WO2022156076A1 - Method for producing aluminum oxide using slag metallurgy technology - Google Patents
Method for producing aluminum oxide using slag metallurgy technology Download PDFInfo
- Publication number
- WO2022156076A1 WO2022156076A1 PCT/CN2021/086846 CN2021086846W WO2022156076A1 WO 2022156076 A1 WO2022156076 A1 WO 2022156076A1 CN 2021086846 W CN2021086846 W CN 2021086846W WO 2022156076 A1 WO2022156076 A1 WO 2022156076A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- slag
- molten
- iron
- bauxite
- vanadium
- Prior art date
Links
- 239000002893 slag Substances 0.000 title claims abstract description 361
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 52
- 238000005516 engineering process Methods 0.000 title claims abstract description 48
- 238000005272 metallurgy Methods 0.000 title claims abstract description 30
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title abstract 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 221
- 229910052742 iron Inorganic materials 0.000 claims abstract description 107
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000000292 calcium oxide Substances 0.000 claims abstract description 79
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 70
- 239000010959 steel Substances 0.000 claims abstract description 70
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000002994 raw material Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 42
- 238000009628 steelmaking Methods 0.000 claims abstract description 24
- 230000004907 flux Effects 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- 229910001570 bauxite Inorganic materials 0.000 claims description 66
- 229910052720 vanadium Inorganic materials 0.000 claims description 59
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 59
- 238000002386 leaching Methods 0.000 claims description 53
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 238000003723 Smelting Methods 0.000 claims description 31
- 238000002844 melting Methods 0.000 claims description 29
- 230000008018 melting Effects 0.000 claims description 28
- 239000011734 sodium Substances 0.000 claims description 28
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 26
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 24
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 21
- 239000010955 niobium Substances 0.000 claims description 18
- 229910052758 niobium Inorganic materials 0.000 claims description 18
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 18
- 229910018626 Al(OH) Inorganic materials 0.000 claims description 17
- 239000003245 coal Substances 0.000 claims description 17
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052804 chromium Inorganic materials 0.000 claims description 15
- 239000011651 chromium Substances 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- WFISYBKOIKMYLZ-UHFFFAOYSA-N [V].[Cr] Chemical compound [V].[Cr] WFISYBKOIKMYLZ-UHFFFAOYSA-N 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 238000010298 pulverizing process Methods 0.000 claims description 12
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 10
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 10
- 239000004571 lime Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229910000616 Ferromanganese Inorganic materials 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 8
- 239000010881 fly ash Substances 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000004927 clay Substances 0.000 claims description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052664 nepheline Inorganic materials 0.000 claims description 6
- 239000010434 nepheline Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- -1 alum Substances 0.000 claims description 5
- 229940037003 alum Drugs 0.000 claims description 5
- 239000010433 feldspar Substances 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 235000019738 Limestone Nutrition 0.000 claims description 4
- 238000010891 electric arc Methods 0.000 claims description 4
- 230000006698 induction Effects 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000013980 iron oxide Nutrition 0.000 claims description 4
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003077 lignite Substances 0.000 claims description 4
- 239000006028 limestone Substances 0.000 claims description 4
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical group C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003830 anthracite Substances 0.000 claims description 3
- 239000002802 bituminous coal Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000003345 natural gas Substances 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 239000008188 pellet Substances 0.000 claims description 3
- 238000011946 reduction process Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052570 clay Inorganic materials 0.000 claims description 2
- 239000003034 coal gas Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 238000002309 gasification Methods 0.000 claims description 2
- 229910052622 kaolinite Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 21
- 238000011084 recovery Methods 0.000 abstract description 18
- 238000005265 energy consumption Methods 0.000 abstract description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 7
- 239000011707 mineral Substances 0.000 abstract description 7
- 235000010755 mineral Nutrition 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000001816 cooling Methods 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract 2
- 239000000155 melt Substances 0.000 abstract 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 abstract 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 abstract 1
- 238000007664 blowing Methods 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 229910001679 gibbsite Inorganic materials 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract 1
- 235000017550 sodium carbonate Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 37
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 22
- 239000004568 cement Substances 0.000 description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 description 11
- 239000001569 carbon dioxide Substances 0.000 description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000004071 soot Substances 0.000 description 5
- 239000005995 Aluminium silicate Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 235000012241 calcium silicate Nutrition 0.000 description 3
- 229910052918 calcium silicate Inorganic materials 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000007885 magnetic separation Methods 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000004131 Bayer process Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- UDSKNCBNKQBDHH-UHFFFAOYSA-N [Nb].[V].[Cr] Chemical compound [Nb].[V].[Cr] UDSKNCBNKQBDHH-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/16—Preparation of alkaline-earth metal aluminates or magnesium aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/164—Calcium aluminates
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/006—Starting from ores containing non ferrous metallic oxides
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/008—Use of special additives or fluxing agents
-
- 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
- C22B21/00—Obtaining aluminium
- C22B21/0007—Preliminary treatment of ores or scrap or any other metal source
-
- 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
- C22B7/006—Wet processes
-
- 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
- Y02P10/10—Reduction of greenhouse gas [GHG] emissions
- Y02P10/143—Reduction of greenhouse gas [GHG] emissions of methane [CH4]
Definitions
- the invention belongs to the technical fields of comprehensive utilization of aluminum-containing mineral resources, slag metallurgy and alumina production, and particularly relates to a method for producing alumina by utilizing slag metallurgy technology.
- the raw material is high-grade bauxite (aluminum-silicon ratio>7), and it is impossible to utilize low-grade bauxite, high iron bauxite, fly ash, coal gangue, nepheline, alum, clay, kaolin and other bauxite resources;
- Red mud contains harmful components such as sodium and radioactive elements, which are difficult to utilize, and hundreds of millions of tons have been accumulated;
- the acid method-alkali method has high acid consumption, high cost, long process, and large environmental pollution
- Magnetic separation technology which covers a large area, has a low yield of iron components, cannot eliminate red mud and recover valuable components such as chromium and vanadium;
- Direct reduction-melting separation technology (CN201510531320.4, CN201510530645.0, CN201810593292.2, CN201910888430.4, CN201910909622.9), there are only suitable for high iron bauxite, high reduction temperature, high energy consumption, CaO flux Disadvantages such as large consumption, high cost, complex equipment, and difficulty in continuous operation;
- Blast furnace ironmaking technology (CN201410048304.5), high recovery rate, has disadvantages such as only suitable for high iron bauxite, high energy consumption, long process, large investment, large consumption of CaO flux, high cost, large environmental pollution, etc. State restricted craftsmanship.
- the raw materials have strong adaptability, not only can process bauxite with high aluminum-silicon ratio, but also bauxite with low aluminum-silicon ratio, high-iron bauxite, polymetallic symbiotic ore, high-aluminum fly ash, high-alumina Aluminum ore resources such as coal gangue and nepheline;
- tailings, tailings or red mud can be directly used to prepare high value-added products, which are environmentally friendly, the whole process can be recycled, and has the characteristics of green, clean and efficient;
- Valuable components such as iron, chromium, vanadium, phosphorus, niobium, CaO, SiO can be recovered at the same time, and the income is high;
- Ferromanganese smelting and magnesium smelting slag are produced in ferromanganese smelting ferroalloy process and metal magnesium smelting process respectively.
- Ferromanganese smelting slag, magnesium smelting slag, molten steel slag and blast furnace slag belong to the high calcium oxide slag system, which contains a large amount of molten CaO, Al 2 O 3 and SiO 2 and other valuable components. More than 600 million tons, cannot be processed or have low added value, and accumulate in large quantities, wasting physical heat and resources.
- the present invention provides a method for producing alumina by utilizing slag metallurgy technology, the specific method comprising: mixing bauxite, alkaline flux, reducing agent, or bauxite and reducing agent,
- the main product is calcium aluminate slag
- the by-product is molten iron or vanadium-containing molten iron or vanadium-chromium-containing molten iron.
- the invention utilizes the high physical heat and chemical activity of high calcium oxide metallurgical slag (melting steel slag, blast furnace slag, ferromanganese smelting slag and magnesium smelting slag), slag bath melting reduction treatment of aluminum ore, and obtains calcium aluminate slag (aluminum smelting slag).
- Acid slag, ultra-high basicity slag (CaO/SiO 2 ⁇ 3) mainly composed of ore phases such as hepta-alumina, calcium aluminate, etc.
- vanadium-containing molten iron self-pulverized calcium aluminate slag after wet Alumina is produced by the method of metallurgical technology.
- Calcium aluminate slag and alumina are the main products, and the by-product is molten iron. It has the characteristics of strong adaptability of raw materials, low energy consumption, low consumption of flux CaO, multi-component recovery, no solid waste discharge, short process, low cost and environmental friendliness. It is a new alumina production method, which can achieve high oxidation Recovery and production of aluminium components in calcium metallurgical slag and bauxite.
- a method for producing alumina by utilizing slag metallurgy technology of the present invention comprises the following steps;
- step 1
- the high calcium oxide metallurgical slag is added to the melting reactor to form reaction slag; the mass percentage of CaO in the high calcium oxide metallurgical slag is ⁇ 30%, which is directly obtained from the metallurgical furnace, and the slag temperature is ⁇ 1100 °C;
- the chemical composition of the molten slag in the molten state is regulated, so that the molten slag in the molten state satisfies the following two conditions at the same time:
- the lower layer of molten iron is directly used as the raw material for steelmaking, and after steelmaking, the obtained molten steel slag is directly returned to step 1 to enter the melting reactor;
- the alkaline flux is one or both of limestone and lime.
- the high calcium oxide metallurgical slag is one or more of molten steel slag, blast furnace slag, ferromanganese smelting slag, and magnesium smelting slag.
- the melting reactor is one of an electric furnace, a submerged arc furnace, an electric arc furnace, a short blast furnace, an induction furnace, a smelting reduction furnace, a thermal insulation slag bag, and a thermal insulation pit, and the smelting reduction temperature is 1400 °C. ⁇ 1650°C.
- the bauxite is bauxite, high iron bauxite (mass percentage content of all Fe>20%), pre-reduced iron-containing bauxite pellets, fly ash, coal gasification.
- slag coal gangue, nepheline, alum, clay, kaolinite, bauxite, feldspar, shale, and red mud.
- the bauxite When the bauxite contains crystal water, it needs to be dried and dehydrated in advance, and the drying temperature is less than 600°C.
- bauxite is powdery or spherical, and is directly added or sprayed into the reaction slag, and the gas for spraying bauxite is preferably nitrogen and/or oxidizing gas; the oxidizing gas is air, oxygen-enriched air One or more of , oxygen and CO 2 .
- the reducing agent is one or more of anthracite, bituminous coal, lignite, pulverized coal, natural gas, coalbed methane, and coal gas, and the solid reducing agent in the reducing agent is directly added or added by injection
- the gas for spraying the solid reducing agent is preferably nitrogen and/or oxidizing gas; the oxidizing gas is one or more of air, oxygen-enriched air, oxygen, and CO 2 .
- the oxidizing gas is one or more of air, oxygen-enriched air, oxygen, and CO 2 .
- the slag bath smelting reduction process is: the process of reducing iron oxides in the raw material to iron, and the reduction rate of iron oxides to metallic iron is ⁇ 90%.
- the chromium, vanadium and niobium in the raw materials all enter the molten iron; the phosphorus component enters the calcium aluminate slag and soot, and the soot is the flue gas generated by the smelting reduction of the slag.
- the molten iron is one of ordinary molten iron, vanadium-containing molten iron, niobium-containing molten iron, and vanadium-chromium-containing molten iron.
- step 3 when the lower layer of molten iron is vanadium-containing molten iron, niobium-containing molten iron, and vanadium-chromium-containing molten iron, first, after vanadium-chromium-niobium steelmaking is carried out, semi-steel and slag are obtained, and the slag is vanadium slag, niobium slag, vanadium slag, vanadium slag, vanadium slag, vanadium slag, vanadium slag.
- the chromium slag the molten steel slag obtained after semi-steel steelmaking is directly returned to step 1 into the melting reactor.
- the leaching residue is used as the raw material for cement production.
- the cooling method of the upper layer calcium aluminate slag is natural air cooling or cooling with the furnace.
- the Na 2 CO 3 solution is preferably a solution with a mass concentration of 70 to 110 g/L, and the leaching temperature is 70 to 110° C.
- the Na 2 CO 3 solution: self-pulverizing calcium aluminate Slag (3 ⁇ 11)mL: 1g, the leaching time is 90 ⁇ 120min.
- the basic principle of a method for producing alumina by utilizing slag metallurgy technology of the present invention is:
- the slag bath smelting reduction technology has the characteristics of reducing production energy consumption, reducing the consumption of flux CaO, eliminating the production of red mud, meeting the raw material requirements of different bauxite, low production cost and environmental friendliness, etc.
- Aluminum technology has vitality and promotion value;
- the SiO contained in it will react with NaOH and consume NaOH, and the present invention adopts the ultra-high basicity by utilizing the high content of CaO in the high-calcium oxide metallurgical slag.
- the dicalcium silicate slag forming technology realizes high calcium oxide metallurgical slag High value-added utilization.
- a method for producing alumina by utilizing slag metallurgy technology of the present invention has the following beneficial effects:
- the raw materials have strong adaptability, not only can process bauxite with high, medium and low ratio of aluminum to silicon, but also can process aluminum such as high iron bauxite, fly ash, coal gangue, nepheline, clay, kaolin, red mud, etc. mineral resources;
- the valuable components such as iron, chromium, vanadium, phosphorus, niobium, CaO, Al 2 O 3 , SiO 2 in the metallurgical slag containing aluminum-containing minerals and high calcium oxide are recovered to realize the metallurgical melting of aluminum-containing minerals and high calcium oxide. Efficient and high-value utilization of slag, and can also process red mud;
- (9) is a new alumina production method, and also an iron-making method
- FIG. 1 is a schematic process flow diagram of a method for producing alumina by utilizing slag metallurgy technology according to the present invention.
- FIG. 1 A method for producing alumina by utilizing slag metallurgy technology is shown in Fig. 1 for its schematic flow diagram, and specifically includes the following steps:
- Step 1 The ferromanganese smelting slag is used as the reaction slag, and the dried and dehydrated high-grade bauxite (A/S>6), pulverized coal and limestone are added to the submerged arc furnace, and the molten state is maintained.
- Carbon dioxide is sprayed into the molten slag to carry out slag bath melting reduction
- the dry and dehydrated high-grade bauxite and pulverized coal are injected into the submerged arc furnace by carbon dioxide injection;
- Step 2 After the slag bath is smelted and reduced, the slag and iron are separated to obtain the lower layer of vanadium-containing molten iron and the upper layer of calcium aluminate slag;
- Step 3 The vanadium-containing molten iron in the lower layer is used as the raw material for vanadium extraction and steelmaking to obtain vanadium slag and semi-steel. After semi-steel steelmaking, molten steel slag is obtained, and the molten steel slag is directly returned to the submerged arc furnace in step 1 as reaction slag. ;
- the leaching condition is that the mass concentration of Na 2 CO 3 is 70 g/L, and the leaching condition is as follows: The temperature is 110°C, according to the liquid-
- the recovery rates of CaO, Al 2 O 3 , SiO 2 , iron and vanadium components in ferromanganese smelting slag and high-grade bauxite are 95%, 86%, 93%, 95% and 80%, respectively. %.
- a method for producing alumina by utilizing slag metallurgy technology comprising the following steps:
- the oxygen-enriched air is sprayed into the molten slag, and the slag bath is melted and reduced;
- Step 2 After the slag bath is smelted and reduced, the slag and iron are separated, and the chromium and vanadium in the raw materials enter the lower layer to obtain the lower layer of vanadium-containing chromium molten iron and the upper layer of calcium aluminate slag; the phosphorus component enters the calcium aluminate slag and soot, and the soot is Flue gas produced by slag smelting reduction.
- Step 3 The lower layer of vanadium-chromium-containing molten iron is used as the raw material for vanadium extraction and steelmaking to obtain vanadium-chromium slag and semi-steel. After the semi-steel is made, molten steel slag is obtained, and the molten steel slag is directly returned to the electric furnace in step 1 and used as a reaction molten steel. slag;
- the recovery rates of CaO, Al 2 O 3 , SiO 2 , iron, chromium, and vanadium components in magnesium smelting slag and high iron bauxite are 96%, 88%, 94%, 96%, and 81%, respectively. with 83%.
- a method for producing alumina by utilizing slag metallurgy technology comprising the following steps:
- Step 2 After the slag bath is melted and reduced, the slag and iron are separated, and the niobium in the raw material enters the lower layer to obtain the lower layer of niobium-containing molten iron and the upper layer of calcium aluminate slag, and the phosphorus component enters the calcium aluminate slag and soot respectively;
- Step 3 The niobium-containing molten iron in the lower layer is used as the raw material for niobium steelmaking to obtain niobium slag and semi-steel. After semi-steel steelmaking, molten steel slag is obtained, and the molten steel slag is directly returned to the smelting reduction furnace in step 1 as reaction slag. ;
- the leaching condition is that the mass concentration of Na 2 CO 3 is 80 g/L, and the leaching temperature is 90 °C, according to the liquid-solid ratio, Na 2 CO 3 solution: self-pulverizing calcium aluminate
- the recovery rates of the components of CaO, Al 2 O 3 , SiO 2 , iron and niobium in the converter molten steel slag and blast furnace slag, low-grade bauxite and high-grade bauxite are 94%, 86%, 93%, 97% and 82%.
- a method for producing alumina by utilizing slag metallurgy technology comprising the following steps:
- Step 1 The converter molten steel slag is used as the reaction slag, and the dried and dehydrated low-grade bauxite (A/S ⁇ 6), high-grade bauxite (A/S>6), lime and lignite are added to the thermal insulation slag.
- Hot air is blown into the molten slag to perform slag bath melting reduction.
- Step 2 after the slag bath is smelted and reduced, the slag and iron are separated to obtain the lower layer of vanadium-containing molten iron and the upper layer of calcium aluminate slag phase;
- Step 3 The lower layer of vanadium-containing molten iron is used as the raw material for vanadium extraction and steelmaking to obtain vanadium slag and semi-steel. After semi-steel steelmaking, molten steel slag is obtained. slag;
- the leaching condition is that the mass concentration of Na 2 CO 3 is 100 g/L, and the leaching temperature is 110 °C, according to the liquid-solid ratio, Na 2 CO 3 solution: self-pulverizing calcium aluminate
- the recovery rates of CaO, Al 2 O 3 , SiO 2 , iron, and vanadium components in the converter molten steel slag and bauxite are 97%, 90%, 95%, 94%, and 85%, respectively.
- a method for producing alumina by utilizing slag metallurgy technology comprising the following steps:
- Step 1 The electric furnace molten steel slag is used as the reaction slag, and the dried and dehydrated high iron bauxite (total Fe>20%), fly ash, lime and lignite are added to the electric arc furnace, and the pre-reduced iron-bearing bauxite is added.
- Hot air is sprayed into the molten slag to carry out slag bath melting reduction
- Step 2 after the slag bath is smelted and reduced, the slag and iron are separated, and the vanadium in the raw material enters the lower layer of molten iron to obtain the lower layer of vanadium-containing molten iron and the upper layer of calcium aluminate slag;
- Step 3 The lower layer of vanadium-containing molten iron is used as the raw material for vanadium extraction and steelmaking to obtain vanadium slag and semi-steel. After the semi-steel is made, molten steel slag is obtained, and the molten steel slag is directly returned to the electric arc furnace in step 1 and used as reaction slag ;
- the recovery rates of CaO, Al 2 O 3 , SiO 2 , iron and vanadium components in the electric furnace molten steel slag, high-speed iron bauxite and fly ash are 95%, 91%, 95%, 95% and 86%. %.
- a method for producing alumina by utilizing slag metallurgy technology comprising the following steps:
- Step 2 After the slag bath is melted and reduced, the slag and iron are separated to obtain the lower layer of vanadium-containing molten iron and the upper layer of calcium aluminate slag;
- Step 3 vanadium-containing molten iron is used as a raw material for vanadium extraction and steelmaking to obtain vanadium slag and semi-steel, and after semi-steel steelmaking, molten steel slag is obtained, and the molten steel slag is directly returned to the short blast furnace in step 1 as reaction slag;
- Step 4 After the calcium aluminate slag is air-cooled to room temperature, the self-pulverized calcium aluminate slag is obtained, and the self-pulverized calcium aluminate slag is obtained (the leaching conditions are: the mass concentration of Na 2 CO 3 is 110 g/L, and the leaching temperature is 110° C.
- the recovery rates of the components of electric furnace molten steel slag, high - speed iron bauxite (total Fe> 20 %), and coal gangue are 94%, 86%, 93%, 93% and 83%.
- a method for producing alumina by utilizing slag metallurgy technology comprising the following steps:
- Step 1 The molten steel slag of the electric furnace is used as the reaction slag, and the dried and dehydrated high-speed iron bauxite (total Fe>20%), coal gangue and lime are added to the smelting reduction furnace, and the molten state is maintained.
- Step 2 after the slag bath is smelted and reduced, the slag and iron are separated to obtain the lower layer of vanadium-containing molten iron and the upper layer of calcium aluminate slag phase;
- Step 3 vanadium-containing molten iron is used as a raw material for vanadium-smelting steelmaking, to obtain vanadium slag and semi-steel, and after semi-steel steelmaking, molten steel slag is obtained, and the molten steel slag is directly returned to the melting reduction furnace in step 1 as reaction slag;
- the recovery rates of CaO, Al 2 O 3 , SiO 2 , iron, chromium, vanadium, and niobium components in electric furnace molten steel slag, high-speed iron bauxite, and coal gangue are 97%, 94%, 96%, and 96%, respectively. 97% and 85%.
- a method for producing alumina by utilizing slag metallurgy technology comprising the following steps:
- Step 1 The converter molten steel slag is used as the reaction slag, and the dried and dehydrated clay, kaolin, bauxite, feldspar, and lime are added to the thermal insulation slag bag, and the molten state is maintained.
- Step 2 after the slag bath is melted and reduced, the slag and iron are separated to obtain the lower layer of molten iron and the upper layer of calcium aluminate slag phase;
- Step 3 molten iron is used as a raw material for steelmaking to obtain molten steel slag, and the molten steel slag is directly returned to the thermal insulation slag bag in step 1 as reaction slag;
- the recovery rates of CaO, Al 2 O 3 , SiO 2 and iron components in converter molten steel slag, clay, kaolin, bauxite and feldspar are 97%, 92%, 96% and 97%.
- a method for producing alumina by utilizing slag metallurgy technology comprising the following steps:
- Step 2 after the slag bath is smelted and reduced, the slag and iron are separated to obtain the lower layer of vanadium-containing molten iron and the upper layer of calcium aluminate slag phase;
- Step 3 Vanadium-containing molten iron is used as the raw material for vanadium steelmaking to obtain vanadium slag and semi-steel. After the semi-steel is made, molten steel slag is obtained. slag;
- the leaching conditions are: the Na 2 CO 3 mass concentration is 80 g/L, and the leaching temperature is 80 °C, according to the liquid-solid ratio, Na 2 CO 3 solution: self-pulverizing calcium aluminate s
- the recovery rates of CaO, Al 2 O 3 , SiO 2 , iron and vanadium components in converter molten steel slag, high-grade bauxite, nepheline and alum are 96%, 88%, 95%, 94%, respectively. % and 82%.
- a method for producing alumina by utilizing slag metallurgy technology comprising the following steps:
- Step 2 after the slag bath is melted and reduced, the slag and iron are separated to obtain the lower layer of vanadium-chromium molten iron and the upper layer of calcium aluminate slag phase;
- Step 3 Vanadium-chromium molten iron is used as the raw material for vanadium-chromium steelmaking to obtain vanadium-chromium slag and semi-steel. After the semi-steel is made, molten steel slag is obtained, and the molten steel slag is directly returned to the induction furnace in step 1 as a reaction slag;
- Step 4 After the calcium aluminate slag is air-cooled to room temperature, the self-pulverized calcium aluminate slag is obtained, and the self-pulverized calcium aluminate slag is obtained (the leaching conditions are: the mass concentration of Na 2 CO 3 is 100 g/L, and the leaching temperature is 90° C.
- the recovery rates of the components of CaO, Al 2 O 3 , SiO 2 , iron, chromium, and vanadium in the converter molten steel slag and high-grade bauxite are 96%, 80%, 96%, 95%, 82%, respectively. % and 81%.
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Abstract
A method for producing aluminum oxide using a slag metallurgy technology, relating to the field of comprehensive utilization of aluminum-containing mineral resources, slag metallurgy, and aluminum oxide production. The method comprises: adding the high-calcium oxide metallurgical slag, aluminum ore, a reducing agent, and a component to a melt reactor, maintaining a molten state, and compounding, in the slag, the following relations being satisfied: the molar ratio of CaO to Al2O3 being greater than 1.6; the mass ratio of CaO to SiO2 being 3.0-5.0; blowing an oxidizing gas, and performing slag bath melt reduction; after reduction, performing slag-iron separation to obtain a liquid iron at the lower layer, performing steelmaking on same to obtain the molten steel slag, and returning same to the melt reactor; and cooling the calcium aluminate slag at the upper layer, adding a Na2CO3 solution, introducing CO2 to obtain Al(OH)3, and calcining same to obtain aluminum oxide. The method has the characteristics of strong raw material adaptability, low energy consumption, small flux CaO consumption, multi-component recovery, no solid waste discharge, short process, low cost, environmental friendliness, etc., and realizes recovery and production of aluminum components in the high-calcium oxide metallurgical slag and the aluminum ore.
Description
本发明属于含铝矿物资源综合利用、熔渣冶金与氧化铝生产的技术领域，具体涉及一种利用熔渣冶金技术生产氧化铝的方法。 The invention belongs to the technical fields of comprehensive utilization of aluminum-containing mineral resources, slag metallurgy and alumina production, and particularly relates to a method for producing alumina by utilizing slag metallurgy technology.
中国是氧化铝产量最多的国家，也是铝土矿进口最多的国家。氧化铝工业生产上主要采用拜尔法、拜尔-烧结法等工艺，现有工艺存在如下缺点：China is the country with the largest alumina production and the largest importer of bauxite. In the industrial production of alumina, the Bayer process, the Bayer-sintering process and other processes are mainly used. The existing processes have the following disadvantages:
(1)原料适应性差。原料为高品位铝土矿(铝硅比>7)，无法利用低品位铝土矿、高铁铝土矿、粉煤灰、煤矸石、霞石、明矾、粘土、高岭土等铝矿资源；(1) Poor adaptability of raw materials. The raw material is high-grade bauxite (aluminum-silicon ratio>7), and it is impossible to utilize low-grade bauxite, high iron bauxite, fly ash, coal gangue, nepheline, alum, clay, kaolin and other bauxite resources;
(2)产生大量赤泥，无法利用。每生产l吨氧化铝就会产生0.7～1.8吨赤泥，全世界每年产生约1.2亿吨。赤泥中含有钠、放射性元素等有害组分，难以利用，已堆积上亿吨；(2) A large amount of red mud is produced and cannot be used. For every 1 ton of alumina produced, 0.7 to 1.8 tons of red mud is produced, and the world produces about 120 million tons every year. Red mud contains harmful components such as sodium and radioactive elements, which are difficult to utilize, and hundreds of millions of tons have been accumulated;
(3)无法实现铝土矿资源中铁、铬、钒、锰、磷等有价组分的回收；(3) The recovery of valuable components such as iron, chromium, vanadium, manganese, and phosphorus in bauxite resources cannot be realized;
(4)存在生产工艺复杂、设备投资大、占地面积大、投资大、成本高、污染大等缺点。(4) There are disadvantages such as complex production process, large equipment investment, large area, large investment, high cost, and large pollution.
针对上述存在问题，国内对氧化铝生产新技术进行了大量研究，研究内容如下：In view of the above existing problems, a lot of research on new technologies for alumina production has been carried out in China. The research contents are as follows:
(1)酸法处理技术，酸耗高、腐蚀严重、设备复杂、环境污染大等；(1) Acid treatment technology, high acid consumption, serious corrosion, complex equipment, and large environmental pollution;
(2)酸法-碱法技术，酸耗高、成本高、流程长、环境污染大等；(2) The acid method-alkali method has high acid consumption, high cost, long process, and large environmental pollution;
(3)反浮选脱硅技术，占地面积大、污染大、无法消除赤泥与回收铁、钒等组分等；(3) Reverse flotation desiliconization technology, which covers a large area, pollutes a lot, cannot eliminate red mud and recover iron, vanadium and other components;
(4)磁选技术，占地面积大、铁组分收率低、无法消除赤泥与回收铬、钒有价组分等；(4) Magnetic separation technology, which covers a large area, has a low yield of iron components, cannot eliminate red mud and recover valuable components such as chromium and vanadium;
(5)悬磁焙烧技术(CN2017105886247.7，CN201710588620.5)，铁组分收率高，仅适于高铁铝土矿，成本高、流程长，无法消除赤泥与回收铬、钒有价组分等；(5) Suspended magnetic roasting technology (CN2017105886247.7, CN201710588620.5), high yield of iron components, only suitable for high-iron bauxite, high cost, long process, unable to eliminate red mud and recover chromium and vanadium valuable components grading;
(6)预还原-磁选技术(CN201911159643.X)，适于高铁铝土矿、磁选效果差、技术难度大、能耗高、炉窑寿命短、设备投资大、流程长、成本高、流程长，无法消除赤泥；(6) Pre-reduction-magnetic separation technology (CN201911159643.X), suitable for high-speed iron bauxite, poor magnetic separation effect, high technical difficulty, high energy consumption, short furnace life, large equipment investment, long process, high cost, The process is long and the red mud cannot be eliminated;
(7)直接还原-熔分技术(CN201510531320.4，CN201510530645.0，CN201810593292.2，CN201910888430.4，CN201910909622.9)，存在仅适于高铁铝土矿、还原温度高、能耗高、CaO熔剂消耗大、成本高、设备复杂、难以连续进行等缺点；(7) Direct reduction-melting separation technology (CN201510531320.4, CN201510530645.0, CN201810593292.2, CN201910888430.4, CN201910909622.9), there are only suitable for high iron bauxite, high reduction temperature, high energy consumption, CaO flux Disadvantages such as large consumption, high cost, complex equipment, and difficulty in continuous operation;
(8)高炉炼铁技术(CN201410048304.5)，回收率高，存在仅适于高铁铝土矿、能耗高、流程长、投资大、CaO熔剂消耗大、成本高、环境污染大等缺点，国家限制工艺。(8) Blast furnace ironmaking technology (CN201410048304.5), high recovery rate, has disadvantages such as only suitable for high iron bauxite, high energy consumption, long process, large investment, large consumption of CaO flux, high cost, large environmental pollution, etc. State restricted craftsmanship.
上述研究无法解决现有工艺存在的等问题，必须开发满足如下要求的新技术：The above research cannot solve the problems existing in the existing process, and new technologies that meet the following requirements must be developed:
(1)原料适应性强，不仅可处理高铝硅比的铝土矿，还可以处理低铝硅比的铝土矿、高铁铝土矿、多金属共生矿、高铝粉煤灰、高铝煤矸石及霞石等铝矿资源；(1) The raw materials have strong adaptability, not only can process bauxite with high aluminum-silicon ratio, but also bauxite with low aluminum-silicon ratio, high-iron bauxite, polymetallic symbiotic ore, high-aluminum fly ash, high-alumina Aluminum ore resources such as coal gangue and nepheline;
(2)无固体废弃物(赤泥等)排放，尾渣、尾矿或赤泥可直接利用，制备高附加值产品，环境友好，整个工艺过程可循环，具有绿色、清洁、高效的特点；(2) No solid waste (red mud, etc.) is discharged, tailings, tailings or red mud can be directly used to prepare high value-added products, which are environmentally friendly, the whole process can be recycled, and has the characteristics of green, clean and efficient;
(3)可同时回收铁、铬、钒、磷、铌、CaO、SiO
2等有价组分，收益高；
( 3 ) Valuable components such as iron, chromium, vanadium, phosphorus, niobium, CaO, SiO can be recovered at the same time, and the income is high;
(4)工艺技术简单、熔剂消耗小、能耗小、投资小、流程短、成本低、环境友好；(4) The process technology is simple, the flux consumption is small, the energy consumption is small, the investment is small, the process is short, the cost is low, and the environment is friendly;
(5)整个工艺过程应实现经济、技术与环境三者的统一。(5) The whole process should realize the unification of economy, technology and environment.
中国专利(CN201611133558.2，CN201611133559.7，CN201610566347.7，CN201610570916.X)提出了钢铁混合熔渣熔融还原炼铁技术，处理含铁物料，获得铁水与硅酸盐熔渣(硅酸盐熔渣，中低碱度熔渣(CaO/SiO
2<2.5)，以硅酸钙、黄长石等矿相为主)，是一种新的炼铁方法，铁水是主产品，熔渣是副产品，水淬后，作为水泥原料，存在附加值低等问题。
Chinese patents (CN201611133558.2, CN201611133559.7, CN201610566347.7, CN201610570916.X) propose iron and steel mixed slag melting reduction ironmaking technology, processing iron-containing materials, and obtaining molten iron and silicate slag (silicate slag) , medium and low basicity slag (CaO/SiO 2 <2.5), mainly calcium silicate, yellow feldspar and other mineral phases), is a new ironmaking method, molten iron is the main product, slag is a by-product, water quenching Later, as a cement raw material, there are problems such as low added value.
锰铁冶炼与镁冶炼熔渣分别产生于锰铁冶炼铁合金工艺与金属镁冶炼工艺。锰铁冶炼熔渣、镁冶炼渣、熔融钢渣及高炉熔渣都属于高氧化钙熔渣体系，含有大量熔融态CaO、Al
2O
3及SiO
2等有价组份，中国每年排放总量达到6亿吨以上，无法处理或附加值低，大量堆积，浪费物理热与资源。
Ferromanganese smelting and magnesium smelting slag are produced in ferromanganese smelting ferroalloy process and metal magnesium smelting process respectively. Ferromanganese smelting slag, magnesium smelting slag, molten steel slag and blast furnace slag belong to the high calcium oxide slag system, which contains a large amount of molten CaO, Al 2 O 3 and SiO 2 and other valuable components. More than 600 million tons, cannot be processed or have low added value, and accumulate in large quantities, wasting physical heat and resources.
针对现有技术中生产氧化铝的问题，本发明提供了一种利用熔渣冶金技术生产氧化铝的方法，具体方法包括：将铝矿、碱性熔剂、还原剂，或铝矿与还原剂，加入到高氧化钙冶金熔渣中，渣浴熔融还原，渣-金分离后，主产品为铝酸钙熔渣，副产品为铁水或含钒铁水或含钒铬铁水。铝酸钙熔渣冷却自粉化后，通过浸出-煅烧工艺，获得氧化铝，浸出渣作为水泥生产的原料。In view of the problem of producing alumina in the prior art, the present invention provides a method for producing alumina by utilizing slag metallurgy technology, the specific method comprising: mixing bauxite, alkaline flux, reducing agent, or bauxite and reducing agent, The main product is calcium aluminate slag, and the by-product is molten iron or vanadium-containing molten iron or vanadium-chromium-containing molten iron. After the calcium aluminate slag is cooled and self-pulverized, alumina is obtained through a leaching-calcining process, and the leaching slag is used as a raw material for cement production.
本发明利用高氧化钙冶金熔渣(熔融钢渣、高炉熔渣、锰铁冶炼熔渣与镁冶炼渣)高物理热与化学活性，渣浴熔融还原处理铝矿，获得铝酸钙熔渣(铝酸盐熔渣，超高碱度熔渣(CaO/SiO
2≥3)，以七铝十二钙、铝酸钙等矿相为主)与含钒铁水，自粉化铝酸钙炉渣经湿法冶金技术生产氧化铝，铝酸钙熔渣与氧化铝是主产品，副产品为铁水。其具有原料适应性强、能耗低、熔剂CaO消耗小、多组分回收、无固废排放、流程短、成本低及环境友好等特点，是一种新的氧化铝生产方法，实现高氧化钙冶金熔渣与铝矿中铝组分的回收与生产。
The invention utilizes the high physical heat and chemical activity of high calcium oxide metallurgical slag (melting steel slag, blast furnace slag, ferromanganese smelting slag and magnesium smelting slag), slag bath melting reduction treatment of aluminum ore, and obtains calcium aluminate slag (aluminum smelting slag). Acid slag, ultra-high basicity slag (CaO/SiO 2 ≥3), mainly composed of ore phases such as hepta-alumina, calcium aluminate, etc.) and vanadium-containing molten iron, self-pulverized calcium aluminate slag after wet Alumina is produced by the method of metallurgical technology. Calcium aluminate slag and alumina are the main products, and the by-product is molten iron. It has the characteristics of strong adaptability of raw materials, low energy consumption, low consumption of flux CaO, multi-component recovery, no solid waste discharge, short process, low cost and environmental friendliness. It is a new alumina production method, which can achieve high oxidation Recovery and production of aluminium components in calcium metallurgical slag and bauxite.
为了实现上述目的，本发明采用的技术方案如下：In order to achieve the above object, the technical scheme adopted in the present invention is as follows:
本发明的一种利用熔渣冶金技术生产氧化铝的方法，包括以下步骤；A method for producing alumina by utilizing slag metallurgy technology of the present invention comprises the following steps;
步骤1：step 1:
将高氧化钙冶金熔渣，加入熔融反应器中，形成反应熔渣；所述的高氧化钙冶金熔渣中CaO的质量百分含量≥30%，由冶金炉直接获得，熔渣温度≥1100℃；The high calcium oxide metallurgical slag is added to the melting reactor to form reaction slag; the mass percentage of CaO in the high calcium oxide metallurgical slag is ≥30%, which is directly obtained from the metallurgical furnace, and the slag temperature is ≥1100 °C;
将铝矿和还原剂，加入反应熔渣中，保持熔融状态，得到熔融状态的熔渣；其中，所述铝矿中氧化铝的质量百分含量≥10%；Adding bauxite and a reducing agent into the reaction slag, maintaining a molten state to obtain molten slag; wherein, the mass percentage of alumina in the bauxite is ≥10%;
其中，通过调节各个原料的加入量，调控熔融状态的熔渣化学组成，使得熔融状态的熔渣同时满足以下两个条件：Wherein, by adjusting the addition amount of each raw material, the chemical composition of the molten slag in the molten state is regulated, so that the molten slag in the molten state satisfies the following two conditions at the same time:
(a)熔融状态的熔渣中，按摩尔比，CaO：Al
2O
3>1.6；
(a) In the molten slag, in molar ratio, CaO:Al 2 O 3 >1.6;
(b)熔融状态的熔渣中，按质量比，CaO：SiO
2=3.0~5.0；
(b) In the molten slag, according to the mass ratio, CaO:SiO 2 =3.0~5.0;
向熔融状态的熔渣中喷吹氧化性气体、或氧化性气体和氮气混合气，进行渣浴熔融还原；Spray oxidizing gas, or a mixture of oxidizing gas and nitrogen into molten slag, to perform slag bath melting reduction;
步骤2：Step 2:
渣浴熔融还原后，渣铁分离，得到下层铁水，上层铝酸钙熔渣；After the slag bath is melted and reduced, the slag and iron are separated to obtain the lower layer of molten iron and the upper layer of calcium aluminate slag;
步骤3：Step 3:
下层铁水直接作为炼钢原料，炼钢后，得到的熔融钢渣，直接返回步骤1进入熔融反应器中；The lower layer of molten iron is directly used as the raw material for steelmaking, and after steelmaking, the obtained molten steel slag is directly returned to step 1 to enter the melting reactor;
步骤4：Step 4:
上层铝酸钙熔渣冷却后，得到自粉化铝酸钙炉渣；自粉化铝酸钙炉渣加入Na
2CO
3溶液浸出，得到铝酸钠溶液和浸出残渣；
After the upper layer of calcium aluminate slag is cooled, self-pulverized calcium aluminate slag is obtained; the self-pulverized calcium aluminate slag is added with Na 2 CO 3 solution for leaching to obtain sodium aluminate solution and leaching residue;
向铝酸钠溶液中，通入CO
2，得到Al(OH)
3，Al(OH)
3煅烧，得到氧化铝。
In the sodium aluminate solution, CO 2 is passed through to obtain Al(OH) 3 , and Al(OH) 3 is calcined to obtain alumina.
所述的步骤1中，进一步的，在反应熔渣中，当调节各个原料的加入量，熔融状态的熔渣不能同时满足以下两个条件：(a)熔融状态的熔渣中，按摩尔比，CaO：Al
2O
3>1.6；(b)熔融状态的熔渣中，按质量比，CaO：SiO
2=3.0~5.0，还可以加入碱性熔剂进行调节。
In the described step 1, further, in the reaction slag, when adjusting the addition amount of each raw material, the molten slag in the molten state cannot satisfy the following two conditions at the same time: (a) in the molten slag in the molten state, the molar ratio , CaO: Al 2 O 3 >1.6; (b) In the molten slag, by mass ratio, CaO: SiO 2 =3.0~5.0, and alkaline flux can also be added to adjust.
作为优选，碱性熔剂为石灰石、石灰中的一种或两种。Preferably, the alkaline flux is one or both of limestone and lime.
所述的步骤1中，作为优选，所述的高氧化钙冶金熔渣为熔融钢渣、高炉熔渣、锰铁冶炼熔渣、镁冶炼渣中的一种或几种。In the step 1, preferably, the high calcium oxide metallurgical slag is one or more of molten steel slag, blast furnace slag, ferromanganese smelting slag, and magnesium smelting slag.
所述的步骤1中，作为优选，熔融反应器为电炉、矿热炉、电弧炉、矮高炉、感应炉、熔融还原炉、保温渣包、保温地坑中的一种，熔融还原温度为1400~1650℃。In the described step 1, preferably, the melting reactor is one of an electric furnace, a submerged arc furnace, an electric arc furnace, a short blast furnace, an induction furnace, a smelting reduction furnace, a thermal insulation slag bag, and a thermal insulation pit, and the smelting reduction temperature is 1400 °C. ~1650℃.
所述的步骤1中，作为优选，铝矿为铝土矿、高铁铝土矿(全Fe的质量百分含量>20%)、预还原含铁铝土矿球团、粉煤灰、煤气化炉渣、煤矸石、霞石、明矾、粘土、高岭石、铝矾土、长石、页岩、赤泥中的一种或几种。In the described step 1, preferably, the bauxite is bauxite, high iron bauxite (mass percentage content of all Fe>20%), pre-reduced iron-containing bauxite pellets, fly ash, coal gasification. One or more of slag, coal gangue, nepheline, alum, clay, kaolinite, bauxite, feldspar, shale, and red mud.
所述的铝矿，当含有结晶水时，需要提前进行干燥脱水处理，干燥温度<600℃。When the bauxite contains crystal water, it needs to be dried and dehydrated in advance, and the drying temperature is less than 600°C.
所述的铝矿为粉末状或球状，直接加入或喷吹入反应熔渣中，喷吹铝矿的气体优选为氮气和/或氧化性气体；所述的氧化性气体为空气、富氧空气、氧气、CO
2中的一种或几种。
Described bauxite is powdery or spherical, and is directly added or sprayed into the reaction slag, and the gas for spraying bauxite is preferably nitrogen and/or oxidizing gas; the oxidizing gas is air, oxygen-enriched air One or more of , oxygen and CO 2 .
所述的步骤1中，作为优选，还原剂为无烟煤、烟煤、褐煤、粉煤、天然气、煤层气、煤气中的一种或几种，还原剂中的固态还原剂直接加入或喷吹加入，喷吹固态还原剂的气体优选为氮气和/或氧化性气体；所述的氧化性气体为空气、富氧空气、氧气、CO
2中的一种或几种。
In the described step 1, preferably, the reducing agent is one or more of anthracite, bituminous coal, lignite, pulverized coal, natural gas, coalbed methane, and coal gas, and the solid reducing agent in the reducing agent is directly added or added by injection, The gas for spraying the solid reducing agent is preferably nitrogen and/or oxidizing gas; the oxidizing gas is one or more of air, oxygen-enriched air, oxygen, and CO 2 .
所述的步骤1中，作为优选，所述的氧化性气体为空气、富氧空气、氧气、CO
2中的一种或几种。
In the step 1, preferably, the oxidizing gas is one or more of air, oxygen-enriched air, oxygen, and CO 2 .
所述的步骤1中，渣浴熔融还原过程为：将原料中铁的氧化物还原成铁的过程，铁氧化物还原为金属铁的还原率≥90%。In the step 1, the slag bath smelting reduction process is: the process of reducing iron oxides in the raw material to iron, and the reduction rate of iron oxides to metallic iron is ≥90%.
所述的步骤2中，进一步的，原料中的铬、钒、铌均进入铁水；磷组分进入铝酸钙熔渣和烟灰，所述的烟灰为熔渣熔融还原产生的烟气。In the step 2, further, the chromium, vanadium and niobium in the raw materials all enter the molten iron; the phosphorus component enters the calcium aluminate slag and soot, and the soot is the flue gas generated by the smelting reduction of the slag.
所述的步骤2中，铁水为普通铁水、含钒铁水、含铌铁水、含钒铬铁水中的一种。In the step 2, the molten iron is one of ordinary molten iron, vanadium-containing molten iron, niobium-containing molten iron, and vanadium-chromium-containing molten iron.
所述的步骤3中，当下层铁水为含钒铁水、含铌铁水、含钒铬铁水时，先经过提钒铬铌炼钢后，得到半钢和渣，渣为钒渣、铌渣、钒铬渣中的一种，半钢炼钢后，得到的熔融钢渣，直接返回步骤1进入熔融反应器中。In the step 3, when the lower layer of molten iron is vanadium-containing molten iron, niobium-containing molten iron, and vanadium-chromium-containing molten iron, first, after vanadium-chromium-niobium steelmaking is carried out, semi-steel and slag are obtained, and the slag is vanadium slag, niobium slag, vanadium slag, vanadium slag, vanadium slag, vanadium slag One of the chromium slag, the molten steel slag obtained after semi-steel steelmaking is directly returned to step 1 into the melting reactor.
所述的步骤4中，进一步的，浸出残渣作为水泥生产的原料。In the step 4, further, the leaching residue is used as the raw material for cement production.
所述的步骤4中，作为优选，上层铝酸钙熔渣冷却方式为自然空冷或随炉冷却。In the step 4, preferably, the cooling method of the upper layer calcium aluminate slag is natural air cooling or cooling with the furnace.
所述的步骤4中，Na
2CO
3溶液优选为质量浓度为70~110g/L的溶液，浸出温度为70~110℃，按液固比，Na
2CO
3溶液：自粉化铝酸钙炉渣=(3~11)mL：1g，浸出时间为90~120min。
In the described step 4, the Na 2 CO 3 solution is preferably a solution with a mass concentration of 70 to 110 g/L, and the leaching temperature is 70 to 110° C. According to the liquid-solid ratio, the Na 2 CO 3 solution: self-pulverizing calcium aluminate Slag=(3~11)mL: 1g, the leaching time is 90~120min.
本发明的一种利用熔渣冶金技术生产氧化铝的方法的基本原理为：The basic principle of a method for producing alumina by utilizing slag metallurgy technology of the present invention is:
(1)渣浴熔融还原技术，利用高氧化钙冶金熔渣物理热、成熟的熔渣体系(低熔化性温度与低粘度等)及高化学活性(高含量的熔融态CaO等)，反应速度快，消除铁、铬、钒、SiO
2等组分对于含铝物相及浸出过程的影响，实现高氧化钙冶金熔渣与铝矿中CaO、Al
2O
3、SiO
2、铁、铬、钒、铌等组分的高效回收；
(1) Slag bath melting reduction technology, using high calcium oxide metallurgical slag physical heat, mature slag system (low melting temperature and low viscosity, etc.) and high chemical activity (high content of molten CaO, etc.), the reaction speed It can eliminate the influence of iron, chromium, vanadium, SiO 2 and other components on the aluminum-containing phase and the leaching process, and realize the high calcium oxide metallurgical slag and CaO, Al 2 O 3 , SiO 2 , iron, chromium, Efficient recovery of vanadium, niobium and other components;
(2)渣浴熔融还原技术，具有降低生产能耗、减小熔剂CaO消耗、消除赤泥的产生、满足不同铝矿的原料要求、生产成本低及环境友好等特点，使火法冶炼生产氧化铝技术具有生命力及推广价值；(2) The slag bath smelting reduction technology has the characteristics of reducing production energy consumption, reducing the consumption of flux CaO, eliminating the production of red mud, meeting the raw material requirements of different bauxite, low production cost and environmental friendliness, etc. Aluminum technology has vitality and promotion value;
(3)利用二氧化碳或二氧化碳混合气，通过CO
2+C=2CO反应，减少还原剂的消耗，实现碳减排与二氧化碳循环利用，减少NO
x与硫排放，易于收尘，环保、清洁、成本低；
(3) Using carbon dioxide or carbon dioxide mixture, through CO 2 +C=2CO reaction, reduce the consumption of reducing agent, realize carbon emission reduction and carbon dioxide recycling, reduce NO x and sulfur emissions, easy to collect dust, environmental protection, cleanliness, cost Low;
(4)超高碱度还原技术(R=CaO/SiO
2≥3)，消除还原条件下SiO
2组分对于含铝物相成渣及浸出过程的影响；
(4) Ultra-high alkalinity reduction technology (R=CaO/SiO 2 ≥3), to eliminate the influence of SiO 2 components on the slag formation and leaching process of aluminum-containing phases under reducing conditions;
(5)铝酸钙成渣技术，实现含铝物相与脉石物相的分离及铝组分的回收；(5) Calcium aluminate slag-forming technology to achieve separation of aluminum-containing phase and gangue phase and recovery of aluminum components;
(6)在铝土矿进行氧化铝溶出时，其含有的SiO
2将会和NaOH反应，消耗NaOH，而本发明通过利用高氧化钙冶金熔渣中CaO的高含量特点，采用超高碱度还原技术(R=CaO/SiO
2≥3)，使得铝矿中的SiO
2形成硅酸二钙，从而避免与Na
+发生反应，该硅酸二钙成渣技术，实现高氧化钙冶金熔渣高附加值利用。
(6) When the bauxite is dissolved out of alumina, the SiO contained in it will react with NaOH and consume NaOH, and the present invention adopts the ultra-high basicity by utilizing the high content of CaO in the high-calcium oxide metallurgical slag. The reduction technology (R=CaO/SiO 2 ≥3) makes the SiO 2 in the bauxite form dicalcium silicate, thereby avoiding the reaction with Na + . The dicalcium silicate slag forming technology realizes high calcium oxide metallurgical slag High value-added utilization.
本发明的一种利用熔渣冶金技术生产氧化铝的方法，相比于现有技术，其有益效果为：Compared with the prior art, a method for producing alumina by utilizing slag metallurgy technology of the present invention has the following beneficial effects:
(1)原料适应性强，不仅可处理高、中、低铝硅比的铝土矿，还可以处理高铁铝土矿、粉煤灰、煤矸石、霞石、粘土、高岭土、赤泥等铝矿资源；(1) The raw materials have strong adaptability, not only can process bauxite with high, medium and low ratio of aluminum to silicon, but also can process aluminum such as high iron bauxite, fly ash, coal gangue, nepheline, clay, kaolin, red mud, etc. mineral resources;
(2)利用高氧化钙冶金熔渣物理热与高化学活性，形成“(熔融渣+铝矿)→渣浴熔融还原熔炼→(含钒铁水+铝酸钙熔渣)→含钒铁水炼钢→(熔融钢渣+钢水)→(熔融渣+铝矿)”的闭路循环工艺，铝酸钙熔渣与钒渣作为提取氧化铝与五氧化二钒的原料，与传统氧化铝生产相比，能耗、成本、CO
2排放量、熔剂CaO加入量、成本等大幅度减少；
(2) Utilize the physical heat and high chemical activity of high calcium oxide metallurgical slag to form "(molten slag + aluminum ore) → slag bath melting reduction smelting → (vanadium-containing molten iron + calcium aluminate slag) → vanadium-containing molten iron steelmaking →(molten steel slag + molten steel)→(molten slag + aluminum ore)" closed-circuit cycle process, calcium aluminate slag and vanadium slag are used as raw materials for the extraction of alumina and vanadium pentoxide, compared with traditional alumina production, the Consumption, cost, CO 2 emissions, flux CaO addition, cost, etc. are greatly reduced;
(3)利用二氧化碳或二氧化碳混合气，通过CO
2+C=2CO反应，减少还原剂的消耗，实现碳减排与二氧化碳循环利用，减少NO
x与硫排放，易于收尘，环保、清洁、成本低；
(3) Using carbon dioxide or carbon dioxide mixture, through CO 2 +C=2CO reaction, reduce the consumption of reducing agent, realize carbon emission reduction and carbon dioxide recycling, reduce NO x and sulfur emissions, easy to collect dust, environmental protection, cleanliness, cost Low;
(4)高氧化钙冶金熔渣带入了大量熔融态熔剂CaO，整个过程无需或少量加入熔剂CaO，成本大幅度下降，同时熔融态熔剂CaO提供了高化学活性与热量，加快反应速度；(4) High calcium oxide metallurgical slag is brought into a large amount of molten flux CaO, the whole process does not need to add flux CaO or a small amount, the cost is greatly reduced, and the molten flux CaO provides high chemical activity and heat, and accelerates the reaction speed;
(5)无固体废弃物(赤泥等)排放，浸出渣可直接作为水泥，环境友好，整个工艺过程可循环，具有绿色、清洁、高效、成本低的特点；(5) No solid waste (red mud, etc.) is discharged, and the leaching slag can be directly used as cement, which is environmentally friendly, the whole process can be recycled, and has the characteristics of green, clean, high efficiency and low cost;
(6)同时回收含铝矿物与高氧化钙冶金熔渣中铁、铬、钒、磷、铌、CaO、Al
2O
3、SiO
2等有价组分，实现含铝矿物与高氧化钙冶金熔渣高效与高值化利用，还可以处理赤泥；
(6) At the same time, the valuable components such as iron, chromium, vanadium, phosphorus, niobium, CaO, Al 2 O 3 , SiO 2 in the metallurgical slag containing aluminum-containing minerals and high calcium oxide are recovered to realize the metallurgical melting of aluminum-containing minerals and high calcium oxide. Efficient and high-value utilization of slag, and can also process red mud;
(7)利用高氧化钙冶金熔渣物理热资源，整个过程无需加热或少量加热，能耗小；(7) Using the physical heat resources of high calcium oxide metallurgical slag, the whole process does not require heating or a small amount of heating, and the energy consumption is small;
(8)短流程渣浴熔融还原工艺，反应速度快；(8) Short-flow slag bath melting reduction process, the reaction speed is fast;
(9)是新的氧化铝生产方法，也是一种炼铁方法；(9) is a new alumina production method, and also an iron-making method;
(10)工艺技术简单、原料适应性强、冶金熔剂消耗小、收率高、设备简单、投资小、能耗低、连续生产、流程短、成本低、环境友好；(10) The process technology is simple, the raw material adaptability is strong, the metallurgical flux consumption is small, the yield is high, the equipment is simple, the investment is small, the energy consumption is low, continuous production, the process is short, the cost is low, and the environment is friendly;
(11)实现熔渣物理热高效利用、矿物重生、含铝资源高效利用与循环的统一。(11) Realize the unity of efficient utilization of slag physical heat, mineral regeneration, and efficient utilization and recycling of aluminum-containing resources.
图1为本发明的一种利用熔渣冶金技术生产氧化铝的方法的工艺流程示意图。FIG. 1 is a schematic process flow diagram of a method for producing alumina by utilizing slag metallurgy technology according to the present invention.
下面根据本发明的具体实施例，来对本发明进行进一步说明，当然，此实施例仅是本发明的一部分实施例，不代表本发明的全部实施例。The present invention will be further described below according to specific embodiments of the present invention. Of course, this embodiment is only a part of the embodiments of the present invention, and does not represent all the embodiments of the present invention.
实施例1Example 1
一种利用熔渣冶金技术生产氧化铝的方法，其流程示意图见图1，具体包括以下步骤：A method for producing alumina by utilizing slag metallurgy technology is shown in Fig. 1 for its schematic flow diagram, and specifically includes the following steps:
步骤1：将锰铁冶炼熔渣作为反应熔渣，和干燥脱水的高品位铝土矿(A/S>6)、粉煤与石灰石加入到矿热炉内，并保持熔融状态，通过调整各个原料的加入量，使得熔融状态的熔渣同时满足以下两个参数：(a)熔渣中CaO/Al
2O
3(摩尔比)=1.61；(b)CaO/SiO
2(质量比)=5.0；
Step 1: The ferromanganese smelting slag is used as the reaction slag, and the dried and dehydrated high-grade bauxite (A/S>6), pulverized coal and limestone are added to the submerged arc furnace, and the molten state is maintained. The amount of raw materials added makes the molten slag satisfy the following two parameters at the same time: (a) CaO/Al 2 O 3 (molar ratio)=1.61 in the molten slag; (b) CaO/SiO 2 (mass ratio)=5.0 ;
向熔融状态的熔渣中喷吹二氧化碳，进行渣浴熔融还原； Carbon dioxide is sprayed into the molten slag to carry out slag bath melting reduction;
其中，干燥脱水的高品位铝土矿和粉煤均采用二氧化碳喷吹加入矿热炉内；Among them, the dry and dehydrated high-grade bauxite and pulverized coal are injected into the submerged arc furnace by carbon dioxide injection;
步骤2： 渣浴熔融还原后，渣铁分离，得到下层含钒铁水和上层铝酸钙熔渣；Step 2: After the slag bath is smelted and reduced, the slag and iron are separated to obtain the lower layer of vanadium-containing molten iron and the upper layer of calcium aluminate slag;
步骤3： 下层含钒铁水作为提钒炼钢的原料，获得钒渣和半钢，半钢炼钢后得到熔融钢渣，熔融钢渣直接返回加入到步骤1中的矿热炉中，作为反应熔渣；Step 3: The vanadium-containing molten iron in the lower layer is used as the raw material for vanadium extraction and steelmaking to obtain vanadium slag and semi-steel. After semi-steel steelmaking, molten steel slag is obtained, and the molten steel slag is directly returned to the submerged arc furnace in step 1 as reaction slag. ;
步骤4：上层铝酸钙熔渣随炉冷却到室温后，获得自粉化铝酸钙炉渣，自粉化铝酸钙炉渣浸出(浸出条件为Na
2CO
3的质量浓度为70g/L，浸出温度为110℃，按液固比，Na
2CO
3溶液：自粉化铝酸钙炉渣=11mL：1g，浸出时间为120min)，获得铝酸钠溶液，向铝酸钠溶液通入CO
2，获得Al(OH)
3，Al(OH)
3煅烧获得氧化铝，浸出残渣作为水泥生产的原料。
Step 4: after the upper layer calcium aluminate slag is cooled to room temperature with the furnace, obtained from the pulverized calcium aluminate slag, and leached from the pulverized calcium aluminate slag (the leaching condition is that the mass concentration of Na 2 CO 3 is 70 g/L, and the leaching condition is as follows: The temperature is 110°C, according to the liquid-solid ratio, Na 2 CO 3 solution: self-pulverizing calcium aluminate slag = 11 mL: 1 g, leaching time is 120 min) to obtain a sodium aluminate solution, and CO 2 is introduced into the sodium aluminate solution, Al(OH) 3 is obtained, Al(OH) 3 is calcined to obtain alumina, and the leaching residue is used as the raw material for cement production.
本实施例中，锰铁冶炼熔渣与高品位铝土矿中CaO、Al
2O
3、SiO
2、铁、钒组分的回收率分别为95%、86%、93%、95%与80%。
In this embodiment, the recovery rates of CaO, Al 2 O 3 , SiO 2 , iron and vanadium components in ferromanganese smelting slag and high-grade bauxite are 95%, 86%, 93%, 95% and 80%, respectively. %.
实施例2Example 2
一种利用熔渣冶金技术生产氧化铝的方法，包括以下步骤：A method for producing alumina by utilizing slag metallurgy technology, comprising the following steps:
步骤1： 以镁冶炼渣作为反应熔渣，加入到电炉内，用空气向反应熔渣中喷入干燥脱水后的高铁铝土矿(全Fe>20%)、石灰石、石灰与无烟煤，电炉加热保持熔融状态，通过调整各个原料的加入量，使得熔融状态的熔渣同时满足以下两个参数：(a)熔渣中CaO/Al
2O
3(摩尔比)=2.0；(b)CaO/SiO
2(质量比)=4.1；
Step 1: Use magnesium smelting slag as reaction slag, add it into the electric furnace, spray dry and dehydrated high iron bauxite (total Fe>20%), limestone, lime and anthracite into the reaction slag with air, and heat in the electric furnace Maintaining the molten state, by adjusting the amount of each raw material added, the molten slag meets the following two parameters at the same time: (a) CaO/Al 2 O 3 (molar ratio)=2.0 in the molten slag; (b) CaO/SiO 2 (mass ratio)=4.1;
向熔融状态的熔渣中喷吹富氧空气，进行渣浴熔融还原；The oxygen-enriched air is sprayed into the molten slag, and the slag bath is melted and reduced;
步骤2： 渣浴熔融还原后，渣铁分离，原料中的铬、钒进入下层，得到下层含钒铬铁水和上层铝酸钙熔渣；磷组分进入铝酸钙熔渣和烟灰，烟灰为熔渣熔融还原产生的烟气。Step 2: After the slag bath is smelted and reduced, the slag and iron are separated, and the chromium and vanadium in the raw materials enter the lower layer to obtain the lower layer of vanadium-containing chromium molten iron and the upper layer of calcium aluminate slag; the phosphorus component enters the calcium aluminate slag and soot, and the soot is Flue gas produced by slag smelting reduction.
步骤3：下层含钒铬铁水作为提钒炼钢的原料，得到钒铬渣和半钢，半钢炼钢后，得到熔融钢渣，熔融钢渣直接返回加入到步骤1中的电炉中，作为反应熔渣；Step 3: The lower layer of vanadium-chromium-containing molten iron is used as the raw material for vanadium extraction and steelmaking to obtain vanadium-chromium slag and semi-steel. After the semi-steel is made, molten steel slag is obtained, and the molten steel slag is directly returned to the electric furnace in step 1 and used as a reaction molten steel. slag;
步骤4：上层铝酸钙熔渣空冷却到室温后，获得自粉化铝酸钙炉渣，自粉化铝酸钙炉渣浸出(浸出条件为：Na
2CO
3质量浓度为110g/L，浸出温度为70℃，按液固比，Na
2CO
3溶液：自粉化铝酸钙炉渣=3mL：1g，浸出时间为90min)，获得铝酸钠溶液，向铝酸钠溶液通入CO
2，获得Al(OH)
3，Al(OH)
3煅烧获得氧化铝，浸出残渣作为水泥生产的原料。
Step 4: after the upper layer calcium aluminate slag is air-cooled to room temperature, obtained from the pulverized calcium aluminate slag, and leached from the pulverized calcium aluminate slag (leaching conditions are: Na 2 CO 3 mass concentration is 110g/L, leaching temperature at 70°C, according to the liquid-solid ratio, Na 2 CO 3 solution: self-pulverizing calcium aluminate slag = 3 mL: 1 g, leaching time 90 min) to obtain a sodium aluminate solution, and introducing CO 2 into the sodium aluminate solution to obtain Al(OH) 3 and Al(OH) 3 are calcined to obtain alumina, and the leaching residue is used as the raw material for cement production.
本实施例中，镁冶炼渣与高铁铝土矿中CaO、Al
2O
3、SiO
2、铁、铬、钒组分的回收率分别为96%、88%、94%、96%、81%与83%。
In this embodiment, the recovery rates of CaO, Al 2 O 3 , SiO 2 , iron, chromium, and vanadium components in magnesium smelting slag and high iron bauxite are 96%, 88%, 94%, 96%, and 81%, respectively. with 83%.
实施例3Example 3
一种利用熔渣冶金技术生产氧化铝的方法，包括以下步骤：A method for producing alumina by utilizing slag metallurgy technology, comprising the following steps:
步骤1：以转炉熔融钢渣和高炉熔渣作为反应熔渣，和烟煤加入到熔融还原炉内，用富氧空气向反应熔渣中喷入干燥脱水后的低品位铝土矿(A/S≤6)、高品位铝土矿(A/S>6)与石灰，加入保持熔融状态，通过调整各个原料的加入量，使得熔融状态的熔渣同时满足以下两个参数：(a)熔渣中CaO/Al
2O
3(摩尔比)=1.8；(b)CaO/SiO
2(质量比)=3.0；
Step 1: Use converter molten steel slag and blast furnace slag as reaction slag, add bituminous coal into the smelting reduction furnace, and spray dry and dehydrated low-grade bauxite (A/S≤ 6), high-grade bauxite (A/S>6) and lime are added to maintain the molten state, and by adjusting the amount of each raw material added, the molten slag in the molten state can satisfy the following two parameters at the same time: (a) In the molten slag CaO/Al 2 O 3 (molar ratio)=1.8; (b) CaO/SiO 2 (mass ratio)=3.0;
向熔融状态的熔渣中喷吹热二氧化碳和氮气混合气体(混合体积为1:1)，进行渣浴熔融还原；Spray hot carbon dioxide and nitrogen mixed gas (mixing volume is 1:1) into the molten slag to carry out slag bath melting reduction;
步骤2：渣浴熔融还原后，渣铁分离，原料中的铌进入下层，得到下层含铌铁水和上层铝酸钙熔渣，磷组分分别进入铝酸钙熔渣与烟灰；Step 2: After the slag bath is melted and reduced, the slag and iron are separated, and the niobium in the raw material enters the lower layer to obtain the lower layer of niobium-containing molten iron and the upper layer of calcium aluminate slag, and the phosphorus component enters the calcium aluminate slag and soot respectively;
步骤3：下层含铌铁水作为提铌炼钢的原料，获得铌渣和半钢，半钢炼钢后得到熔融钢渣，熔融钢渣直接返回加入到步骤1中的熔融还原炉中，作为反应熔渣；Step 3: The niobium-containing molten iron in the lower layer is used as the raw material for niobium steelmaking to obtain niobium slag and semi-steel. After semi-steel steelmaking, molten steel slag is obtained, and the molten steel slag is directly returned to the smelting reduction furnace in step 1 as reaction slag. ;
步骤4：上层铝酸钙熔渣空冷到室温后，获得自粉化铝酸钙炉渣，自粉化铝酸钙炉渣(浸出条件为Na
2CO
3的质量浓度为80g/L，浸出温度为90℃，按液固比，Na
2CO
3溶液：自粉化铝酸钙炉渣=5mL：1g，浸出时间为100min)，获得铝酸钠溶液，向铝酸钠溶液通入CO
2，获得Al(OH)
3，Al(OH)
3煅烧获得氧化铝，浸出残渣作为水泥生产的原料。
Step 4: after the upper layer calcium aluminate slag is air-cooled to room temperature, the self-pulverized calcium aluminate slag is obtained, and the self-pulverized calcium aluminate slag (the leaching condition is that the mass concentration of Na 2 CO 3 is 80 g/L, and the leaching temperature is 90 ℃, according to the liquid-solid ratio, Na 2 CO 3 solution: self-pulverizing calcium aluminate slag=5mL: 1g, leaching time is 100min) to obtain sodium aluminate solution, pass CO 2 into the sodium aluminate solution to obtain Al ( OH) 3 and Al(OH) 3 are calcined to obtain alumina, and the leaching residue is used as the raw material for cement production.
本实施例中，转炉熔融钢渣和高炉熔渣、低品位铝土矿、高品位铝土矿中CaO、Al
2O
3、SiO
2、铁、铌组分的回收率为94%、86%、93%、97%与82%。
In this example, the recovery rates of the components of CaO, Al 2 O 3 , SiO 2 , iron and niobium in the converter molten steel slag and blast furnace slag, low-grade bauxite and high-grade bauxite are 94%, 86%, 93%, 97% and 82%.
实施例4Example 4
一种利用熔渣冶金技术生产氧化铝的方法，包括以下步骤：A method for producing alumina by utilizing slag metallurgy technology, comprising the following steps:
步骤1：将转炉熔融钢渣作为反应熔渣，和干燥脱水后的低品位铝土矿(A/S≤6)、高品位铝土矿(A/S>6)、石灰与褐煤加入到保温渣包内，保持熔融状态，通过调整各个原料的加入量，使得熔融状态的熔渣同时满足以下两个参数：(a)熔渣中CaO/Al
2O
3(摩尔比)=1.7；(b)CaO/SiO
2(质量比)=3.5；
Step 1: The converter molten steel slag is used as the reaction slag, and the dried and dehydrated low-grade bauxite (A/S≤6), high-grade bauxite (A/S>6), lime and lignite are added to the thermal insulation slag. In the bag, keep the molten state, and adjust the addition amount of each raw material, so that the molten slag in the molten state satisfies the following two parameters at the same time: (a) CaO/Al 2 O 3 (molar ratio)=1.7 in the molten slag; (b) CaO/SiO 2 (mass ratio)=3.5;
向熔融状态的熔渣中喷吹热空气，进行渣浴熔融还原。Hot air is blown into the molten slag to perform slag bath melting reduction.
步骤2：渣浴熔融还原后，渣铁分离，得到下层含钒铁水和上层铝酸钙熔渣相；Step 2: after the slag bath is smelted and reduced, the slag and iron are separated to obtain the lower layer of vanadium-containing molten iron and the upper layer of calcium aluminate slag phase;
步骤3：下层含钒铁水作为提钒炼钢的原料，获得钒渣，和半钢，半钢炼钢后得到熔融钢渣，熔融钢渣直接返回加入到步骤1中的保温渣包中，作为反应熔渣；Step 3: The lower layer of vanadium-containing molten iron is used as the raw material for vanadium extraction and steelmaking to obtain vanadium slag and semi-steel. After semi-steel steelmaking, molten steel slag is obtained. slag;
步骤4：上层铝酸钙熔渣空冷到室温后，获得自粉化铝酸钙炉渣，自粉化铝酸钙炉渣(浸出条件为Na
2CO
3的质量浓度为100g/L，浸出温度为110℃，按液固比，Na
2CO
3溶液：自粉化铝酸钙炉渣=6mL：1g，浸出时间为95min)，获得铝酸钠溶液，向铝酸钠溶液通入CO
2，获得Al(OH)
3，Al(OH)
3煅烧获得氧化铝，浸出残渣作为水泥生产的原料。
Step 4: after the upper layer calcium aluminate slag is air-cooled to room temperature, the self-pulverized calcium aluminate slag is obtained, and the self-pulverized calcium aluminate slag (the leaching condition is that the mass concentration of Na 2 CO 3 is 100 g/L, and the leaching temperature is 110 ℃, according to the liquid-solid ratio, Na 2 CO 3 solution: self-pulverizing calcium aluminate slag=6mL: 1g, leaching time is 95min) to obtain sodium aluminate solution, pass CO 2 into the sodium aluminate solution to obtain Al ( OH) 3 and Al(OH) 3 are calcined to obtain alumina, and the leaching residue is used as the raw material for cement production.
本实施例中，转炉熔融钢渣与铝土矿中CaO、Al
2O
3、SiO
2、铁、钒组分的回收率分别为97%、90%、95%、94%与85%。
In this embodiment, the recovery rates of CaO, Al 2 O 3 , SiO 2 , iron, and vanadium components in the converter molten steel slag and bauxite are 97%, 90%, 95%, 94%, and 85%, respectively.
实施例5Example 5
一种利用熔渣冶金技术生产氧化铝的方法，包括以下步骤：A method for producing alumina by utilizing slag metallurgy technology, comprising the following steps:
步骤1：将电炉熔融钢渣作为反应熔渣，和干燥脱水后的高铁铝土矿(全Fe>20%)、粉煤灰、石灰与褐煤加入到电弧炉内，加入预还原含铁铝土矿球团，保持熔融状态，通过调整各个原料的加入量，使得熔融状态的熔渣同时满足以下两个参数：(a)熔渣中CaO/Al
2O
3(摩尔比)=1.8；(b)CaO/SiO
2(质量比)=4.2；
Step 1: The electric furnace molten steel slag is used as the reaction slag, and the dried and dehydrated high iron bauxite (total Fe>20%), fly ash, lime and lignite are added to the electric arc furnace, and the pre-reduced iron-bearing bauxite is added. The pellet is kept in a molten state, and by adjusting the amount of each raw material added, the molten slag in the molten state meets the following two parameters at the same time: (a) CaO/Al 2 O 3 (molar ratio) in the slag = 1.8; (b) CaO/SiO 2 (mass ratio)=4.2;
向熔融状态的熔渣中喷吹热空气，进行渣浴熔融还原；Hot air is sprayed into the molten slag to carry out slag bath melting reduction;
步骤2：渣浴熔融还原后，渣铁分离，原料中的钒进入下层铁水，得到下层含钒铁水和上层铝酸钙熔渣；Step 2: after the slag bath is smelted and reduced, the slag and iron are separated, and the vanadium in the raw material enters the lower layer of molten iron to obtain the lower layer of vanadium-containing molten iron and the upper layer of calcium aluminate slag;
步骤3：下层含钒铁水作为提钒炼钢的原料，获得钒渣和半钢，半钢炼钢后，得到熔融钢渣，熔融钢渣直接返回加入到步骤1中的电弧炉中，作为反应熔渣；Step 3: The lower layer of vanadium-containing molten iron is used as the raw material for vanadium extraction and steelmaking to obtain vanadium slag and semi-steel. After the semi-steel is made, molten steel slag is obtained, and the molten steel slag is directly returned to the electric arc furnace in step 1 and used as reaction slag ;
步骤4：上层铝酸钙熔渣空冷到室温后，获得自粉化铝酸钙炉渣，自粉化铝酸钙炉渣(浸出条件为：Na
2CO
3质量浓度为90g/L，浸出温度为100℃，按液固比，Na
2CO
3溶液：自粉化铝酸钙炉渣=8mL：1g，浸出时间为100min)，获得铝酸钠溶液，向铝酸钠溶液通入CO
2，获得Al(OH)
3，Al(OH)
3煅烧获得氧化铝，浸出残渣作为水泥生产的原料。
Step 4: after the upper layer calcium aluminate slag is air-cooled to room temperature, the self-pulverized calcium aluminate slag is obtained, and the self-pulverized calcium aluminate slag (leaching conditions are: Na 2 CO 3 mass concentration is 90g/L, and the leaching temperature is 100 ℃, according to the liquid-solid ratio, Na 2 CO 3 solution: self-pulverizing calcium aluminate slag = 8mL: 1g, leaching time is 100min) to obtain sodium aluminate solution, pass CO 2 into the sodium aluminate solution to obtain Al ( OH) 3 and Al(OH) 3 are calcined to obtain alumina, and the leaching residue is used as the raw material for cement production.
本实施例中，电炉熔融钢渣、高铁铝土矿、粉煤灰中CaO、Al
2O
3、SiO
2、铁、钒组分的回收率为95%、91%、95%、95%与86%。
In this embodiment, the recovery rates of CaO, Al 2 O 3 , SiO 2 , iron and vanadium components in the electric furnace molten steel slag, high-speed iron bauxite and fly ash are 95%, 91%, 95%, 95% and 86%. %.
实施例6Example 6
一种利用熔渣冶金技术生产氧化铝的方法，包括以下步骤：A method for producing alumina by utilizing slag metallurgy technology, comprising the following steps:
步骤1：将电炉熔融钢渣作为反应熔渣，加入到矮高炉内，用氮气向反应熔渣中喷入干燥脱水后的高铁铝土矿(全Fe>20%)、煤矸石、石灰保持熔融状态，通过调整各个原料的加入量，使得熔融状态的熔渣同时满足以下两个参数：(a)熔渣中CaO/Al
2O
3(摩尔比)=1.7；(b)CaO/SiO
2(质量比)=4.0；
Step 1: Use the molten steel slag of the electric furnace as the reaction slag, add it into the short blast furnace, and spray the dried and dehydrated high iron bauxite (total Fe>20%), coal gangue and lime into the reaction slag with nitrogen to keep the molten state , by adjusting the addition amount of each raw material, so that the molten slag in the molten state satisfies the following two parameters at the same time: (a) CaO/Al 2 O 3 (molar ratio)=1.7 in the molten slag; (b) CaO/SiO 2 (mass ratio) = 4.0;
向熔融状态的熔渣中喷吹热空气与天然气，进行渣浴熔融还原；Blow hot air and natural gas into the molten slag to carry out slag bath melting reduction;
步骤2：渣浴熔融还原后，渣铁分离，得到下层含钒铁水和上层铝酸钙熔渣；Step 2: After the slag bath is melted and reduced, the slag and iron are separated to obtain the lower layer of vanadium-containing molten iron and the upper layer of calcium aluminate slag;
步骤3：含钒铁水作为提钒炼钢的原料，获得钒渣和半钢，半钢炼钢后，得到熔融钢渣，熔融钢渣直接返回加入到步骤1中的矮高炉中，作为反应熔渣；Step 3: vanadium-containing molten iron is used as a raw material for vanadium extraction and steelmaking to obtain vanadium slag and semi-steel, and after semi-steel steelmaking, molten steel slag is obtained, and the molten steel slag is directly returned to the short blast furnace in step 1 as reaction slag;
步骤4：铝酸钙熔渣空冷到室温后，获得自粉化铝酸钙炉渣，自粉化铝酸钙炉渣(浸出条件为：Na
2CO
3质量浓度为110g/L，浸出温度为110℃，按液固比，Na
2CO
3溶液：自粉化铝酸钙炉渣=7mL：1g，浸出时间为120min)，获得铝酸钠溶液，向铝酸钠溶液通入CO
2，获得Al(OH)
3，Al(OH)
3煅烧获得氧化铝，浸出残渣作为水泥生产的原料。
Step 4: After the calcium aluminate slag is air-cooled to room temperature, the self-pulverized calcium aluminate slag is obtained, and the self-pulverized calcium aluminate slag is obtained (the leaching conditions are: the mass concentration of Na 2 CO 3 is 110 g/L, and the leaching temperature is 110° C. , according to the liquid-solid ratio, Na 2 CO 3 solution: self-pulverizing calcium aluminate slag=7mL: 1g, leaching time is 120min) to obtain sodium aluminate solution, pass CO 2 into the sodium aluminate solution to obtain Al(OH ) 3 , Al(OH) 3 is calcined to obtain alumina, and the leaching residue is used as the raw material for cement production.
本实施例中，电炉熔融钢渣、高铁铝土矿(全Fe>20%)、煤矸石中CaO、Al
2O
3、SiO
2、铁、钒组分的回收率分别为94%、86%、93%、93%与83%。
In the present embodiment, the recovery rates of the components of electric furnace molten steel slag, high - speed iron bauxite (total Fe> 20 %), and coal gangue are 94%, 86%, 93%, 93% and 83%.
实施例7Example 7
一种利用熔渣冶金技术生产氧化铝的方法，包括以下步骤：A method for producing alumina by utilizing slag metallurgy technology, comprising the following steps:
步骤1：将电炉熔融钢渣作为反应熔渣，和干燥脱水后的高铁铝土矿(全Fe>20%))、煤矸石、石灰加入到熔融还原炉内，保持熔融状态，通过调整各个原料的加入量，使得熔融状态的熔渣同时满足以下两个参数：(a)熔渣中CaO/Al
2O
3(摩尔比)=1.9；(b)CaO/SiO
2(质量比)=3.9；
Step 1: The molten steel slag of the electric furnace is used as the reaction slag, and the dried and dehydrated high-speed iron bauxite (total Fe>20%), coal gangue and lime are added to the smelting reduction furnace, and the molten state is maintained. The amount of addition makes the molten slag satisfy the following two parameters at the same time: (a) CaO/Al 2 O 3 (molar ratio)=1.9 in the molten slag; (b) CaO/SiO 2 (mass ratio)=3.9;
向熔融状态的熔渣中喷吹热空气与煤层气，进行渣浴熔融还原；Blow hot air and coalbed methane into the molten slag to carry out slag bath melting reduction;
步骤2：渣浴熔融还原后，渣铁分离，得到下层含钒铁水和上层铝酸钙熔渣相；Step 2: after the slag bath is smelted and reduced, the slag and iron are separated to obtain the lower layer of vanadium-containing molten iron and the upper layer of calcium aluminate slag phase;
步骤3：含钒铁水作为提钒炼钢的原料，获得钒渣和半钢，半钢炼钢后得到熔融钢渣，熔融钢渣直接返回加入到步骤1中的熔融还原炉中，作为反应熔渣；Step 3: vanadium-containing molten iron is used as a raw material for vanadium-smelting steelmaking, to obtain vanadium slag and semi-steel, and after semi-steel steelmaking, molten steel slag is obtained, and the molten steel slag is directly returned to the melting reduction furnace in step 1 as reaction slag;
步骤4：铝酸钙熔渣空冷到室温后，获得自粉化铝酸钙炉渣，自粉化铝酸钙炉渣(浸出条件为：Na
2CO
3的质量浓度为100g/L，浸出温度为100℃，按液固比，Na
2CO
3溶液：自粉化铝酸钙炉渣=4mL：1g，浸出时间为120min)，获得铝酸钠溶液，向铝酸钠溶液通入CO
2，获得Al(OH)
3，Al(OH)
3煅烧获得氧化铝，浸出残渣作为水泥生产的原料。
Step 4: after the calcium aluminate slag is air-cooled to room temperature, the self-pulverized calcium aluminate slag is obtained, and the self-pulverized calcium aluminate slag (leaching conditions are: the mass concentration of Na 2 CO 3 is 100 g/L, and the leaching temperature is 100 ℃, according to the liquid-solid ratio, Na 2 CO 3 solution: self-pulverizing calcium aluminate slag=4mL: 1g, leaching time is 120min) to obtain sodium aluminate solution, pass CO 2 into the sodium aluminate solution to obtain Al ( OH) 3 and Al(OH) 3 are calcined to obtain alumina, and the leaching residue is used as the raw material for cement production.
本实施例中，电炉熔融钢渣、高铁铝土矿、煤矸石中CaO、Al
2O
3、SiO
2、铁、铬、钒、铌组分的回收率分别为97%、94%、96%、97%与85%。
In this embodiment, the recovery rates of CaO, Al 2 O 3 , SiO 2 , iron, chromium, vanadium, and niobium components in electric furnace molten steel slag, high-speed iron bauxite, and coal gangue are 97%, 94%, 96%, and 96%, respectively. 97% and 85%.
实施例8Example 8
一种利用熔渣冶金技术生产氧化铝的方法，包括以下步骤：A method for producing alumina by utilizing slag metallurgy technology, comprising the following steps:
步骤1：将转炉熔融钢渣作为反应熔渣，和干燥脱水后的粘土、高岭土、铝矾土、长石、石灰加入到保温渣包内，保持熔融状态，通过调整各个原料的加入量，使得熔融状态的熔渣同时满足以下两个参数：(a)熔渣中CaO/Al
2O
3(摩尔比)=2.0；(b)CaO/SiO
2(质量比)=3.2；
Step 1: The converter molten steel slag is used as the reaction slag, and the dried and dehydrated clay, kaolin, bauxite, feldspar, and lime are added to the thermal insulation slag bag, and the molten state is maintained. The slag in the state meets the following two parameters at the same time: (a) CaO/Al 2 O 3 (molar ratio)=2.0 in the slag; (b) CaO/SiO 2 (mass ratio)=3.2;
向熔融状态的熔渣中喷吹热空气与煤气，进行渣浴熔融还原；Spray hot air and gas into the molten slag to carry out slag bath melting reduction;
步骤2：渣浴熔融还原后，渣铁分离，得到下层铁水和上层铝酸钙熔渣相；Step 2: after the slag bath is melted and reduced, the slag and iron are separated to obtain the lower layer of molten iron and the upper layer of calcium aluminate slag phase;
步骤3：铁水作为炼钢的原料，获得熔融钢渣，熔融钢渣直接返回加入到步骤1中的保温渣包中，作为反应熔渣；Step 3: molten iron is used as a raw material for steelmaking to obtain molten steel slag, and the molten steel slag is directly returned to the thermal insulation slag bag in step 1 as reaction slag;
步骤4：铝酸钙熔渣空冷到室温后，获得自粉化铝酸钙炉渣，自粉化铝酸钙炉渣(浸出条件为Na
2CO
3质量浓度为80g/L，浸出温度为110℃，按液固比，Na
2CO
3溶液：自粉化铝酸钙炉渣=5mL：1g，浸出时间为100min)，获得铝酸钠溶液，向铝酸钠溶液通入CO
2，获得Al(OH)
3，Al(OH)
3煅烧获得氧化铝，浸出残渣作为水泥生产的原料。
Step 4: after the calcium aluminate slag is air-cooled to room temperature, the self-pulverized calcium aluminate slag is obtained, and the self-pulverized calcium aluminate slag (the leaching condition is that the Na 2 CO 3 mass concentration is 80 g/L, and the leaching temperature is 110° C., According to the liquid-solid ratio, Na 2 CO 3 solution: self-pulverizing calcium aluminate slag = 5mL: 1g, leaching time is 100min) to obtain a sodium aluminate solution, pass CO 2 into the sodium aluminate solution to obtain Al(OH) 3. Al(OH) 3 is calcined to obtain alumina, and the leaching residue is used as the raw material for cement production.
本实施例中，转炉熔融钢渣、粘土、高岭土、铝矾土、长石中CaO、Al
2O
3、SiO
2、铁组分的回收率为97%、92%、96%与97%。
In this embodiment, the recovery rates of CaO, Al 2 O 3 , SiO 2 and iron components in converter molten steel slag, clay, kaolin, bauxite and feldspar are 97%, 92%, 96% and 97%.
实施例9Example 9
一种利用熔渣冶金技术生产氧化铝的方法，包括以下步骤：A method for producing alumina by utilizing slag metallurgy technology, comprising the following steps:
步骤1：将转炉熔融钢渣作为反应熔渣加入到温度为1600℃的保温地坑内，用二氧化碳气向反应熔渣中喷入干燥脱水后的高品位铝土矿(A/S>6)、霞石与明矾，加入石灰，保持熔融状态，通过调整各个原料的加入量，使得熔融状态的熔渣同时满足以下两个参数：(a)熔渣中CaO/Al
2O
3(摩尔比)=2.2；(b)CaO/SiO
2(质量比)=3.1；
Step 1: The converter molten steel slag is added to the heat preservation pit with a temperature of 1600 ℃ as the reaction slag, and the high-grade bauxite (A/S>6), charcoal ore after drying and dehydration is sprayed into the reaction slag with carbon dioxide gas. Stone and alum, add lime, keep molten state, by adjusting the addition amount of each raw material, make the molten slag in molten state satisfy the following two parameters at the same time: (a) CaO/Al 2 O 3 (molar ratio)=2.2 in the molten slag ; (b) CaO/SiO 2 (mass ratio)=3.1;
向熔融状态的熔渣中喷吹热空气与粉煤，进行渣浴熔融还原；Blow hot air and pulverized coal into the molten slag to carry out slag bath melting reduction;
步骤2：渣浴熔融还原后，渣铁分离，得到下层含钒铁水和上层铝酸钙熔渣相；Step 2: after the slag bath is smelted and reduced, the slag and iron are separated to obtain the lower layer of vanadium-containing molten iron and the upper layer of calcium aluminate slag phase;
步骤3：含钒铁水作为提钒炼钢的原料，获得钒渣和半钢，将半钢炼钢后，得到熔融钢渣，熔融钢渣直接返回加入到步骤1中的保温地坑中，作为反应熔渣；Step 3: Vanadium-containing molten iron is used as the raw material for vanadium steelmaking to obtain vanadium slag and semi-steel. After the semi-steel is made, molten steel slag is obtained. slag;
步骤4：铝酸钙熔渣空冷到室温后，获得自粉化铝酸钙炉渣，自粉化铝酸钙炉渣浸出(浸出条件为：Na
2CO
3质量浓度为80g/L，浸出温度为80℃，按液固比，Na
2CO
3溶液：自粉化铝酸钙炉渣=6mL：1g，浸出时间为100min)，获得铝酸钠溶液，向铝酸钠溶液通入CO
2，获得Al(OH)
3，Al(OH)
3煅烧获得氧化铝，浸出残渣作为水泥生产的原料。
Step 4: after the calcium aluminate slag is air-cooled to room temperature, obtained from the pulverized calcium aluminate slag, and leached from the pulverized calcium aluminate slag (the leaching conditions are: the Na 2 CO 3 mass concentration is 80 g/L, and the leaching temperature is 80 ℃, according to the liquid-solid ratio, Na 2 CO 3 solution: self-pulverizing calcium aluminate slag=6mL: 1g, leaching time is 100min) to obtain sodium aluminate solution, pass CO 2 into the sodium aluminate solution to obtain Al ( OH) 3 and Al(OH) 3 are calcined to obtain alumina, and the leaching residue is used as the raw material for cement production.
本实施例中，转炉熔融钢渣、高品位铝土矿、霞石与明矾中CaO、Al
2O
3、SiO
2、铁、钒组分的回收率分别为96%、88%、95%、94%与82%。
In this embodiment, the recovery rates of CaO, Al 2 O 3 , SiO 2 , iron and vanadium components in converter molten steel slag, high-grade bauxite, nepheline and alum are 96%, 88%, 95%, 94%, respectively. % and 82%.
实施例10Example 10
一种利用熔渣冶金技术生产氧化铝的方法，包括以下步骤：A method for producing alumina by utilizing slag metallurgy technology, comprising the following steps:
步骤1：将转炉熔融钢渣作为反应熔渣加入到感应炉内，用二氧化碳和氮气混合气向反应熔渣中喷入干燥脱水后的高品位铝土矿(A/S>6)，保持熔融状态，通过调整各个原料的加入量，使得熔融状态的熔渣同时满足以下两个参数：(a)熔渣中CaO/Al
2O
3(摩尔比)=1.4；(b)CaO/SiO
2(质量比)=4.9；
Step 1: Add the molten steel slag of the converter into the induction furnace as the reaction slag, and spray the dried and dehydrated high-grade bauxite (A/S>6) into the reaction slag with a mixture of carbon dioxide and nitrogen to keep the molten state , by adjusting the addition amount of each raw material, so that the molten slag in the molten state satisfies the following two parameters at the same time: (a) CaO/Al 2 O 3 (molar ratio)=1.4 in the molten slag; (b) CaO/SiO 2 (mass ratio) = 4.9;
向熔融状态的熔渣中喷吹纯氧与粉煤，进行渣浴熔融还原；Inject pure oxygen and pulverized coal into the molten slag to carry out slag bath melting reduction;
步骤2：渣浴熔融还原后，渣铁分离，得到下层含钒铬铁水和上层铝酸钙熔渣相；Step 2: after the slag bath is melted and reduced, the slag and iron are separated to obtain the lower layer of vanadium-chromium molten iron and the upper layer of calcium aluminate slag phase;
步骤3：含钒铬铁水作为提钒铬炼钢的原料，获得钒铬渣和半钢，半钢炼钢后，得到熔融钢渣，熔融钢渣直接返回加入到步骤1中的感应炉中，作为反应熔渣；Step 3: Vanadium-chromium molten iron is used as the raw material for vanadium-chromium steelmaking to obtain vanadium-chromium slag and semi-steel. After the semi-steel is made, molten steel slag is obtained, and the molten steel slag is directly returned to the induction furnace in step 1 as a reaction slag;
步骤4：铝酸钙熔渣空冷到室温后，获得自粉化铝酸钙炉渣，自粉化铝酸钙炉渣(浸出条件为：Na
2CO
3质量浓度为100g/L，浸出温度为90℃，按液固比，Na
2CO
3溶液：自粉化铝酸钙炉渣=4mL：1g，浸出时间为110min)，获得铝酸钠溶液，向铝酸钠溶液通入CO
2，获得Al(OH)
3，Al(OH)
3煅烧获得氧化铝，浸出残渣作为水泥生产的原料。
Step 4: After the calcium aluminate slag is air-cooled to room temperature, the self-pulverized calcium aluminate slag is obtained, and the self-pulverized calcium aluminate slag is obtained (the leaching conditions are: the mass concentration of Na 2 CO 3 is 100 g/L, and the leaching temperature is 90° C. , according to the liquid-solid ratio, Na 2 CO 3 solution: self-pulverizing calcium aluminate slag=4mL: 1g, leaching time is 110min) to obtain sodium aluminate solution, pass CO 2 into the sodium aluminate solution to obtain Al(OH ) 3 , Al(OH) 3 is calcined to obtain alumina, and the leaching residue is used as the raw material for cement production.
本实施例中，转炉熔融钢渣与高品位铝土矿中CaO、Al
2O
3、SiO
2、铁、铬、钒组分的回收率分别为96%、80%、96%、95%、82%与81%。
In this example, the recovery rates of the components of CaO, Al 2 O 3 , SiO 2 , iron, chromium, and vanadium in the converter molten steel slag and high-grade bauxite are 96%, 80%, 96%, 95%, 82%, respectively. % and 81%.
Claims (10)
- 一种利用熔渣冶金技术生产氧化铝的方法，其特征在于，包括以下步骤；A method for producing alumina by utilizing slag metallurgy technology, is characterized in that, comprises the following steps;步骤1：step 1:将高氧化钙冶金熔渣，加入熔融反应器中，形成反应熔渣；所述的高氧化钙冶金熔渣中CaO的质量百分含量≥30%，由冶金炉直接获得，熔渣温度≥1100℃；The high calcium oxide metallurgical slag is added to the melting reactor to form reaction slag; the mass percentage of CaO in the high calcium oxide metallurgical slag is ≥30%, which is directly obtained from the metallurgical furnace, and the slag temperature is ≥1100 °C;将铝矿和还原剂，加入反应熔渣中，保持熔融状态，得到熔融状态的熔渣；其中，所述铝矿中氧化铝的质量百分含量≥10%；Adding bauxite and a reducing agent into the reaction slag, maintaining a molten state to obtain molten slag; wherein, the mass percentage of alumina in the bauxite is ≥10%;其中，通过调节各个原料的加入量，调控熔融状态的熔渣化学组成，使得熔融状态的熔渣同时满足以下两个条件：Wherein, by adjusting the addition amount of each raw material, the chemical composition of the molten slag in the molten state is regulated, so that the molten slag in the molten state satisfies the following two conditions at the same time:(a)熔融状态的熔渣中，按摩尔比，CaO：Al 2O 3>1.6； (a) In the molten slag, in molar ratio, CaO:Al 2 O 3 >1.6;(b)熔融状态的熔渣中，按质量比，CaO：SiO 2=3.0~5.0； (b) In the molten slag, according to the mass ratio, CaO:SiO 2 =3.0~5.0;向熔融状态的熔渣中喷吹氧化性气体、或氧化性气体和氮气混合气，进行渣浴熔融还原；Spray oxidizing gas, or a mixture of oxidizing gas and nitrogen into molten slag, to perform slag bath melting reduction;步骤2：Step 2:渣浴熔融还原后，渣铁分离，得到下层铁水，上层铝酸钙熔渣；After the slag bath is melted and reduced, the slag and iron are separated to obtain the lower layer of molten iron and the upper layer of calcium aluminate slag;步骤3：Step 3:下层铁水直接作为炼钢原料，炼钢后，得到的熔融钢渣，直接返回步骤1进入熔融反应器中；The lower layer of molten iron is directly used as the raw material for steelmaking, and after steelmaking, the obtained molten steel slag is directly returned to step 1 to enter the melting reactor;步骤4：Step 4:上层铝酸钙熔渣冷却后，得到自粉化铝酸钙炉渣；自粉化铝酸钙炉渣加入Na 2CO 3溶液浸出，得到铝酸钠溶液和浸出残渣； After the upper layer of calcium aluminate slag is cooled, self-pulverized calcium aluminate slag is obtained; the self-pulverized calcium aluminate slag is added with Na 2 CO 3 solution for leaching to obtain sodium aluminate solution and leaching residue;向铝酸钠溶液中，通入CO 2，得到Al(OH) 3，Al(OH) 3煅烧，得到氧化铝。 In the sodium aluminate solution, CO 2 is passed through to obtain Al(OH) 3 , and Al(OH) 3 is calcined to obtain alumina.
- 根据权利要求1所述的利用熔渣冶金技术生产氧化铝的方法，其特征在于，在反应熔渣中，当调节各个原料的加入量，熔融状态的熔渣不能同时满足以下两个条件：(a)熔融状态的熔渣中，按摩尔比，CaO：Al 2O 3>1.6；(b)熔融状态的熔渣中，按质量比，CaO：SiO 2=3.0~5.0，加入碱性熔剂进行调节；碱性熔剂为石灰石、石灰中的一种或两种。 The method for utilizing slag metallurgy to produce alumina according to claim 1, is characterized in that, in the reaction slag, when adjusting the add-on of each raw material, the molten slag in molten state cannot satisfy the following two conditions simultaneously: ( a) In molten slag, CaO:Al 2 O 3 >1.6 in molar ratio; (b) In molten slag, in mass ratio, CaO:SiO 2 =3.0~5.0, add alkaline flux to carry out Adjustment; the alkaline flux is one or both of limestone and lime.
- 根据权利要求1或2所述的利用熔渣冶金技术生产氧化铝的方法，其特征在于，所述的步骤1中，高氧化钙冶金熔渣为熔融钢渣、高炉熔渣、锰铁冶炼熔渣、镁冶炼渣中的一种或几种。The method for producing alumina by utilizing slag metallurgy technology according to claim 1 or 2, wherein in the step 1, the high calcium oxide metallurgical slag is molten steel slag, blast furnace slag, and ferromanganese smelting slag , one or more of magnesium smelting slag.
- 根据权利要求1或2所述的利用熔渣冶金技术生产氧化铝的方法，其特征在于，所述的步骤1中，熔融反应器为电炉、矿热炉、电弧炉、矮高炉、感应炉、熔融还原炉、保温渣包、保温地坑中的一种，熔融还原温度为1400~1650℃。The method for producing alumina using slag metallurgy technology according to claim 1 or 2, wherein in the step 1, the melting reactor is an electric furnace, a submerged arc furnace, an electric arc furnace, a low blast furnace, an induction furnace, One of the smelting reduction furnace, thermal insulation slag bag and thermal insulation pit, the smelting reduction temperature is 1400~1650℃.
- 根据权利要求1或2所述的利用熔渣冶金技术生产氧化铝的方法，其特征在于，所述的步骤1中，铝矿为铝土矿、全Fe的质量百分含量>20%的高铁铝土矿、预还原含铁铝土矿球团、粉煤灰、煤气化炉渣、煤矸石、霞石、明矾、粘土、高岭石、铝矾土、长石、页岩、赤泥中的一种或几种；The method for producing alumina using slag metallurgy technology according to claim 1 or 2, characterized in that, in the step 1, the bauxite is bauxite, high iron with a mass percentage content of all Fe>20% Bauxite, pre-reduced iron-bearing bauxite pellets, fly ash, coal gasification slag, coal gangue, nepheline, alum, clay, kaolinite, bauxite, feldspar, shale, red mud one or more;所述的铝矿，当含有结晶水时，需要提前进行干燥脱水处理，干燥温度<600℃；When the bauxite contains crystal water, it needs to be dried and dehydrated in advance, and the drying temperature is less than 600°C;所述的铝矿为粉末状或球状，直接加入或喷吹入反应熔渣中，喷吹铝矿的气体为氮气和/或氧化性气体；所述的氧化性气体为空气、富氧空气、氧气、CO 2中的一种或几种。 Described bauxite is powdery or spherical, and is directly added or sprayed into the reaction slag, and the gas for spraying bauxite is nitrogen and/or oxidizing gas; the oxidizing gas is air, oxygen-enriched air, One or more of oxygen and CO 2 .
- 根据权利要求1或2所述的利用熔渣冶金技术生产氧化铝的方法，其特征在于，所述的步骤1中，还原剂为无烟煤、烟煤、褐煤、粉煤、天然气、煤层气、煤气中的一种或几种，还原剂中的固态还原剂直接加入或喷吹加入，喷吹固态还原剂的气体为氮气和/或氧化性气体；所述的氧化性气体为空气、富氧空气、氧气、CO 2中的一种或几种。 The method for producing alumina using slag metallurgy technology according to claim 1 or 2, characterized in that, in the step 1, the reducing agent is anthracite, bituminous coal, lignite, pulverized coal, natural gas, coalbed methane, coal gas One or more, the solid reducing agent in the reducing agent is directly added or added by spraying, and the gas for spraying the solid reducing agent is nitrogen and/or oxidizing gas; the oxidizing gas is air, oxygen-enriched air, One or more of oxygen and CO 2 .
- 根据权利要求1或2所述的利用熔渣冶金技术生产氧化铝的方法，其特征在于，所述的步骤1中，氧化性气体为空气、富氧空气、氧气、CO 2中的一种或几种。 The method for producing alumina using slag metallurgy technology according to claim 1 or 2, wherein in the step 1, the oxidizing gas is one of air, oxygen-enriched air, oxygen, and CO 2 or several.
- 根据权利要求1或2所述的利用熔渣冶金技术生产氧化铝的方法，其特征在于，所述的步骤1中，渣浴熔融还原过程为：将原料中铁的氧化物还原成铁的过程，铁氧化物还原为金属铁的还原率≥90%。The method for producing alumina using slag metallurgy technology according to claim 1 or 2, characterized in that, in the step 1, the slag bath smelting reduction process is: a process of reducing iron oxides in the raw materials to iron, The reduction rate of iron oxides to metallic iron is ≥90%.
- 根据权利要求1或2所述的利用熔渣冶金技术生产氧化铝的方法，其特征在于，所述的步骤2中，铁水为普通铁水、含钒铁水、含铌铁水、含钒铬铁水中的一种；当下层铁水为含钒铁水、含铌铁水、含钒铬铁水时，先经过提钒铬铌炼钢后，得到半钢和渣，渣为钒渣、铌渣、钒铬渣中的一种，半钢炼钢后，得到的熔融钢渣，直接返回步骤1进入熔融反应器中。The method for producing alumina by utilizing slag metallurgy technology according to claim 1 or 2, wherein in the step 2, the molten iron is ordinary molten iron, vanadium-containing molten iron, niobium-containing molten iron, and vanadium-chromium-containing molten iron. One; when the lower layer of molten iron is vanadium-containing molten iron, niobium-containing molten iron, and vanadium-chromium-containing molten iron, the semi-steel and slag are obtained after vanadium, chromium and niobium steel is first extracted, and the slag is vanadium slag, niobium slag, and vanadium-chromium slag. One, after semi-steel steelmaking, the obtained molten steel slag is directly returned to step 1 into the melting reactor.
- 根据权利要求1或2所述的利用熔渣冶金技术生产氧化铝的方法，其特征在于，所述的步骤4中，Na 2CO 3溶液为质量浓度为70~110g/L的溶液，浸出温度为70~110℃，按液固比，Na 2CO 3溶液：自粉化铝酸钙炉渣=(3~11)mL：1g，浸出时间为90~120min。 The method for producing alumina by utilizing slag metallurgy technology according to claim 1 or 2, wherein in the step 4, the Na 2 CO 3 solution is a solution with a mass concentration of 70-110 g/L, and the leaching temperature It is 70~110℃, according to the liquid-solid ratio, Na 2 CO 3 solution: self-pulverizing calcium aluminate slag=(3~11)mL: 1g, and the leaching time is 90~120min.
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