CN113526886A - Method for removing iron and preparing green vanadium and iron-based pigment by using titanium white waste acid - Google Patents
Method for removing iron and preparing green vanadium and iron-based pigment by using titanium white waste acid Download PDFInfo
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- CN113526886A CN113526886A CN202110823671.8A CN202110823671A CN113526886A CN 113526886 A CN113526886 A CN 113526886A CN 202110823671 A CN202110823671 A CN 202110823671A CN 113526886 A CN113526886 A CN 113526886A
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- iron
- acid
- acid leaching
- gypsum
- solid
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 395
- 239000002253 acid Substances 0.000 title claims abstract description 238
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 184
- 238000000034 method Methods 0.000 title claims abstract description 101
- 239000002699 waste material Substances 0.000 title claims abstract description 98
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 235000010215 titanium dioxide Nutrition 0.000 title claims abstract description 63
- 239000000049 pigment Substances 0.000 title claims abstract description 31
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 29
- 239000010440 gypsum Substances 0.000 claims abstract description 176
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 176
- 238000002386 leaching Methods 0.000 claims abstract description 137
- 239000010936 titanium Substances 0.000 claims abstract description 116
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 116
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 115
- 239000007787 solid Substances 0.000 claims abstract description 67
- 239000007788 liquid Substances 0.000 claims abstract description 65
- 238000000926 separation method Methods 0.000 claims abstract description 43
- 238000001035 drying Methods 0.000 claims abstract description 38
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 33
- 239000013078 crystal Substances 0.000 claims abstract description 31
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 22
- 239000012535 impurity Substances 0.000 claims abstract description 17
- 230000009466 transformation Effects 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 230000009471 action Effects 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims description 49
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 36
- 150000004683 dihydrates Chemical class 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000007654 immersion Methods 0.000 claims description 20
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 claims description 18
- 239000007800 oxidant agent Substances 0.000 claims description 18
- 238000005554 pickling Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 16
- 238000002425 crystallisation Methods 0.000 claims description 14
- 230000001590 oxidative effect Effects 0.000 claims description 14
- 239000004408 titanium dioxide Substances 0.000 claims description 14
- 230000008025 crystallization Effects 0.000 claims description 12
- 230000003472 neutralizing effect Effects 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 11
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 8
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- 208000005156 Dehydration Diseases 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 3
- 235000021110 pickles Nutrition 0.000 abstract description 35
- 239000000047 product Substances 0.000 abstract description 22
- 239000004566 building material Substances 0.000 abstract description 18
- 239000000243 solution Substances 0.000 description 60
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 18
- 239000002994 raw material Substances 0.000 description 18
- 239000002910 solid waste Substances 0.000 description 12
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 11
- 238000000498 ball milling Methods 0.000 description 10
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 10
- 239000003607 modifier Substances 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000011780 sodium chloride Substances 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000004568 cement Substances 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000003828 vacuum filtration Methods 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- 239000002440 industrial waste Substances 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229910001448 ferrous ion Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 3
- 238000009270 solid waste treatment Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 description 1
- CKLJMWTZIZZHCS-UWTATZPHSA-N L-Aspartic acid Natural products OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910004878 Na2S2O4 Inorganic materials 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229960005261 aspartic acid Drugs 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- KIZFHUJKFSNWKO-UHFFFAOYSA-M calcium monohydroxide Chemical compound [Ca]O KIZFHUJKFSNWKO-UHFFFAOYSA-M 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
- C04B11/262—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke waste gypsum other than phosphogypsum
-
- 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
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/14—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/02—Methods and apparatus for dehydrating gypsum
- C04B11/028—Devices therefor characterised by the type of calcining devices used therefor or by the type of hemihydrate obtained
- C04B11/032—Devices therefor characterised by the type of calcining devices used therefor or by the type of hemihydrate obtained for the wet process, e.g. dehydrating in solution or under saturated vapour conditions, i.e. to obtain alpha-hemihydrate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a method for removing iron and preparing green vanadium and iron-based pigment by using titanium white waste acid. The method comprises the steps of performing acid leaching treatment on titanium gypsum by using titanium white waste acid to enrich iron in the titanium white waste acid, and performing solid-liquid separation to obtain iron-enriched pickle liquor and solids; carrying out acid leaching treatment on the obtained acid leaching solution circularly, and carrying out acid leaching treatment on new titanium gypsum by using the acid leaching solution obtained in each acid leaching treatment until iron impurities in the acid leaching solution are saturated; then, the obtained iron saturated pickle liquor and the obtained solid are treated by two paths: drying and crystal transformation processing are carried out on the solid to obtain high-strength alpha-type semi-hydrated gypsum which can be used as a building material; for the iron saturated pickle liquor, firstly removing iron for the first time, and cooling and crystallizing under the action of a reducing agent to obtain green vanadium and acid pickle liquor after the first iron removal; and then carrying out secondary iron removal on the acid leaching solution subjected to the primary iron removal to obtain the iron-based pigment and a secondary iron-removal acid leaching solution. The method can effectively remove iron and obtain high-value products.
Description
Technical Field
The invention relates to the field of treatment of industrial waste acid, in particular to a method for removing iron and preparing green vanadium and iron-based pigment by using titanium white waste acid.
Background
Titanium dioxide is a white inorganic pigment, and the main component of the titanium dioxide is titanium dioxide. The production method of titanium dioxide mainly comprises a sulfuric acid method and a chlorination method, and 91 percent of titanium dioxide is produced by the sulfuric acid method at present in China. The sulfuric acid method has simple and reliable process, but has large amount of three wastes. The titanium white waste acid is a waste acid solution which is obtained by mixing unreacted free sulfuric acid and new sulfuric acid generated by hydrolysis reaction during the acidolysis of titanium concentrate by a sulfuric acid method and filtering and separating the aqueous solution and metatitanic acid. When 1t of titanium dioxide is produced, 5-8 t of waste acid containing 19-23% of sulfuric acid is produced, so that the comprehensive utilization approach is limited. The detection data of titanium white waste acid of various enterprises can obtain that the content of each element in the waste acid is Fe most, and then the elements of Ti, Mg, A1 and Mn. Harmful heavy metal elements such As Cr, Ni, As, Pb and the like are not contained in a large amount in waste acid, but are not disposable or sold due to toxicity, and therefore, the harmful heavy metal elements need to be subjected to harmless treatment.
At present, besides the waste acid is used for rust removal of acid-washing steel plates in steel mills, the treatment method of iron white waste acid mainly comprises two methods: one is a treatment method based on terminal discharge of wastewater; and the other treatment method is based on the recycling of waste acid.
The former method mainly adopts chemical neutralization to remove impurities in the waste acid, and the conventional treatment is to utilize lime, limestone or lime milk, etc. to respectively mainly contain calcium oxide (CaO) and calcium carbonate (CaCO)3) And calcium hydroxide (CaOH)2) Neutralizing alkaline substances and waste acid with acid and alkali, precipitating, and separating mud and water to obtain byproduct iron-containing titanium gypsum (CaSO)4) And the like. The waste acid treated by the neutralization method has the disadvantages that ferric hydroxide and other various impurity wastes are inevitably doped in a neutralization product (such as calcium sulfate) due to a large amount of iron ions contained in the waste acid, the waste acid is not beneficial to recycling, and if the waste acid is subjected to landfill treatment, a large amount of solid wastes (titanium gypsum) generated still cause secondary pollution to the environment. More importantly, valuable resources such as sulfuric acid, ferrous sulfate, scandium, titanium, vanadium, manganese and the like in the waste acid are wasted.
The latter mainly adopts the following modes: the membrane filtering process includes evaporation concentration, pressed membrane distillation, etc. and the process can obtain relatively pure sulfuric acid for reuse after concentration. But the concentration of the sulfuric acid recovered by the method is low, the efficiency is not high, and because the gypsum powder is too fine, the film is easy to block, the industrialization is not easy to realize, and the actual popularization and utilization degree is not high; ② a concentration crystallization method, including an immersion combustion method and a freezing crystallization method, the concentration method has the advantages of high thermal efficiency and high concentration of finished acid, but the energy consumption is large. The high temperature causes severe corrosion of the equipment, and has higher requirements on the material of the equipment; extraction method, this method can separate the valuable element in the waste acid, but the extractant and extraction series that need will increase the cost; fourthly, other methods, such as diffusion dialysis, microfiltration and the like, recover the copperas and concentrate the sulfuric acid for recycling. At present, direct evaporation concentration is the most main method for recovering titanium white waste acid, but because more ferrous ions exist in the titanium white waste acid, ferrous sulfate is easily crystallized and separated out in the evaporation concentration process, and the concentration process is influenced, the ferrous ions in the titanium white waste acid need to be removed firstly. Under certain conditions, ferrous ions precipitate as copperas salts. The precipitate can be obtained as light green crystals, which are called copperas in industry. The byproduct copperas obtained from titanium dioxide production has a content of more than 90%, and can meet the requirements of various purposes only by slightly purifying.
Most of the titanium white waste acid in the current industry is neutralized into titanium gypsum by a neutralization mode, and particularly about 48 percent of the titanium gypsum is neutralized into the titanium gypsum. At present, titanium dioxide is treated by most titanium gypsum in a slag yard storage mode, and enterprises need to consume huge storage yard construction and maintenance cost every year. Because the comprehensive utilization rate of the titanium gypsum is low, the healthy development of the titanium dioxide industry in China is severely restricted by a large amount of emission, the emission amount of the titanium gypsum in China is about 2600 ten thousand tons in 2020, and the accumulated titanium gypsum stockpiling amount is nearly 2 hundred million tons. At present, the comprehensive utilization ways of titanium gypsum are as follows: replacing natural gypsum to be used as a cement buffering agent; producing a gelled material; producing a wall material; manufacturing a roadbed material; used for soil improvement agents; reducing to prepare calcium oxide, sulfuric acid and the like. The method for preparing calcium oxide by reducing carbon, sulfur and pyrite and the sulfuric acid method have the characteristics of simple process, large-scale production, realization of internal circulation of sulfur resources in a plant and the like, have some patents in the aspects of phosphogypsum, desulfurized gypsum and the like, but are limited by high energy consumption, low titanium gypsum decomposition rate, smoke SO2Low concentration, unstable calcium oxide quality and the like, and no mature process is applied to actual production.
For years, the work of utilizing titanium white waste acid and titanium gypsum has been studied and developed, the comprehensive utilization rate of the titanium gypsum is less than 10%, and the main problems of utilizing the titanium gypsum are as follows in essence: (1) the titanium gypsum has high content of impurities such as iron (Fe is approximately equal to 5%), red is difficult to be used as a building material, abrasion of raw material grinding equipment is accelerated, cement hydration (slow setting) is hindered, and the prepared super-sulfate cement has the problem that iron and organic phases exceed standards. (2) The titanium gypsum has high water content (> 50%), and the cost of filter pressing and drying treatment is too high, so that the titanium gypsum is only marginally accepted by cement factories. In addition, due to the regional problems, most titanium gypsum production enterprises are remote, cement plants are rare in some regions, and economic development in some regions is relatively lagged, so that the market demand of the regions and the surrounding markets for gypsum products is limited, the distance from the production place of the titanium gypsum products to the market is far away from the reasonable transportation radius of the titanium gypsum products, and the dilemma of lost sales is caused. (3) The crystal particles in the titanium gypsum are smaller, and the relationship between the principle of forming solid matters for the second time and the structural strength is unclear. So that the preparation of the crystal whisker, the filling material and the like is not stable enough, the strength is not enough, and the market competitiveness is not good.
In recent years, the contradiction between economic development and resource environment of China is continuously intensified, and the problems of land occupation and environment occupation caused by the massive stockpiling of titanium gypsum are reflected by the contradiction.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for removing iron and preparing green vanadium and iron-based pigments by using titanium white waste acid. The method provided by the invention can directly remove iron ions in the titanium white waste acid, so that titanium white gypsum is not generated any more, alpha-type semi-hydrated gypsum with higher strength for building materials is obtained, and meanwhile, the method can obtain high-value products of green vanadium and iron-based pigment, and improves the utilization rate of calcium, iron and sulfur resources in the titanium white waste acid.
The invention provides a method for removing iron and preparing green vanadium and iron-based pigment by using titanium dioxide waste acid, which comprises the following steps:
a) acid leaching treatment:
carrying out acid leaching on titanium gypsum by using titanium white waste acid, and then carrying out solid-liquid separation to obtain acid leaching solution and solid;
b) and (3) circulating acid leaching treatment:
taking titanium gypsum, and performing acid leaching and solid-liquid separation on the titanium gypsum again according to the acid leaching process of the step a) by using the acid leaching solution obtained in the step a), so as to obtain acid leaching solution and solid again;
the above processes are repeated in a circulating way, the pickling liquid obtained by each pickling process is taken as the dipping liquid of the next pickling process, and the pickling process is repeated until the iron impurities in the obtained pickling liquid are saturated, so that the pickling liquid and the solid matter saturated with iron are obtained;
c) preparing alpha-type semi-hydrated gypsum:
drying the solid obtained after each acid leaching treatment to obtain beta type dihydrate gypsum;
carrying out crystal transformation reaction on the beta-type hemihydrate gypsum under the action of a crystal transformation agent to obtain alpha-type hemihydrate gypsum;
d) iron removal for the first time:
mixing the acid leaching solution saturated by iron with a reducing agent, and then carrying out cooling crystallization and solid-liquid separation to obtain green vanadium and an acid leaching solution subjected to first iron removal;
e) and (3) removing iron for the second time:
mixing the acid leaching solution after the first iron removal, a neutralizing agent and an oxidant, standing for precipitation and carrying out solid-liquid separation to obtain a precipitate Fe (OH)3And acid immersion liquid after second iron removal;
for the Fe (OH)3Carrying out dehydration treatment to obtain an iron-based pigment;
the steps c) and d) are not limited in order.
Preferably, in the step a), the acid leaching temperature is 50-100 ℃, and the time is 1-4 h.
Preferably, in the step a), the liquid-solid ratio of the acid leaching is 4-10.
Preferably, in the step d), the reducing agent is one or more selected from ascorbic acid, sodium thiosulfate and ferrous ammonium sulfate.
Preferably, the mass ratio of the reducing agent to the total amount of the titanium gypsum in the step d) is 1: 5-10.
Preferably, in the step d), the cooling crystallization conditions are as follows: cooling to 10-30 ℃, and keeping for 1-6 h.
Preferably, in the step e), the neutralizing agent is NaOH and/or KOH;
the dosage of the neutralizing agent is such that the pH value of the system reaches 2.0-4.0.
Preferably, in step e), the oxidizing agent is selected from H2O2、NaClO4And MnO2One or more of the above;
the mass ratio of the oxidant to the acid immersion liquid after the first iron removal is 1: 10-20.
Preferably, in the step a), the mass fraction of sulfuric acid in the titanium white waste acid is 5-30%.
Preferably, in the step c), the drying temperature is 50-70 ℃ and the drying time is 4-10 h;
the iron-based pigment is iron oxide red and/or iron oxide yellow.
The method comprises the steps of performing acid leaching treatment on titanium gypsum by using titanium white waste acid to enrich iron in the titanium white waste acid, and performing solid-liquid separation to obtain iron-enriched pickle liquor and solids; carrying out acid leaching treatment on the obtained acid leaching solution circularly, and carrying out acid leaching treatment on new titanium gypsum by using the acid leaching solution obtained in each acid leaching treatment until iron impurities in the acid leaching solution are saturated; then the obtained iron saturated pickle liquor and solid are treated by two paths. The solid matter is dried to obtain beta-type hemihydrate gypsum, and then crystal transformation treatment is carried out to obtain alpha-type hemihydrate gypsum with higher strength and capable of being used as building materials. For the iron saturated pickle liquor, firstly removing iron for the first time, and cooling and crystallizing under the action of a reducing agent to obtain green vanadium and acid pickle liquor after the first iron removal; and then carrying out secondary iron removal on the acid leaching solution subjected to the primary iron removal to obtain an iron-based pigment (iron red or iron yellow) and a secondary iron-removal acid leaching solution.
The invention utilizes the waste liquid of titanium white waste acid to treat the solid waste of titanium gypsum to obtain the high-strength gypsum for building materials, thereby not only obtaining building material products, but also obtaining the high-strength gypsum for building materials by treating the solid waste with the waste acid, achieving the purpose of greatly absorbing the solid waste of the waste acid and the titanium gypsum, greatly reducing the economic and environmental protection pressure of the solid waste treatment of enterprises, and realizing the low-carbon process of treating waste with waste and changing waste into valuable. In addition, the acid leaching solution is subjected to iron removal twice, short-range online separation of iron elements in the titanium white waste acid is realized, titanium gypsum is hopefully prevented from being generated from the source (titanium gypsum is a byproduct in the existing waste acid treatment process), the existing titanium gypsum solid waste is consumed, a new titanium gypsum byproduct cannot be generated, high-value products such as green vanadium, iron-based pigment and the like are formed in the iron removal treatment, the in-plant circulation of calcium and sulfur elements is realized, and the utilization rate of calcium, iron and sulfur resources in the titanium white waste acid is improved. Therefore, the treatment process not only obtains the high-strength gypsum product for building materials, but also is a treatment route for treating wastes with wastes and changing wastes into valuables, consumes a large amount of waste acid and titanium gypsum solid wastes, does not generate new titanium gypsum byproducts, and can also obtain high-value products such as green vanadium, iron-based pigments (iron red or iron yellow) and the like.
The experimental result shows that the residual iron content of the pickle liquor obtained by the method is below 455ppm, and the iron removal rate of the titanium gypsum raw material is above 90%; high-value products of green vanadium and iron-based pigments are obtained at the same time.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
Fig. 1 is a schematic flow chart of a processing method according to an embodiment of the present invention.
Detailed Description
The invention provides a method for removing iron and preparing green vanadium and iron-based pigment by using titanium dioxide waste acid, which comprises the following steps:
a) acid leaching treatment:
carrying out acid leaching on titanium gypsum by using titanium white waste acid, and then carrying out solid-liquid separation to obtain acid leaching solution and solid;
b) and (3) circulating acid leaching treatment:
taking titanium gypsum, and performing acid leaching and solid-liquid separation on the titanium gypsum again according to the acid leaching process of the step a) by using the acid leaching solution obtained in the step a), so as to obtain acid leaching solution and solid again;
the above processes are repeated in a circulating way, the pickling liquid obtained by each pickling process is taken as the dipping liquid of the next pickling process, and the pickling process is repeated until the iron impurities in the obtained pickling liquid are saturated, so that the pickling liquid and the solid matter saturated with iron are obtained;
c) preparing alpha-type semi-hydrated gypsum:
drying the solid obtained after each acid leaching treatment to obtain beta type dihydrate gypsum;
carrying out crystal transformation reaction on the beta-type hemihydrate gypsum under the action of a crystal transformation agent to obtain alpha-type hemihydrate gypsum;
d) iron removal for the first time:
mixing the acid leaching solution saturated by iron with a reducing agent, and then carrying out cooling crystallization and solid-liquid separation to obtain green vanadium and an acid leaching solution subjected to first iron removal;
e) and (3) removing iron for the second time:
mixing the acid leaching solution after the first iron removal, a neutralizing agent and an oxidant, standing for precipitation and carrying out solid-liquid separation to obtain a precipitate Fe (OH)3And acid immersion liquid after second iron removal;
for the Fe (OH)3Carrying out dehydration treatment to obtain an iron-based pigment;
the steps c) and d) are not limited in order.
The invention utilizes the waste liquid of titanium white waste acid to treat the solid waste of titanium gypsum to obtain the high-strength gypsum for building materials, thereby not only obtaining building material products, but also obtaining the high-strength gypsum for building materials by treating the solid waste with the waste acid, achieving the purpose of greatly absorbing the solid waste of the waste acid and the titanium gypsum, greatly reducing the economic and environmental protection pressure of the solid waste treatment of enterprises, and realizing the low-carbon process of treating waste with waste and changing waste into valuable. In addition, the acid leaching solution is subjected to iron removal twice, short-range online separation of iron elements in the titanium white waste acid is realized, titanium gypsum is hopefully prevented from being generated from the source (titanium gypsum is a byproduct in the existing waste acid treatment process), the existing titanium gypsum solid waste is consumed, a new titanium gypsum byproduct cannot be generated, high-value products such as green vanadium, iron-based pigment (iron red or iron yellow) and the like are formed in the iron removal treatment, in-plant circulation of calcium and sulfur elements is realized, and the utilization rate of calcium, iron and sulfur resources in the titanium white waste acid is improved. Therefore, the treatment process not only obtains the high-strength gypsum product for building materials, but also is a treatment route for treating wastes with wastes and changing wastes into valuables, consumes a large amount of waste acid and titanium gypsum solid wastes, does not generate new titanium gypsum byproducts, and can also obtain high-value products such as green vanadium, iron-based pigment and the like.
Referring to fig. 1, fig. 1 is a schematic flow chart of a processing method according to an embodiment of the present invention.
With respect to step a): acid leaching treatment: and (3) carrying out acid leaching on the titanium gypsum by using titanium white waste acid, and then carrying out solid-liquid separation to obtain acid leaching solution and solid.
In the invention, the titanium white waste acid is preferably titanium white waste acid with the mass fraction of sulfuric acid of 5-30%. In some embodiments of the invention, the mass fraction of sulfuric acid in the titanium white spent acid is 5%, 10%, 20%, or 30%.
In the present invention, the titanium gypsum is preferably used in advance by: drying, ball milling and sieving. Wherein the drying temperature is preferably 50-80 ℃, and the drying time is preferably 2-6 h. And (3) preferably obtaining titanium gypsum powder with the granularity of 150-500 mu m by ball milling and sieving. And performing acid leaching treatment by taking the titanium gypsum powder as a raw material.
In the invention, the liquid-solid ratio of the titanium white waste acid to the titanium gypsum acid leaching is preferably 4-10. The liquid-solid ratio refers to the liquid-solid mass ratio, namely the mass ratio of the titanium white waste acid liquid to the titanium gypsum solid.
In the invention, the acid leaching temperature is preferably 50-100 ℃, and in some embodiments of the invention, the temperature is 70 ℃. The time for acid leaching is preferably 1-4 h, and in some embodiments of the invention, the time is 2 h. In the acid leaching process, the iron element in the titanium gypsum is enriched in the titanium white waste acid.
In the present invention, after the acid leaching treatment, solid-liquid separation is performed. In the present invention, the solid-liquid separation is preferably performed by vacuum filtration. And after solid-liquid separation, respectively obtaining pickle liquor and solids.
With respect to step b): and (3) circulating acid leaching treatment: taking titanium gypsum, and performing acid leaching and solid-liquid separation on the titanium gypsum again according to the acid leaching process of the step a) by using the acid leaching solution obtained in the step a), so as to obtain acid leaching solution and solid again; and (4) circularly repeating the processes, and repeating the process of acid leaching by taking the acid leaching solution obtained by each acid leaching treatment as the steeping solution of the next acid leaching treatment until iron impurities in the obtained acid leaching solution are saturated to obtain the acid leaching solution and solid with saturated iron.
In the invention, the pickle liquor obtained in the step a) is used as the steeping liquor, titanium gypsum is additionally taken, and the acid leaching and solid-liquid separation are carried out again according to the acid leaching process in the step a), so that the pickle liquor and solid are obtained again.
Among them, the titanium gypsum is preferably also previously used: drying, ball milling and sieving. The conditions of each operation are the same as those described above, i.e. the same ranges of the condition parameters as those described above are selected, but are independently selected from the ranges of the condition parameters as step a), and are not necessarily the same as the specific parameters used in the step a), and the specific ranges of the condition parameters are not described herein again.
Similarly, the conditions of the solid-to-liquid ratio of the acid leaching treatment, the temperature and time of the acid leaching treatment, etc. are the same as those described above, i.e. the conditions are selected from the same condition parameter ranges as described above, but are independently selected from the condition parameter ranges as described above in step a), and are not necessarily the same as the specific parameters used in the implementation of step a), and the specific condition parameter ranges are not repeated herein.
The invention circularly repeats the processes, and the pickle liquor obtained by each acid leaching treatment is taken as the steeping liquor of the next acid leaching treatment to repeat the processes of acid leaching treatment (including acid leaching and solid-liquid separation) until the iron impurities in the obtained pickle liquor are saturated, thereby respectively obtaining the pickle liquor saturated with iron and solid.
The operating conditions in each cyclic acid leaching are also identical to those described above, i.e. the ranges of the same condition parameters are selected as described above, but are independently selected from the ranges of the condition parameters as described above in step a) and are not necessarily the same as the specific parameters used in carrying out step a), and the specific ranges of the condition parameters are not described herein again.
The invention respectively obtains pickle liquor and solid matter saturated with iron through the acid leaching treatment and the circulating acid leaching treatment of the steps a) to b). The invention processes the two products in two paths, and for solid, the step c) is carried out, and for the pickle liquor saturated by iron, the steps d) to e) are carried out. The present invention does not have to limit the order of step c) and step d).
With respect to step c): preparing alpha-type semi-hydrated gypsum: drying the solid obtained after each acid leaching treatment to obtain beta type dihydrate gypsum; and carrying out crystal transformation reaction on the beta-type hemihydrate gypsum under the action of a crystal transformation agent to obtain the alpha-type hemihydrate gypsum.
In the invention, the drying temperature is preferably 50-70 ℃, and the drying time is preferably 4-10 h. Drying to obtain beta type dihydrate gypsum.
In the present invention, the method for realizing the crystal transformation reaction is preferably: the salt solution, the crystal modifier and the beta-type dihydrate gypsum are mixed and reacted to convert the beta-type dihydrate gypsum into the alpha-type hemihydrate gypsum.
In the present invention, the specific operation process of the above method preferably includes: s1, adding a crystal transformation agent into the salt solution, heating to a target temperature, adding beta-type dihydrate gypsum, and carrying out constant-temperature dynamic reaction to obtain a reaction solution; and S2, carrying out solid-liquid separation on the reaction liquid, and drying the obtained solid to obtain the alpha-type semi-hydrated gypsum.
Wherein:
the mass concentration of the salt solution (i.e., aqueous NaCl solution) is preferably 15% to 30%. The liquid-solid ratio of the salt solution to the beta-type dihydrate gypsum is preferably 5-10.
The crystal modifier is preferably an organic acid crystal modifier, and more preferably one or more of maleic acid, L-aspartic acid, succinic acid, phthalic acid and citric acid. The invention selects proper crystal transformation agent to transform beta type dihydrate gypsum into alpha type hemihydrate gypsum with higher strength than the beta type dihydrate gypsum, thus obtaining the product for building materials. The mass ratio of the crystal modifier to the beta-type dihydrate gypsum is preferably 1 to (1000-10000).
The target temperature is preferably 90-102 ℃, and more preferably 100 ℃. The reaction time is preferably 0.2-1 h. The reaction is a constant temperature dynamic reaction, namely, the reaction is continuously stirred in the reaction process. The stirring speed is preferably 200-600 r/min, and more preferably 400 r/min. Through the reaction, the beta type dihydrate gypsum solid in the system is converted into alpha type hemihydrate gypsum solid.
The solid-liquid separation mode is preferably suction filtration, so that rapid separation is realized. The temperature for drying the obtained solid is preferably 40-80 ℃, and more preferably 60 ℃. The drying time is preferably 4-8 h. After the drying, ball milling is preferably carried out; the ball milling speed is preferably 150-250 rpm, and the time is preferably 1-3 h; and (3) performing ball milling to obtain the alpha-type semi-hydrated gypsum powder.
In the present invention, when the solid obtained in steps a) to b) is treated as described above to prepare the alpha-hemihydrate gypsum powder, the treatment can be carried out in two ways: the first mode is that after each time of acid leaching treatment to obtain solid matter, the treatment of the step c) is carried out, and alpha-type semi-hydrated gypsum is obtained by multiple times; in the second mode, after the whole cycle of acid leaching is finished, the solids obtained by each acid leaching treatment are combined together, and then the treatment of the step c) is carried out, so that the alpha-hemihydrate gypsum is obtained at one time.
According to the invention, through the steps a) -c), the industrial wastes, namely titanium dioxide waste acid and titanium gypsum, are used as main raw materials, and are treated by impregnation and the like, so that the high-strength gypsum as a building material is obtained, the industrial wastes are greatly digested, and the environmental protection pressure and the waste treatment cost are reduced.
With respect to step d): iron removal for the first time: and mixing the acid leaching solution saturated by iron and a reducing agent, and then carrying out cooling crystallization and solid-liquid separation to obtain green vanadium and the acid leaching solution subjected to the first iron removal.
In the invention, the reducing agent is preferably one or more of ascorbic acid, sodium thiosulfate and ferrous ammonium sulfate. In the invention, the mass ratio of the reducing agent to the total amount of the titanium gypsum is preferably 1 to (5-10); wherein the total amount of the titanium gypsum is the sum of the dosage of the titanium gypsum raw materials adopted in each acid leaching in the steps a) to b). The temperature of the mixing is not particularly limited, and may be carried out at room temperature. Fe in pickle liquor is reduced by reducing agent3+Reduction to Fe2+Taking reducing agent sodium thiosulfate as an example, the reaction principle is as follows: fe2O3+Na2S2O4+3H2SO4→2FeSO4+2SO2↑+Na2SO4+3H2O。
In the invention, the cooling crystallization temperature is preferably 10-30 ℃; the holding time is preferably 1 to 6 hours. Tong (Chinese character of 'tong')Supercooling and crystallizing, and gradually crystallizing at the bottom of the container to form green vanadium (FeSO)4·7H2O), and separating the bottom solid crystal from the supernatant through solid-liquid separation. In the present invention, the solid-liquid separation method is not particularly limited, and may be a conventional separation method in the art. After solid-liquid separation, the green vanadium and the acid immersion liquid after the first iron removal are respectively obtained.
With respect to step e): and (3) removing iron for the second time: mixing the acid leaching solution after the first iron removal, a neutralizing agent and an oxidant, standing for precipitation and carrying out solid-liquid separation to obtain a precipitate Fe (OH)3And acid immersion liquid after second iron removal; for the Fe (OH)3And (4) dehydrating to obtain the iron-based pigment.
In the present invention, the neutralizing agent is preferably NaOH and/or KOH. The neutralizing agent is preferably added in the form of an aqueous solution. The dosage of the neutralizing agent is preferably that the pH value of the system reaches 2.0-4.0.
In the present invention, the oxidizing agent is preferably H2O2、NaClO4And MnO2One or more of them. The mass ratio of the oxidant to the acid immersion liquid subjected to the first iron removal is preferably 1: 10-20.
In the present invention, the mixing temperature is not particularly limited, and may be carried out at room temperature. Mixing, standing for precipitation and solid-liquid separation, specifically, standing in a precipitation device to separate precipitate Fe (OH)3And obtaining acid immersion liquid after iron removal for the second time.
The invention relates to the sediment Fe (OH)3And (4) dehydrating to obtain the iron-based pigment. The dehydration treatment is drying treatment. The drying temperature is preferably 60-100 ℃, and the drying time is preferably 2-4 h. And drying to obtain the iron-based pigment. The iron-based pigment is iron oxide red (namely Fe)2O3) And/or ferrite yellow (i.e., Fe)2O3·H2O)。
In the invention, the acid immersion liquid after the second iron removal can be recycled, and the steps d) to e) are carried out by taking the acid immersion liquid as the raw material liquid to continuously obtain the green vanadium and the iron-based pigment.
The invention provides a method for removing iron and preparing green vanadium and iron-based pigment by using titanium white waste acid, which takes industrial waste, namely titanium white waste acid and titanium gypsum, as main raw materials, and utilizes acid leaching and a series of controllable preparation to obtain high-strength gypsum as a building material, and simultaneously crystallize out copperas and precipitate out ferric hydroxide to prepare the iron-based pigment; the waste water can be recycled. The aims of low cost, short process and large-scale digestion and stockpiling of titanium gypsum are achieved, and the concept of 'treating waste by waste' and treating the source of the titanium gypsum (without producing the titanium gypsum) is hopefully realized. The method conforms to the national economic development direction of carbon neutralization, and has important significance for the reasonable utilization of resources and the sustainable development of the titanium white industry and the building material industry in China. The invention takes titanium gypsum and titanium white waste acid as raw materials, the waste acid is subjected to iron removal, cooling crystallization and pH precipitation as technical cores, and high-strength gypsum, copperas and iron-based pigment are used as main product guides to form a whole set of sulfuric acid method titanium gypsum cleaning treatment process, so that the utilization rate of calcium, iron and sulfur resources is improved, the invention has stronger economic and social benefits, surplus capacity for industrialized solution of titanium dioxide in China is obtained, and certain driving demonstration effect is provided for product structure upgrade, and the invention completely conforms to the key points of direction and support provided by national key industry adjustment and happy planning.
The method provided by the invention has the following beneficial effects:
(1) the method provides a low-carbon process route which utilizes titanium-containing waste acid to remove iron impurities in the titanium white gypsum to obtain high-strength gypsum for building materials, achieves the purpose of consuming a large amount of titanium gypsum, greatly lightens the economic and environmental protection pressure of solid waste treatment of enterprises, and realizes 'treatment of waste by waste' and 'changing waste into valuable'. Specifically, element phase reconstruction is adopted to increase the number of phase boundaries/crystal boundaries, strengthen the wet separation-chemical leaching process of impurities such as iron in titanium gypsum and titanium-containing waste acid, remove more than 90% of iron impurities in the titanium gypsum, and select a proper crystal transformation agent to transform beta type dihydrate gypsum into alpha type hemihydrate gypsum with higher strength.
(2) The waste acid is reduced, crystallized to obtain copperas and oxidized to obtain Fe (OH)3The integrated process realizes the in-plant circulation of calcium and sulfur elements while obtaining high-value products of copperas and iron-based pigments. The short-distance on-line separation of the iron element in the titanium white waste acid is realized by utilizing the separation processAnd the production of titanium gypsum is hopeful to be avoided from the source.
(3) Simple production process, less energy consumption, cyclic utilization, low cost, high benefit and contribution to popularization and application.
The experimental result shows that the residual iron content of the pickle liquor obtained by the method is below 455ppm, and the iron removal rate of the titanium gypsum raw material is above 90%; and simultaneously obtains high-value products of green vanadium and iron oxide red.
The method provided by the invention has the following values:
(1) the ecological value of the project is as follows: most of titanium gypsum production areas in China are in underdeveloped areas, and belong to key areas of precise poverty alleviation in China, the areas are in typical ecological fragile areas in China, and titanium gypsum is not suitable for large-scale stockpiling.
(2) The project environmental value is as follows: on one hand, the titanium gypsum is pretreated in the titanium gypsum process realized by the project, and valuable elements are separated and left in an enterprise; on the other hand, the project realizes the large amount of titanium gypsum and titanium white waste acid, greatly reduces the pressure of the titanium gypsum on the upstream environment of the Yangtze river in the processes of conversion and stockpiling, and greatly improves the technical space of resource utilization of the titanium gypsum.
(3) The regional social value is as follows: the project area simultaneously utilizes the titanium white waste acid and the titanium gypsum to be cooperatively treated, and is a project technical structural raw material, and the project can effectively realize regional cooperative innovation and typical innovation and originality of regional solid waste overall resource utilization.
(4) The economic value of the enterprise: the method has the advantages of short project flow, simple process and low cost, produces high-value products of building materials of gypsum, copperas and iron-based pigment, has remarkable economic benefit, improves the profitability and comprehensive competitiveness of enterprises, is beneficial to transformation and upgrading of the enterprises, and has wide application prospect.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims. The treatment of the following examples was carried out according to the scheme shown in FIG. 1.
Example 1
S1, acid leaching treatment:
titanium white waste acid 100g (H) is utilized2SO45 percent of mass percent) is carried out on the titanium gypsum, the liquid-solid ratio is 5, the acid leaching temperature is 70 ℃, the time is 2 hours, and then the solid and the acid leaching solution are obtained respectively by vacuum filtration and separation.
S2, circulating acid leaching:
and (4) taking the titanium gypsum and the pickle liquor obtained in the step S1 as raw materials, carrying out next acid leaching treatment according to the process and conditions in the step S1, and circulating for 4 times until iron impurities in the obtained pickle liquor are saturated to obtain the pickle liquor saturated with iron and a solid.
S3, preparation of alpha-type hemihydrate gypsum:
mixing the solids obtained after the acid leaching treatment, and drying at 60 ℃ for 6 hours to obtain beta type dihydrate gypsum;
adding a crystal transformation agent citric acid into a NaCl solution (the mass concentration is 15%), heating to 100 ℃, adding beta-type dihydrate gypsum, and carrying out constant-temperature dynamic reaction at the stirring speed of 400 r/min. Wherein, the mass ratio of the crystal modifier to the beta-type dihydrate gypsum is 1: 1000, and the liquid-solid ratio of the NaCl solution to the beta-type dihydrate gypsum is 10. And after the reaction is finished, carrying out rapid suction filtration on the reaction liquid, drying the obtained solid at 60 ℃, and carrying out ball milling to obtain the alpha-type semi-hydrated gypsum powder.
S4, removing iron for the first time:
at room temperature, after adding a sodium thiosulfate reducing agent into the obtained iron saturated pickle liquor (the mass ratio of the reducing agent to the total amount of the titanium gypsum is 1: 10), cooling to 25 ℃ for crystallization for 4h, and then carrying out solid-liquid separation to obtain green vanadium and acid immersion liquor after first iron removal.
S5, removing iron for the second time:
at room temperatureThen, NaOH solution (in an amount to make the pH of the system 3) and an oxidizing agent H were added to the obtained first iron-removed acid leaching solution2O2(the mass ratio of the oxidant to the acid leaching solution after the first iron removal is 1: 20), standing in a precipitation device to separate out a precipitate Fe (OH)3And obtaining acid immersion liquid after iron removal for the second time.
The resulting precipitate Fe (OH)3Drying and dehydrating at 60 deg.C for 2h to obtain iron oxide red (i.e. Fe)2O3)。
And (3) testing results:
the residual iron ion content of the acid leaching solution after the second iron removal obtained in step S5 was measured, and the result showed that the residual iron content was 387 ppm.
And (4) comparing and calculating the iron content in the beta type dihydrate gypsum obtained in the step (S3) with the iron content in the titanium gypsum raw material to obtain the iron removal rate. The titanium gypsum raw material is gypsum which contains a large amount of iron and is red, and beta-type dihydrate gypsum is obtained after acid leaching treatment and drying, wherein the iron removal rate of the titanium gypsum is (the iron content in the original titanium gypsum raw material-the iron content in the beta-type dihydrate gypsum) divided by the iron content in the original titanium gypsum raw material; assuming that the iron content in the original titanium gypsum raw material is 9 and the iron content in the obtained beta-type dihydrate gypsum is 1, the iron removal rate of the titanium gypsum is (9-1) ÷ 9 ═ 89%. According to the above calculation formula, the iron removal rate of the titanium gypsum in example 1 is 90.2%.
Example 2
S1, acid leaching treatment:
titanium white waste acid 100g (H) is utilized2SO410 percent of mass percent) is carried out on the titanium gypsum, the liquid-solid ratio is 5, the acid leaching temperature is 70 ℃, the time is 2 hours, and then the solid and the acid leaching solution are obtained respectively by vacuum filtration and separation.
S2, circulating acid leaching:
and (4) taking the titanium gypsum and the pickle liquor obtained in the step S1 as raw materials, carrying out next acid leaching treatment according to the process and conditions in the step S1, and circulating for 4 times until iron impurities in the obtained pickle liquor are saturated to obtain the pickle liquor saturated with iron and a solid.
S3, preparation of alpha-type hemihydrate gypsum:
mixing the solids obtained after the acid leaching treatment, and drying at 60 ℃ for 6 hours to obtain beta type dihydrate gypsum;
adding sodium citrate as a crystal modifier into NaCl solution (with the mass concentration of 20%), heating to 100 ℃, adding beta-type dihydrate gypsum, and carrying out constant-temperature dynamic reaction at the stirring speed of 400 r/min. Wherein, the mass ratio of the crystal modifier to the beta-type dihydrate gypsum is 1: 4000, and the liquid-solid ratio of the NaCl solution to the beta-type dihydrate gypsum is 8. And after the reaction is finished, carrying out rapid suction filtration on the reaction liquid, drying the obtained solid at 60 ℃, and carrying out ball milling to obtain the alpha-type semi-hydrated gypsum powder.
S4, removing iron for the first time:
at room temperature, after adding a sodium thiosulfate reducing agent into the obtained iron saturated pickle liquor (the mass ratio of the reducing agent to the total amount of titanium gypsum is 1: 7), cooling to 25 ℃ for crystallization for 4h, and then carrying out solid-liquid separation to obtain green vanadium and acid immersion liquor after first iron removal.
S5, removing iron for the second time:
at room temperature, NaOH solution (in an amount to make the pH of the system 3) and an oxidant H were added to the acid leaching solution after the first iron removal2O2(the mass ratio of the oxidant to the acid leaching solution after the first iron removal is 1: 15), standing in a precipitation device to separate out a precipitate Fe (OH)3And obtaining acid immersion liquid after iron removal for the second time.
The resulting precipitate Fe (OH)3Drying and dehydrating at 60 deg.C for 2h to obtain iron oxide red (i.e. Fe)2O3)。
And (3) testing results:
the test procedure of example 1 showed that the acid leaching solution after the second iron removal obtained in step S5 had a residual iron content of 432ppm and the titanium gypsum had an iron removal rate of 92.0%.
Example 3
S1, acid leaching treatment:
titanium white waste acid 100g (H) is utilized2SO4The mass fraction is 20 percent), performing acid leaching treatment on the titanium gypsum, wherein the liquid-solid ratio is 5, the acid leaching temperature is 70 ℃, and the time is 2 hours, and then performing vacuum filtration and separation to obtain a solid and an acid leaching solution respectively.
S2, circulating acid leaching:
and (4) taking the titanium gypsum and the pickle liquor obtained in the step S1 as raw materials, carrying out next acid leaching treatment according to the process and conditions in the step S1, and circulating for 4 times until iron impurities in the obtained pickle liquor are saturated to obtain the pickle liquor saturated with iron and a solid.
S3, preparation of alpha-type hemihydrate gypsum:
mixing the solids obtained after the acid leaching treatment, and drying at 60 ℃ for 6 hours to obtain beta type dihydrate gypsum;
adding sodium citrate as a crystal modifier into NaCl solution (with the mass concentration of 25%), heating to 100 ℃, adding beta-type dihydrate gypsum, and carrying out constant-temperature dynamic reaction at the stirring speed of 400 r/min. Wherein, the mass ratio of the crystal transformation agent to the beta-type dihydrate gypsum is 1: 6000, and the liquid-solid ratio of the NaCl solution to the beta-type dihydrate gypsum is 6. And after the reaction is finished, carrying out rapid suction filtration on the reaction liquid, drying the obtained solid at 60 ℃, and carrying out ball milling to obtain the alpha-type semi-hydrated gypsum powder.
S4, removing iron for the first time:
at room temperature, after adding a sodium thiosulfate reducing agent into the obtained iron saturated pickle liquor (the mass ratio of the reducing agent to the total amount of the titanium gypsum is 1: 10), cooling to 25 ℃ for crystallization for 6 hours, and then carrying out solid-liquid separation to obtain green vanadium and acid immersion liquor after first iron removal.
S5, removing iron for the second time:
at room temperature, NaOH solution (in an amount to make the pH of the system 3) and an oxidant H were added to the acid leaching solution after the first iron removal2O2(the mass ratio of the oxidant to the acid leaching solution after the first iron removal is 1: 12), standing in a precipitation device to separate out a precipitate Fe (OH)3And obtaining acid immersion liquid after iron removal for the second time.
The resulting precipitate Fe (OH)3Drying and dehydrating at 80 deg.C for 2h to obtain iron oxide red (i.e. Fe)2O3)。
And (3) testing results:
the test procedure of example 1 showed that the residual iron content in the second iron-removed acid leachate obtained in step S5 was 451ppm, and the iron removal rate of the titanium gypsum was 94.3%.
Example 4
S1, acid leaching treatment:
titanium white waste acid 100g (H) is utilized2SO430 percent of mass percent) is carried out on the titanium gypsum, the liquid-solid ratio is 5, the acid leaching temperature is 70 ℃, the time is 2 hours, and then the solid and the acid leaching solution are obtained respectively by vacuum filtration and separation.
S2, circulating acid leaching:
and (4) taking the titanium gypsum and the pickle liquor obtained in the step S1 as raw materials, carrying out next acid leaching treatment according to the process and conditions in the step S1, and circulating for 4 times until iron impurities in the obtained pickle liquor are saturated to obtain the pickle liquor saturated with iron and a solid.
S3, preparation of alpha-type hemihydrate gypsum:
mixing the solids obtained after the acid leaching treatment, and drying at 60 ℃ for 6 hours to obtain beta type dihydrate gypsum;
adding sodium citrate as a crystal modifier into NaCl solution (with the mass concentration of 30%), heating to 100 ℃, adding beta-type dihydrate gypsum, and carrying out constant-temperature dynamic reaction at the stirring speed of 400 r/min. Wherein, the mass ratio of the crystal modifier to the beta-type dihydrate gypsum is 1: 10000, and the liquid-solid ratio of the NaCl solution to the beta-type dihydrate gypsum is 5. And after the reaction is finished, carrying out rapid suction filtration on the reaction liquid, drying the obtained solid at 60 ℃, and carrying out ball milling to obtain the alpha-type semi-hydrated gypsum powder.
S4, removing iron for the first time:
at room temperature, after adding a sodium thiosulfate reducing agent into the obtained iron saturated pickle liquor (the mass ratio of the reducing agent to the total amount of the titanium gypsum is 1: 10), cooling to 25 ℃ for crystallization for 6 hours, and then carrying out solid-liquid separation to obtain green vanadium and acid immersion liquor after first iron removal.
S5, removing iron for the second time:
at room temperature, NaOH solution (in an amount to make the pH of the system 3) and an oxidant H were added to the acid leaching solution after the first iron removal2O2(the mass ratio of the oxidant to the acid leaching solution after the first iron removal is 1: X), standing in a precipitation device to separate out a precipitate Fe (OH)3And obtaining acid immersion liquid after iron removal for the second time.
The resulting precipitate Fe (OH)3Drying and dehydrating at 80 deg.C for 2h to obtain iron oxide red (i.e. Fe)2O3)。
And (3) testing results:
the test conducted according to the test method of example 1 revealed that the residual iron content in the second iron-removed acid leachate obtained in step S5 was 347ppm, and the iron removal rate of the titanium gypsum was 96.5%.
The foregoing examples are provided to facilitate an understanding of the principles of the invention and their core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that approximate the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A method for removing iron and preparing green vanadium and iron-based pigment by utilizing titanium dioxide waste acid is characterized by comprising the following steps:
a) acid leaching treatment:
carrying out acid leaching on titanium gypsum by using titanium white waste acid, and then carrying out solid-liquid separation to obtain acid leaching solution and solid;
b) and (3) circulating acid leaching treatment:
taking titanium gypsum, and performing acid leaching and solid-liquid separation on the titanium gypsum again according to the acid leaching process of the step a) by using the acid leaching solution obtained in the step a), so as to obtain acid leaching solution and solid again;
the above processes are repeated in a circulating way, the pickling liquid obtained by each pickling process is taken as the dipping liquid of the next pickling process, and the pickling process is repeated until the iron impurities in the obtained pickling liquid are saturated, so that the pickling liquid and the solid matter saturated with iron are obtained;
c) preparing alpha-type semi-hydrated gypsum:
drying the solid obtained after each acid leaching treatment to obtain beta type dihydrate gypsum;
carrying out crystal transformation reaction on the beta-type hemihydrate gypsum under the action of a crystal transformation agent to obtain alpha-type hemihydrate gypsum;
d) iron removal for the first time:
mixing the acid leaching solution saturated by iron with a reducing agent, and then carrying out cooling crystallization and solid-liquid separation to obtain green vanadium and an acid leaching solution subjected to first iron removal;
e) and (3) removing iron for the second time:
mixing the acid leaching solution after the first iron removal, a neutralizing agent and an oxidant, standing for precipitation and carrying out solid-liquid separation to obtain a precipitate Fe (OH)3And acid immersion liquid after second iron removal;
for the Fe (OH)3Carrying out dehydration treatment to obtain an iron-based pigment;
the steps c) and d) are not limited in order.
2. The method according to claim 1, wherein the acid leaching is carried out at 50-100 ℃ for 1-4 h in step a).
3. The method of claim 1, wherein the liquid-solid ratio of the acid leaching in the step a) is 4-10.
4. The method according to claim 1, wherein in the step d), the reducing agent is one or more selected from ascorbic acid, sodium thiosulfate and ferrous ammonium sulfate.
5. The method as claimed in claim 1 or 4, wherein the mass ratio of the reducing agent to the total amount of the titanium gypsum in the step d) is 1: 5-10.
6. The method according to claim 1, wherein in the step d), the cooling crystallization conditions are as follows: cooling to 10-30 ℃, and keeping for 1-6 h.
7. The method according to claim 1, wherein in step e), the neutralizing agent is NaOH and/or KOH;
the dosage of the neutralizing agent is such that the pH value of the system reaches 2.0-4.0.
8. The method according to claim 1, wherein in step e), the oxidizing agent is selected from H2O2、NaClO4And MnO2One or more of the above;
the mass ratio of the oxidant to the acid immersion liquid after the first iron removal is 1: 10-20.
9. The method according to claim 1, wherein in the step a), the mass fraction of sulfuric acid in the titanium white waste acid is 5-30%.
10. The method according to claim 1, wherein in the step c), the drying temperature is 50-70 ℃ and the drying time is 4-10 h;
the iron-based pigment is iron oxide red and/or iron oxide yellow.
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