CN105621496B - A kind of method that siderochrome solid waste prepares chromium modified micaceous iron oxide - Google Patents
A kind of method that siderochrome solid waste prepares chromium modified micaceous iron oxide Download PDFInfo
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- CN105621496B CN105621496B CN201511004776.1A CN201511004776A CN105621496B CN 105621496 B CN105621496 B CN 105621496B CN 201511004776 A CN201511004776 A CN 201511004776A CN 105621496 B CN105621496 B CN 105621496B
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- siderochrome
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- iron oxide
- micaceous iron
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 179
- 239000011651 chromium Substances 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 67
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 59
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000002910 solid waste Substances 0.000 title claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 93
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 74
- 239000012535 impurity Substances 0.000 claims abstract description 40
- 238000000926 separation method Methods 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 24
- 229910052742 iron Inorganic materials 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 13
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000011084 recovery Methods 0.000 claims abstract description 10
- 239000002351 wastewater Substances 0.000 claims abstract description 9
- 238000001514 detection method Methods 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 176
- 239000010802 sludge Substances 0.000 claims description 50
- 238000001556 precipitation Methods 0.000 claims description 48
- 238000001914 filtration Methods 0.000 claims description 28
- 230000003647 oxidation Effects 0.000 claims description 23
- 238000007254 oxidation reaction Methods 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 19
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 15
- 238000004090 dissolution Methods 0.000 claims description 14
- 239000011790 ferrous sulphate Substances 0.000 claims description 14
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 14
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 14
- 239000006227 byproduct Substances 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 11
- 239000002699 waste material Substances 0.000 claims description 11
- 239000007790 solid phase Substances 0.000 claims description 10
- 229910001430 chromium ion Inorganic materials 0.000 claims description 5
- 230000033228 biological regulation Effects 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 18
- 238000000576 coating method Methods 0.000 abstract description 18
- 239000002994 raw material Substances 0.000 abstract description 18
- 230000007797 corrosion Effects 0.000 abstract description 13
- 238000005260 corrosion Methods 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 239000000843 powder Substances 0.000 description 26
- 239000010935 stainless steel Substances 0.000 description 22
- 229910001220 stainless steel Inorganic materials 0.000 description 22
- 238000005406 washing Methods 0.000 description 20
- 239000000047 product Substances 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 15
- 238000004140 cleaning Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 239000001034 iron oxide pigment Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 238000009713 electroplating Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052627 muscovite Inorganic materials 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000005253 cladding Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001651 emery Inorganic materials 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000005272 metallurgy Methods 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 229910000604 Ferrochrome Inorganic materials 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910001120 nichrome Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000746 Structural steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910001315 Tool steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- ZLXPLDLEBORRPT-UHFFFAOYSA-M [NH4+].[Fe+].[O-]S([O-])(=O)=O Chemical compound [NH4+].[Fe+].[O-]S([O-])(=O)=O ZLXPLDLEBORRPT-UHFFFAOYSA-M 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940010514 ammonium ferrous sulfate Drugs 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000002585 base Substances 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
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000010730 cutting oil Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000005342 ion exchange 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
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229910003145 α-Fe2O3 Inorganic materials 0.000 description 1
Classifications
-
- 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
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention relates to a kind of method that siderochrome solid waste prepares chromium modified micaceous iron oxide.The present invention is to be machined, during chromate waste water disposal etc. the siderochrome solid waste that produces as raw material, by the way that acid is molten, impurity is separated and recovery, siderochrome composition detection, siderochrome component ratio are adjusted, aoxidize, adjust pH value, Hydrothermal Synthesiss process, the chromium modified micaceous iron oxide with good Corrosion Protection is directly produced.The production of micaceous iron oxide is modified a step with chromium and completed in the present invention, not only shortens the production procedure of modified micaceous iron oxide, while also solving existing siderochrome solid waste iron, chromium separation difficulty, environmental pressure weight recycles the low problem of added value.Have the advantages that wide raw material sources, low cost, environmental protection and added value are high using coating chromium modified micaceous iron oxide produced by the invention.
Description
Technical field
The invention belongs to recycling economy technical field, more particularly to the process such as one kind is to be machined, chromate waste water disposal
The siderochrome solid waste of middle generation is raw material, the method that the chromium modified micaceous iron oxide of corrosion resistance is prepared using hydro-thermal method.
Background technology
Chromium is one of most widely used addition element in steel production, can significantly improve the intensity of material, hardness, wear-resisting
Property, inoxidizability, corrosion resistance etc., are widely used in structural steel, tool steel, stainless steel, heat resisting steel etc..Chrome-bearing steel iron material
It can be produced in the process such as grinding, milling a large amount of by ferrochrome particle, emery wheel abrasive grain, emery wheel additive and grinding
The siderochrome grinding waste material that coolant etc. is mixed.These siderochrome sludge contain a large amount of Fe, Cr valuable metals, great recovery valency
Value.However, abrasive material, emery wheel additive etc. are mutually embedding attached with ferrochrome particle in siderochrome sludge, cause follow-up separation very tired
Difficulty, meanwhile, also containing substantial amounts of cutting oil etc. in siderochrome sludge, which in turns increases the difficulty that siderochrome sludge is recycled.Mesh
Before, siderochrome sludge is worked as waste disposal by China's mechanical industry and metallurgy industry, and both land occupation, pollution environment, were caused again
The significant wastage of secondary resource.
At present, most of iron-based grinding waste material not only results in secondary resource by as the raw material for returning stove melting
Low side is utilized, while will also result in environmental pollution.Chinese patent 200510010031 discloses one kind and utilizes grinding and milling
Cut processing and belong to powder and metallic particles is processed into consutrode needed for electroslag furnace, the side of reproduction alloy steel casting
Method.This method has raw material availability height, using existing；Chinese patent 201010230229 discloses one kind with iron-based waste material
For raw material, the manufacture method of corrosion-resistant abrasion-proof ceramic lining metal pipe material is prepared using thermit reaction.Metal prepared by the invention
Tubing can be widely used for the powder, mud, Tailings transportation of the industries such as metallurgy, mine, electric power, coal.There is work in the inventive method
Skill high energy consumption, the shortcoming of high cost；Chinese patent 201010230531 discloses a kind of the pollution-free sharp again of iron-based grinding waste material
With method, including oil removing, heat treatment, screening, proportioning, obtained iron(-)base powder can be used for powder metallurgy structural part, magnetic
Grinding, thermal spraying etc. are multi-field.Such reuse method has the advantages that waste utilization rate is high, it is also possible to it is attached to there is product
The problems such as value added relatively low, processing procedure easily causes environmental pollution.
With industrial expansions such as plating, metallurgy, process hides, printing and dyeing, the discharge capacity of chromate waste water is increasing, to electroplate row
Exemplified by industry, according to incompletely statistics, the waste electroplating liquor containing chromium that China discharges every year surpasses 4,000,000,000 m3.Comprehensive treatment effect, industry are practical
Property and processing cost, ferrous salt reduction precipitation method is one of most widely used chromate waste water method of disposal both at home and abroad at present, its
Handling principle is as follows：
（1）Reduction and detoxication：3Fe2+ + Cr6+ → Cr3+ + 3Fe3+；
（2）Precipitation：Fe3+ + OH- → Fe(OH)3↓；Cr3+ + OH- → Cr(OH)3↓；
The Cr of severe toxicity6+Cr is reduced into by cheap ferrous salt3+, then with Cr (OH)3Form be precipitated out, can obtain
Obtain preferably removing toxic substances and recovering effect.However, due to Cr3+And Fe3+Precipitate interval with close pH value, chromate waste water processing
The siderochrome sludge of substantial amounts can be produced afterwards.Cr (OH) in siderochrome sludge3Cr may be slowly oxidized under field conditions (factors)6 +, and then secondary pollution is caused to environment.Table 1 is typical siderochrome sludge（Acid-washing stainless steel sludge, plating siderochrome sludge and process hides
Sludge）Leaching Heavy Metals test result, it can be seen that Cr leaching concentrations are far above national toxicity criterion in siderochrome sludge.
The typical siderochrome sludge heavy-metal Leaching of table 1（mg/L）
| Element | Total Cr | Cr6+ | Cd2+ | Zn2+ | Pb2+ |
| GB5085.3-2007 | ≤15 | ≤5 | ≤1 | ≤100 | ≤5 |
| Acid-washing stainless steel siderochrome sludge | 80 | 35 | 0.4 | 52 | 3.1 |
| Electroplating sludge | 43.21 | 26.2 | 0.16 | 17.21 | 0.71 |
| Leather-making mud | 32.1 | 15.7 | 0.12 | 10.36 | 0.27 |
At present, the reuse method of siderochrome sludge can be roughly divided into pyrogenic process and the major class of wet method two.Chinese patent
201410383658 disclose a kind of method that high siderochrome sewage sludge harmlessness is recycled：High siderochrome sludge is mixed with coal first
Close, dried and be calcined successively in Sealing Arrangement, clinker is obtained after cooling.Then, clinker is crushed, sieve after
To rust cleaning sand；Chinese patent 201310447422.9 provides a kind of method that acid-washing stainless steel sludge prepares nichrome：First,
Alkali lye is added into acid-washing stainless steel sludge to obtain neutral sludge.Then, by obtained neutral sludge carry out revolution kiln drying,
In coke and starch ball, rotary kiln nichrome is obtained after the process such as reducing and smelting, plasma electric stove fusing smelting；It is Chinese special
Profit 201410206530 discloses a kind of process for disposing acid-washing stainless steel sludge, as follows：In acid-washing stainless steel sludge
Appropriate reducing agent is uniformly mixed, is burnt under a reducing atmosphere according to processing steps such as warming up period, reduction period, soak and cooldown periods
Form brick.Then appropriate reducing agent is uniformly mixed in acid-washing stainless steel sludge, brick is sintered under a reducing atmosphere.Siderochrome is dirty
The pyrogenic processing method of mud has cost relatively low, the advantages of product purpose is extensive, but there is also added value of product is low, energy consumption
The problems such as high, processing procedure easily causes environmental pollution.
Chinese patent 201210205195.4 discloses a kind of acid-washing stainless steel sludge green extraction of chromium and the method for nickel, should
Method is directed to acid-washing stainless steel Heavy Metals in Sludge ion（Cr6+、Cr3+、Ni2+）, use H2SO4Heavy metal ion therein is soaked
Go out, the nontoxic pickling sludge and leachate of heavy metal free ion are obtained after filtering.NaHSO is added into leachate3, by Cr6+Also
It is former into Cr3+.Then NaOH is used to adjust pH of leaching solution for 7.5 ~ 10.0 by Cr3+、Ni2+Precipitation, filtering, drying form Cr
(OH)3With Ni (OH)2Metallurgical raw material.Finally, using the F in lime precipitation filtrate-And SO4 2-.This method has poisonous ion solution
Malicious thorough, with low cost advantage.But in this method, Cr3+、Ni2+Eventually as Cr (OH)3With Ni (OH)2Metallurgical raw material is returned
Receive and utilize, there is also the relatively low shortcoming of added value of product；Chinese patent 201210141865 discloses a kind of acid-washing stainless steel and given up
With sludge heavy-metal its recovery method as resource in water, including：First with sulfuric acid stainless steel acid cleaning waste water and sludge, and add
Additive suppresses the leaching of iron.Then, oxidant is added in leaching liquid, by Mn（II）It is oxidized to manganese dioxide.It is molten after oxidation
Liquid passes through anion-exchange column, and enriching and recovering Cr VI after adsorption saturation, is regenerated using regenerative agent, is returned from regenerated liquid
Receive chromate.Finally, the nickel in ion exchange water outlet is reclaimed using neutralization precipitation method.This method can realize acid-washing stainless steel sludge
Middle manganese, chromium, the multistage distribution of nickel are reclaimed, there is also technological process length, cost is higher the problem of；
Micaceous iron oxide, is a kind of flake pigment of stable chemical performance, and main chemical compositions are α-Fe2O3.Mica is aoxidized
The special two-dimensional sheet structure of iron powder body makes it have excellent adhesive force, significant uv reflectance ability in application, together
When micaceous iron oxide also there is the features such as stable chemical nature, nonpoisonous and tasteless, electric conductivity are good, high temperature resistant, resistance to saltfog are good,
It is widely used in the fields such as anticorrosive paint, anticorrosive paint, filler.At present, the preparation method of artificial mica synthesis iron oxide
Mainly there are high-temperature molten salt method, vapor phase method and hydro-thermal method etc..
United States Patent (USP) 4676838 discloses a kind of preparation about platelet shaped iron oxide pigment and the method used：By three
Added after valency ferrous solution or the neutralized processing of suspension in sodium hydroxide medium, the hydro-thermal presoma of formation is obtained after hydro-thermal reaction
To flake ferric oxide pigment.The micaceous iron oxide that the inventive method is produced has the advantages that purity is high, well-crystallized, but due to
It is raw material completely using pure material, haves the shortcomings that cost of material is high；Chinese patent 201010136709.6 discloses a kind of fused salt
The method that method prepares micaceous iron oxide, this method is using the mixture of iron ammonium sulfate or ferrous sulfate or both as source of iron, with sulphur
The mixture of hydrochlorate or chloride or both is fluxing agent, melts after mixing and obtains micaceous iron oxide.The inventive method is present
Process energy consumption is high, the shortcoming of high cost；Chinese patent CN 100390072C disclose a kind of using titanium white by product ferrous sulfate as original
Expect, by dissolving the processes such as purification, oxidation, predecessor generation, hydro-thermal reaction crystallization and post processing, prepare particle diameter and color controllable
The method of micaceous iron oxide.The inventive method is using the ferrous sulfate by-product of high-purity as raw material, and the method purified using dissolving
Raw material is purified, there is applicable raw materials narrow range；Chinese patent 201210475290 discloses a kind of cold rolling iron cement and prepared
The preparation method of micaceous iron oxide, the oily iron mud that this method is produced using in cold rolling of strip steel process as raw material, by acid it is molten,
De-oiling and recovery, oxidation, precipitation, hydro-thermal reaction, produce coating micaceous iron oxide powder, and its quality meets national standard
（HG/T3006-1997）And international standard（ISO10601-2007）.The invention is separated using the method for regulation solution ph, gone
Removal of impurity cation, has widened the source of micaceous iron oxide raw materials for production to a certain extent, but the invention is equally with applicable
Material in low impurity cationic content, using having the shortcomings that certain limitation.
At present, mainly have available for the micaceous iron oxide method of modifying for improving Corrosion Protection：Inorganic matter cladding process and have
Machine corrosion inhibiter cladding process.Chinese patent 201310263649.8 discloses a kind of nano-oxide cladding micaceous iron oxide antirust face
The preparation method of material：Titanyl sulfate and/or solution of zinc sulfate are slowly added into micaceous iron oxide solution, stirring reaction.Connect
, while stirring add calcium hydroxide and/or calcium oxide in above-mentioned reaction system, ultimately generate nano titanium oxide and/or
The micaceous iron oxide of nano zine oxide cladding；Chinese patent 200810012660 discloses a kind of environmental-friendly polyaniline modified micaceous
Iron oxide anticorrosive coating and preparation method thereof：Polyaniline-coated layer, place are formed on micaceous iron oxide surface using oxidative polymerization method
Micaceous iron oxide after reason has passivation to metal, and the phytic acid clad on micaceous iron oxide surface also functions to inhibition to metal
Effect.It this method solve that existing MIO coating antiseptic property is poor, must contain in manufacturing process with the use of harmful
The problem of lead and chromate pigment.Foregoing invention is raw material using finished product micaceous iron oxide, and cost is higher.
The content of the invention
The invention discloses the preparation method that a kind of siderochrome solid waste prepares chromium modified micaceous iron oxide.The present invention is added with machinery
The siderochrome solid waste produced during work, chromate waste water disposal etc. is raw material, by the way that acid is molten, impurity is separated and reclaimed, siderochrome composition
Detection, the adjustment of siderochrome component ratio, oxidation, regulation pH value, Hydrothermal Synthesiss process, are directly produced with good Corrosion Protection
Chromium modified micaceous iron oxide.The production of micaceous iron oxide is modified a step with chromium and completed in the present invention, not only shortens modified cloud
The production procedure of female iron oxide, while also solving existing siderochrome solid waste iron, chromium separation difficulty, environmental pressure weight is recycled attached
Value added low problem.Have that raw material sources are wide, low cost, green using coating chromium modified micaceous iron oxide produced by the invention
The advantages of environmental protection and added value are high.
The present invention is for the purpose of the recycling of siderochrome solid waste is recycled, by the way that acid is molten, impurity is separated and reclaimed, siderochrome composition
Detection, the adjustment of siderochrome component ratio, oxidation, regulation pH value, Hydrothermal Synthesiss process, are directly produced with good Corrosion Protection
Chromium modified micaceous iron oxide.Specific method comprises the following steps：
（1）Acid is molten：Use H2SO4Solution dissolves siderochrome sludge, H2SO4Gram-equivalent number be siderochrome sludge in Fe, Cr gram equivalents
Several 1.2 ~ 3.0 times, solution temperature is 80 DEG C, dissolution time 3h ~ 6h；
（2）Impurity is separated and reclaimed：Mixed liquor of the acid after molten is stood, separates, reclaim the sour insoluble solid of mixed liquor bottom
Phase impurity.Then, mixed liquor is centrifuged, separates, reclaims organic impurities therein；
（3）Siderochrome composition detection：Iron, the concentration of chromium ion in solution after checked for impurities separation；
（4）Siderochrome component ratio is adjusted：According to siderochrome composition detection result, siderochrome component ratio in solution is calculated：{ m
(Cr)/［ m (Fe)+m (Cr) ］ }（M is quality）.Such as ratio then adds a certain amount of industrial by-product ferrous sulfate more than 5%
Into solution, until siderochrome component ratio reaches 1% ~ 5%；
（5）Oxidation：H is added dropwise in solution after being adjusted to siderochrome component ratio2O2Solution is aoxidized, by the Fe in solution2 +It is oxidized to Fe3+, the H of dropwise addition2O2Gram-equivalent number is Fe in filtrate2+The 40% ~ 100% of gram-equivalent number；
（6）Adjust pH value：The pH value for adjusting solution after oxidation with 5mol/L NaOH solutions obtains siderochrome to 6 ~ 8 after filtering
Mixed precipitation；
（7）Hydrothermal Synthesiss：Siderochrome mixed precipitation is well mixed with NaOH solution, hydro-thermal conjunction is carried out in hydrothermal reaction kettle
Into, NaOH solution concentration 12mo/L ~ 16mol/L, the solid-to-liquid ratio 1 of siderochrome mixed precipitation and NaOH solution:10~1:20, hydro-thermal is closed
Into 200 DEG C ~ 260 DEG C of temperature, Hydrothermal Synthesiss time 4h ~ 10h.
Advantages of the present invention：The present invention is to be machined, during chromate waste water disposal etc. the siderochrome solid waste that produces to be former
Material, produces the chromium modified micaceous iron oxide with good Corrosion Protection.The production of micaceous iron oxide changes with chromium in the present invention
Property one step complete, the production procedure of modified micaceous iron oxide is not only shortened, while also solving existing siderochrome solid waste iron, chromium point
From difficulty, environmental pressure weight recycles the low problem of added value.Using coating produced by the invention chromium modified micaceous iron oxide
Have the advantages that wide raw material sources, low cost, environmental protection and added value are high.
Brief description of the drawings
Fig. 1 is process chart of the invention.
The X-ray diffraction analysis chart for the chromium modified micaceous iron oxide that Fig. 2 is prepared for the present invention.
The ESEM shape appearance figure for the chromium modified micaceous iron oxide that Fig. 3 is prepared for the present invention.
Embodiment
Embodiment 1：
Use H2SO4Solution dissolves siderochrome grinding waste material, H2SO4Gram-equivalent number be siderochrome sludge in Fe gram-equivalent number 1.2
Times, 80 DEG C of solution temperature, dissolution time 3h.Mixed liquor of the acid after molten is stood, separates, reclaim the sour insoluble solid of mixed liquor bottom
Phase impurity.Then, mixed liquor is centrifuged, separates, reclaims organic impurities therein.After checked for impurities separation in solution
M (Cr)/［ m (Fe)+m (Cr) ］ mass ratio is 3% in the concentration of iron, chromium ion, solution.It is molten after being adjusted to siderochrome component ratio
H is added dropwise in liquid2O2Solution is aoxidized, by the Fe in solution2+It is oxidized to Fe3+, the H of dropwise addition2O2Gram-equivalent number is Fe in filtrate2+
The 40% of gram-equivalent number.Then, the pH value for adjusting solution after oxidation with 5mol/L NaOH solutions obtains siderochrome and mixed to 6 after filtering
Close precipitation.Siderochrome mixed precipitation is well mixed with NaOH solution, Hydrothermal Synthesiss, NaOH solution are carried out in hydrothermal reaction kettle
The solid-to-liquid ratio 1 of concentration 12mo/L, siderochrome mixed precipitation and NaOH solution:10,200 DEG C of Hydrothermal Synthesiss temperature, Hydrothermal Synthesiss time
4h.Through filtering, cleaning, being dried to obtain chromium modified micaceous iron oxide powder after the completion of hydro-thermal reaction.After testing, micaceous iron oxide powder
Body purity 98.1%, product quality meets coating mica-iron oxide pigment chinese national standard（HG/T 3006-1997）And state
Border standard（ISO 10601-2007）Requirement；Compared to common micaceous iron oxide, the corrosion resistant of the chromium modified micaceous iron oxide of preparation
Corrosion can be significantly improved.
Embodiment 2：
Use H2SO4Solution dissolves siderochrome grinding waste material, H2SO4Gram-equivalent number be siderochrome sludge in Fe gram-equivalent number 3.0
Times, 80 DEG C of solution temperature, dissolution time 6h.Mixed liquor of the acid after molten is stood, separates, reclaim the sour insoluble solid of mixed liquor bottom
Phase impurity.Then, mixed liquor is centrifuged, separates, reclaims organic impurities therein.After checked for impurities separation in solution
M (Cr)/［ m (Fe)+m (Cr) ］ mass ratio is 3% in the concentration of iron, chromium ion, solution.It is molten after being adjusted to siderochrome component ratio
H is added dropwise in liquid2O2Solution is aoxidized, by the Fe in solution2+It is oxidized to Fe3+, the H of dropwise addition2O2Gram-equivalent number is Fe in filtrate2+
The 100% of gram-equivalent number.Then, the pH value for adjusting solution after oxidation with 5mol/L NaOH solutions obtains siderochrome and mixed to 8 after filtering
Close precipitation.Siderochrome mixed precipitation is well mixed with NaOH solution, Hydrothermal Synthesiss, NaOH solution are carried out in hydrothermal reaction kettle
The solid-to-liquid ratio 1 of concentration 16mo/L, siderochrome mixed precipitation and NaOH solution:20,260 DEG C of Hydrothermal Synthesiss temperature, Hydrothermal Synthesiss time
10h.Through filtering, cleaning, being dried to obtain chromium modified micaceous iron oxide powder after the completion of hydro-thermal reaction.After testing, micaceous iron oxide
Powder purity 98.7%, product quality meets coating mica-iron oxide pigment chinese national standard（HG/T 3006-1997）With
International standard（ISO 10601-2007）Requirement；Compared to common micaceous iron oxide, the chromium modified micaceous iron oxide of preparation it is resistance to
Corrosive nature is significantly improved.
Embodiment 3：
Use H2SO4Solution dissolves siderochrome grinding waste material, H2SO4Gram-equivalent number be siderochrome sludge in Fe gram-equivalent number 2.0
Times, 80 DEG C of solution temperature, dissolution time 5h.Mixed liquor of the acid after molten is stood, separates, reclaim the sour insoluble solid of mixed liquor bottom
Phase impurity.Then, mixed liquor is centrifuged, separates, reclaims organic impurities therein.After checked for impurities separation in solution
M (Cr)/［ m (Fe)+m (Cr) ］ mass ratio is 3% in the concentration of iron, chromium ion, solution.It is molten after being adjusted to siderochrome component ratio
H is added dropwise in liquid2O2Solution is aoxidized, by the Fe in solution2+It is oxidized to Fe3+, the H of dropwise addition2O2Gram-equivalent number is Fe in filtrate2+
The 70% of gram-equivalent number.Then, the pH value for adjusting solution after oxidation with 5mol/L NaOH solutions obtains siderochrome and mixed to 7 after filtering
Close precipitation.Siderochrome mixed precipitation is well mixed with NaOH solution, Hydrothermal Synthesiss, NaOH solution are carried out in hydrothermal reaction kettle
The solid-to-liquid ratio 1 of concentration 16mo/L, siderochrome mixed precipitation and NaOH solution:15,240 DEG C of Hydrothermal Synthesiss temperature, Hydrothermal Synthesiss time
6h.Through filtering, cleaning, being dried to obtain chromium modified micaceous iron oxide powder after the completion of hydro-thermal reaction.After testing, micaceous iron oxide powder
Body purity 98.6%, product quality meets coating mica-iron oxide pigment chinese national standard（HG/T 3006-1997）And state
Border standard（ISO 10601-2007）Requirement；Compared to common micaceous iron oxide, the corrosion resistant of the chromium modified micaceous iron oxide of preparation
Corrosion can be significantly improved.
Embodiment 4：
Use H2SO4Solution dissolves acid-washing stainless steel sludge, H2SO4Gram-equivalent number be acid-washing stainless steel sludge in Fe gram
1.2 times of equivalents, 80 DEG C of solution temperature, dissolution time 3h.Mixed liquor of the acid after molten is stood, separation, recovery mixed liquor bottom
Sour insoluble solid phase impurity.A certain amount of industrial by-product ferrous sulfate is added to after impurity separation in solution, until siderochrome into
Point ratio reaches 5%.H is added dropwise in solution after being adjusted to siderochrome component ratio2O2Solution is aoxidized, by the Fe in solution2+Oxygen
Turn to Fe3+, the H of dropwise addition2O2Gram-equivalent number is Fe in filtrate2+The 40% of gram-equivalent number.Then, adjusted with 5mol/L NaOH solutions
The pH value of solution obtains siderochrome mixed precipitation to 5 after oxidation after filtering.Siderochrome mixed precipitation is well mixed with NaOH solution,
Carry out Hydrothermal Synthesiss in hydrothermal reaction kettle, NaOH solution concentration 12mo/L, the solid-to-liquid ratio of siderochrome mixed precipitation and NaOH solution
1:10,200 DEG C of Hydrothermal Synthesiss temperature, Hydrothermal Synthesiss time 4h.Change after the completion of hydro-thermal reaction through filtering, cleaning, be dried to obtain chromium
Property micaceous iron oxide powder.After testing, micaceous iron oxide powder purity 97.8%, product quality meets coating micaceous iron oxide
Pigment chinese national standard（HG/T 3006-1997）And international standard（ISO 10601-2007）Requirement；Compared to common mica
Iron oxide, the decay resistance of the chromium modified micaceous iron oxide of preparation is significantly improved.
Embodiment 5：
Use H2SO4Solution dissolves acid-washing stainless steel sludge, H2SO4Gram-equivalent number be acid-washing stainless steel sludge in Fe gram
3.0 times of equivalents, 80 DEG C of solution temperature, dissolution time 6h.Mixed liquor of the acid after molten is stood, separation, recovery mixed liquor bottom
Sour insoluble solid phase impurity.A certain amount of industrial by-product ferrous sulfate is added to after impurity separation in solution, until siderochrome into
Point ratio reaches 1%.H is added dropwise in solution after being adjusted to siderochrome component ratio2O2Solution is aoxidized, by the Fe in solution2+Oxygen
Turn to Fe3+, the H of dropwise addition2O2Gram-equivalent number is Fe in filtrate2+The 100% of gram-equivalent number.Then, adjusted with 5mol/L NaOH solutions
The pH value of solution obtains siderochrome mixed precipitation to 8 after whole oxidation after filtering.Siderochrome mixed precipitation is mixed with NaOH solution
It is even, carry out Hydrothermal Synthesiss in hydrothermal reaction kettle, NaOH solution concentration 14mo/L, siderochrome mixed precipitation and NaOH solution are consolidated
Liquor ratio 1:20,260 DEG C of Hydrothermal Synthesiss temperature, Hydrothermal Synthesiss time 10h.Through filtering, cleaning, be dried to obtain after the completion of hydro-thermal reaction
Chromium modified micaceous iron oxide powder.After testing, micaceous iron oxide powder purity 98.8%, product quality meets coating mica oxygen
Change iron pigment chinese national standard（HG/T 3006-1997）And international standard（ISO 10601-2007）Requirement；Compared to common
Micaceous iron oxide, the decay resistance of the chromium modified micaceous iron oxide of preparation is significantly improved.
Embodiment 6：
Use H2SO4Solution dissolves acid-washing stainless steel sludge, H2SO4Gram-equivalent number be acid-washing stainless steel sludge in Fe gram
2.0 times of equivalents, 80 DEG C of solution temperature, dissolution time 5h.Mixed liquor of the acid after molten is stood, separation, recovery mixed liquor bottom
Sour insoluble solid phase impurity.A certain amount of industrial by-product ferrous sulfate is added to after impurity separation in solution, until siderochrome into
Point ratio reaches 3%.H is added dropwise in solution after being adjusted to siderochrome component ratio2O2Solution is aoxidized, by the Fe in solution2+Oxygen
Turn to Fe3+, the H of dropwise addition2O2Gram-equivalent number is Fe in filtrate2+The 60% of gram-equivalent number.Then, adjusted with 5mol/L NaOH solutions
The pH value of solution obtains siderochrome mixed precipitation to 7 after oxidation after filtering.Siderochrome mixed precipitation is well mixed with NaOH solution,
Carry out Hydrothermal Synthesiss in hydrothermal reaction kettle, NaOH solution concentration 14mo/L, the solid-to-liquid ratio of siderochrome mixed precipitation and NaOH solution
1:15,240 DEG C of Hydrothermal Synthesiss temperature, Hydrothermal Synthesiss time 5h.Change after the completion of hydro-thermal reaction through filtering, cleaning, be dried to obtain chromium
Property micaceous iron oxide powder.After testing, micaceous iron oxide powder purity 98.2%, product quality meets coating micaceous iron oxide
Pigment chinese national standard（HG/T 3006-1997）And international standard（ISO 10601-2007）Requirement；Compared to common mica
Iron oxide, the decay resistance of the chromium modified micaceous iron oxide of preparation is significantly improved.
Embodiment 7：
Use H2SO4Solution dissolves chromium containing electroplating sludge, H2SO4Gram-equivalent number be chromium containing electroplating sludge in Fe gram equivalent
1.2 times of number, 80 DEG C of solution temperature, dissolution time 3h.Mixed liquor of the acid after molten is stood, separation, the acid for reclaiming mixed liquor bottom
Insoluble solid phase impurity.A certain amount of industrial by-product ferrous sulfate is added to after impurity separation in solution, until siderochrome composition ratio
Example reaches 5%.H is added dropwise in solution after being adjusted to siderochrome component ratio2O2Solution is aoxidized, by the Fe in solution2+It is oxidized to
Fe3+, the H of dropwise addition2O2Gram-equivalent number is Fe in filtrate2+The 100% of gram-equivalent number.Then, oxygen is adjusted with 5mol/L NaOH solutions
The pH value of solution obtains siderochrome mixed precipitation to 5 after change after filtering.Siderochrome mixed precipitation is well mixed with NaOH solution,
Carry out Hydrothermal Synthesiss in hydrothermal reaction kettle, NaOH solution concentration 12mo/L, the solid-to-liquid ratio 1 of siderochrome mixed precipitation and NaOH solution:
10,200 DEG C of Hydrothermal Synthesiss temperature, Hydrothermal Synthesiss time 4h.It is modified after the completion of hydro-thermal reaction through filtering, cleaning, being dried to obtain chromium
Micaceous iron oxide powder.After testing, micaceous iron oxide powder purity 98.1%, product quality meets coating micaceous iron oxide face
Expect chinese national standard（HG/T 3006-1997）And international standard（ISO 10601-2007）Requirement；Compared to common mica oxygen
Change iron, the decay resistance of the chromium modified micaceous iron oxide of preparation is significantly improved.
Embodiment 8：
Use H2SO4Solution dissolves acid-washing stainless steel sludge, H2SO4Gram-equivalent number be chromium containing electroplating sludge in Fe gram work as
Measure 3.0 times of number, 80 DEG C of solution temperature, dissolution time 6h.Mixed liquor of the acid after molten is stood, separates, reclaim mixed liquor bottom
The insoluble solid phase impurity of acid.A certain amount of industrial by-product ferrous sulfate is added to after impurity separation in solution, until siderochrome composition
Ratio reaches 1%.H is added dropwise in solution after being adjusted to siderochrome component ratio2O2Solution is aoxidized, by the Fe in solution2+Oxidation
For Fe3+, the H of dropwise addition2O2Gram-equivalent number is Fe in filtrate2+The 40% of gram-equivalent number.Then, oxygen is adjusted with 5mol/L NaOH solutions
The pH value of solution obtains siderochrome mixed precipitation to 8 after change after filtering.Siderochrome mixed precipitation is well mixed with NaOH solution,
Carry out Hydrothermal Synthesiss in hydrothermal reaction kettle, NaOH solution concentration 14mo/L, the solid-to-liquid ratio 1 of siderochrome mixed precipitation and NaOH solution:
20,260 DEG C of Hydrothermal Synthesiss temperature, Hydrothermal Synthesiss time 10h.It is modified after the completion of hydro-thermal reaction through filtering, cleaning, being dried to obtain chromium
Micaceous iron oxide powder.After testing, micaceous iron oxide powder purity 98.6%, product quality meets coating micaceous iron oxide face
Expect chinese national standard（HG/T 3006-1997）And international standard（ISO 10601-2007）Requirement；Compared to common mica oxygen
Change iron, the decay resistance of the chromium modified micaceous iron oxide of preparation is significantly improved.
Embodiment 9：
Use H2SO4Solution dissolves acid-washing stainless steel sludge, H2SO4Gram-equivalent number be acid-washing stainless steel sludge in Fe gram
2.0 times of equivalents, 80 DEG C of solution temperature, dissolution time 5h.Mixed liquor of the acid after molten is stood, separation, recovery mixed liquor bottom
Sour insoluble solid phase impurity.A certain amount of industrial by-product ferrous sulfate is added to after impurity separation in solution, until siderochrome into
Point ratio reaches 3%.H is added dropwise in solution after being adjusted to siderochrome component ratio2O2Solution is aoxidized, by the Fe in solution2+Oxygen
Turn to Fe3+, the H of dropwise addition2O2Gram-equivalent number is Fe in filtrate2+The 60% of gram-equivalent number.Then, adjusted with 5mol/L NaOH solutions
The pH value of solution obtains siderochrome mixed precipitation to 7 after oxidation after filtering.Siderochrome mixed precipitation is well mixed with NaOH solution,
Carry out Hydrothermal Synthesiss in hydrothermal reaction kettle, NaOH solution concentration 14mo/L, the solid-to-liquid ratio of siderochrome mixed precipitation and NaOH solution
1:15,240 DEG C of Hydrothermal Synthesiss temperature, Hydrothermal Synthesiss time 5h.Change after the completion of hydro-thermal reaction through filtering, cleaning, be dried to obtain chromium
Property micaceous iron oxide powder.After testing, micaceous iron oxide powder purity 97.9%, product quality meets coating micaceous iron oxide
Pigment chinese national standard（HG/T 3006-1997）And international standard（ISO 10601-2007）Requirement；Compared to common mica
Iron oxide, the decay resistance of the chromium modified micaceous iron oxide of preparation is significantly improved.
Embodiment 10：
Use H2SO4Solution dissolves leather-making mud, H2SO4Gram-equivalent number be leather-making mud in Fe 1.2 times of gram-equivalent number,
80 DEG C of solution temperature, dissolution time 3h.Mixed liquor of the acid after molten is stood, separation, the sour insoluble solid phase for reclaiming mixed liquor bottom
Impurity.A certain amount of industrial by-product ferrous sulfate is added to after impurity separation in solution, until siderochrome component ratio reaches 5%.
H is added dropwise in solution after being adjusted to siderochrome component ratio2O2Solution is aoxidized, by the Fe in solution2+It is oxidized to Fe3+, it is added dropwise
H2O2Gram-equivalent number is Fe in filtrate2+The 100% of gram-equivalent number.Then, with solution after the adjustment oxidation of 5mol/L NaOH solutions
PH value to 5, siderochrome mixed precipitation is obtained after filtering.Siderochrome mixed precipitation is well mixed with NaOH solution, in hydro-thermal reaction
Carry out Hydrothermal Synthesiss in kettle, NaOH solution concentration 12mo/L, the solid-to-liquid ratio 1 of siderochrome mixed precipitation and NaOH solution:10, hydro-thermal
200 DEG C of synthesis temperature, Hydrothermal Synthesiss time 4h.Through filtering, cleaning, being dried to obtain the modified micaceous oxidation of chromium after the completion of hydro-thermal reaction
Iron powder body.After testing, micaceous iron oxide powder purity 98.3%, product quality meets the Chinese state of coating mica-iron oxide pigment
Family's standard（HG/T 3006-1997）And international standard（ISO 10601-2007）Requirement；Compared to common micaceous iron oxide, system
The decay resistance of standby chromium modified micaceous iron oxide is significantly improved.
Embodiment 11：
Use H2SO4Solution dissolves leather-making mud, H2SO4Gram-equivalent number be leather-making mud in Fe 3.0 times of gram-equivalent number,
80 DEG C of solution temperature, dissolution time 6h.Mixed liquor of the acid after molten is stood, separation, the sour insoluble solid phase for reclaiming mixed liquor bottom
Impurity.A certain amount of industrial by-product ferrous sulfate is added to after impurity separation in solution, until siderochrome component ratio reaches 1%.
H is added dropwise in solution after being adjusted to siderochrome component ratio2O2Solution is aoxidized, by the Fe in solution2+It is oxidized to Fe3+, it is added dropwise
H2O2Gram-equivalent number is Fe in filtrate2+The 40% of gram-equivalent number.Then, solution after oxidation is adjusted with 5mol/L NaOH solutions
PH value obtains siderochrome mixed precipitation to 8 after filtering.Siderochrome mixed precipitation is well mixed with NaOH solution, in hydrothermal reaction kettle
The solid-to-liquid ratio 1 of middle carry out Hydrothermal Synthesiss, NaOH solution concentration 14mo/L, siderochrome mixed precipitation and NaOH solution:20, hydro-thermal is closed
Into 260 DEG C of temperature, Hydrothermal Synthesiss time 10h.Through filtering, cleaning, being dried to obtain the modified micaceous oxidation of chromium after the completion of hydro-thermal reaction
Iron powder body.After testing, micaceous iron oxide powder purity 98.4%, product quality meets the Chinese state of coating mica-iron oxide pigment
Family's standard（HG/T 3006-1997）And international standard（ISO 10601-2007）Requirement；Compared to common micaceous iron oxide, system
The decay resistance of standby chromium modified micaceous iron oxide is significantly improved.
Embodiment 12：
Use H2SO4Solution dissolves leather-making mud, H2SO4Gram-equivalent number be leather-making mud in Fe 2.0 times of gram-equivalent number,
80 DEG C of solution temperature, dissolution time 5h.Mixed liquor of the acid after molten is stood, separation, the sour insoluble solid phase for reclaiming mixed liquor bottom
Impurity.A certain amount of industrial by-product ferrous sulfate is added to after impurity separation in solution, until siderochrome component ratio reaches 3%.
H is added dropwise in solution after being adjusted to siderochrome component ratio2O2Solution is aoxidized, by the Fe in solution2+It is oxidized to Fe3+, it is added dropwise
H2O2Gram-equivalent number is Fe in filtrate2+The 60% of gram-equivalent number.Then, solution after oxidation is adjusted with 5mol/L NaOH solutions
PH value obtains siderochrome mixed precipitation to 7 after filtering.Siderochrome mixed precipitation is well mixed with NaOH solution, in hydrothermal reaction kettle
The solid-to-liquid ratio 1 of middle carry out Hydrothermal Synthesiss, NaOH solution concentration 14mo/L, siderochrome mixed precipitation and NaOH solution:15, hydro-thermal is closed
Into 240 DEG C of temperature, Hydrothermal Synthesiss time 5h.Through filtering, cleaning, be dried to obtain chromium modified micaceous iron oxide after the completion of hydro-thermal reaction
Powder.After testing, micaceous iron oxide powder purity 98.6%, product quality meets coating mica-iron oxide pigment China national
Standard（HG/T 3006-1997）And international standard（ISO 10601-2007）Requirement；Compared to common micaceous iron oxide, prepare
The decay resistance of chromium modified micaceous iron oxide significantly improve.
Claims (3)
1. a kind of method that siderochrome solid waste prepares chromium modified micaceous iron oxide, it is characterised in that methods described includes dirty to siderochrome
Mud carries out molten acid, impurity separation and recovery, composition detection, component ratio adjustment, oxidation, regulation pH value, Hydrothermal Synthesiss successively, obtains
Obtain chromium modified micaceous iron oxide；
Comprise the following steps that：
(1) acid is molten：Use H2SO4Solution dissolves siderochrome sludge, H2SO4Gram-equivalent number be Fe, Cr gram-equivalent number in siderochrome sludge
1.2~3.0 times, solution temperature is 80 DEG C, dissolution time 3h~6h；
(2) impurity separation and recovery：Mixed liquor of the acid after molten is stood, the sour insoluble solid phase for separating, reclaiming mixed liquor bottom is miscellaneous
Matter, then centrifuges mixed liquor, separates, reclaims organic impurities；
(3) siderochrome composition detection：Iron, the concentration of chromium ion in solution after checked for impurities separation；
(4) siderochrome component ratio is adjusted：According to siderochrome composition detection result, siderochrome component ratio in solution is calculated：{m(Cr)/[m
(Fe)+m (Cr)] }, the m is quality, when ratio value is more than 5%, then into solution plus by industrial by-product ferrous sulfate, until
Siderochrome component ratio reaches 1%~5%；
(5) aoxidize：H is added dropwise in solution after being adjusted to siderochrome component ratio2O2Solution is aoxidized, by the Fe in solution2+Oxidation
For Fe3+, the H of dropwise addition2O2Gram-equivalent number is Fe in filtrate2+The 40%~100% of gram-equivalent number；
(6) pH value is adjusted：The pH value for adjusting solution after oxidation with 5mol/L NaOH solutions obtains siderochrome and mixed to 6~8 after filtering
Close precipitation；
(7) Hydrothermal Synthesiss：Siderochrome mixed precipitation is well mixed with NaOH solution, Hydrothermal Synthesiss are carried out in hydrothermal reaction kettle.
2. the method that a kind of siderochrome solid waste according to claim 1 prepares chromium modified micaceous iron oxide, it is characterised in that：Iron
Chromium solid waste mainly includes the siderochrome sludge produced in siderochrome grinding waste material, chromate waste water disposal process.
3. the method that a kind of siderochrome solid waste according to claim 1 prepares chromium modified micaceous iron oxide, it is characterised in that：Water
In thermal synthesis, NaOH solution concentration 12mo/L~16mol/L, the solid-to-liquid ratio 1 of siderochrome mixed precipitation and NaOH solution:10~1:
20,200 DEG C~260 DEG C of Hydrothermal Synthesiss temperature, Hydrothermal Synthesiss time 4h~10h.
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| CN1944274A (en) * | 2006-10-24 | 2007-04-11 | 湘潭大学 | Method for preparing mica iron oxide by hydrothermal reaction and crystallizing |
| CN102923789A (en) * | 2012-07-16 | 2013-02-13 | 北京科技大学 | Method for preparing mica iron oxide through cold-rolled iron mud |
| CN104556227A (en) * | 2013-08-29 | 2015-04-29 | 唐翔 | Technology for preparing chromate by carbon ferrochrome liquid-phase oxidation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1944274A (en) * | 2006-10-24 | 2007-04-11 | 湘潭大学 | Method for preparing mica iron oxide by hydrothermal reaction and crystallizing |
| CN102923789A (en) * | 2012-07-16 | 2013-02-13 | 北京科技大学 | Method for preparing mica iron oxide through cold-rolled iron mud |
| CN104556227A (en) * | 2013-08-29 | 2015-04-29 | 唐翔 | Technology for preparing chromate by carbon ferrochrome liquid-phase oxidation |
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| Title |
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| "New technology for recyclingmaterials from oily cold rollingmill sludge";Bo Liu et al.;《International Journal of Minerals, Metallurgy and Materials》;20131231;第20卷(第12期);第1142页第2-5段和图1以及表1、第1143页第1-3段、第1146页第4-5段 * |
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