CN105621496A - Method for preparing chromium modified mica iron oxide through iron-chromium solid waste - Google Patents
Method for preparing chromium modified mica iron oxide through iron-chromium solid waste Download PDFInfo
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- CN105621496A CN105621496A CN201511004776.1A CN201511004776A CN105621496A CN 105621496 A CN105621496 A CN 105621496A CN 201511004776 A CN201511004776 A CN 201511004776A CN 105621496 A CN105621496 A CN 105621496A
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- siderochrome
- solution
- chromium
- iron oxide
- iron
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000011651 chromium Substances 0.000 title claims abstract description 85
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 62
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 60
- 239000002910 solid waste Substances 0.000 title claims abstract description 18
- 239000010445 mica Substances 0.000 title abstract description 51
- 229910052618 mica group Inorganic materials 0.000 title abstract description 51
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 title abstract 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 176
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 80
- 229910052742 iron Inorganic materials 0.000 claims abstract description 66
- 238000000926 separation method Methods 0.000 claims abstract description 30
- 239000012535 impurity Substances 0.000 claims abstract description 27
- 230000003647 oxidation Effects 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 22
- 238000004090 dissolution Methods 0.000 claims abstract description 15
- 239000002351 wastewater Substances 0.000 claims abstract description 10
- 238000001514 detection method Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 140
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 134
- 238000001556 precipitation Methods 0.000 claims description 46
- 239000011259 mixed solution Substances 0.000 claims description 33
- 238000001914 filtration Methods 0.000 claims description 28
- 238000011084 recovery Methods 0.000 claims description 27
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 15
- 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
- 239000007790 solid phase Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 239000006227 byproduct Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002699 waste material Substances 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 5
- 229910001430 chromium ion Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 abstract description 21
- 239000011248 coating agent Substances 0.000 abstract description 19
- 238000000576 coating method Methods 0.000 abstract description 19
- 230000007797 corrosion Effects 0.000 abstract description 18
- 238000005260 corrosion Methods 0.000 abstract description 18
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000004064 recycling Methods 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000003754 machining Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 29
- 239000010935 stainless steel Substances 0.000 description 22
- 229910001220 stainless steel Inorganic materials 0.000 description 22
- 238000005406 washing Methods 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 18
- 239000000047 product Substances 0.000 description 16
- 238000004140 cleaning Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 13
- 239000001034 iron oxide pigment Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000009713 electroplating Methods 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 230000002829 reductive effect Effects 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
- 230000015572 biosynthetic process 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 238000005272 metallurgy Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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
- 239000002585 base Substances 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 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
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-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
- 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
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 230000002421 anti-septic effect Effects 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
- 239000000919 ceramic Substances 0.000 description 1
- 239000004927 clay 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
- 238000011161 development Methods 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
- 238000000605 extraction Methods 0.000 description 1
- 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 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 1
- 239000011499 joint compound Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 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
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 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
- 239000007921 spray Substances 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
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000003832 thermite Substances 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
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
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 invention relates to a method for preparing a chromium modified mica iron oxide through iron-chromium solid waste. Iron chromium solid waste generated during machining and chromium-containing wastewater disposal is adopted as raw materials, and the chromium modified mica iron oxide with the good corrosion resistance is directly generated through the working procedures of acid dissolution, impurity separation and recycling, iron chromium component detection, iron chromium component ratio adjustment, oxidation, pH value adjustment and hydro-thermal synthesis. Generation of the mica iron oxide and chromium modification are completed in one step, the production process of the modified mica iron oxide is simplified, and meanwhile the problems that iron and chromium separation is difficult, environmental burdens are large and the recycling additional value is low during existing iron chromium solid waste are solved. The chromium modified mica iron oxide for coating has the advantages of being wide in raw material source, low in cost, environmentally friendly, high in additional value and the like.
Description
Technical field
The invention belongs to recycling economy technical field, particularly relate to a kind of siderochrome solid waste produced in the processes such as mechanical workout, chromate waste water disposal as raw material, employing hydrothermal method prepares the method for the chromium modified micaceous iron oxide of erosion resistance.
Background technology
Chromium is one of addition element most widely used in Iron and Steel Production, can significantly improve the intensity of material, hardness, wear resistance, oxidation-resistance, erosion resistance etc., be widely used in structure iron, tool steel, stainless steel, high temperature steel etc. Chrome-bearing steel iron material can produce the siderochrome grinding waste material mixed in a large number by ferrochrome exothermic particle, emery wheel abrasive grain, emery wheel additive and grinding coolant etc. in the course of processing such as grinding, milling. These siderochrome mud contain a large amount of Fe, Cr valuable metal, have recovery value. But, in siderochrome mud, abrasive material, emery wheel additive etc. are mutual embedding attached with ferrochrome exothermic particle, cause follow-up separation very difficult, meanwhile, also containing a large amount of machining oils etc. in siderochrome mud, which in turns increases the difficulty of siderochrome mud recycling. At present, siderochrome mud is worked as waste disposal by China's mechanical industry and metallurgy industry, both land occupation, contaminate environment, cause again the significant wastage of secondary resource.
At present, most iron-based grinding waste materials, by as the raw material returning stove melting, the low side of secondary resource not only being caused to utilize, also can cause environmental pollution simultaneously. Chinese patent 200510010031 discloses a kind of ground finish and that Milling Process is got off and belong to powder and metallic particles is processed into the consumable electrode needed for electroslag furnace, the method for regenerative ratio alloy steel casting of utilizing. The method has raw material availability height, it is existing to utilize; Chinese patent 201010230229 discloses a kind of taking iron base waste material as raw material, utilizes thermite reaction to prepare manufacture method corrosion-resistant, abrasion-proof ceramic lining metal pipe material. Metal pipe material prepared by this invention can extensively for the powder of the industries such as metallurgy, mine, electric power, coal, mud, Tailings transportation. The shortcoming that this inventive method exists process energy consumption height, cost is high; Chinese patent 201010230531 discloses the pollution-free reuse method of a kind of iron-based grinding waste material, comprises oil removing, thermal treatment, screening, proportioning, and it is multi-field that the iron(-)base powder obtained can be used for powder metallurgy structural part, magnetically grinding, thermospray etc. Such reuse method has waste utilization rate advantages of higher, it is also possible to exist, added value of product is lower, treating processes easily causes the problems such as environmental pollution.
Along with the development of the industry such as plating, metallurgy, process hides, printing and dyeing, the quantity discharged of chromate waste water increases day by day, and for electroplating 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, industrial applicibility and processing cost, ferrous salt reduction precipitation method is one of current chromate waste water method of disposal the most widely used both at home and abroad, and its handling principle is as follows:
(1) reduction and detoxication: 3Fe2++Cr6+��Cr3++3Fe3+;
(2) precipitate: Fe3++OH-��Fe(OH)3��; Cr3++OH-��Cr(OH)3��;
The Cr of severe toxicity6+It is reduced into Cr by cheap ferrous salt3+, then with Cr (OH)3Form precipitate out, preferably removing toxic substances and recovering effect can be obtained. But, due to Cr3+And Fe3+Having between close pH value settling region, chromate waste water can produce the siderochrome mud of substantial amounts after processing. Cr (OH) in siderochrome mud3May slow oxidation be Cr under natural condition6+, and then environment is caused secondary pollution. Table 1 is that typical case's siderochrome mud (acid-washing stainless steel mud, plating siderochrome mud and leather-making mud) heavy metal leaches toxotest result, it can be seen that in siderochrome mud, Cr leaches concentration far above country toxicity criterion.
Table 1 typical case's siderochrome sludge heavy-metal leaches toxicity (mg/L)
| Element | Total Cr | Cr6+ | Cd2+ | Zn2+ | Pb2+ 1 --> |
| GB5085.3-2007 | ��15 | ��5 | ��1 | ��100 | ��5 |
| Acid-washing stainless steel siderochrome mud | 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 mud can be roughly divided into fire method and the big class of wet method two. Chinese patent 201410383658 discloses a kind of method that high siderochrome sewage sludge harmlessness is recycled: is first mixed with coal by high siderochrome mud, carries out drying and roasting successively, obtain grog after cooling in Sealing Arrangement. Then, undertaken grog pulverizing, sieve after obtain rust cleaning sand; Chinese patent 201310447422.9 provides a kind of acid-washing stainless steel mud to prepare the method for nichrome: first, adds alkali lye to obtain neutral mud in acid-washing stainless steel mud. Then, after the neutral mud obtained is carried out the operation such as reducing and smelting in rotary kiln oven dry, coke and starch ball, rotary kiln, plasma electric stove fusing smelting, obtain nichrome; Chinese patent 201410206530 discloses a kind of processing method disposing acid-washing stainless steel mud, as follows: in acid-washing stainless steel mud, evenly to mix appropriate reductive agent, sinter brick into according to processing steps such as preheating phase, reduction period, insulation phase and cooldown periods under a reducing atmosphere. Then in acid-washing stainless steel mud, evenly mix appropriate reductive agent, sinter brick under a reducing atmosphere into. The advantages such as it is lower that the pyrogenic processing method of siderochrome mud has cost, and end-use is extensive, but also also exist that added value of product is low, energy consumption height, treating processes easily cause the problems such as environmental pollution.
Chinese patent 201210205195.4 discloses a kind of method of acid-washing stainless steel mud green extraction of chromium and nickel, and the method is for heavy metal ion (Cr in acid-washing stainless steel mud6+��Cr3+��Ni2+), use H2SO4Heavy metal ion wherein is leached, after filtration, obtains nontoxic pickling mud and the leach liquor of heavy metal free ion. NaHSO is added in leach liquor3, by Cr6+It is reduced into Cr3+. Then NaOH is adopted to regulate pH of leaching solution to be 7.5 ~ 10.0 by Cr3+��Ni2+Precipitation, filtration, dry formation Cr (OH)3With Ni (OH)2Metallurgical raw material. Finally, it may also be useful to the F in lime precipitation filtrate-And SO4 2-. The method has the removing toxic substances of poisonous ion thoroughly, advantage with low cost. But in the method, Cr3+��Ni2+Final as Cr (OH)3With Ni (OH)2Metallurgical raw material is recycled, and also there is the shortcoming that added value of product is lower; Chinese patent 201210141865 discloses in a kind of stainless steel acid cleaning waste water and sludge heavy-metal its recovery method as resource, comprising: first with in sulfuric acid lixiviate stainless steel acid cleaning waste water and mud, and add the leaching that additive suppresses iron. Then, leaching liquid adds oxygenant, by Mn(II) it is oxidized to Manganse Dioxide. After oxidation, solution is through anion-exchange column, enriching and recovering sexavalent chrome, adsorb saturated after, adopt regenerator to regenerate, from regenerated liquid, reclaim chromic salt. Finally, moderate water-cut stage is utilized to reclaim the nickel in ion-exchange water outlet. The method can realize manganese in acid-washing stainless steel mud, chromium, nickel multistage distribution reclaim, also there is technical process length, problem that cost is higher;
Iron mica is the lamellar pigment of a kind of stable chemical performance, and main chemical compositions is ��-Fe2O3. The special two-dimensional sheet structure of iron mica powder body makes it have excellent sticking power, significant uv reflectance ability when application, iron mica also has the features such as chemical property is stable, nonpoisonous and tasteless, conductivity is good, high temperature resistant, resistance to salt(spray)fog is good simultaneously, is widely used in the fields such as anticorrosive paint, heavy-duty coating, filler. At present, the preparation method of artificial mica synthesis ferric oxide mainly contains high-temperature molten salt method, vapor phase process and hydrothermal method etc.
United States Patent (USP) 4676838 discloses a kind of about the preparation of platelet shaped iron oxide pigment and the method for use: ferric iron solution or suspension are added after neutralizing treatment in sodium hydroxide medium, and the hydro-thermal presoma of formation obtains flake ferric oxide pigment after hydro-thermal reaction. The iron mica that this inventive method is produced has the advantages such as purity height, crystallization be good, but owing to using pure material for raw material completely, there is the shortcoming that raw materials cost is high; Chinese patent 201010136709.6 discloses a kind of method that molten-salt growth method prepares iron mica, the method is taking ferrous ammonium sulphate or ferrous sulfate or both mixtures as source of iron, taking vitriol or muriate or both mixtures as fusing assistant, melting after mixing and iron mica. The shortcoming that this inventive method exists process energy consumption height, cost is high; Chinese patent CN100390072C discloses a kind of taking titanium white by product ferrous sulfate as raw material, by dissolving the operations such as purification, oxidation, precursor generation, hydro-thermal reaction crystallization and aftertreatment, prepares particle diameter and the method for color controllable iron mica. This inventive method is taking the ferrous sulfate by-product of high purity as raw material, and adopts the method purification raw material dissolving purification, there is the shortcoming of applicable raw materials narrow range; Chinese patent 201210475290 discloses the preparation method of the clay standby iron mica of a kind of cold rolling iron, the oil-containing iron mud that the method produces in the cold rolling of strip steel course of processing is as raw material, by acid-soluble, de-oiling and recovery, oxidation, precipitation, hydro-thermal reaction, producing coating iron mica powder, its quality meets national standard (HG/T3006-1997) and international standard (ISO10601-2007). This invention adopts the method separation regulating solution ph, removes impurity cationic, widen the source of iron mica raw materials for production to a certain extent, but this invention has the material that is applicable to low impurity cationic content equally, application has the shortcoming of certain limitation.
At present, can be used for improving the iron mica method of modifying of Corrosion Protection to mainly contain: inorganics cladding process and organic inhibitor cladding process. Chinese patent 201310263649.8 discloses the preparation method of the coated iron mica rust-stabilising pigment of a kind of nano-oxide: slowly join in iron mica solution by titanyl sulfate and/or solution of zinc sulfate, stirring reaction. Then, while stirring calcium hydroxide and/or calcium oxide are added in above-mentioned reaction system, final generate nano titanium oxide and/or the coated iron mica of nano zine oxide; Chinese patent 200810012660 discloses a kind of environmental-friendly polyaniline modified micaceous iron oxide anticorrosive coating and its preparation method: utilize oxidative polymerization method to form polyaniline coating layer on iron mica surface, metal is had passivation by the iron mica after process, and metal is also played the effect of inhibition by the phytic acid coating layer on iron mica surface. This method solve existing MIO coating antiseptic property poor, manufacturing processed must contain problem that is plumbous and chromate pigments with the use of harmful. Foregoing invention all uses finished product iron mica for raw material, and cost is higher.
Summary of the invention
The present invention discloses the preparation method that a kind of siderochrome solid waste prepares chromium modified micaceous iron oxide. The siderochrome solid waste that the present invention produces in the processes such as mechanical workout, chromate waste water disposal is as raw material, by acid-soluble, magazins' layout and recovery, siderochrome composition detection, the adjustment of siderochrome component proportions, oxidation, adjust ph, Hydrothermal Synthesis operation, direct production goes out to have the chromium modified micaceous iron oxide of good Corrosion Protection. In the present invention, the production of iron mica and chromium modification one step complete, and not only shorten the Production Flow Chart of modified micaceous iron oxide, also solve existing siderochrome solid waste iron, chromium separation difficulty, environmental pressure weight simultaneously, the problems such as recycling added value is low. The coating chromium modified micaceous iron oxide adopting the present invention to produce has that raw material sources are wide, cost is low, environmental protection and added value advantages of higher.
The present invention is for the purpose of the resource utilization recycling of siderochrome solid waste, by acid-soluble, magazins' layout and recovery, siderochrome composition detection, the adjustment of siderochrome component proportions, oxidation, adjust ph, Hydrothermal Synthesis operation, direct production goes out to have the chromium modified micaceous iron oxide of good Corrosion Protection. Concrete grammar comprises the following steps:
(1) acid-soluble: to use H2SO4Solubilize siderochrome mud, H2SO4Gram-equivalent number be 1.2 ~ 3.0 times of Fe, Cr gram-equivalent number in siderochrome mud, solvent temperature is 80 DEG C, dissolution time 3h ~ 6h;
(2) magazins' layout and recovery: the mixed solution after acid-soluble is left standstill, the sour insoluble solid phase impurity bottom separation, recovery mixed solution. Then, by mixed solution centrifugation, separation, recovery organic impurities wherein;
(3) siderochrome composition detection: the concentration of iron, chromium ion in the rear solution of checked for impurities separation;
(4) siderochrome component proportions adjustment: according to siderochrome composition detection result, calculates siderochrome component proportions in solution: { m (Cr)/�� m (Fe)+m (Cr) �� } (m is quality). If this ratio is more than 5%, then a certain amount of industrial by-product ferrous sulfate is joined in solution, until siderochrome component proportions reaches 1% ~ 5%;
(5) it is oxidized: the solution after adjusting to siderochrome component proportions drips and adds H2O2Solution is oxidized, by the Fe in solution2+It is oxidized to Fe3+, drip the H added2O2Gram-equivalent number is Fe in filtrate2+The 40% ~ 100% of gram-equivalent number;
(6) adjust ph: with pH value to 6 ~ 8 of solution after the adjustment oxidation of 5mol/LNaOH solution, obtain siderochrome mixed precipitation after filtration;
(7) Hydrothermal Synthesis: siderochrome mixed precipitation is mixed with NaOH solution, hydrothermal reaction kettle carries out Hydrothermal Synthesis, NaOH solution concentration 12mo/L ~ 16mol/L, the solid-to-liquid ratio 1:10 of siderochrome mixed precipitation and NaOH solution ~ 1:20, Hydrothermal Synthesis temperature 200 DEG C ~ 260 DEG C, Hydrothermal Synthesis time 4h ~ 10h.
The advantage of the present invention: the siderochrome solid waste that the present invention produces in the processes such as mechanical workout, chromate waste water disposal, as raw material, produces the chromium modified micaceous iron oxide with good Corrosion Protection. In the present invention, the production of iron mica and chromium modification one step complete, and not only shorten the Production Flow Chart of modified micaceous iron oxide, also solve existing siderochrome solid waste iron, chromium separation difficulty, environmental pressure weight simultaneously, the problems such as recycling added value is low. The coating chromium modified micaceous iron oxide adopting the present invention to produce has that raw material sources are wide, cost is low, environmental protection and added value advantages of higher.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the present invention.
Fig. 2 is the X-ray diffraction analysis chart of chromium modified micaceous iron oxide prepared by the present invention.
Fig. 3 is the scanning electron microscope shape appearance figure of chromium modified micaceous iron oxide prepared by the present invention.
Embodiment
Embodiment 1:
Use H2SO4Solubilize siderochrome grinding waste material, H2SO4Gram-equivalent number be the gram-equivalent number 1.2 times of Fe in siderochrome mud, solvent temperature 80 DEG C, dissolution time 3h. Mixed solution after acid-soluble is left standstill, the sour insoluble solid phase impurity bottom separation, recovery mixed solution. Then, by mixed solution centrifugation, separation, recovery organic impurities wherein. The concentration of iron, chromium ion in the rear solution of checked for impurities separation, in solution, m (Cr)/�� m (Fe)+m (Cr) �� mass ratio is 3%. Solution after adjusting to siderochrome component proportions drips and adds H2O2Solution is oxidized, by the Fe in solution2+It is oxidized to Fe3+, drip the H added2O2Gram-equivalent number is Fe in filtrate2+The 40% of gram-equivalent number. Then, by the pH value to 6 of solution after the adjustment oxidation of 5mol/LNaOH solution, siderochrome mixed precipitation after filtration, is obtained. Siderochrome mixed precipitation is mixed with NaOH solution, hydrothermal reaction kettle carries out Hydrothermal Synthesis, NaOH solution concentration 12mo/L, the solid-to-liquid ratio 1:10 of siderochrome mixed precipitation and NaOH solution, Hydrothermal Synthesis temperature 200 DEG C, Hydrothermal Synthesis time 4h. Hydro-thermal reaction obtains chromium modified micaceous iron oxide powder body through filtration, cleaning, drying after completing. After testing, iron mica powder purity 98.1%, quality product meets coating mica-iron oxide pigment China national standard (HG/T3006-1997) and the requirement of international standard (ISO10601-2007); Comparing common iron mica, the corrosion resistance nature of the chromium modified micaceous iron oxide of preparation significantly improves.
Embodiment 2:
Use H2SO4Solubilize siderochrome grinding waste material, H2SO4Gram-equivalent number be the gram-equivalent number 3.0 times of Fe in siderochrome mud, solvent temperature 80 DEG C, dissolution time 6h. Mixed solution after acid-soluble is left standstill, the sour insoluble solid phase impurity bottom separation, recovery mixed solution. Then, by mixed solution centrifugation, separation, recovery organic impurities wherein. The concentration of iron, chromium ion in the rear solution of checked for impurities separation, in solution, m (Cr)/�� m (Fe)+m (Cr) �� mass ratio is 3%. Solution after adjusting to siderochrome component proportions drips and adds H2O2Solution is oxidized, by the Fe in solution2+It is oxidized to Fe3+, drip the H added2O2Gram-equivalent number is Fe in filtrate2+The 100% of gram-equivalent number. Then, by the pH value to 8 of solution after the adjustment oxidation of 5mol/LNaOH solution, siderochrome mixed precipitation after filtration, is obtained. Siderochrome mixed precipitation is mixed with NaOH solution, hydrothermal reaction kettle carries out Hydrothermal Synthesis, NaOH solution concentration 16mo/L, the solid-to-liquid ratio 1:20 of siderochrome mixed precipitation and NaOH solution, Hydrothermal Synthesis temperature 260 DEG C, Hydrothermal Synthesis time 10h. Hydro-thermal reaction obtains chromium modified micaceous iron oxide powder body through filtration, cleaning, drying after completing. After testing, iron mica powder purity 98.7%, quality product meets coating mica-iron oxide pigment China national standard (HG/T3006-1997) and the requirement of international standard (ISO10601-2007); Comparing common iron mica, the corrosion resistance nature of the chromium modified micaceous iron oxide of preparation significantly improves.
Embodiment 3:
Use H2SO4Solubilize siderochrome grinding waste material, H2SO4Gram-equivalent number be the gram-equivalent number 2.0 times of Fe in siderochrome mud, solvent temperature 80 DEG C, dissolution time 5h. Mixed solution after acid-soluble is left standstill, the sour insoluble solid phase impurity bottom separation, recovery mixed solution. Then, by mixed solution centrifugation, separation, recovery organic impurities wherein. The concentration of iron, chromium ion in the rear solution of checked for impurities separation, in solution, m (Cr)/�� m (Fe)+m (Cr) �� mass ratio is 3%. Solution after adjusting to siderochrome component proportions drips and adds H2O2Solution is oxidized, by the Fe in solution2+It is oxidized to Fe3+, drip the H added2O2Gram-equivalent number is Fe in filtrate2+The 70% of gram-equivalent number. Then, by the pH value to 7 of solution after the adjustment oxidation of 5mol/LNaOH solution, siderochrome mixed precipitation after filtration, is obtained. Siderochrome mixed precipitation is mixed with NaOH solution, hydrothermal reaction kettle carries out Hydrothermal Synthesis, NaOH solution concentration 16mo/L, the solid-to-liquid ratio 1:15 of siderochrome mixed precipitation and NaOH solution, Hydrothermal Synthesis temperature 240 DEG C, Hydrothermal Synthesis time 6h. Hydro-thermal reaction obtains chromium modified micaceous iron oxide powder body through filtration, cleaning, drying after completing. After testing, iron mica powder purity 98.6%, quality product meets coating mica-iron oxide pigment China national standard (HG/T3006-1997) and the requirement of international standard (ISO10601-2007); Comparing common iron mica, the corrosion resistance nature of the chromium modified micaceous iron oxide of preparation significantly improves.
Embodiment 4:
Use H2SO4Solubilize acid-washing stainless steel mud, H2SO4Gram-equivalent number be the gram-equivalent number 1.2 times of Fe in acid-washing stainless steel mud, solvent temperature 80 DEG C, dissolution time 3h. Mixed solution after acid-soluble is left standstill, the sour insoluble solid phase impurity bottom separation, recovery mixed solution. A certain amount of industrial by-product ferrous sulfate is joined after magazins' layout in solution, until siderochrome component proportions reaches 5%. Solution after adjusting to siderochrome component proportions drips and adds H2O2Solution is oxidized, by the Fe in solution2+It is oxidized to Fe3+, drip the H added2O2Gram-equivalent number is Fe in filtrate2+The 40% of gram-equivalent number. Then, by the pH value to 5 of solution after the adjustment oxidation of 5mol/LNaOH solution, siderochrome mixed precipitation after filtration, is obtained. Siderochrome mixed precipitation is mixed with NaOH solution, hydrothermal reaction kettle carries out Hydrothermal Synthesis, NaOH solution concentration 12mo/L, the solid-to-liquid ratio 1:10 of siderochrome mixed precipitation and NaOH solution, Hydrothermal Synthesis temperature 200 DEG C, Hydrothermal Synthesis time 4h. Hydro-thermal reaction obtains chromium modified micaceous iron oxide powder body through filtration, cleaning, drying after completing. After testing, iron mica powder purity 97.8%, quality product meets coating mica-iron oxide pigment China national standard (HG/T3006-1997) and the requirement of international standard (ISO10601-2007); Comparing common iron mica, the corrosion resistance nature of the chromium modified micaceous iron oxide of preparation significantly improves.
Embodiment 5:
Use H2SO4Solubilize acid-washing stainless steel mud, H2SO4Gram-equivalent number be the gram-equivalent number 3.0 times of Fe in acid-washing stainless steel mud, solvent temperature 80 DEG C, dissolution time 6h. Mixed solution after acid-soluble is left standstill, the sour insoluble solid phase impurity bottom separation, recovery mixed solution. A certain amount of industrial by-product ferrous sulfate is joined after magazins' layout in solution, until siderochrome component proportions reaches 1%. Solution after adjusting to siderochrome component proportions drips and adds H2O2Solution is oxidized, by the Fe in solution2+It is oxidized to Fe3+, drip the H added2O2Gram-equivalent number is Fe in filtrate2+The 100% of gram-equivalent number. Then, by the pH value to 8 of solution after the adjustment oxidation of 5mol/LNaOH solution, siderochrome mixed precipitation after filtration, is obtained. Siderochrome mixed precipitation is mixed with NaOH solution, hydrothermal reaction kettle carries out Hydrothermal Synthesis, NaOH solution concentration 14mo/L, the solid-to-liquid ratio 1:20 of siderochrome mixed precipitation and NaOH solution, Hydrothermal Synthesis temperature 260 DEG C, Hydrothermal Synthesis time 10h. Hydro-thermal reaction obtains chromium modified micaceous iron oxide powder body through filtration, cleaning, drying after completing. After testing, iron mica powder purity 98.8%, quality product meets coating mica-iron oxide pigment China national standard (HG/T3006-1997) and the requirement of international standard (ISO10601-2007); Comparing common iron mica, the corrosion resistance nature of the chromium modified micaceous iron oxide of preparation significantly improves.
Embodiment 6:
Use H2SO4Solubilize acid-washing stainless steel mud, H2SO4Gram-equivalent number be the gram-equivalent number 2.0 times of Fe in acid-washing stainless steel mud, solvent temperature 80 DEG C, dissolution time 5h. Mixed solution after acid-soluble is left standstill, the sour insoluble solid phase impurity bottom separation, recovery mixed solution. A certain amount of industrial by-product ferrous sulfate is joined after magazins' layout in solution, until siderochrome component proportions reaches 3%. Solution after adjusting to siderochrome component proportions drips and adds H2O2Solution is oxidized, by the Fe in solution2+It is oxidized to Fe3+, drip the H added2O2Gram-equivalent number is Fe in filtrate2+The 60% of gram-equivalent number. Then, by the pH value to 7 of solution after the adjustment oxidation of 5mol/LNaOH solution, siderochrome mixed precipitation after filtration, is obtained. Siderochrome mixed precipitation is mixed with NaOH solution, hydrothermal reaction kettle carries out Hydrothermal Synthesis, NaOH solution concentration 14mo/L, the solid-to-liquid ratio 1:15 of siderochrome mixed precipitation and NaOH solution, Hydrothermal Synthesis temperature 240 DEG C, Hydrothermal Synthesis time 5h. Hydro-thermal reaction obtains chromium modified micaceous iron oxide powder body through filtration, cleaning, drying after completing. After testing, iron mica powder purity 98.2%, quality product meets coating mica-iron oxide pigment China national standard (HG/T3006-1997) and the requirement of international standard (ISO10601-2007); Comparing common iron mica, the corrosion resistance nature of the chromium modified micaceous iron oxide of preparation significantly improves.
Embodiment 7:
Use H2SO4Solubilize chromium containing electroplating mud, H2SO4Gram-equivalent number be the gram-equivalent number 1.2 times of Fe in chromium containing electroplating mud, solvent temperature 80 DEG C, dissolution time 3h. Mixed solution after acid-soluble is left standstill, the sour insoluble solid phase impurity bottom separation, recovery mixed solution. A certain amount of industrial by-product ferrous sulfate is joined after magazins' layout in solution, until siderochrome component proportions reaches 5%. Solution after adjusting to siderochrome component proportions drips and adds H2O2Solution is oxidized, by the Fe in solution2+It is oxidized to Fe3+, drip the H added2O2Gram-equivalent number is Fe in filtrate2+The 100% of gram-equivalent number. Then, by the pH value to 5 of solution after the adjustment oxidation of 5mol/LNaOH solution, siderochrome mixed precipitation after filtration, is obtained. Siderochrome mixed precipitation is mixed with NaOH solution, hydrothermal reaction kettle carries out Hydrothermal Synthesis, NaOH solution concentration 12mo/L, the solid-to-liquid ratio 1:10 of siderochrome mixed precipitation and NaOH solution, Hydrothermal Synthesis temperature 200 DEG C, Hydrothermal Synthesis time 4h. Hydro-thermal reaction obtains chromium modified micaceous iron oxide powder body through filtration, cleaning, drying after completing. After testing, iron mica powder purity 98.1%, quality product meets coating mica-iron oxide pigment China national standard (HG/T3006-1997) and the requirement of international standard (ISO10601-2007); Comparing common iron mica, the corrosion resistance nature of the chromium modified micaceous iron oxide of preparation significantly improves.
Embodiment 8:
Use H2SO4Solubilize acid-washing stainless steel mud, H2SO4Gram-equivalent number be the gram-equivalent number 3.0 times of Fe in chromium containing electroplating mud, solvent temperature 80 DEG C, dissolution time 6h. Mixed solution after acid-soluble is left standstill, the sour insoluble solid phase impurity bottom separation, recovery mixed solution. A certain amount of industrial by-product ferrous sulfate is joined after magazins' layout in solution, until siderochrome component proportions reaches 1%. Solution after adjusting to siderochrome component proportions drips and adds H2O2Solution is oxidized, by the Fe in solution2+It is oxidized to Fe3 +, drip the H added2O2Gram-equivalent number is Fe in filtrate2+The 40% of gram-equivalent number. Then, by the pH value to 8 of solution after the adjustment oxidation of 5mol/LNaOH solution, siderochrome mixed precipitation after filtration, is obtained. Siderochrome mixed precipitation is mixed with NaOH solution, hydrothermal reaction kettle carries out Hydrothermal Synthesis, NaOH solution concentration 14mo/L, the solid-to-liquid ratio 1:20 of siderochrome mixed precipitation and NaOH solution, Hydrothermal Synthesis temperature 260 DEG C, Hydrothermal Synthesis time 10h. Hydro-thermal reaction obtains chromium modified micaceous iron oxide powder body through filtration, cleaning, drying after completing. After testing, iron mica powder purity 98.6%, quality product meets coating mica-iron oxide pigment China national standard (HG/T3006-1997) and the requirement of international standard (ISO10601-2007); Comparing common iron mica, the corrosion resistance nature of the chromium modified micaceous iron oxide of preparation significantly improves.
Embodiment 9:
Use H2SO4Solubilize acid-washing stainless steel mud, H2SO4Gram-equivalent number be the gram-equivalent number 2.0 times of Fe in acid-washing stainless steel mud, solvent temperature 80 DEG C, dissolution time 5h. Mixed solution after acid-soluble is left standstill, the sour insoluble solid phase impurity bottom separation, recovery mixed solution. A certain amount of industrial by-product ferrous sulfate is joined after magazins' layout in solution, until siderochrome component proportions reaches 3%. Solution after adjusting to siderochrome component proportions drips and adds H2O2Solution is oxidized, by the Fe in solution2+It is oxidized to Fe3+, drip the H added2O2Gram-equivalent number is Fe in filtrate2+The 60% of gram-equivalent number. Then, by the pH value to 7 of solution after the adjustment oxidation of 5mol/LNaOH solution, siderochrome mixed precipitation after filtration, is obtained. Siderochrome mixed precipitation is mixed with NaOH solution, hydrothermal reaction kettle carries out Hydrothermal Synthesis, NaOH solution concentration 14mo/L, the solid-to-liquid ratio 1:15 of siderochrome mixed precipitation and NaOH solution, Hydrothermal Synthesis temperature 240 DEG C, Hydrothermal Synthesis time 5h. Hydro-thermal reaction obtains chromium modified micaceous iron oxide powder body through filtration, cleaning, drying after completing. After testing, iron mica powder purity 97.9%, quality product meets coating mica-iron oxide pigment China national standard (HG/T3006-1997) and the requirement of international standard (ISO10601-2007); Comparing common iron mica, the corrosion resistance nature of the chromium modified micaceous iron oxide of preparation significantly improves.
Embodiment 10:
Use H2SO4Solubilize leather-making mud, H2SO4Gram-equivalent number be the gram-equivalent number 1.2 times of Fe in leather-making mud, solvent temperature 80 DEG C, dissolution time 3h. Mixed solution after acid-soluble is left standstill, the sour insoluble solid phase impurity bottom separation, recovery mixed solution. A certain amount of industrial by-product ferrous sulfate is joined after magazins' layout in solution, until siderochrome component proportions reaches 5%. Solution after adjusting to siderochrome component proportions drips and adds H2O2Solution is oxidized, by the Fe in solution2+It is oxidized to Fe3+, drip the H added2O2Gram-equivalent number is Fe in filtrate2+The 100% of gram-equivalent number. Then, by the pH value to 5 of solution after the adjustment oxidation of 5mol/LNaOH solution, siderochrome mixed precipitation after filtration, is obtained. Siderochrome mixed precipitation is mixed with NaOH solution, hydrothermal reaction kettle carries out Hydrothermal Synthesis, NaOH solution concentration 12mo/L, the solid-to-liquid ratio 1:10 of siderochrome mixed precipitation and NaOH solution, Hydrothermal Synthesis temperature 200 DEG C, Hydrothermal Synthesis time 4h. Hydro-thermal reaction obtains chromium modified micaceous iron oxide powder body through filtration, cleaning, drying after completing. After testing, iron mica powder purity 98.3%, quality product meets coating mica-iron oxide pigment China national standard (HG/T3006-1997) and the requirement of international standard (ISO10601-2007); Comparing common iron mica, the corrosion resistance nature of the chromium modified micaceous iron oxide of preparation significantly improves.
Embodiment 11:
Use H2SO4Solubilize leather-making mud, H2SO4Gram-equivalent number be the gram-equivalent number 3.0 times of Fe in leather-making mud, solvent temperature 80 DEG C, dissolution time 6h. Mixed solution after acid-soluble is left standstill, the sour insoluble solid phase impurity bottom separation, recovery mixed solution. A certain amount of industrial by-product ferrous sulfate is joined after magazins' layout in solution, until siderochrome component proportions reaches 1%. Solution after adjusting to siderochrome component proportions drips and adds H2O2Solution is oxidized, by the Fe in solution2+It is oxidized to Fe3+, drip the H added2O2Gram-equivalent number is Fe in filtrate2+The 40% of gram-equivalent number. Then, by the pH value to 8 of solution after the adjustment oxidation of 5mol/LNaOH solution, siderochrome mixed precipitation after filtration, is obtained. Siderochrome mixed precipitation is mixed with NaOH solution, hydrothermal reaction kettle carries out Hydrothermal Synthesis, NaOH solution concentration 14mo/L, the solid-to-liquid ratio 1:20 of siderochrome mixed precipitation and NaOH solution, Hydrothermal Synthesis temperature 260 DEG C, Hydrothermal Synthesis time 10h. Hydro-thermal reaction obtains chromium modified micaceous iron oxide powder body through filtration, cleaning, drying after completing. After testing, iron mica powder purity 98.4%, quality product meets coating mica-iron oxide pigment China national standard (HG/T3006-1997) and the requirement of international standard (ISO10601-2007); Comparing common iron mica, the corrosion resistance nature of the chromium modified micaceous iron oxide of preparation significantly improves.
Embodiment 12:
Use H2SO4Solubilize leather-making mud, H2SO4Gram-equivalent number be the gram-equivalent number 2.0 times of Fe in leather-making mud, solvent temperature 80 DEG C, dissolution time 5h. Mixed solution after acid-soluble is left standstill, the sour insoluble solid phase impurity bottom separation, recovery mixed solution. A certain amount of industrial by-product ferrous sulfate is joined after magazins' layout in solution, until siderochrome component proportions reaches 3%. Solution after adjusting to siderochrome component proportions drips and adds H2O2Solution is oxidized, by the Fe in solution2+It is oxidized to Fe3+, drip the H added2O2Gram-equivalent number is Fe in filtrate2+The 60% of gram-equivalent number. Then, by the pH value to 7 of solution after the adjustment oxidation of 5mol/LNaOH solution, siderochrome mixed precipitation after filtration, is obtained. Siderochrome mixed precipitation is mixed with NaOH solution, hydrothermal reaction kettle carries out Hydrothermal Synthesis, NaOH solution concentration 14mo/L, the solid-to-liquid ratio 1:15 of siderochrome mixed precipitation and NaOH solution, Hydrothermal Synthesis temperature 240 DEG C, Hydrothermal Synthesis time 5h. Hydro-thermal reaction obtains chromium modified micaceous iron oxide powder body through filtration, cleaning, drying after completing. After testing, iron mica powder purity 98.6%, quality product meets coating mica-iron oxide pigment China national standard (HG/T3006-1997) and the requirement of international standard (ISO10601-2007); Comparing common iron mica, the corrosion resistance nature of the chromium modified micaceous iron oxide of preparation significantly improves.
Claims (5)
1. a siderochrome solid waste prepares the method for chromium modified micaceous iron oxide, it is characterized in that, described method comprises and siderochrome mud carries out acid-soluble, magazins' layout and recovery, composition detection, component proportions adjustment, oxidation successively, regulates PH value, Hydrothermal Synthesis, acquisition chromium modified micaceous iron oxide.
2. a kind of siderochrome solid waste according to claim 1 prepares the method for chromium modified micaceous iron oxide, and concrete steps are as follows:
(1) acid-soluble: to use H2SO4Solubilize siderochrome mud, H2SO4Gram-equivalent number be 1.2 ~ 3.0 times of Fe, Cr gram-equivalent number in siderochrome mud, solvent temperature is 80 DEG C, dissolution time 3h ~ 6h;
(2) magazins' layout and recovery: the mixed solution after acid-soluble is left standstill, the sour insoluble solid phase impurity bottom separation, recovery mixed solution, then by mixed solution centrifugation, separation, recovery organic impurities;
(3) siderochrome composition detection: the concentration of iron, chromium ion in the rear solution of checked for impurities separation;
(4) siderochrome component proportions adjustment: according to siderochrome composition detection result, calculate siderochrome component proportions in solution: { m (Cr)/�� m (Fe)+m (Cr) �� }, described m is quality, when ratio value is more than 5%, then add industrial by-product ferrous sulfate in solution, until siderochrome component proportions reaches required scope;
(5) it is oxidized: the solution after adjusting to siderochrome component proportions drips and adds H2O2Solution is oxidized, by the Fe in solution2+It is oxidized to Fe3+, drip the H added2O2Gram-equivalent number is Fe in filtrate2+The 40% ~ 100% of gram-equivalent number;
(6) adjust ph: with pH value to 6 ~ 8 of solution after the adjustment oxidation of 5mol/LNaOH solution, obtain siderochrome mixed precipitation after filtration;
(7) Hydrothermal Synthesis: siderochrome mixed precipitation mixed with NaOH solution, carries out Hydrothermal Synthesis in hydrothermal reaction kettle, obtains chromium modified micaceous iron oxide.
3. a kind of siderochrome solid waste according to claim 2 prepares the method for chromium modified micaceous iron oxide, it is characterised in that: siderochrome solid waste mainly comprises in siderochrome grinding waste material, chromate waste water disposal process the siderochrome mud produced.
4. a kind of siderochrome solid waste according to claim 2 prepares the method for chromium modified micaceous iron oxide, it is characterised in that: after siderochrome component proportions adjusts, m (Cr)/�� m (Fe)+m (Cr) �� in solution } it is 1% ~ 5%.
5. a kind of siderochrome solid waste according to claim 2 prepares the method for chromium modified micaceous iron oxide, it is characterized in that: in Hydrothermal Synthesis, NaOH solution concentration 12mo/L ~ 16mol/L, the solid-to-liquid ratio 1:10 of siderochrome mixed precipitation and NaOH solution ~ 1:20, Hydrothermal Synthesis temperature 200 DEG C ~ 260 DEG C, Hydrothermal Synthesis time 4h ~ 10h.
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| CN109680155A (en) * | 2018-12-26 | 2019-04-26 | 北京科技大学 | A kind of method of nickeliferous straight-chromiun stainless steel dirt mud harmlessness disposing and resource utilization |
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| CN109680155A (en) * | 2018-12-26 | 2019-04-26 | 北京科技大学 | A kind of method of nickeliferous straight-chromiun stainless steel dirt mud harmlessness disposing and resource utilization |
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