CN114990330A - Chromium slag harmless recycling treatment method, active micro powder material composition and active micro powder material - Google Patents
Chromium slag harmless recycling treatment method, active micro powder material composition and active micro powder material Download PDFInfo
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- CN114990330A CN114990330A CN202210590986.7A CN202210590986A CN114990330A CN 114990330 A CN114990330 A CN 114990330A CN 202210590986 A CN202210590986 A CN 202210590986A CN 114990330 A CN114990330 A CN 114990330A
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- chromium slag
- pellets
- slag
- chromium
- tailings
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- 239000002893 slag Substances 0.000 title claims abstract description 138
- 239000011651 chromium Substances 0.000 title claims abstract description 134
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 130
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000000463 material Substances 0.000 title claims abstract description 117
- 239000000203 mixture Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000000843 powder Substances 0.000 title claims abstract description 57
- 238000004064 recycling Methods 0.000 title claims abstract description 23
- 239000008188 pellet Substances 0.000 claims abstract description 69
- 230000009467 reduction Effects 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000007885 magnetic separation Methods 0.000 claims abstract description 37
- 230000001603 reducing effect Effects 0.000 claims abstract description 33
- 230000008569 process Effects 0.000 claims abstract description 28
- 229910000604 Ferrochrome Inorganic materials 0.000 claims abstract description 22
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 230000004907 flux Effects 0.000 claims abstract description 19
- 239000011230 binding agent Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 12
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 86
- 239000000292 calcium oxide Substances 0.000 claims description 43
- 235000012255 calcium oxide Nutrition 0.000 claims description 43
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 34
- 238000005245 sintering Methods 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 24
- 239000011734 sodium Substances 0.000 claims description 22
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 20
- 230000000694 effects Effects 0.000 claims description 19
- 238000010791 quenching Methods 0.000 claims description 16
- 230000000171 quenching effect Effects 0.000 claims description 16
- 229910000831 Steel Inorganic materials 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000010959 steel Substances 0.000 claims description 12
- 239000000571 coke Substances 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000010802 sludge Substances 0.000 claims description 9
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 8
- 239000004568 cement Substances 0.000 claims description 8
- 239000010436 fluorite Substances 0.000 claims description 8
- 239000010881 fly ash Substances 0.000 claims description 8
- 239000010440 gypsum Substances 0.000 claims description 8
- 229910052602 gypsum Inorganic materials 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 235000019738 Limestone Nutrition 0.000 claims description 6
- 239000004927 clay Substances 0.000 claims description 6
- 230000003750 conditioning effect Effects 0.000 claims description 6
- 239000006028 limestone Substances 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 6
- -1 clinker Substances 0.000 claims description 5
- 235000017550 sodium carbonate Nutrition 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001021 Ferroalloy Inorganic materials 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000006004 Quartz sand Substances 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 239000010459 dolomite Substances 0.000 claims description 3
- 229910000514 dolomite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 239000008399 tap water Substances 0.000 claims description 3
- 235000020679 tap water Nutrition 0.000 claims description 3
- 239000010865 sewage Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 31
- 229910052742 iron Inorganic materials 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 9
- 239000003546 flue gas Substances 0.000 description 9
- 238000005265 energy consumption Methods 0.000 description 8
- 239000004566 building material Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 230000036571 hydration Effects 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 229910000423 chromium oxide Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 239000002918 waste heat Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 2
- 239000003830 anthracite Substances 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/16—Sintering; Agglomerating
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/243—Binding; Briquetting ; Granulating with binders inorganic
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/244—Binding; Briquetting ; Granulating with binders organic
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a chromium slag harmless recycling treatment method, an active micro powder material composition and an active micro powder material. The harmless recycling treatment method of the chromium slag comprises the following steps: firstly, mixing chromium slag, a fusing agent, a reducing agent, an optional fusing agent, an optional binder and optional water to obtain a mixture, and preparing the mixture into a mixed material ball; then reducing and roasting the mixed material pellets to obtain reduced pellets; and carrying out magnetic separation treatment on the reduced pellets to obtain reduced ferrochromium ore powder and tailings, wherein the quaternary alkalinity of the mixture is 0.18-0.88. By applying the technical scheme of the invention, the raw materials such as the chromium slag, the flux, the reducing agent and the like are adopted to prepare the mixed material ball with the specific quaternary alkalinity, and the reduced ferrochromium ore powder and the tailings are obtained by subsequent reduction roasting and magnetic separation, so that the process is simple, the recovery rate of iron is more than 82 percent, the recovery rate of chromium is more than 75 percent, and the direct value conversion of the tailings is realized while the recovery rates of iron and chromium are improved.
Description
Technical Field
The invention relates to the technical field of hazardous waste treatment, in particular to a harmless recycling treatment method of chromium slag, an active micro powder material composition and an active micro powder material.
Background
Chromium is an important metal element, and the metal chromium has the characteristics of light weight, high temperature resistance, high strength, corrosion resistance and the like, is commonly used in various industrial productions of aerospace, steel, ships, nuclear power, chemical industry and the like, and is also widely applied in military industry. In nature, chromium is mainly chromite FeCr 2 O 4 In the form of chromium (iii) and metallic chromium is generally obtained by reduction of chromium oxide with aluminium or by electrolysis of chromium ammosilane or chromic acid. The preparation of the chromium oxide is to obtain sodium chromate after oxidizing roasting, leaching and filtering the chromite, and the sodium chromate is reduced and roasted to obtain the chromium oxide.
However, after the chromite is subjected to oxidizing roasting, leaching and filtering, a large amount of hexavalent chromium can be generated, and the hexavalent chromium has toxicity and carcinogenicity, can harm life safety and belongs to dangerous solid waste. According to the relevant national regulations, the chromium slag can be treated as common solid waste after being subjected to detoxification treatment, the treatment process not only brings huge economic pressure to enterprises, but also has potential safety hazards, and the harmless and resource utilization of the chromium slag needs to be realized in an effective way, so that waste is turned into wealth.
The existing chromium slag innocent treatment method has complex process, and the detoxified chromium slag can not directly realize value conversion, and has potential safety hazard after long-term stacking.
Disclosure of Invention
The invention mainly aims to provide a chromium slag harmless resource treatment method, an active micro powder material and an active micro powder material, so as to solve the problems that the existing chromium slag harmless treatment method is complex in process, the detoxified chromium slag cannot directly realize value conversion, and potential safety hazards exist in long-term storage.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for harmless resource treatment of chromium slag, comprising: step S1, mixing the chromium slag, the flux, the reducing agent, the optional fluxing agent, the optional binder and the optional water to obtain a mixture, and preparing the mixture into a mixed material ball; step S2, reducing and roasting the mixed material pellets to obtain reduced pellets; step S3, carrying out magnetic separation treatment on the reduced pellets to obtain reduced ferrochromium ore powder and tailings; in step S1, the quaternary basicity m (CaO + MgO)/m (Al) of the mixture is 2 O 3 +SiO 2 ) Is 0.18-0.88.
Further, in step S1, the chromium slag is calcium-free roasted chromium slag, and the calcium-free roasted chromium slag preferably contains the following components by mass percent: fe 2 O 3 25％-50％，Cr 2 O 3 2％-14％，Al 2 O 3 13％-22％，MgO 6％-14％，CaO 0.1％-1.2％，SiO 2 4% -10% and Na 2 O 5％-15％。
Further, in step S1, the mass ratio of the chromium slag, the flux, the fluxing agent, the reducing agent, the binder and the water is 100:0.1-18:0-10:5-30:0-16: 0-20;
preferably, the pentavalent basicity m (Na) of the mix 2 O+CaO+MgO)/m(Al 2 O 3 +SiO 2 ) Is 0.55-1.30.
Further, the flux comprises at least one of limestone, quicklime, dolomite, steel slag, carbide slag, quartz sand or tailings, and preferably comprises at least one of fluorite or soda ash; the reducing agent preferably comprises at least one of coal, coke, semi coke and waste graphite electrode; the binder preferably comprises at least one of clay, sludge, oil sludge and cement; the water preferably comprises at least one of tap water, reclaimed water or production wastewater; the diameter of the mixed pellet is preferably 20 to 80nm, more preferably 20 to 50 nm.
Further, step S2 includes: step S21, aging the mixed material ball, wherein the aging time is preferably 1-3 days, and the aged material ball is obtained; and step S22, reducing and roasting the aged pellets.
Further, the water content of the aged pellet is 9-18 wt%.
Further, the step S22 includes: carrying out initial sintering on the aged material balls to obtain initial sintered products; and (3) carrying out reduction roasting on the initial sintering product to obtain the reduction pellets, wherein preferably, the initial sintering is carried out in a neutral or reducing atmosphere, and the reduction roasting is carried out in the reducing atmosphere.
Further, the temperature of the initial sintering is 500-800 ℃, and the time is 1-3 h.
Furthermore, the temperature of the reduction roasting is 1200-1450 ℃, and the time is 1-2 h.
Further, before the magnetic separation treatment of the reduced pellets, step S3 further includes a cooling treatment process of the reduced pellets, preferably, the reduced pellets are cooled to a temperature of not more than 300 ℃ and then subjected to the magnetic separation treatment, preferably, the time of cooling from the temperature of reduction roasting to a temperature of not more than 300 ℃ is not more than 20min, and the cooling mode is preferably at least one of air quenching or water quenching;
further, the cooling process includes: the reduced pellet is cooled to be less than or equal to 1100 ℃ by water quenching, and then cooled to be less than or equal to 300 ℃ by air quenching.
Further, before the magnetic separation of the reduced pellets, the step S3 further includes: and crushing the reduced pellets to obtain reduced particles, wherein the particle size of the reduced particles is preferably less than or equal to 100 meshes.
According to another aspect of the present invention there is provided an active micropowder material composition comprising a micropowder body, a conditioning body and an activity stimulant, the micropowder body being any of the tailings provided in the first aspect of the present invention.
Furthermore, the mass ratio of the tailings, the adjusting body and the activity excitant is 100:20-70: 1-10.
Further, the adjusting material comprises at least one of fly ash, blast furnace slag, steel slag, ferroalloy slag or furnace slag.
Further, the activity activator comprises at least one of quicklime, cement, clinker, gypsum, water glass or sodium hydroxide.
According to a third aspect of the present invention, there is provided an active micropowder material having a specific surface area of 350m or more 2 Per kg, the active micro powder material is prepared from any one of the active micro powder material compositions provided by the second aspect of the invention.
By applying the technical scheme of the invention, the chromium slag, the flux, the reducing agent, the optional fluxing agent, the optional binder and the optional water are prepared into the mixed material ball with the specific quaternary alkalinity, the mixed material ball is reduced and roasted to obtain the reduced pellet, and the reduced pellet is subjected to magnetic separation to obtain the reduced ferrochromium ore powder and the tailings, so that the process is simple, the production efficiency is high, and the manpower and material resources can be effectively saved. The recovery rate of iron is more than 82 percent, the recovery rate of chromium is more than 75 percent, the reduced ferrochrome ore powder can be directly used as a material for steel smelting production, the tailings can be directly used as a raw material of a building material, the direct value conversion of the tailings is realized while the recovery rates of iron and chromium are improved, and a new solution is provided for full recovery and full component recycling of valuable components of the chromium slag.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As analyzed by the background art of the application, the existing chromium slag innocent treatment method has complex process, the detoxified chromium slag can not directly realize value conversion, and the long-term stacking has potential safety hazard. In order to simplify the harmless treatment of the chromium slag and realize the direct value conversion of the detoxified chromium slag, the application provides a harmless resource treatment method of the chromium slag.
In an exemplary embodiment of the present application, there is provided a method for harmless recycling of chromium slag, the method comprising: step S1, mixing chromium slag, flux, reducing agent,Mixing an optional fluxing agent, an optional binder and optional water to obtain a mixture, and preparing the mixture into a mixed material ball; step S2, reducing and roasting the mixed material pellets to obtain reduced pellets; step S3, performing magnetic separation treatment on the reduced pellets to obtain reduced ferrochromium ore powder and tailings; in step S1, the quaternary basicity m (CaO + MgO)/m (Al) of the mixture 2 O 3 +SiO 2 ) Is 0.18-0.88.
The quaternary basicity m (CaO + MgO)/m (Al) is defined above 2 O 3 +SiO 2 ) Refers to the total mass of CaO and MgO and Al in the mixture 2 O 3 And SiO 2 Of the total mass of the cell. The quaternary alkalinity is between 0.18 and 0.88 by adjusting the mass ratio of the raw materials in the mixture.
According to the chromium slag harmless recycling treatment method provided by the application, the chromium slag, the fusing agent, the reducing agent, the optional fluxing agent, the optional binding agent and the optional water are prepared into the mixed material ball with the specific quaternary alkalinity, the mixed material ball is subjected to reduction roasting to obtain the reduced pellet, then the reduced pellet is subjected to magnetic separation to obtain the tailings of the reduced ferrochromium ore powder, so that the process is simple, the production efficiency is high, the manpower and material resources can be effectively saved, the recovery rate of iron is more than 82%, and the recovery rate of chromium is more than 75%. The ferrochromium ore powder can be directly used as a material for steel smelting production, the tailings can be directly used as a raw material of a building material, the direct value conversion of the tailings is realized while the recovery rates of iron and chromium are improved, and a new solution is provided for full recovery and full component recycling of valuable components of chromium slag.
The quaternary alkalinity m (CaO + MgO)/m (Al) of the mixture is controlled 2 O 3 +SiO 2 ) 0.18 to 0.88 makes MgO and Al 2 O 3 Magnesium aluminate spinel is generated in the reduction roasting process, which is beneficial to the subsequent separation of magnetic separation and ferrochrome mineral powder, and the recovery rate of chromium and iron is improved. In addition, the quaternary alkalinity m (CaO + MgO)/m (Al) of the mixture is controlled by the application 2 O 3 +SiO 2 ) Is 0.18 to 0.88, overcomes the technical prejudice that quaternary alkalinity needs to be more than or equal to 0.9 to realize quaternary slag system balance, simultaneously ensures that the reduction roasting process is simpler,the energy consumption is saved, and the good separation of the tailings and the reduced ferrochromium ore powder can be realized through magnetic separation subsequently.
Typically, but not by way of limitation, the quaternary basicity m (CaO + MgO)/m (Al) of the mix 2 O 3 +SiO 2 ) Such as 0.18, 0.20, 0.22, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85 or 0.88,
the type of the chromium slag is not limited, and any chromium slag capable of being mixed with the flux, the reducing agent, the optional fluxing agent, the optional binder and the optional water to form the quaternary alkalinity can be used, including but not limited to calcium-free roasted chromium slag and calcium-roasted chromium slag.
The type of the flux is not limited, and any substance capable of melting the chromium slag can be used, including but not limited to at least one of limestone, dolomite, steel slag, carbide slag, quartz sand or tailings, and especially when the flux is one or a mixture of more of steel slag, carbide slag or tailings, the flux can save energy and change waste into valuable.
The type of the flux is not limited, and any material capable of lowering the melting temperature of the chromium slag may be used, including but not limited to fluorite or soda ash. The type of the reducing agent is not limited, and includes, but is not limited to, any one of coal, coke, semi coke, waste graphite electrode or a mixture of at least two of the above. In order to enhance the reducing effect of the reducing agent, it is preferable that the carbon content of the reducing agent is 50 wt% or more.
The type of the binder is not limited, and any one or a mixture of at least two of clay, oil sludge, cement, and sludge may be used as the binder, from the viewpoint of cost saving.
The type of the water is not limited, and tap water, reclaimed water, production sewage and the like can be mixed with the chromium slag, the flux, the reducing agent, the optional fluxing agent and the optional binder to form the mixture.
In order to facilitate the preparation of the chromium slag, the flux, the fluxing agent, the reducing agent, the binder and the water into the mixture with the quaternary alkalinity, the chromium slag is preferably calcium-free roasted chromium slag, so that the calcium-free roasted chromium slag can be easily mixed with various fluxes and various fluxing agents to form the mixture.
The calcium-free roasted chromium slag is industrial waste slag discharged in the process of producing chromium salt by using a calcium-free roasting process technology, and in some embodiments of the application, the calcium-free roasted chromium slag comprises the following components in percentage by mass: fe 2 O 3 25％-50％，Cr 2 O 3 2％-14％，Al 2 O 3 13％-22％，MgO 6％-14％，CaO 0.1％-1.2％，SiO 2 4% -10% and Na 2 O5％-15％。
In order to facilitate the formation of a mixture having a quaternary basicity of 0.18 to 0.88, in some embodiments, the mass ratio of the calcium-free roasted chromium slag, the flux, the reducing agent, the binder and the water is preferably 100:0.1 to 18:0 to 10:5 to 30:0 to 16:0 to 20.
In some embodiments of the present application, the pentabasic alkalinity (Na) of the above-described blend 2 O+CaO+MgO)/(Al 2 O 3 +SiO 2 ) 0.55-1.30 to control Na in the mixture 2 The dosage of O raw material is not limited by Na 2 The excessive O dosage and other components in the mixture salify to influence the effect of reduction roasting, so that the balance of a five-element slag system is realized, the reduction roasting process is simpler, the energy consumption is saved, and the tailings and the reduced ferrochromium ore powder can be better separated through magnetic separation subsequently.
The above five-membered alkalinity refers to Na in the mixture 2 O, CaO sum of MgO and Al 2 O 3 And SiO 2 By adjusting the ratio of the total mass of Na in the mixture 2 O、CaO、MgO、Al 2 O 3 And SiO 2 The weight content of the alkaline agent is that the alkalinity of the quinary is between 0.55 and 1.30.
In some embodiments, it is preferable to control the particle size of the mixing material ball to be 20-80mm, especially when the particle size of the mixing material ball is 20-50mm, the reduction of the mixing material ball is more sufficient, and the recovery rate of the reduced ferrochromium ore powder is higher.
Typically, but not by way of limitation, in calcium-free roasted chromium slag, Fe 2 O 3 Such as 25%, 30%, 35%, 40%, 45% or 50% by mass; cr (chromium) component 2 O 3 The mass content of (b) is, for example, 2%, 5%, 8%, 10%, 12% or 14%; al (Al) 2 O 3 Such as 13%, 15%, 18%, 20% or 22% by mass; the MgO content is, for example, 6%, 7%, 8%, 10%, 12% or 14% by mass; the CaO content is, for example, 0.1%, 0.2%, 0.5%, 0.8%, 1.0% or 1.2% by mass; SiO 2 2 Such as 4%, 5%, 6%, 8% or 10% by mass; na (Na) 2 The O content is, for example, 5%, 8%, 10%, 12%, or 15% by mass. In the mixture, the mass ratio of the calcium-free roasted chromium slag to the flux is 100:0.1, 100:0.2, 100:0.5, 100:0.8, 100:1, 100:2, 100:5, 100:10, 100:12, 100:15 or 100: 18; the mass ratio of the calcium-free roasted chromium slag to the fluxing agent is 100:0, 100:1, 100:2, 100:3, 100:5, 100:8 or 100: 10; the mass ratio of the calcium-free roasted chromium slag to the reducing agent is 100:5, 100:8, 100:10, 100:12, 100:15, 100:18, 100:200, 100:25 or 100: 30; the mass ratio of the calcium-free roasted chromium slag to the binder is 100:0, 100:1, 100:2, 100:3, 100:5, 100:6, 100:7, 100:8, 100:10, 100:12 or 100: 16; the mass ratio of the calcium-free roasted chromium slag to the water is 100:0, 100:1, 100:2, 100:3, 100:5, 100:8, 100:10, 100:12, 100:15, 100:18 or 100: 20. The mixed material ball has a particle diameter of 20mm, 30mm, 40mm, 50mm, 60mm or 80 mm.
In some embodiments, in order to save energy consumption of reduction roasting and improve the sufficiency of the reduction of the mixed material balls, it is preferable that the step S2 includes: step S21, the mixed material balls are firstly processed to obtain aged material balls; and step S22, reducing and roasting the aged pellets.
Through carrying out aging treatment with the mixture ball, can effectively improve the intensity of mixture ball on the one hand, avoid it to fracture in reduction roasting process and influence reduction effect, on the other hand can effectively reduce the water content of mixture ball, practices thrift reduction roasting energy consumption. The preferred aging time is 1-3 days, which is beneficial to the more compact combination of the raw materials in the mixed material ball and the increase of the mechanical strength of the mixed material ball, and on the other hand, the water content in the mixed material ball is also reduced and reaches a stable level, thus saving the energy consumption of the subsequent reduction roasting. When the water content of the aged pellets is preferably 9-18 wt%, the energy consumption of reduction roasting can be effectively saved.
In order to fully utilize the residual heat of the flue gas and save energy consumption, the step S22 preferably includes: and carrying out initial sintering on the aged pellets to obtain initial sintered products, and carrying out reduction roasting on the initial sintered products to obtain reduced pellets. In order to avoid loss caused by oxidation of the reducing agent during the initial sintering process, it is preferable that the initial sintering is performed in a neutral or weakly reducing atmosphere, and the reduction roasting is performed in a reducing atmosphere to avoid reoxidation of the roasted slag.
The neutral or weakly reducing atmosphere is O 2 An atmosphere having a concentration of less than 1% v and a CO concentration in the range of 0-2% v; the reducing atmosphere refers to an atmosphere having an oxygen concentration of 0% and a CO concentration in the range of 2.1 to 8 v%. The initial sintering and the reduction roasting have low requirements on atmosphere, can be realized by adopting a rotary kiln, simplifies the requirements on equipment by the reduction roasting, and is easy to realize.
In order to further improve the energy utilization rate and the utilization efficiency of the flue gas waste heat, in some embodiments, the aging ball is preferably subjected to initial dry sintering at 800 ℃ for 1-3h, sintering and pre-reduction processes may also occur at the contact interface of various material particles in the aging ball, and the strength is increased, so as to obtain an initial sintered product. In the process of initial sintering, flue gas discharged in subsequent reduction roasting is used for providing heat, so that the waste heat of the flue gas is fully utilized, residual CO in the flue gas and air are mixed and combusted in the drying and sintering process for releasing heat, the aged pellets are dried and pre-reduced by combining the waste heat of the flue gas, the energy consumption in the subsequent reduction roasting process is further reduced, and the heat efficiency is improved.
In order to further deeply reduce the iron oxide and the chromium oxide in the chromium slag, the temperature for reducing and roasting the initial sintered product is preferably 1200-1450 ℃ for 1-2 h.
Typically, but not limitatively, the temperature of the initial sintering is, for example, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃ or 800 ℃, and the time of the initial sintering is, for example, 1h, 1.5h, 2h, 2.5h or 3 h; the reduction roasting temperature is 1200 deg.C, 1250 deg.C, 1300 deg.C, 1350 deg.C, 1400 deg.C or 1450 deg.C, and the reduction roasting time is 1h, 1.2h, 1.5h, 1.8h or 2 h.
In order to avoid oxidation of the reduced pellets during the process of reducing the temperature from the roasting temperature and reduce the recovery rate of iron and chromium, in some embodiments, before the magnetic separation of the reduced pellets, step S3 further includes a process of cooling the reduced pellets, preferably cooling the reduced pellets to 300 ℃ or less and then performing the magnetic separation, preferably cooling the reduced pellets to 300 ℃ or less for 20min or less, the cooling manner is not limited, and from the viewpoint of saving the cost and simplifying the process, preferably, either one of air quenching or water quenching or a combination of the air quenching and the water quenching is used. The method for rapidly cooling the reduction pellets is different from the traditional chromium slag reduction magnetic separation mode, the traditional chromium slag reduction magnetic separation mode is convenient for magnetic separation in order to improve the particle size of magnetic substances, the reduced chromium slag is usually cooled slowly, so that the magnetic separation tailings have high crystalline phase content and almost no glass phase is separated out, the hydration activity is low, most of the follow-up tailings are used as auxiliary materials of building materials, and the utilization value is low. Although the rapid cooling mode of the reduction pellets can lead to the fact that a part of metal elements cannot be separated from the tailings through magnetic separation, the mass content of the glass phase in the tailings is 30% -80%, the rapid cooling mode has potential hydration activity, the rapid cooling mode not only can be used as an auxiliary material of a building material, but also can improve the performance of an active micro powder material when being used as a raw material of the active micro powder material, the utilization value is greatly improved, and the rapid cooling mode is more beneficial to realizing full-component resource utilization of chromium slag resources.
In some embodiments of the present application, the cooling process includes: the reduced pellets are cooled to be less than or equal to 1100 ℃ by adopting water quenching, and then cooled by adopting air quenching, so that the cooling time is shortened, and the cooling efficiency is improved. In order to avoid the oxidation of the reduced pellets, FeSO is preferably used in water quenching 4 Spraying the aqueous solution on the surface of the reduction pellets for water quenching, and FeSO 4 The aqueous solution has weak reducibility, is more beneficial to protecting the reduction pellets from oxidation, and is FeSO 4 The mass concentration of the aqueous solution of (2) is preferably 0.1% to 10%.
In order to further improve the recovery rate of chromium and iron, it is preferable that the step S3 further includes, before the magnetic separation treatment of the reduced pellets: and crushing the reduction pellets to obtain reduction particles, wherein the particle size of the reduction particles is less than or equal to 100 meshes. The crushing mode includes, but is not limited to, various conventional modes and combinations thereof, such as three-stage crushing and grinding combination.
In order to improve the grade and recovery rate of the reduced ferrochromium ore powder obtained by magnetic separation, in some embodiments, in step S3, the magnetic induction intensity during magnetic separation is preferably 100-. When the magnetic induction intensity is too high, the attractive force between magnetic poles is strong, and then fine particles containing more impurities can be absorbed and recovered, so that the magnetic separation recovery rate is high, but the grade is reduced; when the magnetic induction intensity is too low, only small particles with high iron content can be absorbed and recovered, the grade of the product is higher, but the recovery rate is lower, and when the magnetic induction intensity is 100-200mT, the high grade and the high recovery rate of the metal can be considered.
The reduced ferrochromium ore powder and the tailings are obtained by magnetic separation of the reduced particles, and the recovery rate of iron in the reduced ferrochromium ore powder is more than 82 percent. The recovery rate of chromium is more than 75 percent, the chromium can be directly used as a material for steel smelting production, the tailings can also be directly used as a raw material of an active micro powder material, the recovery of ferrochrome and the direct value conversion of the tailings are realized, and a new solution is provided for the full recovery and full component recycling of valuable components of the chromium slag.
In another exemplary embodiment of the present application, an active micro powder material composition is provided, the active micro powder material composition comprises a micro powder body, a conditioning agent and an active exciting agent, wherein the micro powder body is tailings separated by any one of the above chromium slag harmless resource treatment methods.
The type of the adjusting material is not limited, the adjusting material can be matched with the tailings to prepare active micro-powder materials, and from the viewpoint of changing waste into valuable, any one or a mixture of more of fly ash, blast furnace slag, steel slag, ferroalloy slag or furnace slag can be selected to be used together with the tailings. The ferroalloy slag includes, but is not limited to, ferronickel slag, ferro-manganese alloy slag, ferrosilicon slag or ferrovanadium slag. The type of the activator is not limited, and substances having an activating property may be used, including but not limited to one or a mixture of at least two of quicklime, cement, clinker, gypsum, water glass, and sodium hydroxide.
In some embodiments of the present application, the above is an active micro powder material composition, the mass ratio of the tailings, the conditioning agent and the activity excitant is preferably 100:20-70:1-10, so as to facilitate preparation of an active micro powder material with excellent hydration activity.
Typically, but not by way of limitation, in the active micropowder material composition, the mass ratio of tailings and the adjusting material is, for example, 100:20, 100:30, 100:40, 100:50, 100:60 or 100: 70; the weight ratio of the tailings and the activity excitant is 100:1, 100:2, 100:5, 100:8 or 100: 10.
In a third exemplary embodiment of the present application, an active micropowder material having a specific surface area of 350m or more is provided 2 /kg, and the active micro powder material is prepared from any one of the active micro powder material compositions.
The active micro powder material is prepared by grinding the active micro powder composition. The active micro powder material has potential hydration activity and can be used as an auxiliary cementing material for building material production enterprises such as outsourcing concrete mixing stations, prefabricated members, wallboards, building blocks and the like. The active micro powder material is used for manufacturing building materials such as concrete, prefabricated parts, building blocks and the like, can reduce the use amount of traditional high-price cement, reduce the cost, reduce the hydration heat strength of the material, prevent the material from cracking and improve the performance of the material.
In addition, the Cr in the active micropowder material leaching solution is detected 6+ And TCr (total chromium content) all meets the extraction toxicity identification of GB5085.3-2007 hazardous waste identification standard, which shows that the tailings are prepared into the active micro-powder material to realize harmless recycling of the tailings.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
Example 1
The embodiment provides a resource recovery processing method of chromium slag, wherein the chromium slag is calcium-free roasted chromium slag and mainly comprises the following components in percentage by mass: fe 2 O 3 36％，Cr 2 O 3 9％，Al 2 O 3 17％，MgO 13％，CaO 0.5％，SiO 2 4% and Na 2 O9%, which comprises the following steps:
(1) mixing chromium slag, limestone, fluorite, coke, sludge and water according to the mass ratio of 100:11:5:12:5:18 to form a mixture, wherein the quaternary alkalinity m (CaO + MgO)/m (Al) of the mixture 2 O 3 +SiO 2 ) 0.88, and a pentabasic basicity m (Na) 2 O+CaO+MgO)/m(Al 2 O 3 +SiO 2 ) Is 1.30; and extruding and pelletizing the mixture by using a ball press to obtain a mixed material ball, wherein the diameter of the particle size of the mixed material ball is 35 +/-15 mm.
(2) Stacking the mixed material balls in a material factory or a material bin, aging for 2 days, determining that the water content in the mixed material balls reaches 12 +/-3 percent to obtain aged material balls, performing initial sintering and drying on the aged material balls at a temperature range of 650 +/-50 ℃ in a flue gas preheating section of a rotary kiln for 2 hours to obtain initial sintering products, and performing reduction roasting on the initial sintering products at a temperature range of 1300 +/-50 ℃ in a high-temperature zone of the rotary kiln for 1.5 hours to obtain reduced pellets, wherein the volume concentration of oxygen in the atmosphere during initial sintering is 0.8 +/-0.1 percent, the volume concentration of CO in the atmosphere during reduction roasting is 1 +/-0.5 percent, the volume concentration of oxygen in the atmosphere during reduction roasting is 0 percent, and the volume concentration of CO in the atmosphere during reduction roasting is 5 +/-1 percent.
(3) Pouring the reduced pellets into a slag ladle or a slag bin, wherein FeSO with the mass concentration of 0.5 percent is adopted in the slag pouring process 4 And spraying the aqueous solution on the surface of the reducing pellets to quickly reduce the temperature of the surface of the reducing pellets to be below 1100 ℃, and then carrying out air cooling on the reducing pellets with cooled surfaces in a slag ladle or a slag bin to reduce the temperature of the reducing pellets to be below 300 ℃, wherein the air cooling time is less than or equal to 20 min.
(4) And (3) carrying out three-stage crushing and grinding treatment on the reduced pellets cooled to below 300 ℃ to obtain reduced particles with the particle size of less than or equal to 100 meshes, carrying out magnetic separation on the reduced particles, wherein the magnetic separation strength is 150mT, so that reduced ferrochromium ore powder is separated, and the remainder is tailings.
Example 2
The embodiment provides a resource recycling treatment method of chromium slag, which is different from the embodiment 1 in that the chromium comprises the following components in percentage by mass: fe 2 O 3 36％，Cr 2 O 3 12％，Al 2 O 3 18％，MgO 6％，CaO 0.1％，SiO 2 15% and Na 2 O12 percent; in the mixture, the mass ratio of the chromium slag, the limestone, the fluorite, the coke, the sludge and the water is 100:0.1:10:18:0:15, and the quaternary alkalinity m (CaO + MgO)/m (Al) of the mixture 2 O 3 +SiO 2 ) 0.18, and a pentabasic basicity (Na) 2 O+CaO+MgO)/(Al 2 O 3 +SiO 2 ) Is 0.55.
Example 3
The embodiment provides a resource recycling treatment method of chromium slag, which is different from the embodiment 1 in that the chromium slag comprises the following components in percentage by mass: fe 2 O 3 50％，Cr 2 O 3 2％，Al 2 O 3 15％，MgO 10％，CaO 1％，SiO 2 7% and Na 2 O8 percent; in the mixture, the mass ratio of the chromium slag, the quicklime, the fluorite, the semi-coke, the clay and the water is 100:3:3:8:5:20, and the quaternary alkalinity m (CaO + MgO)/m (Al) of the mixture 2 O 3 +SiO 2 ) 0.6, and a pentabasic basicity (Na) 2 O+CaO+MgO)/(Al 2 O 3 +SiO 2 ) Is 0.96.
Example 4
The embodiment provides a resource recycling treatment method of chromium slag, which is different from the embodiment 1 in that the chromium slag comprises the following components in percentage by mass: fe 2 O 3 25％，Cr 2 O 3 14％，Al 2 O 3 22％，MgO 14％，CaO 1％，SiO 2 10% and Na 2 O14 percent; in the mixture, the mass ratio of the chromium slag, the quicklime, the fluorite, the semi-coke, the clay and the water is 100:22:12:13:3:10, and the mass ratio of the chromium slag, the quicklime, the fluorite, the semi-coke, the clay and the water is fourBasic value m (CaO + MgO)/m (Al) 2 O 3 +SiO 2 ) 0.85, and a pentabasic basicity (Na) 2 O+CaO+MgO)/(Al 2 O 3 +SiO 2 ) Was 1.27.
Example 5
The embodiment provides a resource recycling method of chromium slag, which is different from the embodiment 1 in that in the step (2), the mixed material balls are stacked in a material factory or a material bin, the aging time is 1h, and the moisture content of the aged material balls is measured to be 15 +/-3%.
Example 6
The embodiment provides a resource recycling method of chromium slag, which is different from the embodiment 1 in that in the step (2), the mixture ball is not aged, the mixture ball is directly sintered and dried initially, and the water content in the mixture ball is measured to be 25 +/-3%.
Example 7
The embodiment provides a resource recycling method of chromium slag, which is different from the embodiment 1 in that in the step (2), an aged material ball is subjected to initial sintering and drying within the range of 550 +/-50 ℃ in a preheating section of flue gas of a rotary kiln for 3 hours to obtain an initial sintered product, and the initial sintered product is subjected to reduction roasting at the high temperature zone of the rotary kiln for 1400 +/-50 ℃ for 1 hour.
Example 8
The embodiment provides a resource recycling method of chromium slag, which is different from the embodiment 1 in that in the step (2), an aged material ball is subjected to initial sintering and drying within the range of 750 +/-50 ℃ in a flue gas preheating section of a rotary kiln for 1h to obtain an initial sintered product, and the initial sintered product is subjected to reduction roasting within the range of 1250 +/-50 ℃ in a high-temperature zone of the rotary kiln for 2 h.
Example 9
This example provides a method for recycling chromium slag, which is different from example 1 in that in step (2), the aged pellets are directly subjected to reduction roasting without initial sintering.
Example 10
The embodiment provides a resource recovery processing method of chromium slag, which is different from the embodiment 1 in that in the step (3), reducing pellets are poured into a slag bin or a slag ladle, and reclaimed water is sprayed onto the surfaces of the reducing pellets in the slag pouring process, so that the temperature of the surfaces of the reducing pellets is quickly reduced to be below 1100 ℃.
Example 11
The embodiment provides a resource recovery processing method of chromium slag, which is different from the embodiment 1 in that in the step (3), reducing pellets are poured into a slag bin or a slag ladle and are naturally cooled to below 300 ℃ by air cooling, and the time for reducing the temperature of the reducing pellets from the reducing roasting temperature to below 300 ℃ is 10 hours.
Example 12
The embodiment provides a resource recycling treatment method of chromium slag, which is different from the embodiment 1 in that in the step (1), the chromium slag, limestone, anthracite, soda ash, cement and water are mixed according to the mass ratio of 100:21:33:15:10:12 to form a mixture, and the quaternary alkalinity m (CaO + MgO)/m (Al) of the mixture is m (CaO + MgO)/m (Al) 2 O 3 +SiO 2 ) 0.88, and a pentabasic basicity (Na) 2 O+CaO+MgO)/(Al 2 O 3 +SiO 2 ) Was 2.2.
Comparative example 1
The comparative example provides a resource recycling treatment method of chromium slag, which is different from the method in example 2 in that in the step (1), the chromium slag comprises the following components in percentage by mass: fe 2 O 3 36％，Cr 2 O 3 12％，Al 2 O 3 18％，MgO6％，CaO 0.1％，SiO 2 15% and Na 2 Mixing O12%, chromium slag, quartz, soda ash, anthracite, sludge and water according to the mass ratio of 100:14:10:16:6:18 to form a mixture, wherein the quaternary alkalinity m (CaO + MgO)/m (Al) of the mixture 2 O 3 +SiO 2 ) 0.13, and a pentabasic basicity (Na) 2 O+CaO+MgO)/(Al 2 O 3 +SiO 2 ) Is 0.51.
Test example 1
The chromium grade, iron grade, chromium recovery rate, iron recovery rate and glass phase content in tailings in the reduced ferrochrome ore powder obtained by magnetic separation in the above examples and comparative examples are respectively measured, and the results are shown in table 1 below.
TABLE 1
Example 13
This example provides an active micropowder material prepared as follows:
(1) mixing the tailings, the fly ash and the gypsum obtained by the magnetic separation in the example 10 according to the mass ratio of 100:60:8 to form an active micro-powder material composition;
(2) the active micro powder material composition is subjected to grinding treatment, so that the specific surface area of slag powder is 400 +/-50 m 2 And/kg, obtaining the active micro powder material.
Example 14
The present example provides an active micropowder material, and the preparation method is different from that in example 13, in step (1), tailings, fly ash and gypsum obtained by magnetic separation in example 10 are mixed according to a mass ratio of 100:50:5 to form an active micropowder material composition, and the remaining steps are the same as those in example 13 and are not described again.
Example 15
The present example provides an active micropowder material, and the preparation method is different from that in example 13, in step (1), tailings, fly ash and gypsum obtained by magnetic separation in example 11 are mixed according to a mass ratio of 100:70:10 to form an active micropowder material composition, and the remaining steps are the same as those in example 12 and are not described again.
Example 16
The embodiment provides an active micropowder material, and the preparation method is different from that in the embodiment 13, in the step (1), tailings, fly ash and gypsum obtained by magnetic separation in the embodiment 11 are mixed according to the mass ratio of 100:20:1 to form an active micropowder material composition, and the rest steps are the same as the embodiment 13 and are not repeated herein.
Example 17
The present example provides an active micropowder material, and the preparation method is different from that in example 13, in step (1), tailings, fly ash and gypsum obtained by magnetic separation in example 11 are mixed according to a mass ratio of 100:50:5 to form an active micropowder material composition, and the remaining steps are the same as those in example 13 and are not described again.
Test example 2
The active micro powder materials provided in the above examples were measured for activity index at 7d and 28d, respectively, and the results are shown in table 2 below.
Wherein, the determination of the active index of the active micropowder material is carried out according to GB/T20491.
TABLE 2
| Activity index (7d) | Activity index (28d) | |
| Example 13 | 59 | 85 |
| Example 14 | 56 | 83 |
| Example 15 | 64 | 89 |
| Example 16 | 55 | 65 |
| Example 17 | 62 | 88 |
In addition, the leaching toxicity of the active fine powder materials provided in the above examples is identified according to GB5085.3-2007, and the results show that Cr in the active fine powder leaching liquid in the above examples is 6+ And TCr (total chromium concentration in standard leach liquor, Cr) 6+ And Cr 3+ Sum), which indicates that the application prepares the tailings into the active micro-powder to realize harmless resource utilization of the tailings.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: by applying the technical scheme of the invention, the chromium slag, the flux, the reducing agent, the optional fluxing agent, the optional binder and the optional water are prepared into the mixed material ball with the specific quaternary alkalinity, the mixed material ball is reduced and roasted to obtain the reduced pellet, and the reduced pellet is subjected to magnetic separation to obtain the reduced ferrochromium ore powder and the tailings, so that the process is simple, the production efficiency is high, and the manpower and material resources can be effectively saved. The recovery rate of iron is more than 82 percent, the recovery rate of chromium is more than 75 percent, the reduced ferrochrome ore powder can be directly used as a material for steel smelting production, the tailings can be directly used as a raw material of a building material, the direct value conversion of the tailings is realized while the recovery rates of iron and chromium are improved, and a new solution is provided for full recovery and full component recycling of valuable components of the chromium slag.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A chromium slag harmless recycling treatment method is characterized by comprising the following steps:
step S1, mixing the chromium slag, the flux, the reducing agent, the optional fluxing agent, the optional binder and the optional water to obtain a mixture, and preparing the mixture into a mixed material ball;
step S2, carrying out reduction roasting on the mixed material pellets to obtain reduced pellets;
step S3, carrying out magnetic separation treatment on the reduced pellets to obtain reduced ferrochromium ore powder and tailings;
in step S1, the quaternary basicity m (CaO + MgO)/m (Al) of the mixture is 2 O 3 +SiO 2 ) Is 0.18-0.88.
2. The chromium slag harmless resource treatment method according to claim 1, wherein in step S1, the chromium slag is calcium-free roasted chromium slag, and the calcium-free roasted chromium slag preferably comprises the following components by mass percent: fe 2 O 3 25％-50％，Cr 2 O 3 2％-14％，Al 2 O 3 13％-22％，MgO 6％-14％，CaO 0.1％-1.2％，SiO 2 4% -10% and Na 2 O 5％-15％；
Preferably, the mass ratio of the chromium slag, the fluxing agent, the reducing agent, the binder and the water is 100:0.1-18:0-10:5-30:0-16: 0-20;
preferably, the pentavalent basicity m (Na) of the mix 2 O+CaO+MgO)/m(Al 2 O 3 +SiO 2 ) Is 0.55-1.30.
3. A chromium slag harmless resource treatment method according to claim 1, wherein said flux comprises at least one of limestone, quicklime, dolomite, steel slag, carbide slag, quartz sand or tailings;
the fluxing agent preferably comprises at least one of fluorite or soda ash;
the reducing agent preferably comprises at least one of coal, coke, semi coke and waste graphite electrode;
the binder preferably comprises at least one of clay, sludge, oil sludge and cement;
the water preferably comprises at least one of tap water, reclaimed water or production sewage;
the diameter of the pellet is preferably 20 to 80mm, more preferably 20 to 50 mm.
4. A chromium slag harmless resource treatment method according to claim 1, wherein said step S2 includes:
step S21, aging the mixed material ball, wherein the aging time is preferably 1-3 days, and the aged material ball is obtained;
step S22, carrying out the reduction roasting on the aged material balls;
preferably, the water content of the aged pellets is 9 to 18 wt%.
5. A chromium slag harmless resource treatment method according to claim 4, wherein said step S22 includes:
carrying out initial sintering on the aged material balls to obtain initial sintering products;
carrying out reduction roasting on the initial sintering product to obtain the reduction pellets, preferably, carrying out the initial sintering under a neutral or weak reducing atmosphere, and carrying out the reduction roasting under the reducing atmosphere;
preferably, the temperature of the initial sintering is 500-800 ℃, and the time is 1-3 h;
preferably, the temperature of the reduction roasting is 1200-1450 ℃, and the time is 1-2 h.
6. A chromium slag harmless resource treatment method according to claim 1, characterized in that before the magnetic separation treatment of the reducing pellets, the step S3 further comprises a process of cooling the reducing pellets, preferably cooling the reducing pellets to 300 ℃ or less and then performing the magnetic separation treatment, preferably cooling the reducing pellets from the temperature of reducing roasting to 300 ℃ or less for 20min or less, wherein the cooling mode is preferably at least one of air quenching or water quenching;
preferably, performing the cooling process includes: the reduced pellets are cooled to be less than or equal to 1100 ℃ by water quenching, and then cooled to be less than or equal to 300 ℃ by air quenching.
7. The chromium slag harmless resource treatment method as claimed in claim 1, wherein before the magnetic separation treatment of the reducing pellets, the step S3 further comprises: and crushing the reduction pellets to obtain reduction particles, wherein the particle size of the reduction particles is preferably less than or equal to 100 meshes.
8. An active micropowder material composition comprising a micropowder body, a conditioning body and an activity stimulant, characterized in that the micropowder body is the tailings of any one of claims 1 to 7.
9. The active micropowder material composition according to claim 8, characterized in that the mass ratio of the tailings, the conditioning body and the activity stimulant is 100:20-70: 1-10;
preferably, the conditioning body comprises at least one of fly ash, blast furnace slag, steel slag, ferroalloy slag, or slag.
Preferably, the activity promoter comprises at least one of quicklime, cement, clinker, gypsum, water glass or sodium hydroxide.
10. An active micropowder material, the specific surface area of the active micropowder material is more than or equal to 350m 2 /kg, characterized in that the active micropowder material is prepared from an active micropowder material composition according to claim 8 or 9.
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