CN114472464A - Method for efficiently recycling iron and phosphorus resources in phosphorus-containing steel slag - Google Patents
Method for efficiently recycling iron and phosphorus resources in phosphorus-containing steel slag Download PDFInfo
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- CN114472464A CN114472464A CN202210042381.4A CN202210042381A CN114472464A CN 114472464 A CN114472464 A CN 114472464A CN 202210042381 A CN202210042381 A CN 202210042381A CN 114472464 A CN114472464 A CN 114472464A
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- 239000002893 slag Substances 0.000 title claims abstract description 143
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 113
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000011574 phosphorus Substances 0.000 title claims abstract description 110
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 90
- 239000010959 steel Substances 0.000 title claims abstract description 90
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000004064 recycling Methods 0.000 title claims abstract description 20
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 18
- 229910000389 calcium phosphate Inorganic materials 0.000 claims abstract description 18
- 235000011010 calcium phosphates Nutrition 0.000 claims abstract description 18
- 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 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000007885 magnetic separation Methods 0.000 claims description 32
- 238000005188 flotation Methods 0.000 claims description 30
- 238000000926 separation method Methods 0.000 claims description 21
- 239000003607 modifier Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 13
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 230000036961 partial effect Effects 0.000 claims description 9
- 229910052810 boron oxide Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 6
- 150000003017 phosphorus Chemical class 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003784 tall oil Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 4
- 229910052909 inorganic silicate Inorganic materials 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims 1
- 229910052911 sodium silicate Inorganic materials 0.000 claims 1
- 239000012141 concentrate Substances 0.000 abstract description 16
- 238000012986 modification Methods 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 7
- 239000002686 phosphate fertilizer Substances 0.000 abstract description 3
- 230000003698 anagen phase Effects 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 27
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 11
- 239000011575 calcium Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 229910052681 coesite Inorganic materials 0.000 description 8
- 229910052906 cristobalite Inorganic materials 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 239000006104 solid solution Substances 0.000 description 8
- 229910052682 stishovite Inorganic materials 0.000 description 8
- 229910052905 tridymite Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000004453 electron probe microanalysis Methods 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910004333 CaFe2O4 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910001341 Crude steel Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- WNQQFQRHFNVNSP-UHFFFAOYSA-N [Ca].[Fe] Chemical compound [Ca].[Fe] WNQQFQRHFNVNSP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052611 pyroxene Inorganic materials 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/02—Magnetic separation acting directly on the substance being separated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/02—Magnetic separation acting directly on the substance being separated
- B03C1/30—Combinations with other devices, not otherwise provided for
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/008—Organic compounds containing oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/016—Macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/06—Depressants
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for efficiently recovering iron and phosphorus resources in phosphorus-containing steel slag, belonging to the technical field of metallurgical resource recycling; book (I)In the invention, the phosphorus-containing steel slag is firstly subjected to slag modification, and then the magnetic Fe is obtained by adopting heat treatment3O4Selectively growing phase and calcium phosphate phase, and finally magnetically recovering the steel slag after heat treatment to achieve the aim of efficiently recovering iron and phosphorus resources in the phosphorus-containing steel slag; the iron-containing concentrate and the phosphorus-containing concentrate separated by the method can be respectively used as raw materials for making iron and phosphate fertilizer, and the tailings can be directly returned to the interior of a steel enterprise for cyclic utilization, so that the environmental load of the steel slag is solved, and the comprehensive utilization of resources is realized.
Description
Technical Field
The invention belongs to the technical field of metallurgical resource recycling, and particularly relates to a method for efficiently recycling iron and phosphorus resources in phosphorus-containing steel slag.
Background
The steel slag is waste generated in the steel making process, and the discharge amount accounts for 15 to 20 percent of the yield of the crude steel. The steel slag contains more phosphorus and sulfur impurities, so that the grade of the steel slag is low, and the utilization rate of the steel slag is only about 20 percent. The accumulation of a large amount of steel slag (more than 5 hundred million tons) not only occupies a large amount of land, but also causes great waste of metallurgical resources and environmental pollution.
Compared with the utilization of the steel slag outside the metallurgical enterprises, a large number of experimental researches and theoretical analysis show that the steel slag is an ideal method for recycling inside the enterprises. In the current recycling method, the metallurgical slag is mainly used as a sintering flux, a blast furnace iron-making flux, a molten iron pretreatment slag agent and the like. However, in recent years, due to the widespread use of high phosphorus ore, the content of phosphorus in steel slag is high, and if the steel slag is simply returned to the interior of a smelting system for recycling, the phosphorus in molten iron is recycled, further phosphorus pollution is caused to steel, the steel quality is deteriorated, and the later dephosphorization burden is also increased. Therefore, the effective enrichment and removal of phosphorus in the steel slag are the premise that the steel slag can be recycled in metallurgical enterprises.
The existing steel slag dephosphorization method can realize steel to a certain extentThe phosphorus in the slag is effectively separated, but the converter steel slag dephosphorization technology does not realize the recovery and the efficient utilization of the iron and the phosphorus in the steel slag. This results in a low phosphorus concentration (P) in the phosphorus-rich phase obtained after separation of the steel slag2O5<10%), thereby the utilization value of the phosphorus resource obtained after separation is low. In order to increase the added value of the phosphorus-rich phase in the steel slag and recycle the iron resource in the steel slag, it is necessary to develop a new method for efficiently recycling the iron and phosphorus resources in the phosphorus-containing steel slag.
Disclosure of Invention
Aiming at the defect that the phosphorus in the phosphorus-rich phase in the steel slag in the prior art is low in grade and difficult to recycle, the invention provides a method for efficiently recycling iron and phosphorus resources in the phosphorus-containing steel slag. In the invention, the phosphorus-containing steel slag is firstly subjected to slag modification, and then the magnetic Fe is obtained by adopting heat treatment3O4Selectively growing phase and calcium phosphate phase, and finally magnetically recovering the steel slag after heat treatment to achieve the aim of efficiently recovering iron and phosphorus resources in the phosphorus-containing steel slag; the iron-containing concentrate and the phosphorus-containing concentrate separated by the method can be respectively used as raw materials for making iron and phosphate fertilizer, and the tailings can be directly returned to the interior of a steel enterprise for cyclic utilization, so that the environmental load of the steel slag is solved, and the comprehensive utilization of resources is realized.
The invention provides a method for efficiently recovering iron and phosphorus resources in phosphorus-containing steel slag, which specifically comprises the following steps:
(1) changing the oxygen partial pressure to PO2<10-4Adding modifier into molten phosphorus-containing steel slag to make iron and phosphorus in the phosphorus-containing steel slag selectively enriched into magnetic Fe3O4Phase and calcium phosphate phase to obtain modified phosphorus-containing steel slag;
(2) the modified phosphorus-containing steel slag is subjected to heat treatment to obtain magnetic Fe3O4Selectively growing with calcium phosphate phase;
(3) cooling, water quenching and crushing the phosphorus-containing steel slag after heat treatment, and then realizing magnetic Fe through magnetic separation3O4And separating the phase from the calcium phosphate phase, and successfully recovering iron and phosphorus resources in the phosphorus-containing steel slag.
Further, in the step (1), the phosphorus-containing steel slag comprises dephosphorizing converter dephosphorizing slag, converter phosphorus-containing slag or electric furnace phosphorus slag.
Further, in the step (1), the modifier is one or more of boron oxide, borate, silicon oxide or borosilicate compound.
Furthermore, in the step (1), the addition amount of the modifier is not more than 10% of the mass sum of the steel slag and the modifier.
Further, in the step (1), the modified phosphorus-containing steel slag has basicity (CaO/SiO)2)＝1.0～3.0。
Further, in the step (2), the temperature of the heat treatment is 1500 ℃ or higher.
Further, in the step (3), the cooling conditions are as follows: and cooling the steel slag after heat treatment to 900-1200 ℃ at the speed of 1-5 ℃/min, and then keeping the temperature for 0.5-2 h.
Further, in the step (3), the pulverization is carried out by crushing to 20mm or less and finely grinding to 300 mesh or less in a ball mill.
Further, in the step (3), the magnetic field intensity is 3-3.6 KOe during magnetic separation, magnetic separation tailings are obtained after separation, and the magnetic separation tailings are subjected to flotation separation.
Further, the flotation separation comprises the following specific steps:
taking oxidized paraffin soap-tall oil as collecting agent, water glass (Na)2SiO4·5H2O) is used as an inhibitor, and the pH value is adjusted to 8.5-9 for ore dressing.
Further, the dosage ratio of the oxidized paraffin soap-tall oil to the magnetic separation tailings is 500-1200g/t, and the dosage ratio of the water glass to the magnetic separation tailings is 3000-3300 g/t.
Further, in the step (3), P in calcium phosphate is separated2O5The content is more than 30 percent.
Compared with the prior art, the invention has the beneficial effects that:
in the present invention, a modifier is added to nCaO. P2O5-2CaO·SiO22 CaO. SiO in solid solution2Take place inverselyThe phosphorus in the slag is enriched in a stable mineral or group of minerals (such as calcium phosphate), and the iron in the slag is enriched in a magnetic iron-rich phase (such as Fe)3O4) And then carrying out heat treatment on the modified slag to ensure that a phosphorus-rich phase and an iron-rich phase selectively grow up, and carrying out magnetic separation on a cooled slag sample after crushing and ball milling to achieve the purposes of effectively separating and recycling iron and phosphorus resources from the phosphorus-containing slag. In the invention, one or more of boron oxide, borate, silicon oxide or borosilicate compound is selected as a modifier, which is easier to react with 3CaO & P2O5-2CaO·SiO22 CaO. SiO in (1)2React to enrich P in2O5Phosphorus-rich phase (3 CaO. P)2O5) Is separated out. The total amount of the modifier is controlled to not more than 10% of the total weight, and the excessive modifier suppresses crystallization of the target phase in such a proportion that P is enriched by the reaction2O5The effect of the independent phosphorus-rich phase is the best.
In the invention, the heat treatment temperature of the steel slag is controlled to be more than 1500 ℃, so that the promotion of the steel slag on the migration of phosphorus and iron ions in the slag can be more fully ensured. After modification, the slag is cooled to 1200 ℃ at the speed of 1-5 ℃/min, and then the temperature is kept for 0.5-2 h. The heat treatment system can promote the growth of target mineral phase crystal grains and is beneficial to improving the subsequent separation effect.
According to the invention, the dephosphorized slag with fine mineral grains, iron and phosphorus dispersed and distributed, and a phosphorus-rich phase and an iron-rich phase embedded and distributed tightly is modified by adding the modifier, so that the occurrence form of phosphorus and iron in the slag is changed and the enrichment effect is achieved, the iron-rich phase is recovered through magnetic separation treatment, and the magnetic separation tailings obtained after separation are subjected to three-coarse one-fine flotation separation to recover the phosphorus-rich phase. According to the invention, the resource recovery of phosphorus and iron elements in the phosphorus-containing slag is realized, the phosphorus content in the recovered phosphorus-rich phase is higher, and the phosphorus-rich phase can be used for producing steel slag phosphate fertilizer through further treatment, so that the resource utilization of the converter steel slag in the agricultural field is promoted. In addition, through the treatment process provided by the open-chain, the iron-rich phase with low phosphorus can be recovered and returned to the converter for use, so that waste is changed into valuable, the problems that the dephosphorized slag occupies fertile fields and pollutes the environment are completely solved, the auxiliary material consumption of the converter is reduced, and the metal yield of the converter is improved. The invention provides a new metallurgical slag resource utilization idea for the public. Meanwhile, the method has the advantages of simplicity, convenience in implementation, low implementation cost, good separation effect and the like.
Compared with the hot splashing method, the hot stuffiness method or the roller method adopted in the prior art to promote the separation of the steel slag and the metallic iron and then the high-mesh iron screening by adopting crushing-magnetic separation, the method saves energy, and the obtained magnetite has higher added value and higher recovery precision.
Drawings
FIG. 1 is a flow chart of a method for efficiently recovering iron and phosphorus resources from phosphorus-containing steel slag.
FIG. 2 is an X-ray diffraction (XRD) pattern of the steel slag sample in example 1.
FIG. 3 is a Scanning Electron Microscope (SEM) picture of a steel slag sample in example 1; in the figure, a is a 0# slag SEM back scattering picture, b is a 2# slag SEM back scattering picture, and c is a 3# slag SEM back scattering picture.
Fig. 4 is an X-ray diffraction (XRD) picture of the steel slag sample after magnetic separation and flotation separation in the embodiment 1.
FIG. 5 is an X-ray diffraction (XRD) pattern of the steel slag sample in example 2.
Fig. 6 is an Electron Probe (EPMA) image of a steel slag sample in example 2, in which a and B are a back scattering image and a partially enlarged view of the sample, respectively, and c to h are surface-scanned images of Ca element, O element, P element, Si element, Fe element, and B element, respectively.
FIG. 7 is a Scanning Electron Microscope (SEM) image of the steel slag sample in example 2, wherein a is a back scattering image of the sample, and b-f are respectively a surface scanning image of O element, Si element, P element, Ca element and Fe element.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, without limiting the scope of the invention thereto.
Example 1:
FIG. 1 shows the efficient recovery of iron from phosphorus-containing steel slagAnd a phosphorus resource recovery method, wherein the five-element slag is separated according to the flow shown in FIG. 1 to recover iron and phosphorus resources, wherein the five-element slag comprises CaO and SiO2、FeO、P2O5、B2O3Marking a sample obtained by sintering the five-element slag sample in an air atmosphere as 0# slag, changing the oxygen partial pressure to 10-6atm to obtain a 1# sample, and continuously adding 6% of B2O3 into the slag on the basis to obtain 2# slag, wherein the specific components are shown in Table 1.
TABLE 1 quinary simulated slag composition (wt.%)
| CaO | SiO2 | FeO | P2O5 | B2O3 | |
| 1# | 38.57 | 15.43 | 36 | 10 | 0 |
| 2# | 34.29 | 13.71 | 36 | 10 | 6 |
The specific steps are as follows:
(1) b is to be2O3Mixing with phosphorus-containing simulated slag, loading into platinum crucible, and placing into VTL-1700 tubular furnace with modifier content within 6-8%;
(2) filling argon into the hearth, and controlling the oxygen partial pressure to be less than 10-4and (atm). Controlling the temperature of the tubular furnace to rise to 1550 ℃ and keeping the temperature for half an hour to fully melt and ladle the slag;
(3) reducing the temperature to 900 ℃ at the speed of 5 ℃/min, preserving the temperature for 120min, and fully promoting nCaO & P2O5Then carrying out water quenching on the heat treatment slag;
(4) drying the water-quenched slag sample, crushing, and ball-milling to below 300 meshes;
(5) and (3) carrying out magnetic separation on the powder slag by using a magnetic separation tube under the condition that the magnetic field intensity is more than 3.0 KOe. Mixing Fe3O4The phosphorus-containing phase and the matrix phase (the perovskite) are retained in the form of magnetic separation tailings.
(6) And performing three-coarse-one-fine flotation separation on the magnetic separation tailings obtained after separation. Oxidized paraffin soap-tall oil is used as a collecting agent (1200 g/t during rough concentration and 500g/t during fine concentration), and water glass (Na)2SiO4·5H2O) is used as an inhibitor (3000 g/t for rough concentration and 500g/t for fine concentration), the pH value is adjusted to 8.5-9, and each ore dressing is carried out for three minutes. The calcium phosphate phase is recovered as a flotation concentrate, while the caduconite remains in the tank as flotation tailings, after which it is obtained by filtration.
The phase analysis of the simulated steel slag and the modified slag in Table 1 was carried out by X-ray diffraction analysis (XRD), and the results are shown in FIG. 2. As can be seen from the figure, the iron in the 0# sample is mainly CaFe2O4In the form of nC2S-C3A P solid solution phase exists. When the partial pressure of oxygen is changed to obtain modified steel slag No. 1, the iron in the slag is mainly Fe3O4In the form of nC2S-C3A P solid solution phase exists. B is further added on the basis of 1# slag2O3Modifying to obtain modified steel slag 2#, wherein Fe is mainly Fe3O4In the form of phosphorus consisting of nC2S-C3The P solid solution phase is transformed into a calcium phosphate phase.
Phase analysis of the simulated steel slag and the modified steel slag in table 1 was performed by scanning electron microscope analysis (SEM), and the results are shown in fig. 3. In FIG. 3(a), the iron-containing phase is a white irregular lamellar structure. The phosphorus-containing phase is an elliptic gray phase. After changing the oxygen partial pressure to obtain a 1# slag sample, the iron-containing phase in fig. 3(b) was changed to a white dendritic spinel structure, and phosphorus continued to exist as an oval gray phase. Continuously adding B2O3Modifying to obtain modified steel slag 2#, and obtaining the morphology shown in figure 3 (c). In FIG. 3(c) the iron-containing phase is still a white dendritic spinel structure, while the phosphorus is transformed from an oval gray phase to a dark gray lath phase. This suggests that changing the oxygen partial pressure will drive the iron element to Fe3O4Is converted to add B2O3Can result in the conversion of solid solution of phosphorus-containing phase in the steel slag into calcium phosphate.
To further determine the elemental composition of each phase, EDS measurements were performed on the different phases and EDS spot analysis at different locations is shown in table 2.
TABLE 2 EDS results of different samples
As can be seen from Table 2 and FIG. 3, the phosphorus-containing phase in FIG. 3(a) is a solid solution phase composed of Ca, Si, O and P, and the white phase is Ca2Fe3.7O4.8. In FIG. 3(b), the dendritic phase is iron oxide and is calculated to have a chemical formula close to that of Fe3O4While the oval gray phase remains unchanged. With the addition of modifier, the elliptical phase is converted into dark gray lath phase, which is composed of Ca, P and O elements and is close to Ca2P0.83O3.51Is a calcium phosphate phase.
In this embodiment, X-ray diffraction (XRD) is performed on the magnetic concentrate, the magnetic tailings, the flotation concentrate and the flotation tailings obtained by the magnetic separation, and X-ray fluorescence analysis (XRF) is performed on the magnetic concentrate, the flotation concentrate and the flotation tailings, which are respectively shown in fig. 4 and table 3.
TABLE 3 XRF results for each isolated product after magnetic separation-flotation separation
Definition of εFeAnd epsilonPThe recovery rates of iron and phosphorus elements are respectively shown in the following calculation formula, wherein m isc1,mc1,mrRespectively representing the quality of magnetic concentrate, flotation concentrate and flotation tailings. OmegaFe1,ωFe2,ωFe3And omegaP1,ωP2,ωP3Respectively representing the proportion of iron and phosphorus elements in magnetic concentrate, flotation concentrate and flotation tailings.
As can be seen from the analysis of the combination of FIG. 4 and Table 3, the slag No. 2 in Table 1 is magnetically separated from the powder slag by a magnetic separation tube under the condition that the magnetic field intensity is greater than 3.0K Oe. After magnetic separation, the magnetic separation rate of iron>85.8 percent of the magnetic separation tailings are subjected to flotation, P2O5Flotation rate of>91.3％。
Example 2:
based on the steel slag component of a certain factory, the oxygen partial pressure is changed and SiO is added into the simulated slag2Modified slag 1# (in slag) is obtained, or SiO is added into the slag2And B2O3Obtaining 2# slag, and continuously adding B2O3Obtaining 3# slag. The composition of the upgraded slag is shown in Table 4.
TABLE 4 simulation of slag composition (wt%)
| CaO | SiO2 | FeO | P2O5 | B2O3 | |
| 1# | 30 | 24 | 36 | 10 | 0 |
| 2# | 28.33 | 22.67 | 36 | 10 | 3 |
| 3# | 27.22 | 21.78 | 36 | 10 | 5 |
The test procedure is as follows:
(1) b is to be2O3Mixing with phosphorus-containing simulated slag, loading into platinum crucible, and placing into VTL-1700 tubular furnace with modifier content within 6-8%;
(2) filling argon into the hearth, and controlling the oxygen partial pressure to be less than 10-4and (atm). Controlling the temperature of the tubular furnace to rise to 1550 ℃ and keeping the temperature for half an hour to fully melt and ladle the slag;
(3) reducing the temperature to 900 ℃ at the speed of 5 ℃/min, preserving the temperature for 120min, and fully promoting nCaO & P2O5Then carrying out water quenching on the heat treatment slag;
(4) drying the water-quenched slag sample, crushing, and ball-milling to below 300 meshes;
(5) and (3) carrying out magnetic separation on the powder slag by using a magnetic separation tube under the condition that the magnetic field intensity is more than 3.0 KOe. Mixing Fe3O4The phosphorus-containing phase and the matrix phase (the calcium spodumene) are retained in the form of magnetic tailings.
(6) And performing three-coarse-one-fine flotation separation on the magnetic separation tailings obtained after separation. Oxidized paraffin soap-tall oil is used as a collecting agent (1200 g/t during rough concentration and 500g/t during fine concentration), and water glass (Na)2SiO4·5H2O) is used as an inhibitor (3000 g/t for rough concentration and 500g/t for fine concentration), the pH value is adjusted to 8.5-9, and each ore dressing is carried out for three minutes. The calcium phosphate phase is recovered as a flotation concentrate, while the caduconite remains in the tank as flotation tailings, after which it is obtained by filtration.
The 3 groups of samples were analyzed using X-ray diffraction analysis (XRD). The results are shown in FIG. 5. Adding SiO2The modified 1# sample mainly contains phosphorus phases of calcium phosphate and nC2S-C3A P solid solution phase. In the process of continuously adding boron oxide for modification on the basis of the No. 1 sample, the solid solution phase is gradually converted into the phosphorus-rich phase of calcium phosphate, and when the boron oxide modification reaches 5 percent, the calcium phosphate can be obviously seenThe diffraction peak intensity of the enriched phase decreased, demonstrating excess boron oxide modification at 5%.
The analysis of the mineral phase composition of the sample using an Electron Probe (EPMA) was performed, and the results are shown in fig. 6, and the element distribution is shown in table 5. Sample # 2 contains mainly four mineral phases: phosphorus-rich C3P phase, magnetic Fe3O4Phase, C2S phase (CaO-SiO)2) And a matrix phase (CaO-SiO)2-FeO). This is consistent with the results obtained with SEM (see figure 5). P in the phosphorus-rich phase2O5Up to 34% and less than 1% in the other phases, indicating that P2O5Mainly enriched in C3In P.
In the example, the EPMA result of the slag No. 2 is considered, and the distribution of each element in the sample can be further clarified by the EPMA. Based on the composition of the slag system, the sample # 2 was subjected to point scanning and area scanning, respectively. The results of the surface scan are shown in FIG. 6, and the results of the spot scan are shown in Table 5:
TABLE 5.2 EPMA results for sample # s
| Spot | B2O3 | SiO2 | Fe2O3 | CaO | P2O5 | total |
| 1 | 4.195 | 40.558 | 33.504 | 23.207 | 0.915 | 102.379 |
| 2 | 3.990 | 40.004 | 33.78 | 22.885 | 1.086 | 101.745 |
| 3 | 1.446 | 0.143 | 103.534 | 0.999 | 0.021 | 106.143 |
| 4 | 2.899 | 0.113 | 104.347 | 0.589 | 0.021 | 107.969 |
| 5 | 5.498 | 5.388 | 2.224 | 53.066 | 34.490 | 100.666 |
| 6 | 7.869 | 5.667 | 2.233 | 53.055 | 34.703 | 103.527 |
| 7 | 17.005 | 42.381 | 4.160 | 39.422 | 1.041 | 104.009 |
| 8 | 16.050 | 43.367 | 4.223 | 39.210 | 1.014 | 103.864 |
Table 5 shows the EPMA point scan results of sample No. 2, and it can be seen from Table 5 that the matrix phase is composed of CaO, Fe2O3，SiO2The components are combined to form a calcium-iron pyroxene phase. The white spinel phase is composed of iron oxide and is Fe3O4. The dark gray lath phase is formed by CaO, P2O5Constituted as a calcium phosphate phase.
In this example, XRF results of the separated products (magnetic concentrate, flotation tailings) after magnetic separation-flotation separation were also examined, wherein the mixture of flotation tailings and flotation concentrate is magnetic tailings, and the examination results are shown in table 6:
TABLE 6 XRF results of the separated products after magnetic separation-flotation combined separation
The calculation formula in the example 1 is adopted to calculate the magnetic separation rate of the iron after the magnetic separation>84.8 percent of magnetic separation tailings are subjected to flotation, P2O5Flotation rate of>92.3％。
FIG. 7 is a Scanning Electron Microscope (SEM) picture of a steel slag sample, wherein four phases are present, namely, a phosphor-containing phase in the form of a strip composed of Ca, P and O, a white spinel phase composed of Fe and O, a matrix perovskite phase composed of Ca, Fe, Si and O, and a perovskite phase.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. A method for efficiently recovering iron and phosphorus resources in phosphorus-containing steel slag is characterized by comprising the following steps:
(1) changing the oxygen partial pressure to PO2<10-4Adding modifier into molten phosphorus-containing steel slag to selectively enrich Fe and P in the steel slag to obtain magnetic Fe3O4Phase and calcium phosphate phase to obtain modified phosphorus-containing steel slag;
(2) carrying out heat treatment on the modified phosphorus-containing steel slag, wherein the heat treatment temperature is more than 1500 ℃;
(3) cooling, water quenching and crushing the phosphorus-containing steel slag after heat treatment, and then realizing magnetic Fe through magnetic separation3O4And separating the phase from the calcium phosphate phase to successfully recover iron and phosphorus resources in the phosphorus-containing steel slag.
2. The method for efficiently recycling iron and phosphorus resources from phosphorus-containing steel slag according to claim 1, wherein in the step (1), the phosphorus-containing steel slag comprises dephosphorized converter dephosphorized slag, converter phosphorus-containing slag or electric furnace phosphorus slag.
3. The method for efficiently recycling iron and phosphorus resources from phosphorus-containing steel slag according to claim 1, wherein in the step (1), the modifier is one or more of boron oxide, borate, silicon oxide or borosilicate compound.
4. The method for efficiently recycling iron and phosphorus resources from phosphorus-containing steel slag according to claim 1, wherein in the step (1), the addition amount of the modifier is not more than 10% of the mass sum of the steel slag and the modifier.
5. The method for efficiently recycling iron and phosphorus resources from phosphorus-containing steel slag according to claim 1, wherein in step (1), the basicity of the modified phosphorus-containing steel slag is 1.0-3.0.
6. The method for efficiently recycling iron and phosphorus resources from phosphorus-containing steel slag according to claim 1, wherein in the step (3), the cooling conditions are as follows: and cooling the steel slag after heat treatment to 900-1200 ℃ at the speed of 1-5 ℃/min, and then keeping the temperature for 0.5-2 h.
7. The method for efficiently recycling iron and phosphorus resources from phosphorus-containing steel slag according to claim 1, wherein in the step (3), the crushing is performed to a size of 20mm or less, and the crushing is performed to a size of 300 meshes or less in a ball mill.
8. The method for efficiently recycling iron and phosphorus resources from phosphorus-containing steel slag according to claim 1, wherein in the step (3), the magnetic field intensity during magnetic separation is 3-3.6 KOe, magnetic separation tailings are obtained after separation, and the magnetic separation tailings are subjected to flotation separation.
9. The method for efficiently recycling iron and phosphorus resources from phosphorus-containing steel slag according to claim 8, wherein the flotation separation comprises the following specific steps: oxidized paraffin soap-tall oil is used as a collecting agent, and sodium silicate Na is used2SiO4·5H2And O is an inhibitor, and the pH value is adjusted to 8.5-9 for ore dressing.
10. The method for efficiently recycling iron and phosphorus resources from phosphorus-containing steel slag according to claim 9, wherein the usage amount ratio of oxidized paraffin soap-tall oil to magnetic separation tailings is 500-1200g/t, and the usage amount ratio of water glass to magnetic separation tailings is 3000-3300 g/t.
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