CN1908207A - Method of comprehensive utilizing iron making blast furnace dust resources - Google Patents
Method of comprehensive utilizing iron making blast furnace dust resources Download PDFInfo
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- CN1908207A CN1908207A CNA2006100486265A CN200610048626A CN1908207A CN 1908207 A CN1908207 A CN 1908207A CN A2006100486265 A CNA2006100486265 A CN A2006100486265A CN 200610048626 A CN200610048626 A CN 200610048626A CN 1908207 A CN1908207 A CN 1908207A
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- iron
- blast furnace
- zinc
- furnace dust
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- 239000000428 dust Substances 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims description 189
- 229910052742 iron Inorganic materials 0.000 title claims description 93
- 239000011701 zinc Substances 0.000 claims abstract description 63
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 63
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000002699 waste material Substances 0.000 claims abstract description 49
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002253 acid Substances 0.000 claims abstract description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002893 slag Substances 0.000 claims abstract description 10
- 230000007935 neutral effect Effects 0.000 claims abstract description 9
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 8
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 8
- 239000004571 lime Substances 0.000 claims abstract description 8
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 8
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 65
- 239000012141 concentrate Substances 0.000 claims description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- 229910052799 carbon Inorganic materials 0.000 claims description 31
- 235000010215 titanium dioxide Nutrition 0.000 claims description 29
- 238000000926 separation method Methods 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 23
- 239000000706 filtrate Substances 0.000 claims description 21
- 238000002386 leaching Methods 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 15
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 14
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 13
- 239000011707 mineral Substances 0.000 claims description 13
- 235000010755 mineral Nutrition 0.000 claims description 13
- 238000005188 flotation Methods 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 230000002000 scavenging effect Effects 0.000 claims description 11
- 229910052595 hematite Inorganic materials 0.000 claims description 10
- 239000011019 hematite Substances 0.000 claims description 10
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 239000004088 foaming agent Substances 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- -1 zinc anions Chemical class 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 239000006148 magnetic separator Substances 0.000 claims description 5
- 239000011268 mixed slurry Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000001238 wet grinding Methods 0.000 claims description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000010665 pine oil Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000003570 air Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 150000001450 anions Chemical class 0.000 claims 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 16
- 239000004408 titanium dioxide Substances 0.000 abstract description 9
- 239000011787 zinc oxide Substances 0.000 abstract description 8
- 238000003723 Smelting Methods 0.000 abstract description 3
- 239000006193 liquid solution Substances 0.000 abstract 1
- 239000006104 solid solution Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 239000001117 sulphuric acid Substances 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 17
- 230000008901 benefit Effects 0.000 description 7
- 230000005484 gravity Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 229910001608 iron mineral Inorganic materials 0.000 description 5
- 238000007885 magnetic separation Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 239000003818 cinder Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000010808 liquid waste Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-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
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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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)
Abstract
the invention discloses a synthetic using method of smelting high-furnace dust, which comprises the following steps: grinding the high-furnace dust with 1.5-15% zinc; proceeding magnetic cobbing; reclassifying to obtain the refined ferric ore; disposing ore tail through waste acid of titanium dioxide with 15-30% sulphuric acid; transmitting the zinc oxide in the solution at zinc sulfate pattern; separating solid and liquid solution through lime; obtaining refined zinc ore through S2-, CO32-, HCO3- ion; floating the immersed slag through neutral oil.
Description
The technical field is as follows: the invention relates to a method for comprehensively utilizing iron-making blast furnace dust resources, belonging to the technical field of mineral processing metallurgy.
Secondly, background art: in the blast furnace iron-making process, a large amount of fine furnace dust is generated, and the furnace dust is subjected to dust collection, washing and the like to form blast furnace dust. Blast furnace dust contains iron and carbon, can be used as a secondary raw material for ironmaking, but because the blast furnace dust contains high zinc and contains low iron grade, if the blast furnace dust is directly sent to sintering ironmaking, the sintering and ironmaking processes are influenced, and meanwhile, zinc resources cannot be recycled.
In recent decades, all countries in the world pay attention to the comprehensive utilization of iron-making blast furnace dust generated by the iron and steel industry, and a great deal of research work is carried out on the comprehensive utilization of blast furnace iron-making dust resources, so that numerous resource recovery and utilization schemes are formed, some successfully implement industrialization, and obtain good economic benefit and environmental benefit. The technical schemes are summarized into three main types, one is a beneficiation-roasting process, the other is a roasting-beneficiation process, and the third is a beneficiation-roasting-beneficiation process.
The technical scheme of ore dressing and roasting focuses on recycling iron resources in the dust of the iron-making blast furnace, and the method comprises the steps of firstly carrying out ore dressing treatment on the dust of the iron-making blast furnace, obtaining iron ore concentrate through magnetic separation and gravity separation, using the iron ore concentrate as an iron-making raw material, then carrying out reduction roasting on ore dressing tailings in a roasting furnace to volatilize non-ferrous metals such as zinc and the like, and recycling the non-ferrous metal resources such as zinc and the like through dust collection. The ore dressing-roasting process can take out iron ore concentrate with a yield of about 30% from the dust of the iron-making blast furnace before roasting, so that nonferrous metals are enriched in tailings, the amount of materials entering roasting is reduced, the investment of pyrogenic roasting is reduced, and the cost is reduced. The disadvantages are that the grade of the selected iron concentrate is not high and the recovery rate of iron is not high.
The roasting-ore dressing process is that firstly, the non-ferrous metals such as zinc in the dust of iron-smelting blast furnace are volatilized by roasting method, the non-ferrous metals such as zinc are recovered from the dust collected from the flue gas, and the roasted cinder is subjected to ore dressing to recover the iron resource which is reduced into metallic iron. The iron concentrate obtained by the process has high grade, high recovery rate of iron and high recovery rate of zinc when the content of zinc in blast furnace dust is high, and the process is a technical scheme with excellent technical indexes. However, in the technical scheme, all blast furnace dust is treated by a pyrogenic process, so that the investment is large, the cost is high, and good economic benefit can be obtained only when the content of nonferrous metals such as zinc is high.
The ore dressing-roasting-ore dressing process is formed by performing ore dressing on the cinder obtained by the ore dressing-roasting process again, and the aim of the subsequent ore dressing is to recover reduced metallic iron in the cinder, so that iron resources are fully recycled. The technical scheme is suitable for the resource comprehensive utilization of the blast furnace dust with low zinc content and difficult iron selection, and the cost for treating the blast furnace dust by the whole process is lower. But the process has more complex flow and larger investment and is suitable for large-scale iron and steel enterprises.
In addition, the iron resource in the blast furnace dust is recoveredby adopting a combined flow of magnetic separation and gravity separation; adopting flotation to recover the carbon in the solution; the technical scheme of recovering zinc in the cyclone is also researched, but the problems of low recovery rate and low product quality exist, so that the technologies are not applied much.
Thirdly, the invention content: the invention aims to provide a process for comprehensively recovering iron, carbon and zinc resources in blast furnace dust by using titanium white waste acid as a leaching reagent. The titanium white waste acid is liquid waste, the blast furnace dust iron separation tailings are solid waste, the titanium white waste acid and the blast furnace dust iron separation tailings are combined together to form raw materials and reagents which are mutually required, the two wastes are effectively changed into valuable resources, the problem of environmental pollution is well solved, and meanwhile, the economic benefit of good dust production is achieved.
The invention is realized by the following technical scheme:
1. ore dressing and recovering iron mineral in blast furnace dust
Blast furnace dust contains zinc 1.5-13%, iron 25-45% and carbon 10-23%.
And (3) wet grinding the blast furnace dust by a ball mill to enable large-particle materials to be ground to be more than 80% of materials with the particle size of less than 0.074 mm. Under the condition that a low-intensity magnetic field magnetic separator with the magnetic field intensity of 500-2500 oersted is adopted, under the condition that the ore pulp weight percentage concentration is 20-50%, the magnetite and other strong magnetic minerals in the ore pulp are recovered through primary roughing, primary concentrating and secondary concentrating. And then under the condition of 20-50% of ore pulp weight percentage concentration, carrying out primary roughing, primary scavenging and primary-secondary concentration on the ore pulp by using a spiral chute to recover weakly magnetic minerals such as hematite and the like, mixing the two products, dehydrating and filtering to obtain mixed iron concentrate containing 45-64% of iron and tailings after iron separation.
2. Recovery of zinc resource from blast furnace dust iron-separating tailings
Concentrating the tailings after iron selection to obtain ore pulp with the solid weight percentage concentration of 40-60%, loading the ore pulp into a pulp preparation tank, and adding titanium dioxide waste acid with the sulfuric acid content of 15-30% to ensure that the solid is solidThe weight ratio of the titanium dioxide waste acid to the liquid is kept at 2-6: 1, the pH value of the ore pulp is less than 2, the titanium dioxide waste acid and the blast furnace dust iron tailings are uniformly mixed to form titanium dioxide waste acid-blast furnace dust iron tailings mixed slurry, the slurry is sent into an acid-resistant stirring barrel, the stirring is carried out for 5-60 minutes at normal temperature at the stirring speed of 100-500 rpm, the titanium dioxide waste acid is added in the stirring process to keep the pH value of the slurry below 2, when 90-98% of zinc in the blast furnace dust iron tailings is transferred into the solution in the form of zinc sulfate, the stirring is stopped, the slurry is concentrated and filtered to obtain primary filtrate and leaching residues, the leaching residues are washed, and the primary filtrate is injected into the stirring tank again to be stirredAdding oxidant into the barrel to make more than 90% of Fe2+Ion oxidation to Fe3+Adding a neutralizing substance into the solution, controlling the pH value of the solution to be 3-3.5, wherein the neutralizing substance comprises blast furnace dust and lime,stirring the solution for 30-90 minutes at the rotating speed of 10-100 rpm, stopping stirring when the iron content of the solution is less than 300mg/L, concentrating and filtering precipitates in the solution to obtain iron slag and secondary filtrate, adding the secondary filtrate into a stirring barrel, and adding S2-、CO3 2-Or HCO3 -Precipitating zinc anions, stirring for 10-30 minutes at the rotating speed of 10-90 r/min to precipitate more than 98% of zinc in the solution, concentrating and filtering the solution containing precipitates to obtain zinc concentrate containing more than 45% of zinc and waste liquid, returning part of the waste liquid for use, and adding lime into the rest waste liquid to neutralize the waste liquid until the waste liquid is neutral and then is discharged after reaching the standard.
3. Leached residue flotation recovery carbon
Adding water into leached residues to form ore pulp with the weight percentage concentration of 20-45%, adding the ore pulp into a stirring barrel with the stirring speed of 300-600 rpm, adding 100-800 g/t of neutral oil, adding 30-120 g/t of foaming agent, stirring for 2-10 minutes, adding the ore pulp into a flotation machine for primary roughing, primary scavenging, secondary scavenging, primary concentrating and secondary concentrating, and concentrating and filtering concentrated products to obtain carbon concentrate containing C45-70% and waste residues.
Technical principle of the invention
1. Technical principle for beneficiation and recovery of iron minerals in blast furnace dust
The iron minerals in the blast furnace dust are mainly magnetite and hematite, and a small part of iron exists in the form of iron silicate. The iron minerals capable of being beneficiated and recovered are magnetite and hematite, the magnetite is strong magnetic mineral and can be well recovered by adopting weak magnetic separation, the hematite is weak magnetic mineral and has large specific gravity, and the hematite can be recovered by adopting a strong magnetic separation, gravity separation and flotation method. In the raw materials used by the invention, hematite is the most main iron mineral, and experiments show that the effects of strong magnetic separation and flotation are not as good as those of gravity separation, and the gravity separation investment is low, so that the hematite mineral is selectively recovered by gravity separation.
2. Leaching principle of titanium white waste acid on zinc oxide
The sulfuric acid in the titanium white waste acid reacts with the zinc oxide in the iron-making blast furnace dust beneficiation tailings according to the following formula:
ZnSO4dissolved in water, so that the solid zinc oxide in the iron-making blast furnace dust beneficiation tailings is leached into the solution. Sulfuric acid in titanium white waste acid is also mixed with part of Fe2O3FeO, CaO and the like, and the reaction formula is as follows:
3. chemical principle of hydrolysis for removing iron
The leaching solution contains part of Fe3+、Fe2+Adding oxidant air, hydrogen peroxide, manganese dioxide and potassium hypochlorite to make Fe2+Is oxidized into Fe3+Adding a neutralizing substance to adjust the pH value of the solution to 2-4.5, and Fe3+The ionic hydrolysis reaction is as follows:
by this reaction, Fe (OH) is added as iron ion3The precipitated form is excluded.
4、S2-、CO3 2-Or HCO3 -Chemical principle of ionic precipitation of zinc ions
S2-、CO3 2-、HCO3 -The chemical reaction of ion precipitation zinc ion is:
by means of this chemical reaction, S is added to the zinc-containing solution2-、CO3 2-、HCO3 -And (3) precipitating zinc ions in the forms of zinc sulfide, basic zinc carbonate and zinc carbonate by using ions, and then obtaining zinc concentrate by solid-liquid separation.
5. Technical principle for recovering carbon by leaching residue flotation
The carbon in the blast furnace dust is mainly coke powder, the surface of the coke powder particle has natural hydrophobicity, neutral oil is added into the leached residue slurry, neutral oil molecules are adsorbed on the surface of the coke powder particle to further enhance the hydrophobicity, and the flotation of the coke powder particle can be well realized by adding a foaming agent and introducing air.
The invention has the following advantages:
1. the zinc in the blast furnace dust mainly exists in the form of free zinc oxide, the granularity is fine, and when the zinc is treated by sulfuric acid at normal temperature, the reaction speed is high, the leaching time is short, and the leaching rate is high;
2. in the wet leaching of zinc oxide, the consumption of sulfuric acid accounts for more than 70% of the total cost, and when the blast furnace dust is treated by commercial sulfuric acid, good economic benefit is difficult to obtain under general conditions because the blast furnace dust contains low zinc, the price of sulfuric acid is high, and the treatment cost is high. The invention adopts the titanium white waste acid which does not cost money as the leaching reagent of the zinc oxide, so that the cost of the zinc oxide wet leaching is greatly reduced.
3. The titanium white waste acid is a large amount of waste liquid pollutant in a titanium dioxide factory of a sulfuric acid method, the investment for treating the waste liquid is large, the cost is high, and the problem of titanium white production of the sulfuric acid method is solved. When the waste acid is used as a leaching reagent of the iron-making blast furnace dust mill tailings, the iron-making blast furnace dust mill tailings become a neutralizer of the waste acid, so that the quantity of alkaline materials such as lime and the like required by waste acid treatment is greatly reduced, and the expense for the waste acid treatment is reduced.
4. The titanium white waste acid is liquid waste, the blast furnace dust iron separation tailings are solid waste, the titanium white waste acid and the blast furnace dust iron separation tailings are combined together to form raw materials and reagents which are mutually required, the two wastes are effectively changed into valuable resources, the problem of environmental pollution is well solved, and meanwhile, good economic benefits can be generated.
Fourthly, explanation of the attached drawings: FIG. 1 is a process flow diagram of the present invention.
The fifth embodiment is as follows:
the first embodiment is as follows:
iron-making blast furnace dust: blast furnace dust from vanadium titano-magnetite iron making: zinc 1.5-13%, iron 25-38%, and carbon 10-20%.
1. The vanadium titano-magnetite ironmaking blast furnace dust is subjected to wet grinding by a ball mill, so that large-particle materials are ground to be less than 0.074mm and the content is more than 80%. The method adopts a low-intensity magnetic separator with the magnetic field intensity of 1500 oersted to perform primary roughing and primary concentration to recover strong magnetic minerals such as magnetite and the like under the condition of 40 percent of ore pulp weight percentage concentration. And then, under the condition of 40 percent of ore pulp weight percentage concentration, carrying out primary roughing, primary scavenging and secondary concentration on the ore pulp by using a spiral chute to recover weakly magnetic minerals such as hematite and the like, mixing the two products, dehydrating and filtering to obtain mixed iron concentrate containing 45 to 48 percent of iron and tailings after iron separation.
2. Concentrating tailings after iron separation to obtain ore pulp with the solid weight percentage concentration of 60%, loading the ore pulp into a pulp preparation tank, adding titanium white waste acid with the sulfuric acid content of 20%, keeping the solid-liquid ratio, namely the solid-liquid ratio, of 2-4: 1, keeping the pH value of the ore pulp tobe less than 2, and uniformly mixing to form the titanium white waste acid-blast furnace dust iron separation tailFeeding the ore mixed slurry into an acid-resistant stirring barrel, stirring at the stirring speed of 100-500 rpm for 5-60 minutes at normal temperature, adding titanium dioxide waste acid in the stirring process to keep the pH value of the slurry below 2, stopping stirring when 90-98% of zinc in the blast furnace dust iron separation tailings is transferred into the solution in the form of zinc sulfate, concentrating and filtering the slurry to obtain primary filtrate and leaching residues, washing the leaching residues, injecting the primary filtrate into the stirring barrel, and introducing air to ensure that more than 90% of Fe is in the form of zinc sulfate2+Ion oxidation to Fe3+Adding neutralizing substance into blast furnace dust to control the pH value of the solution to be 3-3.5, stirring for 50-90 minutes at the rotating speed of 10-100 revolutions per minute, stopping stirring when the iron content of the solution is less than 300mg/L, concentrating and filtering precipitates in the solution to obtain iron slag and secondary filtrate, adding the secondary filtrate into a stirring barrel, and adding sodium sulfide (S)2-) Stirring for 10-30 min at 10-90 rpm to precipitate 98% zinc, concentrating and filtering the solution containing precipitate to obtain zinc concentrate containing zinc over 45% and waste liquid, returning part of the waste liquid for reuse, and adding lime to neutralize the rest waste liquid to neutrality for reaching the standard.
3. Leaching slag, adding water to form ore pulp with the weight percentage concentration of 35%, adding the ore pulp into a stirring barrel with the stirring speed of 300-600 rpm, adding 600g/t of neutral oil kerosene, adding 80g/t of foaming agent pine oil, stirring for 2-10 minutes, adding the ore pulp into a flotation machine for primary roughing, primaryscavenging and primary concentration, and concentrating and filtering concentrated products to obtain carbon concentrate containing C45-65%.
The main technical indexes are as follows:
the blast furnace dust of the vanadium titano-magnetite ironmaking blast furnace contains 1.5 to 13 percent of zinc, 25 to 38 percent of iron and 10 to 20 percent of carbon;
iron-containing grade of the iron ore concentrate is 45-48 percent;
the recovery rate of iron in the iron ore concentrate is more than or equal to 50 percent;
the carbon grade of the carbon concentrate is 45 to 65 percent;
the recovery rate of the carbon in the carbon concentrate is more than or equal to 60 percent;
the zinc grade of the zinc concentrate is more than or equal to 45 percent;
the recovery rate of zinc in the zinc concentrate is more than or equal to 80 percent.
Example two:
iron-making blast furnace dust: magnetite iron-making blast furnace dust: 2.3 to 10 percent of zinc, 30 to 40 percent of iron and 12 to 21 percent of carbon.
1. Wet grinding magnetite iron-smelting blast furnace dust in a ball mill to grind large-particle material to less than 0.074mm and over 80%. And (3) carrying out primary roughing and secondary concentration on the ore pulp with the weight percentage concentration of 30% by using a low-intensity magnetic field magnetic separator with the magnetic field intensity of 800-2000 oersted to recover strong magnetic minerals such as magnetite. And then, under the condition of 40 percent of ore pulp weight percentage concentration, carrying out rough concentration, scavenging and fine concentration once to recover weakly magnetic minerals such as hematite and the like, mixing the two products, dehydrating and filtering to obtain mixed iron concentrate containing 55 to 63 percent of iron and tailings after iron separation.
2. Concentrating tailings after iron separation to obtain ore pulp with the solid weight percentage concentration of 50%, loading the ore pulp into a pulp preparation tank, adding titanium white waste acid with the sulfuric acid weight percentage content of 18% -30%, keeping the solid-liquid ratio at 3-6: 1 and the pH value less than 2, uniformly mixing to form titanium white waste acid-iron making blast furnace dust iron separation tailings mixed slurry, sending the slurry into an acid-resistant stirring barrel, stirring at the normal temperature for 10-60 minutes at the stirring speed of 300 r/min, adding titanium white waste acid during stirring to keep the pH value of the slurry below 2, stopping stirring when 90% -98% of zinc in the blast furnace dust iron separation tailings is transferred into solution in the form of zinc sulfate, concentrating and filtering the slurry to obtain primary filtrate and leaching residues, washing the residues, injecting the primary filtrate into the stirring barrel again, and adding hydrogen peroxide to ensure that more than 90% of Fe is added2+Ion oxidation to Fe3+Adding lime to control the pH value of the solution to be 3-3.5, stirring at the rotating speed of 10-100 rpm for 30-90 minutes, stopping stirring when the iron content of the solution is less than 300mg/L, concentrating and filtering precipitates in the solution to obtain iron slag and secondary filtrate, adding the secondary filtrate into a stirring barrel, and adding sodium Carbonate (CO)3 2-) Stirring for 10-30 minutes at a rotating speed of 10-90 rpm to precipitate more than 98% of zinc in the solutionPrecipitating, concentrating and filtering the solution containing precipitate to obtain solution containing zinc greater than 45% of zinc concentrate and waste liquor.
3. Adding water into leached residues to form 40% of ore pulp by weight percentage, adding the ore pulp into a stirring barrel with the stirring speed of 300-600 rpm, adding 550g/t of neutral oil diesel oil, adding 100g/t of foaming agent pine oil, stirring for 2-10 minutes, adding the ore pulp into a flotation machine for primary roughing, primary scavenging and primary concentration, and concentrating and filtering concentrated products to obtain carbon concentrate containing C50% -70%.
The main technical indexes are as follows:
the magnetite iron-making blast furnace dust contains 2.3-10% of zinc, 30-40% of iron and 12-21% of carbon;
iron ore concentrate contains 55 to 63 percent of iron grade;
the recovery rate of iron in the iron ore concentrate is more than or equal to 65 percent;
the carbon grade of the carbon concentrate is 50 to 70 percent;
the recovery rate of the carbon in the carbon concentrate is more than or equal to 65 percent;
the zinc grade of the zinc concentrate is more than or equal to 45 percent;
the recovery rate of zinc in the zinc concentrate is more than or equal to 80 percent.
Example three:
iron-making blast furnace dust: mixing iron ore and blast furnace dust: zinc content is 2-13%, iron content is 26-43%, and carbon content is 12-23%.
1. Wet grinding the mixed iron ore ironmaking blast furnace dust by a ball mill to grind large-particle materials to be less than 0.074mm and more than 80 percent. And carrying out primary roughing on the ore pulp with the weight percentage concentration of 45% by using a low-intensity magnetic field magnetic separator with the magnetic fieldintensity of 1000-2500 oersted, and carrying out primary concentration to recover strong magnetic minerals such as magnetite. And then, under the condition of 40 percent of ore pulp weight percentage concentration, carrying out primary roughing, primary scavenging and secondary concentration on the ore pulp by using a spiral chute to recover weakly magnetic minerals such as hematite and the like, mixing the two products, dehydrating and filtering to obtain mixed iron concentrate containing 52-58 percent of iron and tailings after iron separation.
2. Concentrating tailings after iron separation to obtain ore pulp with the solid weight percentage concentration of 40%, loading the ore pulp into a pulp preparation tank, adding titanium dioxide waste acid with the sulfuric acid content of 25%, keeping the weight ratio of solid to liquid, namely the solid-liquid ratio, at 4-6: 1, and enabling the ore pulp to be in a solid-liquid ratio stateThe pH value is less than 2, titanium white waste acid-iron-making blast furnace dust iron-separation tailings mixed slurry is formed by uniformly mixing, the slurry is sent into an acid-resistant stirring barrel, stirring is carried out for 10-60 minutes at normal temperature at the stirring speed of 100-500 r/min, the titanium white waste acid is added in the stirring process to keep the pH value of the slurry below 2, when 90% -98% of zinc in the blast furnace dust iron-separation tailings is transferred into solution in the form of zinc sulfate, stirring is stopped, the slurry is concentrated and filtered to obtain primary filtrate and leaching slag, the leaching slag is washed, the primary filtrate is injected into the stirring barrel again, and the primary filtrate is addedManganese dioxide makes more than 90% of Fe2+Ion oxidation to Fe3+Adding lime to control the pH value of the solution to be 3-3.5, stirring at the rotating speed of 50-100 rpm for 30-90 minutes, stopping stirring when the iron content of the solution is less than 300mg/L, concentrating and filtering precipitates in the solution to obtain iron slag and secondary filtrate, adding the secondary filtrate into a stirring barrel, and adding sodium bicarbonate (HCO)3 -) Stirring for 10-30 minutes at the rotating speed of 10-90 r/min to precipitate more than 98% of zinc in the solution, and concentrating and filtering the solution containing precipitates to obtain zinc concentrate and waste liquid containing more than 45% of zinc.
3. Leaching slag, adding water to form 40 wt% ore pulp, adding the ore pulp into a stirring barrel with the stirring speed of 300-600 rpm, adding 400g/t neutral oil diesel oil, adding 90g/t foaming agent pine oil, stirring for 2-10 minutes, adding the ore pulp into a flotation machine for primary roughing, primary scavenging and primary concentration, and concentrating and filtering concentrated products to obtain carbon concentrate containing C50-70%.
The main technical indexes are as follows:
the blast furnace dust of the mixed iron ore ironmaking contains 2 to 13 percent of zinc, 26 to 43 percent of iron and 12 to 23 percent of carbon;
the iron-containing grade of the iron ore concentrate is 52 to 58 percent;
the recovery rate of iron in the iron ore concentrate is more than or equal to 65 percent;
the carbon grade of the carbon concentrate is 50 to 70 percent;
the recovery rate of the carbon in the carbon concentrate is more than or equal to 65 percent;
the zinc grade of the zinc concentrate is more than or equal to 45 percent;
the recovery rate of zinc in the zinc concentrate is more than or equal to 80 percent.
Claims (7)
1. A method for comprehensively utilizing the dust resources of an iron-making blast furnace is characterized by comprising the following steps of,
the blast furnace dust is subjected to wet grinding by a ball mill, so that large-particle materials in the blast furnace dust are ground to be more than 80% of materials with the particle size of less than 0.074 mm. Adopting a low-intensity magnetic field magnetic separator with the magnetic field intensity of 500-2500 oersted to carry out primary roughing at the weight percentage concentration of 20-50% of ore pulp, carrying out primary to secondary concentration to recover strong magnetic minerals such as magnetite and the like, then carrying out primary roughing, primary scavenging and primary to secondary concentration to recover weak magnetic minerals such as hematite and the like by using a spiral chute at the weight percentage concentration of 20-50% of ore pulp, mixing, concentrating and filtering the two products to obtain mixed iron concentrate containing 45-64% of iron and tailings after iron selection;
concentrating tailings after iron separation to obtain ore pulp with the solid weight percentage concentration of 40% -60%, loading the ore pulp into a pulp preparation tank, adding titanium white waste acid to keep the weight ratio of solid to liquid at 2-6: 1 and the pH value of the ore pulp to be less than 2, uniformly mixing to form mixed slurry, feeding the slurry into an acid-resistant stirring barrel, stirring at the normal temperature for 5-60 minutes at the stirring speed of 100-500 r/min, adding the titanium white waste acid to keep the pH value of the slurry below 2 in the stirring process, stopping stirring when 90% -98% of zinc in the iron tailings after iron separation of blast furnace dust is transferred into the solution in the form of zinc sulfate, concentrating and filtering the slurry to obtain primary filtrate and leaching residues, washing the leaching residues, injecting the primary filtrate into the stirring barrel, adding an oxidant to enable more than 90% of Fe to be transferred into the solution2+Ion oxidation to Fe3+Adding a neutralizing substance to control the pH value of the solution to be 3-3.5, stirring at the rotating speed of 10-100 rpm for 30-90 minutes, stopping stirring when the iron content of the solution is less than 300mg/L, concentrating and filtering precipitates in the solution to obtain iron slag and secondary filtrate, adding the secondary filtrate into a stirring barrel, and adding S2-、CO3 2-Or HCO3 -Precipitating zinc anions, stirring for 10-30 minutes at the rotating speed of 10-90 r/min to precipitate more than 98% of zinc in the solution, and precipitatingConcentrating and filtering the solution of the precipitate to obtain zinc concentrate containing more than 45% of zinc and waste liquid;
adding water into leached residues to form ore pulp with the weight percentage concentration of 20-45%, adding the ore pulp into a stirring barrel with the stirring speed of 300-600 rpm, adding 100-800 g/t of neutral oil, adding 30-120 g/t of foaming agent, stirring for 2-10 minutes, adding the ore pulp into a flotation machine for primary roughing, primary scavenging, secondary scavenging, primary concentrating and secondary concentrating, and concentrating and filtering concentrated products to obtain carbon concentrate containing C45-70% and waste residues.
2. The method for comprehensively utilizing the dust resources of the iron-making blast furnace according to claim 1, wherein the sulfuric acid content of the titanium white waste acid is 15-30%.
3. The method for comprehensively utilizing the blast furnace dust resource of the iron making according to the claim 1 or 2, characterized in that the blast furnace dust contains 1.5-13% of zinc, 25-45% of iron and 10-23% of carbon.
4. The method for comprehensively utilizing iron-making blast furnace dust resources as claimed in claim 1, 2 or 3, wherein the oxidant comprises one of air, hydrogen peroxide and manganese dioxide.
5. The method for comprehensively utilizing ironmaking blast furnace dust resources according to claim 1, 2, 3 or 4, characterized in that the neutralizing substance is one of ironmaking blast furnace dust and lime.
6. The method of comprehensive utilization of iron-making blast furnace dust resources as claimed in claim 1, 2, 3, 4 or 5, wherein anion S containing precipitated zinc2-、CO3 2-Or HCO3 -The substance(s) of (a) is sodium sulfide, sodium carbonate or sodium bicarbonate, respectively.
7. The method for comprehensively utilizing iron-making blast furnace dust resources as claimed in any one of claims 1 to 6, wherein the foaming agent is pine oil.
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