CN105967191A - Process and device for preparing gas-phase white carbon black by taking red mud as raw material - Google Patents
Process and device for preparing gas-phase white carbon black by taking red mud as raw material Download PDFInfo
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- CN105967191A CN105967191A CN201610534958.8A CN201610534958A CN105967191A CN 105967191 A CN105967191 A CN 105967191A CN 201610534958 A CN201610534958 A CN 201610534958A CN 105967191 A CN105967191 A CN 105967191A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 36
- 230000008569 process Effects 0.000 title claims abstract description 18
- 239000002994 raw material Substances 0.000 title claims abstract description 10
- 239000006229 carbon black Substances 0.000 title abstract description 4
- 239000002253 acid Substances 0.000 claims abstract description 92
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 35
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 18
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 14
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 14
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 14
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 14
- 238000010521 absorption reaction Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims abstract description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 6
- 238000004438 BET method Methods 0.000 claims abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011737 fluorine Substances 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 238000004064 recycling Methods 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims description 127
- 239000000498 cooling water Substances 0.000 claims description 40
- 239000007789 gas Substances 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 15
- 239000012065 filter cake Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 238000003860 storage Methods 0.000 claims description 13
- 239000002912 waste gas Substances 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000003595 mist Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000009434 installation Methods 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000035699 permeability Effects 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- 239000002826 coolant Substances 0.000 claims description 6
- 238000007885 magnetic separation Methods 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000005259 measurement Methods 0.000 claims description 4
- 239000003082 abrasive agent Substances 0.000 claims description 3
- 238000010306 acid treatment Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000006200 vaporizer Substances 0.000 claims description 3
- 239000012491 analyte Substances 0.000 claims description 2
- 229950000845 politef Drugs 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 230000000452 restraining effect Effects 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims 1
- 235000019628 coolness Nutrition 0.000 claims 1
- 229960002050 hydrofluoric acid Drugs 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 3
- 241000196324 Embryophyta Species 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 241000872198 Serjania polyphylla Species 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- 230000009102 absorption Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000003517 fume Substances 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000004131 Bayer process Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 229910003978 SiClx Inorganic materials 0.000 description 2
- 229910004014 SiF4 Inorganic materials 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 244000070406 Malus silvestris Species 0.000 description 1
- 229910003910 SiCl4 Inorganic materials 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000404 calcium aluminium silicate Substances 0.000 description 1
- 235000012215 calcium aluminium silicate Nutrition 0.000 description 1
- WNCYAPRTYDMSFP-UHFFFAOYSA-N calcium aluminosilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O WNCYAPRTYDMSFP-UHFFFAOYSA-N 0.000 description 1
- 229940078583 calcium aluminosilicate Drugs 0.000 description 1
- 229910052663 cancrinite Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000003895 groundwater pollution Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/181—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process
- C01B33/183—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process by oxidation or hydrolysis in the vapour phase of silicon compounds such as halides, trichlorosilane, monosilane
- C01B33/184—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process by oxidation or hydrolysis in the vapour phase of silicon compounds such as halides, trichlorosilane, monosilane by hydrolysis of tetrafluoride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/10—Compounds containing silicon, fluorine, and other elements
- C01B33/103—Fluosilicic acid; Salts thereof
-
- 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
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/50—Fluorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- 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
- C22B59/00—Obtaining rare earth metals
-
- 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
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Silicon Compounds (AREA)
Abstract
The invention provides a process for preparing gas-phase white carbon black by taking red mud as a raw material at a low temperature and recycling metal. In the process, wastes including the red mud and the like are used as the raw materials and are reacted with fluorine-containing acid liquid, hydrochloric acid and nitric acid to prepare the product gas-phase white carbon black with a high additional value and AlF3 and rare earth elements are recycled; in the prepared product, the content of SiO2 is more than 99.9 percent and the specific surface area measured by a multi-point BET method is: 350m<2>/g to 500m<2>/g, so that the effect of changing wastes into valuable things is realized; after acidic gas generated in the preparation process is absorbed by a negative-pressure water absorption tank, corresponding acid liquid can be prepared; when the acid liquid is concentrated to a certain concentration, the acid liquid can be circularly utilized. Meanwhile, the invention further provides a production device used for the process; all parts of the production device are common devices in chemical plants and the cost is low, so that large-scale industrial production can be realized.
Description
Technical field
The present invention relates to a kind of process utilizing red mud to prepare gas-phase silica and device, belong to chemical industry and purify and environmental protection
Technical field.
Background technology
According to " mineral products comprehensive utilization " first phase in 2016, " the red mud comprehensive utilization of publication Zhu Xiaobo, Li Wang, Guan Xuemao
Present Research and analysis " literary composition introduces: red mud is the tailings produced during bauxite into alumina, because it contains greatly
The bloodstone of amount forms bronzing, therefore referred to as red mud.Red mud is broadly divided into sintering process, Bayer process and combination method three kind
Type, due to feedstock property and the difference of process for making alumina, the chemical composition of various places red mud is also not quite similar, the most red
In mud, main chemical compositions is aluminium oxide, silicon dioxide, ferrum oxide, calcium oxide, titanium dioxide, sodium oxide and magnesium oxide,
Also have rhenium, gallium, yttrium, scandium, niobium, tantalum, uranium, thorium and lanthanide series etc..The mineral composition of red mud and alumina producing work
Skill is closely related with the kind of additive in production process, typically contains bloodstone, calcium aluminosilicate hydrate, cancrinite, calcium titanium
Ore deposit, dolomite, calcium aluminoferrite etc..Red mud is a kind of alkaline pollution source, if not being acted upon, can cause body of groundwater and
Soil pollution, the red mud of exposed stacking, because its granularity is superfine, can fly upward with the wind, cause air pollution.Along with red mud produces
Give birth to the cumulative year after year of amount and the prominent of environmental problem, in the urgent need to taking effective measures such solid waste of process.
It is poor that China's bauxite resource belongs to high alumina, high silicon, low ferrum, a hydraulic aluminium profiles, stripping property ability, and its type is special
Very, in addition to Guangxi pingguo's Aluminum uses pure Bayer process, most of Chinalcos use sintering or combination method to smelt aluminium oxide,
In red mud, aluminium oxide remaining quantity is the highest, alkali content is low, silicon oxide and calcium oxide content higher, iron oxide content is the lowest.
At present, red mud comprehensive utilizating research mainly includes three below aspect: one is extraction and the recovery of valuable metal, as
Leaching precipitation and carry aluminum, the rare metals such as ferrum, acid leaching extraction scandium, titanium, vanadium are selected in magnetizing roast；Two is the preparation of construction material,
As prepared non-burning brick and cement etc.；Three is the preparation of adsorbing material, is mainly used in waste water and processes.
Vapor phase method is prepared the raw material of white carbon and is generally Silicon chloride., oxygen (or air) and hydrogen, under high temperature reaction and
Become.Its chemical equation is: SiCl4+2H2+O2—>SiO2+ 4HCl, Silicon chloride. at high temperature gasifies (flame temperature
1000～1800 DEG C) after, under the high temperature of about 1800 DEG C, carry out vapor phase hydrolysis with a certain amount of hydrogen and oxygen (or air)；
The fume colloidal silica granule now generated is superfine, forms aerosol with gas, is difficult to trapping, therefore makes it first at collector
In be gathered into larger particles, then through cyclone collection, be re-fed into deacidification furnace, with nitrogenous air blowing gas phase dioxy
SiClx to pH value is 4～6 to be finished product.China produces the enterprise of gas-phase silica at present and mostly uses this method, and this method is also
It it is the production method of the most general gas-phase silica.Ye You enterprise of China uses methyl trichlorosilane to produce gas phase Linesless charcoal
Black, and have successfully completed industrialized production.The production technology of fume colloidal silica now does not only exist high-temperature process,
But also use breakneck and inflammable and explosive hydrogen and oxygen, in its production process, the operating environment of workman compares
Arduous；Safety coefficient is required the highest.Consult related data and Chinese patent literature, do not find to utilize other raw materials raw
Produce the relevant report of gas-phase silica.
If red mud can be carried out secondary operations utilization, it is combined with the preparation of gas-phase silica, be used for preparing gas
Phase white carbon black product, then will solve the thorny technical problem of above-mentioned two in this area, has the most progressive.
Summary of the invention
The invention provides a kind of with red mud as a raw material, prepare manufacturing technique method and the device of fume colloidal silica；It becomes
Avoid to merit and use hydrogen and oxygen and the technical process of pyrohydrolysis now during fume colloidal silica, also solve
The problem that current red mud can not efficiently utilize, the present invention additionally provides simultaneously and can produce gas-phase silica at normal temperatures and pressures
The novel technique of product and process units.
Realizing the technical scheme that above-mentioned purpose of the present invention used is:
A kind of technique preparing gas-phase silica with red mud as a raw material, it is characterised in that comprise the following steps: (1), by fluorine-containing
Acid solution, mixes with one or both in nitric acid, hydrochloric acid, prepares mix acid liquor standby；Red mud is mixed with hydrogen peroxide
Pelletize after conjunction, is ground to the fineness of below 200 mesh after drying, and magnetic separation removes ferrum therein, then removes with by hydrochloric acid is molten
Filter after the metal-oxide in red mud after magnetic separation and rare earth element, collect filter cake standby；
(2), mix acid liquor is put in reactor, the waste gas absorption in the agitating device of unlatching reactor and response system
Device, puts into the powder that filter cake or filter cake obtain after drying, pulverizing in reactor；
(3), the reaction temperature controlled in reactor be 75～90 DEG C, Fluohydric acid. in mix acid liquor or hexafluosilicic acid and filter cake
Or the silicon dioxde reaction in powder generates silicon tetrafluoride gas, the acid will volatilized in silicon tetrafluoride gas and mix acid liquor
Property gas and steam are brought in cooling reactor by negative pressure together；
(4), the chilling temperature controlled in cooling reactor be 0～36 DEG C, mixed gas react in cooling reactor generate HF,
Cl2/NO2、SiO2·nH2O, wherein HF and Cl2/NO2Taken out of from cooling reactor by negative pressure, and be only absorbed by the water generation can
For reusable Fluohydric acid., hydrochloric acid/nitric acid, SiO2·nH2O condenses on absorption chiller in cooling reactor, collects
SiO in cooling reactor2·nH2O；
(5), by collected SiO2·nH2O carries out negative pressure preheating in vacuum heater, removes the acidity wherein remained
Gas HF and Cl2/NO2, it is dried the most again, can be prepared by gas-phase silica product after drying, SiO in product2
Content is more than 99.9%, and its multiple spot BET method measurement the specific area is not less than 380m2/g；
(6) silicon dioxide during, in a kettle., fluorine-containing acid solution decomposes filter cake or powder；Hydrochloric acid and nitric acid then analyte
Residual metallic in material, the metal after decomposition is stayed in mix acid liquor with the form of ion and salt；Material in reactor is anti-
Should filter after completing, isolate the AlF in filtering residue3；Then filtrate is sent in vaporizer and is evaporated, obtain residue,
Use dense sulfuric acid treatment residue, recycling TiO2。
The mass concentration of described Fluohydric acid. or volumetric concentration are 2～30%, and the mass concentration of hexafluosilicic acid or volumetric concentration are
10～30%, the mass concentration of nitric acid or volumetric concentration are 2～30%, the mass concentration of hydrochloric acid or volumetric concentration be 10%～
30%.
Filtrate after filtering in step (1) first with in alkali and after, add sulfuric acid solution, after precipitate and separate goes out calcium sulfate,
Add Fluohydric acid., after precipitate and separate goes out aluminum trifluoride, then with oxalic acid extract and separate Extraction of rare earth element；Remaining molten
Liquid alkali liquor regulates pH value=8.5～9, precipitates, filters to isolate hydrated ferric oxide., and calcining hydrated ferric oxide. i.e. can be aoxidized
Iron oxide red product, finally concentrates filtrate, adds hexafluosilicic acid, the fluosilicate that can be precipitated and hydrochloric acid；Hydrochloric acid is through pure
Return again to after change use.
The acid mist gas gas water tourie produced during evaporation in step (6) carries out absorption and becomes acid solution, when acid solution reaches
After finite concentration, returning again to workshop and re-use, unabsorbed tail gas acid fog absorption tower empties after being neutralized process.
Present invention also offers the device in above-mentioned technique, described device includes that hot-air sends into system, chemical reaction
System, cooling system and waste gas absorbing system, wherein air for storing compressed air and is entered by hot-air feeding system
Send in chemical reaction system after row heating；Described chemical reaction system is made up of acid solution storage tank, feed bin and reactor, acid
Liquid storage tank is connected with reactor by pipeline with the bottom of feed bin, is provided with agitating device in reactor, reactor interior
Lining for heatproof, acidproof, high-abrasive material, bottom reactor above, be provided with an annular pipe, on pipe uniformly
Air-vent or permeability cell are distributed, in reactor, are provided with the vertical tube that the pipe with annular of more than is connected, described
The top of vertical tube is sent into system by the pipe valve on the kettle cover of reactor with hot-air and is connected；Still inwall from top to bottom or from
Lower and on be provided with and be close to still wall and helically wire tetrafluoro bundle of capillary tubes, the two ends up and down of this tube bank respectively with still wall
Outer cold and hot medium is connected by its valve, by being passed through cold and hot medium, for response system in still to the capillary tube in restraining
Offer is heated or cooled.
Cooling system is composed in series by one-level cooling reactor and two grades of cooling reactors；Wherein one-level cooling reactor is connected with reactor,
The kettle cover of reactor is provided with a pipeline being connected and be deep into one-level cooling reactor bottom center, one-level with one-level cooling reactor
Cooling reactor be internally provided with chiller, the bottom of one-level cooling reactor is provided with outlet valve, on the kettle cover of one-level cooling reactor
It is provided with the pipeline for two grades of cooling reactor bottom center that is connected with two grades of cooling reactors and is deep into, two grades of described cooling reactors
Be internally provided with chiller, the bottom of two grades of cooling reactors is provided with outlet valve；It is provided with on the kettle cover of two grades of cooling reactors
A piece pipeline being connected with waste gas absorbing system, described waste gas absorbing system by more than one negative pressure water tourie and
Acid mist absorbing device forms, and the top of negative pressure water tourie is provided with pipeline and by pipeline and drawing in acid mist absorbing device
Blower fan is connected.
Described hot-air is sent into system and is included air compressor, air storage tank, air heater and pipeline, air pressure
Contracting machine, air storage tank and air heater are connected by pipeline, and pipeline is additionally provided with valve and instrument.
A diameter of 10～20mm's and towards different permeability cells, adjacent permeability cell it are evenly distributed with on described pipe
Between spacing be 50～150mm, and the angle stretched out between direction of adjacent permeability cell is 60～120 °, reaction
Being provided with two vertical tubes in still, described two vertical tubes are connected to the two ends, left and right of pipe.
The chiller of described one-level cooling reactor is made up of rotating shaft and cooling disk, and described rotating shaft is that an outer wrap has poly-
The hollow circular-tube of tetrafluoroethene, the top of rotating shaft is stretched out on the kettle cover by one-level cooling reactor, is provided with one from upper in rotating shaft
Cooling water pipe A under and, the top of cooling water pipe A is water inlet end and water inlet end is connected with cooling water source；In rotating shaft all
The even cooling disk that is distributed, described cooling disk is fixed in rotating shaft with rotating shaft for the center of circle, and rotates with rotating shaft, institute
Stating cooling disk is hollow structure, and the inside of all cooling disks is provided with the cooling water pipe B of distribution in spiral shape, and
The neighbouring cooling water pipe B in cooling disk joins end to end, the cooling water pipe B's in the cooling disk of bottommost
Water inlet end is connected with the bottom of cooling water pipe A, and the water side of the cooling water pipe B in the cooling disk of top is led to
Hollow circular-tube, the cooling water discharged in cooling water pipe B is overflowed by the top of rotating shaft；It is uniformly distributed on described cooling disk
There is the passage mutual dislocation on vertical passage, and neighbouring cooling disk.
The kettle cover of described one-level cooling reactor is provided with the manhole of vacuum meter and easy access, on the kettle cover of one-level cooling reactor also
Being provided with compressed air blowning installation, compressed air blowning installation is connected with compressed gas source.
The described chiller in two grades of cooling reactors is multilamellar fin structure, and the still wall of two grades of cooling reactors is provided with cooling
Water inlet and coolant outlet, cooling water inlet is connected with the water inlet of orlop fin, and cooling water is by undermost wing
Sheet flow into, described fin is Curved Continuous folded structure, and the end of the adjacent fin of two-layer up and down is connected, coolant outlet with
The outlet of the superiors' fin is connected；Compressed air blowning installation, compressed air it is provided with on the kettle cover of two grades of cooling reactors
Blowning installation is connected with compressed gas source, and the kettle cover of two grades of cooling reactors is provided with vacuum meter, and its kettle cover and bottom all set
There is the manhole of easy access.
Described negative pressure water tourie is provided with two, and two negative pressure water touries are in series or are connected in parallel.
Compared with prior art, technical scheme provided by the present invention have the advantage that 1, the present invention useless with red mud etc.
Gurry, as raw material, is prepared into the product gas phase white carbon of high added value, SiO in obtained product2Content is big
In 99.9%, its multiple spot BET method measurement the specific area is not less than 350m2/ g, has therefore reached the effect turned waste into wealth.
2, preparation technology provided by the present invention belongs to a kind of brand-new technique thinking, solves existing gas-phase silica and prepares
High-temperature process in the presence of technique, use the shortcomings such as breakneck inflammable and explosive hydrogen and oxygen.The present invention is carried
The production technology of confession can be prepared at normal temperatures and pressures.3, produced sour gas in the preparation technology of the present invention
After negative pressure water tourie absorbs, it is possible to prepare corresponding acid solution, can be recycled after acid solution is concentrated to certain concentration,
The cost in producing and the problem of environmental protection treatment waste water can be greatly saved.4, the process units energy that the present invention provides
Enough realize large-scale industrial production, and used parts are chemical plant common tool, with low cost.5, originally
Invention can be for the TiO in red mud2, rare earth element and hydrated ferric oxide. reclaim, there is the biggest economic benefit.
Accompanying drawing explanation
The overall structure schematic diagram of the preparation facilities that Fig. 1 provides for the present invention；
Fig. 2 is the structural representation cooling down disk in one-level cooling reactor；
Fig. 3 is the structural representation of fin in two grades of cooling reactors；
In figure: 1-acid solution storage tank, 2-feed bin, 3-reactor, 4-agitating device, 5-pipe, 6-vertical tube, 7-one-level cools down
Still, bis-grades of cooling reactors of 8-, 9-outlet valve, 10-negative pressure water tourie, 11-acid mist absorbing device, 12-air compressor,
13-air storage tank, 14-air heater, 15-rotating shaft, 16-cools down disk, 17-cooling water pipe A, 18-passage,
19-fin.
Detailed description of the invention
Below in conjunction with the accompanying drawings and the present invention is done detailed specific description by specific embodiment, but protection scope of the present invention is also
It is not limited to following example.
The structure of the preparation facilities provided in the present embodiment as it is shown in figure 1, described device include hot-air send into system,
Chemical reaction system, cooling system and waste gas absorbing system, wherein hot-air sends into system for storing compressed air also
Sending into after heating air in chemical reaction system, described hot-air is sent into system and is included air compressor 12, sky
Gas holding vessel 13, air heater 14 and pipeline, air compressor 12, air storage tank 13 and air heater
14 are connected by pipeline, and pipeline is additionally provided with valve and instrument.
Described chemical reaction system is made up of acid solution storage tank 1, feed bin 2 and reactor 3, acid solution storage tank 1 and feed bin 2
Bottom is connected with reactor 3 by pipeline, is provided with agitating device 4 in reactor 3, the liner of reactor be heatproof,
Acidproof, high-abrasive material, specifically selects carborundum, fluorine material, graphite material etc..200mm above bottom reactor 3
At Zuo You, it is provided with an annular pipe 5, a diameter of the 100 of described pipe～200mm, on described pipe 5 all
Even be distributed a diameter of 10～20mm's and towards different permeability cells, the adjacent spacing between permeability cell be 50～
150mm, and the angle stretched out between direction of adjacent permeability cell is 60～120 °.Two and ring it is provided with in reactor
The vertical tube 6 that the pipe of shape is connected, two vertical tubes 6 are connected to the two ends, left and right of pipe 5, the top of described vertical tube 6
Hold and be connected with hot-air feeding system by the pipe valve on the kettle cover of reactor.Still wall in reactor has spiral to hang
Hook, for heating or the polytetrafluoroethylene capillary bundle of cooling in supporting still.
Cooling system is composed in series by one-level cooling reactor 7 and two grades of cooling reactors 8；Wherein one-level cooling reactor 7 and reactor 3
Being connected, the kettle cover of reactor 3 is provided with one and is connected with one-level cooling reactor 7 and is deep into one-level cooling reactor bottom center
Pipeline, one-level cooling reactor 7 be internally provided with chiller, the chiller of described one-level cooling reactor is by rotating shaft 15
Forming with cooling disk 16, described rotating shaft 15 is the hollow circular-tube that an outer wrap has politef, the top of rotating shaft
End stretches out on the kettle cover by one-level cooling reactor, is provided with a top-down cooling water pipe A17, cooling water pipe in rotating shaft
The top of A is water inlet end and water inlet end is connected with cooling water source；Cooling disk 16 it is evenly distributed with in rotating shaft 15.Cold
But the structure of disk is as in figure 2 it is shown, described cooling disk 16 is fixed in rotating shaft with rotating shaft 15 for the center of circle, and with
Rotating shaft rotates, and described cooling disk is hollow structure, and the inside of all cooling disks is provided with the cold of distribution in spiral shape
But the cooling water pipe B in water pipe B, and neighbouring cooling disk joins end to end, cold in the cooling disk of bottommost
But the water inlet end of water pipe B is connected with the bottom of cooling water pipe A, the cooling water pipe B's in the cooling disk of top
Lead to hollow circular-tube in water side, and the cooling water discharged in cooling water pipe B is overflowed by the top of rotating shaft.Described cooling disk
On be evenly distributed with vertical passage 18, and the passage mutual dislocation on neighbouring cooling disk, to ensure it
The cooling effect of gas.A diameter of the 10 of described passage～20mm, the adjacent centre-to-centre spacing between passage is
20mm～30mm.
The kettle cover of described one-level cooling reactor is provided with the manhole of vacuum meter and easy access, on the kettle cover of one-level cooling reactor also
Being provided with compressed air blowning installation, compressed air blowning installation is connected with compressed gas source.The still of one-level cooling reactor 7
Cover and be provided with a pipeline being connected with two grades of cooling reactors 8 and be deep into two grades of cooling reactor 8 bottom center.One-level cools down
The bottom of still is provided with outlet valve 9.
Two grades of described cooling reactors 8 be internally provided with chiller, the described chiller in two grades of cooling reactors is many
Layer fin structure, the still wall of two grades of cooling reactors 8 is provided with cooling water inlet and coolant outlet, cooling water inlet with
The water inlet of lower floor's fin is connected, cooling water flowed into by undermost fin, described fin 19 in Curved Continuous folded structure,
Its structure is as shown in Figure 3.The end of the adjacent fin of two-layer up and down is connected, and coolant outlet goes out with the superiors' fin
The mouth of a river is connected, and cooling water enters from orlop fin, flows out to one layer of fin topmost.The kettle cover of two grades of cooling reactors
On be provided with compressed air blowning installation, compressed air blowning installation is connected with compressed gas source, during discharging with compression sky
Air-blowing is swept.The kettle cover of two grades of cooling reactors is provided with vacuum meter, and its kettle cover and bottom are designed with the manhole of easy access.Two
The bottom of level cooling reactor is provided with outlet valve 9；Be provided with on the kettle cover of two grades of cooling reactors 8 one with waste gas absorbing system phase
The pipeline connected.
Described waste gas absorbing system is made up of two negative pressure water touries 10 and acid mist absorbing device 11, two negative pressure water
Tourie is in series or is connected in parallel.The top of negative pressure water tourie is provided with pipeline and by pipeline and acid mist absorbing device
In air-introduced machine be connected.Acid mist after two grades of water touries absorb in acid mist absorbing device with the droplet of liquid caustic soda solution
It is discharged into again in air after occurring to neutralize reaction, follows when giving workshop after the concentration that the acid solution of negative pressure water tourie reaches certain
Ring uses.
As a example by the red mud that Henan mining company is produced, the detailed preparation technology of the present invention is elaborated below,
Through analyzing, in this red mud, each constituent content is as follows: CaO:39～43%, Fe2O3: 10～12.6%, SiO2: 18.9～
20.7%, Al2O3: 5.96～8%, MgO:2.15～2.6%, K2O:0.47～0.59%, Na2O:2.58～2.68%,
TiO2: 6.13～6.7%.Concrete production stage is as follows:
(1), by one or both in Fluohydric acid., hexafluosilicic acid, mix with one or both in nitric acid, hydrochloric acid,
Preparing mix acid liquor, Fluohydric acid., hexafluosilicic acid, nitric acid or hydrochloric acid are technical grade；Or use industrial by-product.
As preferably, the mass concentration of described Fluohydric acid. or volumetric concentration are 2～30%, the mass concentration of hexafluosilicic acid or volume
Concentration is 10～30%, and the mass concentration of nitric acid or volumetric concentration are 2～30%, the mass concentration of hydrochloric acid or volumetric concentration
It is 10%～30%.
Pelletize after being mixed with hydrogen peroxide by red mud, is ground to the fineness of below 200 mesh after drying, and magnetic separation removes wherein
Ferrum, then with by hydrochloric acid molten except after the metal-oxide in the red mud after magnetic separation and rare earth element filter, collect filter cake standby.
Filtrate after filtering in above-mentioned steps first with in alkali and after, add sulfuric acid solution, after precipitate and separate goes out calcium sulfate, then
Add Fluohydric acid., after precipitate and separate goes out aluminum trifluoride, then with oxalic acid extract and separate Extraction of rare earth element；Remaining solution
Regulating pH value=8.5～9 with alkali liquor, precipitate, filter to isolate hydrated ferric oxide., calcining hydrated ferric oxide. i.e. can get ferrum oxide
Red product, finally concentrates filtrate, adds hexafluosilicic acid, the fluosilicate that can be precipitated and hydrochloric acid；Hydrochloric acid is purified
After return again to use.
(2), mix acid liquor is put in reactor, the waste gas absorption in the agitating device of unlatching reactor and response system
The powder that device, filter cake or filter cake obtain after drying, pulverizing is slowly put in reactor.
(3) if containing Fluohydric acid. in the mix acid liquor put into, owing to it and silicon dioxde reaction process are heat releases
Process, then the cooling water valve needing to open outside reaction response still maintains reaction temperature 75～90 DEG C.If the mixed acid put into
Liquid does not contains Fluohydric acid. and contains hexafluosilicic acid, then need the steam opening reacting kettle jacketing slowly to heat to reactor.Mixing
Fluohydric acid. or hexafluosilicic acid in acid solution generate silicon tetrafluoride gas, this gas one with the silicon dioxde reaction in filter cake or powder
It is partially soluble in the water of reaction system the silicon dioxide formed in hexafluosilicic acid continuation dissolving red mud, the tetrafluoro that another part overflows
Brought in cooling reactor by negative pressure together with the nitric acid/HCl gas of SiClx gas and volatilization and steam.
(4), the chilling temperature controlled in cooling reactor be 0～36 DEG C, mixed gas react in cooling reactor generate HF,
Cl2/NO2、SiO2·nH2O, chemical equation is as follows:
SiF4+4HNO3+nH2O=4HF ↑+4NO2↑+SiO2·nH2O
SiF4+4HCl+nH2O=4HF ↑+Cl2↑+SiO2·nH2O
Wherein HF and Cl2/NO2Overflow from one-level cooling reactor and two grades of cooling reactors, enter waste gas absorbing system and by water
Absorbing generation and be available for reusable Fluohydric acid., hydrochloric acid/nitric acid, this Fluohydric acid., hydrochloric acid/nitric acid are concentrated to certain concentration
After can be recycled；The cost in producing and the problem of environmental protection treatment waste water are the most greatly saved.
And SiO2·nH2O slowly condenses on absorption cooling disk in one-level cooling reactor, solidifying from starting on cooling disk
Poly-, then knot, in glittering and translucent spherical particle, flocks together as fish roe the most naturally, the most attractive in appearance, work as one-level
When the cooling disk of cooling reactor gathers a certain amount, opening of rotary shaft device, rotating shaft drives cooling disc rotary, centrifugal
Under the effect of power, material is thrown to still wall, then blows to the bottom of one-level cooling reactor by compressed air, through the outlet valve of bottom
It is sent to drying process；After having processed the material of one-level cooling reactor, two grades of cooling reactors the most directly open compressed air valve,
After directly the material condensed being blown to bottom, the outlet valve through bottom is sent to drying process；
(5), owing to material contains moisture, it is acidity, and the waving of Fluohydric acid., Silicon fluoride. and nitric acid or HCl gas
The property sent out is extremely strong, the most before it is dried, first by collected SiO2·nH2O carries out negative pressure preheating in vacuum heater, removes
Remove sour gas HF and Cl wherein remained2/NO2, it is dried the most again, can be prepared by gas-phase silica after drying
Product, SiO in product2Content is more than 99.9%, and its multiple spot BET method measurement the specific area is not less than 380m2/g。
(6), the acid solution in above-mentioned course of reaction: the silicon dioxide in Fluohydric acid. or hexafluosilicic acid decomposing materials；Hydrochloric acid with
Other metals in nitric acid then decomposing materials, alkali metal；Nitric acid primarily serves Oxidation in the process, and hydrochloric acid plays
Complexing.Metal after decomposition is then stayed in acid solution with ion and corresponding salt；After having reacted, filtered while hot, filter
Slag is a small amount of aluminum trifluoride and fluosilicate；Filtrate sends into evaporator evaporation while hot, the acid mist gas gas produced during evaporation
Carry out more than two grades absorptions with water tourie and become acid solution, after acid solution reaches finite concentration, return again to workshop profit the most again
With, unabsorbed tail gas acid fog absorption tower empties after being neutralized process；After the acid solution in vaporizer is evaporated, with dense
The dry slag of sulfuric acid treatment, recycling TiO2。
Claims (10)
1. the technique preparing gas-phase silica with red mud as a raw material, it is characterised in that comprise the following steps: (1), will contain
Fluoric acid liquid, mixes with one or both in nitric acid, hydrochloric acid, prepares mix acid liquor standby；By red mud and hydrogen peroxide
Pelletize after mixing, is ground to the fineness of below 200 mesh after drying, and magnetic separation removes ferrum therein, then with molten by hydrochloric acid
Except filtering after the metal-oxide in the red mud after magnetic separation and rare earth element, collect filter cake standby；
(2), mix acid liquor is put in reactor, the waste gas absorption in the agitating device of unlatching reactor and response system
Device, puts into the powder that filter cake or filter cake obtain after drying, pulverizing in reactor；
(3), the reaction temperature controlled in reactor be 75～90 DEG C, Fluohydric acid. in mix acid liquor or hexafluosilicic acid and filter cake
Or the silicon dioxde reaction in powder generates silicon tetrafluoride gas, the acid will volatilized in silicon tetrafluoride gas and mix acid liquor
Property gas and steam are brought in cooling reactor by negative pressure together；
(4), the chilling temperature controlled in cooling reactor be 0～36 DEG C, mixed gas react in cooling reactor generate HF,
Cl2/NO2、SiO2·nH2O, wherein HF and Cl2/NO2Taken out of from cooling reactor by negative pressure, and be only absorbed by the water generation can
For reusable Fluohydric acid., hydrochloric acid/nitric acid, SiO2·nH2O condenses on absorption chiller in cooling reactor, collects
SiO in cooling reactor2·nH2O；
(5), by collected SiO2·nH2O carries out negative pressure preheating in vacuum heater, removes the acidity wherein remained
Gas HF and Cl2/NO2, it is dried the most again, can be prepared by gas-phase silica product after drying, SiO in product2
Content is more than 99.9%, and its multiple spot BET method measurement the specific area is not less than 380m2/g；
(6) silicon dioxide during, in a kettle., fluorine-containing acid solution decomposes filter cake or powder；Hydrochloric acid and nitric acid then analyte
Residual metallic in material, the metal after decomposition is stayed in mix acid liquor with the form of ion and salt；Material in reactor is anti-
Should filter after completing, isolate the AlF in filtering residue3；Then filtrate is sent in vaporizer and is evaporated, obtain residue,
Use dense sulfuric acid treatment residue, recycling TiO2。
The technique preparing gas-phase silica the most according to claim 1, it is characterised in that: described Fluohydric acid.
Mass concentration or volumetric concentration are 2～30%, and the mass concentration of hexafluosilicic acid or volumetric concentration are 10～30%, the matter of nitric acid
Amount concentration or volumetric concentration are 2～30%, and the mass concentration of hydrochloric acid or volumetric concentration are 10%～30%.
The technique preparing gas-phase silica the most according to claim 1, it is characterised in that: step (1) filters
After filtrate first with in alkali and after, add sulfuric acid solution, after precipitate and separate goes out calcium sulfate, add Fluohydric acid., precipitation point
After separating out aluminum trifluoride, then with oxalic acid extract and separate Extraction of rare earth element；Remaining solution alkali liquor regulates pH value
=8.5～9, precipitate, filter to isolate hydrated ferric oxide., calcining hydrated ferric oxide. i.e. can get iron oxide red product, finally will
Filtrate concentrates, and adds hexafluosilicic acid, the fluosilicate that can be precipitated and hydrochloric acid；Return again to after hydrochloric acid is purified use.
The technique preparing gas-phase silica the most according to claim 1, it is characterised in that: evaporation in step (6)
Time the acid mist gas gas water tourie that produces carry out absorption and become acid solution, after acid solution reaches finite concentration, return again to car
Between re-use, unabsorbed tail gas acid fog absorption tower is neutralized after process and empties.
5. the device in technique described in claim 1, it is characterised in that: described device includes that hot-air send
Entering system, chemical reaction system, cooling system and waste gas absorbing system, wherein hot-air feeding system is used for storing pressure
Contracting air and send into after air is heated chemical reaction system and in；Described chemical reaction system is by acid solution storage tank, material
Storehouse and reactor composition, acid solution storage tank is connected with reactor by pipeline with the bottom of feed bin, is provided with and stirs in reactor
Mixing device, the liner of reactor is heatproof, acidproof, high-abrasive material, bottom reactor above, be provided with an annular
Pipe, pipe is evenly distributed with air-vent or permeability cell, be provided with in reactor more than one with annular pipe
The vertical tube being connected, the top of described vertical tube is sent into system by the pipe valve on the kettle cover of reactor with hot-air and is connected；
Still inwall is provided with from top to bottom or from bottom to top is close to still wall and helically wire tetrafluoro bundle of capillary tubes, this tube bank
Cold and hot medium outside two ends are respectively with still wall up and down is connected by its valve, by being passed through cold and hot Jie to the capillary tube in restraining
Matter, provides for response system in still and is heated or cooled.
Cooling system is composed in series by one-level cooling reactor and two grades of cooling reactors；Wherein one-level cooling reactor is connected with reactor,
The kettle cover of reactor is provided with a pipeline being connected and be deep into one-level cooling reactor bottom center, one-level with one-level cooling reactor
Cooling reactor be internally provided with chiller, the bottom of one-level cooling reactor is provided with outlet valve, on the kettle cover of one-level cooling reactor
It is provided with the pipeline for two grades of cooling reactor bottom center that is connected with two grades of cooling reactors and is deep into, two grades of described cooling reactors
Be internally provided with chiller, the bottom of two grades of cooling reactors is provided with outlet valve；It is provided with on the kettle cover of two grades of cooling reactors
A piece pipeline being connected with waste gas absorbing system, described waste gas absorbing system by more than one negative pressure water tourie and
Acid mist absorbing device forms, and the top of negative pressure water tourie is provided with pipeline and by pipeline and drawing in acid mist absorbing device
Blower fan is connected.
Device the most according to claim 5, it is characterised in that: described hot-air is sent into system and is included air pressure
Contracting machine, air storage tank, air heater and pipeline, air compressor, air storage tank and air heater pass through
Pipeline is connected, and pipeline is additionally provided with valve and instrument.
Device the most according to claim 5, it is characterised in that: be evenly distributed with on described pipe a diameter of 10～
20mm's and towards different permeability cells, the adjacent spacing between permeability cell is 50～150mm, and adjacent ventilative
The angle stretched out between direction of pipe is 60～120 °, is provided with two vertical tubes in reactor, and described two vertical tubes connect respectively
It is connected to the two ends, left and right of pipe.
Device the most according to claim 5, it is characterised in that: the chiller of described one-level cooling reactor is by rotating shaft and cold
But disk composition, described rotating shaft is the hollow circular-tube that an outer wrap has politef, and the top of rotating shaft is cold by one-level
But stretching out on the kettle cover of still, be provided with a top-down cooling water pipe A in rotating shaft, the top of cooling water pipe A is for entering
Water end (W.E.) and water inlet end are connected with cooling water source；Being evenly distributed with cooling disk in rotating shaft, described cooling disk with rotating shaft is
The center of circle is fixed in rotating shaft, and rotates with rotating shaft, and described cooling disk is hollow structure, all cooling disks interior
Portion is provided with the cooling water pipe B head and the tail phase in the cooling water pipe B of distribution in spiral shape, and neighbouring cooling disk
Even, the water inlet end of cooling water pipe B in the cooling disk of bottommost is connected with the bottom of cooling water pipe A, top
Cooling disk in the water side of cooling water pipe B lead to hollow circular-tube, the cooling water discharged in cooling water pipe B is by turning
The top of axle is overflowed；It is evenly distributed with on vertical passage, and neighbouring cooling disk on described cooling disk
Passage mutual dislocation.
Device the most according to claim 8, it is characterised in that: the kettle cover of described one-level cooling reactor is provided with very
Empty table and the manhole of easy access, the kettle cover of one-level cooling reactor is additionally provided with compressed air blowning installation, and compressed air is blown
Device of air is connected with compressed gas source.
Device the most according to claim 5, it is characterised in that: the described chiller in two grades of cooling reactors is
Multilamellar fin structure, the still wall of two grades of cooling reactors is provided with cooling water inlet and coolant outlet, cooling water inlet with
The water inlet of lower floor's fin is connected, and cooling water is flowed into by undermost fin, and described fin is Curved Continuous folded structure, phase
The end of the adjacent fin of two-layer up and down is connected, and coolant outlet is connected with the outlet of the superiors' fin；Two grades of coolings
Being provided with compressed air blowning installation on the kettle cover of still, compressed air blowning installation is connected with compressed gas source, and two grades cold
But the kettle cover of still is provided with vacuum meter, and its kettle cover and bottom are designed with the manhole of easy access.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112609074A (en) * | 2020-10-28 | 2021-04-06 | 广西大学 | Method for recovering iron, aluminum and sodium from Bayer process red mud |
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| CN102351150A (en) * | 2011-07-11 | 2012-02-15 | 多氟多化工股份有限公司 | Method for preparing hydrogen fluoride and coproducing white carbon black with silicon tetrafluoride |
| US20120082610A1 (en) * | 2010-10-02 | 2012-04-05 | Channon Matthew J | Fluorspar/Iodide process for reduction,purificatioin, and crystallization of silicon |
| CN105110344A (en) * | 2015-08-19 | 2015-12-02 | 六盘水师范学院 | Method and apparatus for preparing fumed silica from coal gangue |
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| CN1458061A (en) * | 2003-04-13 | 2003-11-26 | 季海水 | Process for extracting CaF2 and SiO2 from fluorite tailing and producing fluorosilicic acid further |
| CN101774587A (en) * | 2010-02-11 | 2010-07-14 | 浙江中宁硅业有限公司 | Method for preparing silicon tetrafluoride by quartz sand |
| US20120082610A1 (en) * | 2010-10-02 | 2012-04-05 | Channon Matthew J | Fluorspar/Iodide process for reduction,purificatioin, and crystallization of silicon |
| CN102351150A (en) * | 2011-07-11 | 2012-02-15 | 多氟多化工股份有限公司 | Method for preparing hydrogen fluoride and coproducing white carbon black with silicon tetrafluoride |
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| CN112609074A (en) * | 2020-10-28 | 2021-04-06 | 广西大学 | Method for recovering iron, aluminum and sodium from Bayer process red mud |
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