product of ferric oxide, and calcining to obtain the ferric oxide.
The prior art discloses a process for extracting iron in the pyrite cinder by an auxiliary agent enhanced acid leaching method, which comprises the steps of mixing the pyrite cinder with an auxiliary agent in a normal pressure reaction kettle, wherein the auxiliary agent is H 2 C 2 O 4 Or (NH) 4 ) 2 C 2 O 4 Adding sulfuric acid solution with the mass concentration of 30-50%, stirring, reacting at the normal pressure of 60-100 ℃ for 2-8 h, carrying out solid-liquid separation after the acid leaching reaction is finished, carrying out iron precipitation operation on acid leaching filtrate containing iron and oxalic acid radical particles, removing impurities from the iron precipitation filter cake, and preparing an iron product, wherein the filtrate contains (NH 4 ) 2 C 2 O 4 Returning to the acid leaching process for recycling. Wherein the solid-liquid ratio of the sulfuric acid solution is 1:4-8, and the mass ratio of the auxiliary agent to the sulfuric acid cinder is 1:5-1:20. (5% -20%)
The above is a technology for extracting metallic iron by conventional acid leaching, but the steel slag/iron-containing phase composition is complex, and contains 19% or more of silicon, such as tricalcium silicate, dicalcium silicate and transition state substances between them, etc., 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 affected by the conventional acid leaching technology.
Disclosure of Invention
The invention provides a method for leaching iron elements in iron ore or steel slag, which aims to overcome the defects that iron elements in the iron ore or steel slag in the prior art are easy to adhere to silicic acid and are filtered and removed in the acid leaching technology, so that the recovery rate of metallic iron is low and the like.
Another object of the present invention is to provide an application of the method for leaching iron element from iron ore or steel slag.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a method for acid leaching of elemental iron in iron ore or steel slag, comprising the steps of:
s1, grinding slag: taking the ground waste residue in the iron ore or steel slag for standby;
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 a combination of a plurality of hydrochloric acid, nitric acid, hydrofluoric acid and oxalic acid;
s3, leaching: adding part of the waste residues in the step S1 into the mixed acid in the step S2 while stirring, adding the fluorine-containing leaching aid, continuously adding the rest waste residues, reacting under preset conditions, and filtering to obtain a product.
Wherein the waste residue is the product of grinding iron ore or steel slag, and concretely, the iron ore is magnetite, hematite, maghemite, ilmenite, limonite or siderite. The steel slag is blast furnace iron-making slag, converter steel slag, open-hearth steel slag or electric furnace steel slag after being crushed. The components in the steel slag mainly comprise dicalcium silicate, tricalcium silicate and dicalcium ferrite, and a large amount of unstable free calcium oxide, ferrous oxide, ferric oxide, magnesium oxide and the like.
In the acid leaching process, tricalcium silicate, dicalcium silicate and transition state substances between the tricalcium silicate and the dicalcium silicate in iron ore or steel slag react with acid to generate silicic acid (containing silica gel), and the reaction equations are respectively as follows:
dicalcium silicate (2 CaO. SiO) 2 )+2H 2 SO 4 (concentration) =h 2 SiO 3 (colloid) +2CaSO 4 +H 2 O，
Tricalcium silicate (3 CaO. SiO) 2 )+3H 2 SO 4 (concentration) =h 2 SiO 3 (colloid) +3CaSO 4 +2H 2 O。
At the same time, 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 (Fe) 2+ Wherein, since the silicic acid colloid is negatively charged colloid, fe with positive charge is easily adsorbed 3+ And Fe (Fe) 2+ If the desorption treatment is not performed, the recovery rate of iron metal will be affected. Moreover, sulfuric acid has a good effect of extracting ferrous iron, but leaching of high-valence iron is difficult, so that the recovery rate of iron is not high, the required time is long, and if the sulfuric acid solution is used for leaching directly, the reaction effect is not ideal.
Compared with the traditional method of treating iron ore or steel slag by adopting single acid, the method adopts the mixed acid as acid leaching solution in the acid leaching process, and combines fluorine-containing leaching aid to treat Fe 3+ And Fe (Fe) 2+ And desorbing the iron ore or steel slag from the silicic acid into the liquid, so that the leaching rate of the iron ore or steel slag is further improved. Specifically, the reaction equation of a mixed acid such as sulfuric acid and hydrochloric acid with iron element 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 ferrous iron extraction effect, and hydrochloric acid, nitric acid, hydrofluoric acid and oxalic acid have good leaching rate on high-valence iron, so that mixed acid is adopted for heating, stirring and cosolvent adding are adopted to promote reaction, so that the leaching rate of iron is improved.
Preferably, the granularity of the waste residue in the step S1 is-0.074 mm,95% or more. Specifically, the raw 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 mixed acid is increased.
Preferably, the addition amount of sulfuric acid and co-acid in step S2 is the product of the amount of theoretical substance and the excess coefficient; the theoretical substance amount of hydrogen ions in the sulfuric acid is 60-80% of the hydrogen ion substance amount required by the total iron in the waste residue, the theoretical substance amount of hydrogen ions in the auxiliary acid is the remaining hydrogen ion substance amount required by the total iron in the waste residue, the excess coefficient of the sulfuric acid is 1-1.5, and the excess coefficient of the auxiliary acid is 1-1.5.
Further preferably, the theoretical amount of hydrogen ions in sulfuric acid is 80% of the amount of hydrogen ion species required for total iron in the waste residue, and the theoretical amount of hydrogen ions in the co-acid is 20% of the amount of hydrogen ion species required for total iron in the waste residue. The excess coefficients of sulfuric acid and co-acid were 1.2.
Preferably, the solid-to-liquid ratio of the waste residue in step S1 to the mixed acid in step S2 is 1kg: (4-10) L.
Preferably, the fluorine-containing leaching aid in step S3 is any one or a combination of a fluoride salt and hydrofluoric acid. The fluorine element and silicon and aluminum existing in the waste residue generate AlF 5 2- And SiF 6 2- The generation of silica-containing colloid and fine solid particles is prevented, so that the forward progress of the reaction between waste residues and mixed acid is facilitated, and the leaching rate of iron element is improved.
Further preferably, the fluorine-containing leaching aid in the step S4 adopts ammonium bifluoride, so that the method is cheaper, the process cost is saved, and the economic benefit is improved.
Preferably, the fluorine-containing leaching aid accounts for 1-5% of the mass of the waste residue.
Further preferably, the fluorine-containing leaching aid accounts for 3% of the mass of the waste residue.
Preferably, a part of waste residues added in the step S3 accounts for 40% -60% of the mass of the waste residues in the step S1. The reaction between the iron element in the waste slag and the mixed acid is exothermic, so a large amount of heat can be released in the reaction process, and the waste slag is added in batches, so that the temperature rise process in the reaction system can be slowed down, the danger caused by the overhigh temperature is avoided, and accidents such as scald and burn are caused.
Further preferably, a part of the waste residue added first in step S3 accounts for 40% of the mass ratio of the waste residue 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 condition in step S4 is: stirring for 1.5h at normal temperature with stirring speed of 300r/min.
The invention also provides an application of the method for leaching the iron element in the iron ore or the steel slag by acid in the iron ore or the steel slag. The iron ore or steel slag in the method has complex phase, high silicon content (19% and above), and easy formation of 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 method, the invention mixes sulfuric acid with any one of hydrochloric acid, nitric acid, hydrofluoric acid and oxalic acid by preparing the mixed acid, and then the fluorine-containing leaching aid is used for leaching the iron element in the waste residue, thus greatly improving the leaching rate of the waste residue, leading the leaching rate of the waste residue to be improved to 92-98 percent by 40-45 percent originally, having simple process and short flow, and greatly improving the leaching rate of iron metal in iron ore, blast furnace iron-making slag, converter waste residue, open-hearth furnace waste residue or electric furnace waste residue.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the present application will be clearly and completely described below in connection with the embodiments of the present application. It will be apparent that the described embodiments are some, but not all, of the embodiments of the present application. All other embodiments, based on the described embodiments, which a person of ordinary skill in the art would obtain without inventive faculty, are within the scope of protection of the present application.
Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
Example 1
A method for acid leaching of elemental iron in iron ore or steel slag, comprising the steps of:
s1, grinding slag: selecting steel slag produced by Guangdong Shaogao Steel Co Ltd of Baowu group, drying and grinding the steel slag, sieving the steel slag with a 200-mesh sieve to obtain ground waste slag, and detecting that the total iron content in the ground waste slag is 19%; the granularity of the waste residue is-0.074 mm,95% or more.
The total iron content is the total iron content of the waste slag determined by chemical analysis and expressed in mass fraction.
S2, acid preparation: 325.68g of 98% sulfuric acid and 169.68g of 35% hydrochloric acid (the iron element in the waste residue is calculated according to ferrous ions, the theoretical substance amount of hydrogen ions in the sulfuric acid is 80% of the hydrogen ion substance amount required by total iron in the waste residue, the theoretical substance amount of hydrogen ions in the auxiliary acid is 20% of the hydrogen ion substance amount required by total iron in the waste residue, the excess coefficients of the sulfuric acid and the auxiliary acid are 1.2) are respectively taken according to a preset proportion, and are mixed, and a proper amount of water is added to prepare 6L solution to obtain mixed acid.
S3, leaching: taking 1kg of waste residue, adding 40% of waste residue into mixed acid under normal temperature, adding ammonium bifluoride accounting for 3% of the mass of the waste residue, adding the rest of the waste residue, stirring for 1.5h under normal temperature, wherein the stirring speed is 400r/min, and filtering to obtain the final product of the iron-rich mother liquor.
Examples 2 to 7
The steps of the iron element leaching methods of examples 2 to 7 are the same as in example 1, except for the following process conditions, specifically, see 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 no mixed acid was formulated and only sulfuric acid was used for leaching 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 formulated and only hydrochloric acid was used for leaching in step S3.
Comparative example 3
The raw material composition, process steps and process conditions of comparative example 3 were similar to those of example 1, except that no mixed acid was formulated and only nitric acid was used for leaching in step S3.
Comparative example 4
The raw material composition, process steps and process conditions of comparative example 4 were similar to those of example 1, except that no mixed acid was formulated and only hydrofluoric acid was used for leaching in step S3.
Comparative example 5
The raw material composition, process steps and process conditions of comparative example 5 were similar to those of example 1, except that no mixed acid was formulated and only oxalic acid was used for leaching in step S3.
Comparative example 6
The raw material composition, 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 compositions, process steps and process conditions of comparative examples 7 to 19 were similar to those of example 1, except that they were as shown in tables 2.1 to 2.3:
TABLE 2.1 Process conditions for comparative examples 7-11
TABLE 2.2 Process conditions for comparative examples 12-16
TABLE 2.3 Process conditions for comparative examples 17 to 19
The leached products of examples 1 to 7 and comparative examples 1 to 19 were tested by the method of titration with reduced potassium dichromate of titanium trichloride, which was used for measuring the total iron content of iron ore of GB-T6730.65-2009, and the leaching rate results were obtained as shown in the following table.
Table 3 leaching rates of iron from waste residues of examples 1 to 4 and comparative examples 1 to 20
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From Table 3, the recovery rate of iron in the waste residues of examples 1-7 is as high as 92% or more, 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.
As is clear from comparative example 1, the leaching rate was only 48% when sulfuric acid was used alone, the leaching effect was extremely different, and high-valence iron such as ferric silicate in the waste residue was 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 alone, namely 64% and 58% respectively, but the leaching effect is still quite different from that of mixed acid, the price of hydrochloric acid and nitric acid is more expensive than that of sulfuric acid, the use amount is large, and the economy is not realized.
As can be seen from comparative example 4, among the species in which iron element in the waste residue is leached with a single acid, hydrofluoric acid is the best, but hydrofluoric acid is expensive, and is generally used for extracting noble metals, and is not economical.
As can be seen from comparative example 5, the leaching rate was only 45% and the leaching effect was poor when only oxalic acid was used for leaching, compared with the same type 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 can inhibit the formation of silica gel and has a great forward promotion effect on leaching of iron element in waste residue.
As can be seen from comparative examples 7 to 10, the amount of sulfuric acid used in the mixed acid is positively correlated with the leaching rate of the iron element, and the leaching rate of the iron element in the waste residue is gradually reduced as the amount of sulfuric acid is gradually reduced.
As can be seen from comparative examples 11 to 14, the amount of the auxiliary acid used in the mixed acid was positively correlated with the leaching rate of the iron element, and the leaching rate of the iron element in the waste residue was gradually decreased as the amount of the auxiliary acid was gradually decreased. 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 conducive to sufficient contact between the reaction materials, resulting in a decrease in leaching rate.
The reaction time was too short and the reaction was insufficient in comparative example 17, resulting in a low final leaching rate.
The stirring speed of comparative examples 18 to 19 was too slow and too fast, resulting in insufficient contact of materials or short contact time, which is unfavorable for the reaction, and thus the final leaching rate was also not desirable.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (3)
1. A method for acid leaching of elemental iron in iron ore or steel slag, comprising the steps of:
s1, grinding slag: taking the ground waste residue in iron ore or steel slag for standby, wherein the total iron content in the waste residue 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 a combination of a plurality of hydrochloric acid, nitric acid, hydrofluoric acid and oxalic acid;
s3, leaching: adding a part of waste residues in the step S1 into the mixed acid in the step S2 while stirring, adding the fluorine-containing leaching aid, continuously adding the rest waste residues, reacting under preset conditions, and filtering to obtain a product;
the granularity of the waste residue in the step S1 is-0.074 mm,95% or more;
the addition amount of the sulfuric acid and the auxiliary acid in the step S2 is the product of the amount of theoretical substances and the excess coefficient; the theoretical substance amount of hydrogen ions in the sulfuric acid is 60-80% of the hydrogen ion substance amount required by the total iron in the waste residue, the theoretical substance amount of hydrogen ions in the auxiliary acid is the remaining hydrogen ion substance amount required by the total iron in the waste residue, the excess coefficient of the sulfuric acid is 1-1.5, and the excess coefficient of the auxiliary acid is 1-1.5;
the solid-to-liquid ratio of the waste residue in the step S1 to the mixed acid in the step S2 is 1kg: (4-10) L;
the fluorine-containing leaching aid in the step S3 is any one or a combination of more of fluoride salt and hydrofluoric acid;
the mass ratio of the fluorine-containing leaching aid in the step S3 relative to the waste residue is 1-5%;
part of waste residues added in the step S3 accounts for 40-60% of the mass of the waste residues in the step S1;
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.
2. The method for acid leaching of iron elements in iron ore or steel slag according to claim 1, wherein before step S2, the waste slag after grinding in step S1 is taken and the total iron content is detected.
3. Use of the method for acid leaching of elemental iron from iron ore or steel slag according to any one of claims 1 to 2 in acid leaching of elemental iron from iron ore or steel slag.
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| CN102230081A (en) * | 2011-04-23 | 2011-11-02 | 大悟华龙吕王石材有限公司 | Acid leaching method for extracting potassium, aluminum and silicon elements from potassium feldspar |
| CN103831442A (en) * | 2014-03-11 | 2014-06-04 | 斯莱登（北京）化工科技有限公司 | Method of manufacturing powered iron from copper-nickel slag |
| CN104831061A (en) * | 2014-12-31 | 2015-08-12 | 金川集团股份有限公司 | Method of recycling nickel, cobalt and iron from low-grade laterite-nickel ore |
| CN104988338A (en) * | 2015-07-30 | 2015-10-21 | 河南理工大学 | Method for extracting vanadium from vanadium titano-magnetite |
| CN105367176A (en) * | 2015-12-02 | 2016-03-02 | 武汉工程大学 | Multi-element comprehensive utilization process for phosphorus-potassium associated ore |
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| CN102230081A (en) * | 2011-04-23 | 2011-11-02 | 大悟华龙吕王石材有限公司 | Acid leaching method for extracting potassium, aluminum and silicon elements from potassium feldspar |
| CN103831442A (en) * | 2014-03-11 | 2014-06-04 | 斯莱登（北京）化工科技有限公司 | Method of manufacturing powered iron from copper-nickel slag |
| CN104831061A (en) * | 2014-12-31 | 2015-08-12 | 金川集团股份有限公司 | Method of recycling nickel, cobalt and iron from low-grade laterite-nickel ore |
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| CN105367176A (en) * | 2015-12-02 | 2016-03-02 | 武汉工程大学 | Multi-element comprehensive utilization process for phosphorus-potassium associated ore |
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