CN107324303A - A kind of method of separation and purification iron, chromium from many metal hazardous wastes - Google Patents
A kind of method of separation and purification iron, chromium from many metal hazardous wastes Download PDFInfo
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- CN107324303A CN107324303A CN201710786889.4A CN201710786889A CN107324303A CN 107324303 A CN107324303 A CN 107324303A CN 201710786889 A CN201710786889 A CN 201710786889A CN 107324303 A CN107324303 A CN 107324303A
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- Prior art keywords
- iron
- filtrate
- chromium
- press filtration
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 240
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 108
- 239000011651 chromium Substances 0.000 title claims abstract description 93
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 63
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 48
- 239000002184 metal Substances 0.000 title claims abstract description 35
- 238000000926 separation method Methods 0.000 title claims abstract description 34
- 238000000746 purification Methods 0.000 title claims abstract description 27
- 239000002920 hazardous waste Substances 0.000 title claims abstract description 21
- 239000010802 sludge Substances 0.000 claims abstract description 43
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 35
- 239000010452 phosphate Substances 0.000 claims abstract description 35
- 239000000047 product Substances 0.000 claims abstract description 25
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910001447 ferric ion Inorganic materials 0.000 claims abstract description 24
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001556 precipitation Methods 0.000 claims abstract description 18
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 17
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 15
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 13
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 230000009467 reduction Effects 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims description 83
- 238000001914 filtration Methods 0.000 claims description 46
- 239000012065 filter cake Substances 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 230000008569 process Effects 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 13
- 230000006641 stabilisation Effects 0.000 claims description 13
- 238000011105 stabilization Methods 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- 230000033228 biological regulation Effects 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- OIDPCXKPHYRNKH-UHFFFAOYSA-J chrome alum Chemical compound [K]OS(=O)(=O)O[Cr]1OS(=O)(=O)O1 OIDPCXKPHYRNKH-UHFFFAOYSA-J 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- RFGNMWINQUUNKG-UHFFFAOYSA-N iron phosphoric acid Chemical compound [Fe].OP(O)(O)=O RFGNMWINQUUNKG-UHFFFAOYSA-N 0.000 claims description 9
- 239000010440 gypsum Substances 0.000 claims description 8
- 229910052602 gypsum Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000004513 sizing Methods 0.000 claims description 6
- 239000002893 slag Substances 0.000 claims description 6
- 239000013589 supplement Substances 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 238000011085 pressure filtration Methods 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 9
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 4
- -1 iron ion Chemical class 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000919 ceramic Substances 0.000 abstract description 2
- 239000000049 pigment Substances 0.000 abstract description 2
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 abstract 1
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 229910000604 Ferrochrome Inorganic materials 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 229910001448 ferrous ion Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 206010064571 Gene mutation Diseases 0.000 description 1
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- 238000003723 Smelting Methods 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
- 229940037003 alum Drugs 0.000 description 1
- 235000011124 aluminium ammonium sulphate Nutrition 0.000 description 1
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 description 1
- XGGLLRJQCZROSE-UHFFFAOYSA-K ammonium iron(iii) sulfate Chemical compound [NH4+].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGGLLRJQCZROSE-UHFFFAOYSA-K 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003344 environmental pollutant Substances 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
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention discloses the phosphate radical selective precipitation Fe that a kind of method of separation and purification iron, chromium from many metal hazardous wastes, the present invention are carried using sludge3+Ferric phosphate is prepared, while making itself and Cr3+Separation；Because phosphate radical also can precipitate C r3+, during use Fe3+Excessive method prevents the formation that chromium phosphate is precipitated；Remaining Fe3+Iron reduction is used for Fe2+, then adjust certain pH value selective precipitation Cr with alkali3+Chromium hydroxide is prepared, realizes that siderochrome is further separated.This method is whole to fully utilize the iron ion and phosphate radical in hazardous waste without heating, with low cost；Waste water, waste residue will not be produced simultaneously, it is environmentally friendly；The product ferric phosphate economic value extracted respectively is high, and available for the raw material of battery material, ceramics etc., chromium hydroxide can be used for the industry raw materials such as pigment, chemical industry.
Description
Technical field
The invention belongs to technical field of wet metallurgy, and in particular to a kind of separation and purification iron from many metal hazardous wastes,
The method of chromium.
Background technology
At present, being mainly containing many metal hazardous wastes for China is produced by industries such as plating, surface treatment, smelting, chemical industry
Sludge or waste water, wherein contain various metals, including iron, chromium, copper, zinc, nickel, cobalt, manganese etc..And chromium is that a kind of toxicity is very strong
Heavy metal, is easily accessible human body cell, and the internal organs such as liver, kidney and DNA are caused with damage, there is cumulative effect in human body, has
There is the danger of carcinogenicity and possible modificator gene mutation.Sludge or discharge of wastewater containing chromium not only easily cause ring into environment
Border water pollution, while causing direct threat to human life and health.Therefore, realize that the harmless treatment of the waste containing chromium is extremely closed
It is important.The innoxious process for treating of the waste containing chromium can generally be divided into two classes：One class is solidification and stabilization technology, and a class is regeneration
Utilize technology.Solidification and stabilization is will to contain chromium solidification of waste in firming body using curing agent, to avoid heavy metal chromium from being lost to
In environment, this method seems slightly not enough in valuable metal recovery using aspect.The characteristics of regeneration is to utilize certain leaching agent
Main target metal is leached, then metal product is extracted using methods such as extraction, precipitation, electrolysis and is utilized, to realize that metal is provided
The circular regeneration in source.
The chemical property of metallic iron and chromium is closely similar, and the separation of the two is always the problem of the research field.Current iron
The method of chromium separation mainly includes electrolysis, extraction and the precipitation method.Certain factory makes the sulphur in sludge acidleach filtrate by electrolysis
Sour chromium and ferric sulfate are changed into chromic ammonium alum and ferriammonium sulfate, then according to its under the conditions of 75 °C solubility difference and reach chromium,
The purpose of iron separation.Zhu Wanpeng etc. realizes that siderochrome is separated using extraction by the use of P204 and P507 as extractant.Wu Jianhui etc.
After the useless ferrochrome of sulfuric acid leaching, the iron in solution is separated with Mohr's salt crystallisation, this method need to react 6 under the conditions of 70 DEG C
H, the then quick h of crystallisation by cooling 24.Wang Fei et al. is with hydrogen peroxide by Fe2+It is oxidized to Fe3+, then with alkali precipitation iron is removed, realize iron
Chromium is separated.Also have and oxalic acid and Fe are used in patent2+Complex-precipitation separates iron and chromium.Electrolysis high energy consumption, equipment is complicated, adds danger
The cost of disposal of dangerous waste.The organic solvent of reusable edible is introduced in extraction, but its service life is limited, adds new
Pollutant.The precipitation method pass through choosing using the metal of variety classes and valence state is different from the solubility product of different precipitating reagents formation compound
Selecting property precipitates and enters row metal separation, and energy consumption is low, and equipment is simple, but needs to select preferable precipitating reagent and control felicity condition,
On the one hand the reagent cost and raising siderochrome separation rate in reduction processing procedure, on the other hand improve iron and chromium secondary metals resource
Value.
It is a kind of whole without heating based on above-mentioned analysis, the iron ion and phosphate radical in hazardous waste are fully utilized, while not
Waste water, waste residue can be produced, it is environmentally friendly, the ferric phosphate and chromium hydroxide of extraction can carry out it is secondary utilize it is dangerous from many metals
Separation and purification iron, the method for chromium are that the industry is badly in need of at present in waste.
The content of the invention
In view of above-mentioned deficiency, the method for separation and purification iron, chromium, whole nothing from many metal hazardous wastes that the present invention is provided
Heating is needed, the iron ion and phosphate radical in hazardous waste is farthest make use of, preparation process will not produce waste water, waste residue,
It is environmentally friendly.
In order to achieve the above object, present invention employs following technical scheme, each material concentration used in the present invention and
Refined iron, the chromium of separation could be used for the secondary of chemical industry and uses in pH value is interval.
Separation and purification iron, the method for chromium comprise the following steps in a kind of many metal hazardous wastes：
（1）Acidleach：Synthesis sludge containing metallic element is subjected to dispensing, water slurrying is added into sludge, while stirring slowly
The H of addition 98%2SO4, regulation pH stabilizations are at 0.5, and stopping acid adding continuing to dissolve, enters each metallic element in sludge
In solution；
（2）Press filtration：Solution after acidleach is subjected to press filtration, press filtration filter residue is washed, washings, which are returned, is used as water of sizing mixing, after washing
Slag carry out purification process, press filtration filtrate continues with into next process；
（3）Rough redingtonite：The filtrate of collection is put into container and stirred, in being slowly added to CaCO under normal pressure3Slurries adjust pH
To 4.0, continue to react, be slowly added to H2O2, while using CaCO3Slurries control pH to 3.8 ~ 4.1, until H2O2By Fe2+Complete oxygen
Turn to Fe3+, then press filtration, obtained filter cake is rough redingtonite, and filtrate enters copper, zinc, nickel, cobalt, manganese separation circuit；
（4）Dissolve crude iron chrome alum：By the H of rough redingtonite filter cake and water slurrying, thereto addition 98%2SO4Adjust pH to 0.5
Iron, chromium is set to enter in solution, then press filtration, filter cake is rough gypsum（Principal component calcium sulphate dihydrate）, purified washing obtains
Gypsum product, filtrate enters next step process；
（5）Reduction：Iron filings, and the H for Jia 98% are added into filtrate2SO4PH to 1.0 ~ 1.5 is kept, by Fe3+It is reduced to Fe2+, also
Original is filtered after finishing；
（6）Heavy chromium：The CaCO of addition 10% into filtrate3Slurries adjust pH to 5.5 precipitate C r3+, the filter cake after press filtration is Cr
(OH)3；
（7）Heavy iron：Fe will be contained2+Filtrate return to rough redingtonite process, and thereto supplement iron or directly further plus
Alkali lye is precipitated, and oxidation in atmosphere obtains Fe (OH)3。
A kind of method of artificial addition phosphate radical separation and purification iron, chromium from many metal hazardous wastes is wherein also provided,
Specially：
A kind of separation and purification iron from many metal hazardous wastes, the method for chromium comprise the following steps：
（1）Acidleach：Synthesis sludge containing metallic element is subjected to dispensing, water slurrying is added into sludge, while stirring slowly
The H of addition 98%2SO4, regulation pH stabilizations are at 0.5, and stopping acid adding continuing to dissolve, enters each metallic element in sludge
In solution；
（2）Press filtration：Solution after acidleach is subjected to press filtration, press filtration filter residue is washed, washings, which are returned, is used as water of sizing mixing, after washing
Slag carry out purification process, press filtration filtrate continues with into next process；
（3）Rough redingtonite：The filtrate of collection is put into container and stirred, in being slowly added to CaCO under normal pressure3Slurries adjust pH
To 4.0, continue to react, be slowly added to H2O2, while using CaCO3Slurries control pH to 3.8 ~ 4.1, until H2O2By Fe2+Complete oxygen
Turn to Fe3+, then press filtration, obtained filter cake is rough redingtonite, and filtrate enters copper, zinc, nickel, cobalt, manganese separation circuit；
（4）Dissolve crude iron chrome alum：By rough redingtonite filter cake and water slurrying, the H2SO4 that 98% is added thereto adjusts pH to 0.5
Iron, chromium is set to enter in solution, then press filtration, filter cake is rough gypsum, and purified washing obtains gypsum product, under filtrate enters
One step process；
（5）Add phosphate radical preparing phosphoric acid iron：Into filtrate, the phosphoric acid of addition 85%, makes Fe in filtrate3+Concentration ratio phosphate radical
High 2 ~ 3 g/L of concentration, room temperature and 300r/min stirring under, be slowly added into filtrate 10% sodium hydroxide solution regulation pH
Value begins with light yellow FePO to 1.54Precipitation generation, pH value reaches to be continued to stir 1h after 2.0 stabilizations, obtains light yellow FePO4
Precipitation, pressure filtration washing, filter cake is finished product ferric phosphate, and filtrate enters next step process；
（6）Reduction：Iron filings, and the H for Jia 98% are added into filtrate2SO4PH to 1.0 ~ 1.5 is kept, by Fe3+It is reduced to Fe2+, also
Original is filtered after finishing；
（7）Heavy chromium：The CaCO of addition 10% into filtrate3Slurries adjust pH to 5.5 precipitate C r3+, the filter cake after press filtration is Cr
(OH)3；
（8）Heavy iron：Fe will be contained2+Filtrate return to rough redingtonite process, and thereto supplement iron or directly further plus
Alkali lye is precipitated, and oxidation in atmosphere obtains Fe (OH)3。
Present invention also offers a kind of method of separation and purification iron, chromium from many metal hazardous wastes containing phosphate radical,
Specially：
Separation and purification iron, the method for chromium comprise the following steps in a kind of many metal hazardous wastes：
（1）Acidleach：Synthesis sludge containing phosphate radical and metallic element is subjected to dispensing, water slurrying is added into sludge, while stirring
Mix the H that side is slowly added to 98%2SO4, regulation pH stabilizations are at 0.5, and stopping acid adding continuing to dissolve, and make each metal member in sludge
Element is entered in solution；
（2）Press filtration：Solution after acidleach is subjected to press filtration, press filtration filter residue is washed, washings, which are returned, is used as water of sizing mixing, after washing
Slag carry out purification process, press filtration filtrate continues with into next process；
（3）Rough redingtonite：The filtrate of collection is put into container and stirred, in being slowly added to CaCO under normal pressure3Slurries adjust pH
To 4.0, continue to react, be slowly added to H2O2, while using CaCO3Slurries control pH to 3.8 ~ 4.1, until H2O2By Fe2+Complete oxygen
Turn to Fe3+, then press filtration, obtained filter cake is rough redingtonite, and filtrate enters copper, zinc, nickel, cobalt, manganese separation circuit；
（4）Preparing phosphoric acid iron：By the H of rough redingtonite filter cake and water slurrying, thereto addition 98%2SO4Regulation pH to 0.5 makes
Iron, chromium are entered in solution, then press filtration, and Fe is supplemented into filtrate3+, make Fe in filtrate3+Concentration ratio phosphate radical concentration it is high
2 ~ 3 g/L, the sodium hydroxide solution for being slowly added to 10% adjusts pH to 2.0, obtains light yellow FePO4Precipitation, pressure filtration washing, filter
Cake is finished product ferric phosphate, and filtrate enters next step process；
（5）Reduction：Iron filings, and the H for Jia 98% are added into filtrate2SO4PH to 1.0 ~ 1.5 is kept, by Fe3+It is reduced to Fe2+, also
Original is filtered after finishing；
（6）Heavy chromium：The CaCO of addition 10% into filtrate3Slurries adjust pH to 5.5 precipitate C r3+, the filter cake after press filtration is Cr
(OH)3；
（7）Heavy iron：Fe will be contained2+Filtrate return to rough redingtonite process, and thereto supplement iron or directly further plus
Alkali lye is precipitated, and oxidation in atmosphere obtains Fe (OH)3。
Further, the metallic element includes but is not limited to iron, chromium, copper, zinc, nickel, cobalt, manganese.
Further, step（1）In the comprehensive sludge dispensing, the mol ratio of total iron and total chromium is 2.5 ~ 3.5:1；It is described
Sludge is with water with 1:1 ~ 5 mass ratio carries out slurrying.
Further, step（4）The slurrying is with 1 by rough redingtonite filter cake and water:1 ~ 3 prepares.
Compared to the prior art the present invention, has the advantage that：
(1) present invention is whole without heating, saves process time, reduces processing cost；
(2) waste water, waste residue will not be produced, it is environmentally friendly；
(3) the product ferric phosphate economic value extracted is high, and available for the raw material of battery material, ceramics etc., chromium hydroxide can be used for
The industry raw material such as pigment, chemical industry；
(4) present invention is using for different situations（Without phosphate radical presence, with the presence of phosphate radical, artificially add phosphate radical）Provide
Three kinds of methods carry out separation and purification iron, chromium from many metal hazardous wastes, expand application；
(5) Cr in the aqueous solution3+The pH value precipitated completely is 6.8, when there is Fe3+In the presence of, Fe3+And Cr3+In pH3.8~4.1
Double salt precipitation redingtonite is formed under part so that chromium precipitation pH value is substantially reduced, and finally realizes chromium and copper, zinc, nickel, cobalt, manganese
Preferably separated Deng element；
(6) excessive ferro element is supplemented into siderochrome alum solution processed, using solubility product principle, control certain pH value makes limited phosphoric acid
Root and Fe3+Formed precipitation without with Cr3+And other impurity element zinc, nickel, copper etc. form precipitation, to reach in preparing phosphoric acid
Excessive Fe is utilized during iron3+Suppress phosphate radical and Cr3+Formed precipitation and realize iron, the initial gross separation of chromium and be made purity it is higher
Phosphoric acid iron product purpose；
(7) Fe is reduced using metallic iron3+, other impurities element is not introduced, by Fe3+Fe is reduced to completely2+Afterwards, appropriate bar is controlled
Part, utilizes Fe2+With Cr3+PH differences are precipitated, chromium and iron can be made preferably to be separated, precipitating reagent calcium carbonate alkaline is weak, slurry pH value
5.4 ~ 6.0, the too high situation of the local basicity of solution will not be produced, is conducive to chromium, iron separation；
(8) excessive calcium carbonate, which can function as filter aid, improves strainability, and it is finally reclaimed with calcium sulfate by-product form.
Obviously, according to the above of the present invention, according to the ordinary technical knowledge and means of this area, this hair is not being departed from
Under the premise of bright above-mentioned basic fundamental thought, the modification of other diversified forms can also be made, replaces or changes.
Brief description of the drawings
Fig. 1 is the process chart of embodiment 3.
Fig. 2 is the relation of iron, chromium content ratio and phosphate radical amount in embodiment 2.
Fig. 3 is the relation of the iron of embodiment 2, chromium rate of deposition and pH value.
Embodiment
We will the invention will be further elaborated with reference to embodiment below.
Embodiment 1
A kind of method of separation and purification iron, chromium from many metal hazardous wastes（Sludge without phosphate radical）
（1）Feedstock analysis
The synthesis sludge without phosphate radical is taken, Fe salt is supplemented into sludge and is mixed, makes Fe：Cr=2.5~3.5:1, use NITRATE BY FLAME ATOMIC
Absorption spectrophotometer analyzes its tenor, the results are shown in Table 1.
Table 1 integrates sludge metal ingredient content table
。
（2）Acidleach is tested
The synthesis sludge 500g of above-mentioned mixing is taken in 2000mL beakers, 1200mL water is added, mechanical agitation is put into beaker, is adjusted
Section the r/min of rotating speed 300 make sludge pulp, 98% sulfuric acid is then slowly added into slurries, during sludge gradually dissolve, add
Sulfuric acid no longer reacts to sludge, continues to stir 30 min, and make pH stable 0.5 or so so that metal in sludge soaks completely
Go out.Filtered after Leach reaction is qualified, obtain filtrate 1360mL, metal concentration, knot are analyzed with flame atomic absorption spectrophotometer
Fruit is shown in Table 2.
Metallic element concentration table in the acidleach filtrate of table 2
。
During amount to consumption the g of 98% sulfuric acid 116.45, acid consumption be 23.29%.
（3）Rough redingtonite
Filtrate after acidleach adjusts pH value 4.0 with 10% calcium carbonate serosity, is slowly added to 30% hydrogen peroxide while being starched with calcium carbonate
Liquid control ph 3.8 ~ 4.1, until ferrous ion complete oxidation is ferric ion by hydrogen peroxide, then press filtration and washs filter
Cake is to neutrality, and obtained filter cake is crude iron chrome alum, altogether 401.02 g.
（4）Crude iron chrome alum dissolves
Obtained crude iron chrome alum is placed in 2000mL beakers, 600mL water is added, mechanical agitation is put into beaker, rotating speed is adjusted
300 r/min make sludge pulp, and 98% sulfuric acid to redingtonite is then slowly added into slurries and is completely dissolved, and continue to stir 30
Min, and make pH stable 0.5 or so so that iron and chromium are leached completely.Filtering, obtains filtrate 823mL, with Flame Atomic Absorption Spectrometry point
The concentration of metal, the results are shown in Table 3 in light luminosity measurement filtrate.
The iron content of table 3, chromium filtrate component table
。
（5）Reduction-heavy chromium
Iron filings are added into above-mentioned filtrate, and add 98% sulfuric acid to keep pH value 1.0 ~ 1.5, ferric ion is reduced to ferrous iron
Ion, reduction is filtered after finishing.The concentration that iron and chromium in filtrate are measured with Atomic absorption is respectively 16.87g/L and 4.49g/L,
Continue to stir 30 min after adding 10% calcium carbonate serosity regulation pH value 5.5, stabilization into filtrate.Filter to get filtrate 825mL, filter
Remaining iron, the concentration of chromium are respectively 15.94g/L and 0.03g/L in liquid；Filter cake 51.53g is obtained, filter cake is dried to perseverance at 105 DEG C
Chromium product is produced again, and it is respectively 12.74%, 2.85% to measure chromium in chromium product, the quality percentage of iron.
（6）Heavy iron
Add after 10% sodium carbonate liquor adjusts pH10.0, stable 30min and filter in upward process filtrate, filter cake is dried at 105 DEG C
Constant weight produces iron product, and it is respectively 29.85%, 0.05% to measure iron in iron product, chromium quality percentage.
Embodiment 2
A kind of method of separation and purification iron, chromium from many metal hazardous wastes（Phosphate radical is added into the sludge without phosphate radical
Separate siderochrome）
（1）Iron content, the preparation of chromium filtrate
Match somebody with somebody the sludge 500g of honest material in Example 1, add 1000mL water slurrys, by the method progress acidleach in embodiment 1, slightly
Redingtonite processed, the dissolving operation of crude iron chrome alum, it is final to obtain filtrate 816mL, survey gold in filtrate with flame atomic absorption spectrophotometer
The concentration of category, the results are shown in Table 4.
The iron content of table 4, chromium filtrate component table
。
（2）Add phosphate radical preparing phosphoric acid iron
Take 5 parts of above-mentioned iron content of 150mL, chromium filtrates（Fe3+：11.05g/L, Cr3+：4.48g/L, iron and chromium concn ratio are 2.47）,
It is respectively placed in 500mL beakers, 85% phosphatase 11 .24,1.41,1.59,1.76,1.94,2.12g is separately added into thereto, is made molten
In liquid the concentration of phosphoric acid be respectively 7.00,8.00,9.00,10.00,11.00,12.00g/L.Stirred in room temperature and 300r/min
Under, 10% sodium hydroxide solution regulation pH value is slowly added into filtrate, pH value 1.5 or so begins with light yellow ferric phosphate precipitation
Generation, pH value reaches to be continued to stir 1h, difference pressure filtration washing filter cake to neutrality after 2.0 stabilizations.By obtained ferric phosphate in 60 DEG C
Under dry to constant weight, survey iron, chromium content ratio and phosphate radical in wherein metal ingredient, product with flame atomic absorption spectrophotometer
The relation of amount is shown in Fig. 2.As shown in Figure 2, when the concentration of phosphate radical in solution is less than 9g/L, iron, chromium in phosphoric acid iron product is made
Content ratio more than 100, iron, chromium than expand more than 50 times, now in solution remaining ferric concentration in more than 2g/L；When
When the concentration of phosphate radical gradually increases in solution, iron, chromium content in phosphoric acid iron product is made to be reduced than gradually, i.e. chromium in ferric phosphate
Content gradually rises.In actual process implementation, ferric phosphate product quality and process efficiency, ferric concentration ratio are considered
High 2 ~ 3 g/L of concentration of phosphate radical is advisable.
（3）Reduction-heavy chromium
Previous step experiment filtrate merges common 800mL, and the concentration for measuring wherein iron and chromium is respectively 1.05g/L and 3.98g/L, to filter
Iron filings are added in liquid, and add 98% sulfuric acid to keep pH value 1.0 ~ 1.5, ferric ion ferrous ion are reduced to, reduction is finished
After filter.The concentration that iron and chromium in filtrate are measured with Atomic absorption is respectively 1.58g/L and 3.98g/L, and filtrate is divided into 5 parts,
Every part of 150mL, it is 3.5,4.0,4.5,5.0,5.5,6.0,6.5 that 10% calcium carbonate serosity is added into filtrate and adjusts pH value respectively,
Continue to stir 30 min after stable, then filter, survey remaining chromium, the concentration of iron in filtrate.Chromium and iron under different pH condition
Rate of deposition is shown in Fig. 3.From the figure 3, it may be seen that in pH value 5.5 ~ 6.0, it is possible to achieve chromium is substantially completely precipitated, now the rate of deposition of iron exists
Less than 10%, therefore selection pH value 5.5 ~ 6.0 separation chromium and iron.Because ferrous ion is easily adsorbed and is oxidized easily, therefore
The rate of deposition of iron is higher.
Embodiment 3
A kind of method of separation and purification iron, chromium from many metal hazardous wastes（The sludge processes of phosphorous acid group are shown in Fig. 1）
（1）Feedstock analysis
The synthesis sludge of phosphorous acid group is taken, Fe is supplemented into sludge3+Salt is mixed, and makes Fe：Cr-=2.5~3.5:1, use NITRATE BY FLAME ATOMIC
Absorption spectrophotometer analyzes its tenor, analyzes phosphate content with visible spectrophotometer, the results are shown in Table 5.
The phosphorous acid group of table 5 integrates sludge metal ingredient table
。
（2）Experiment
The synthesis sludge 500g of above-mentioned mixing is taken in 2000mL beakers, 1000mL water is added, carried out by the method in embodiment 1
Acidleach, rough redingtonite, crude iron chrome alum dissolving step.Main iron content, chromium, the filtrate 1045mL of phosphate radical are finally given, its is dense
Degree is respectively：12.23g/L、4.59g/L、12.78g/L.
Trivalent ferrous solution is supplemented into above-mentioned filtrate, makes many 2.5g/ of concentration of ferric concentration ratio phosphate radical in solution
L, 10% sodium hydroxide solution is then added into solution and adjusts pH2.0, and iron and phosphate radical are heavy in ferric phosphate form under this condition
Form sediment, and ferric concentration is more than phosphate radical in system, can effectively prevent chromium from being precipitated by phosphate radical entrainment.PH stable 1h
Afterwards, filter, filtrate enters subsequent processing；Filter cake is phosphoric acid iron product, is dried to constant weight at 60 DEG C, its constituent analysis is shown in Table 6.
The ferric phosphate constituent analysis table of table 6
。
Iron filings are added in upward process filtrate, and add 98% sulfuric acid to keep pH value 1.0 ~ 1.5, by ferric ion completely also
Originally it was ferrous ion, filtering, it is respectively 3.087g L and 5.850g L to measure iron in filtrate, chromium concn（Ferrochrome ratio is
1.90）.It is 5.5 that 10% calcium carbonate serosity regulation pH value is added into filtrate, continues to stir 30min, filtration washing filter cake after stabilization
To neutral, the chromium hydroxide product that the filter cake obtains for primary purification, it is 33.05 to measure ferrochrome ratio in filter cake.
Continuation is precipitated again by filter cake sulfuric acid dissolution, plus after iron reduction, carries out secondary purification, what secondary purification was obtained
Chromium hydroxide product dries to constant weight at 105 DEG C, and the grade for measuring chromium is 25.67%, iron 0.165%, and ferrochrome ratio is 155.30.
Claims (6)
1. a kind of method of separation and purification iron, chromium from many metal hazardous wastes, it is characterised in that this method includes following step
Suddenly：
（1）Acidleach：Synthesis sludge containing metallic element is subjected to dispensing, water slurrying is added into sludge, while stirring slowly
The H of addition 98%2SO4, regulation pH stabilizations are at 0.5, and stopping acid adding continuing to dissolve, enters each metallic element in sludge
In solution；
（2）Press filtration：Solution after acidleach is subjected to press filtration, press filtration filter residue is washed, washings, which are returned, is used as water of sizing mixing, after washing
Slag carry out purification process, press filtration filtrate continues with into next process；
（3）Rough redingtonite：The filtrate of collection is put into container and stirred, in being slowly added to CaCO under normal pressure3Slurries adjust pH to
4.0, continue to react, be slowly added to H2O2, while using CaCO3Slurries control pH to 3.8 ~ 4.1, until H2O2By Fe2+Complete oxidation
For Fe3+, then press filtration, obtained filter cake is rough redingtonite, and filtrate enters copper, zinc, nickel, cobalt, manganese separation circuit；
（4）Dissolve crude iron chrome alum：By the H of rough redingtonite filter cake and water slurrying, thereto addition 98%2SO4Regulation pH to 0.5 makes
Iron, chromium are entered in solution, then press filtration, and filter cake is rough gypsum, and purified washing obtains gypsum product, and filtrate enters next
Walk process；
（5）Reduction：Iron filings, and the H for Jia 98% are added into filtrate2SO4PH to 1.0 ~ 1.5 is kept, by Fe3+It is reduced to Fe2+, also
Original is filtered after finishing；
（6）Heavy chromium：The CaCO of addition 10% into filtrate3Slurries adjust pH to 5.5 precipitate C r3+, the filter cake after press filtration is Cr
(OH)3；
（7）Heavy iron：Fe will be contained2+Filtrate return to rough redingtonite process, and thereto supplement iron or directly further plus
Alkali lye is precipitated, and oxidation in atmosphere obtains Fe (OH)3。
2. a kind of method of separation and purification iron, chromium from many metal hazardous wastes, it is characterised in that this method includes following step
Suddenly：
（1）Acidleach：Synthesis sludge containing metallic element is subjected to dispensing, water slurrying is added into sludge, while stirring slowly
The H of addition 98%2SO4, regulation pH stabilizations are at 0.5, and stopping acid adding continuing to dissolve, enters each metallic element in sludge
In solution；
（2）Press filtration：Solution after acidleach is subjected to press filtration, press filtration filter residue is washed, washings, which are returned, is used as water of sizing mixing, after washing
Slag carry out purification process, press filtration filtrate continues with into next process；
（3）Rough redingtonite：The filtrate of collection is put into container and stirred, in being slowly added to CaCO under normal pressure3Slurries adjust pH to
4.0, continue to react, be slowly added to H2O2, while using CaCO3Slurries control pH to 3.8 ~ 4.1, until H2O2By Fe2+Complete oxidation
For Fe3+, then press filtration, obtained filter cake is rough redingtonite, and filtrate enters copper, zinc, nickel, cobalt, manganese separation circuit；
（4）Dissolve crude iron chrome alum：By rough redingtonite filter cake and water slurrying, the H2SO4 that 98% is added thereto adjusts pH to 0.5
Iron, chromium is set to enter in solution, then press filtration, filter cake is rough gypsum, and purified washing obtains gypsum product, under filtrate enters
One step process；
（5）Add phosphate radical preparing phosphoric acid iron：Into filtrate, the phosphoric acid of addition 85%, makes Fe in filtrate3+Concentration ratio phosphate radical
High 2 ~ 3 g/L of concentration, under room temperature and 300r/min stirrings, 10% sodium hydroxide solution regulation pH value is slowly added into filtrate
To 1.5, light yellow FePO is begun with4Precipitation generation, pH value reaches to be continued to stir 1h after 2.0 stabilizations, obtains light yellow FePO4It is heavy
Form sediment, pressure filtration washing, filter cake is finished product ferric phosphate, filtrate enters next step process；
（6）Reduction：Iron filings, and the H for Jia 98% are added into filtrate2SO4PH to 1.0 ~ 1.5 is kept, by Fe3+It is reduced to Fe2+, also
Original is filtered after finishing；
（7）Heavy chromium：The CaCO of addition 10% into filtrate3Slurries adjust pH to 5.5 precipitate C r3+, the filter cake after press filtration is Cr
(OH)3；
（8）Heavy iron：Fe will be contained2+Filtrate return to rough redingtonite process, and thereto supplement iron or directly further plus
Alkali lye is precipitated, and oxidation in atmosphere obtains Fe (OH)3。
3. a kind of method of separation and purification iron, chromium from many metal hazardous wastes, it is characterised in that this method includes following step
Suddenly：
（1）Acidleach：Synthesis sludge containing phosphate radical and metallic element is subjected to dispensing, water slurrying is added into sludge, while stirring
Mix the H that side is slowly added to 98%2SO4, regulation pH stabilizations are at 0.5, and stopping acid adding continuing to dissolve, and make each metal member in sludge
Element is entered in solution；
（2）Press filtration：Solution after acidleach is subjected to press filtration, press filtration filter residue is washed, washings, which are returned, is used as water of sizing mixing, after washing
Slag carry out purification process, press filtration filtrate continues with into next process；
（3）Rough redingtonite：The filtrate of collection is put into container and stirred, in being slowly added to CaCO under normal pressure3Slurries adjust pH to
4.0, continue to react, be slowly added to H2O2, while using CaCO3Slurries control pH to 3.8 ~ 4.1, until H2O2By Fe2+Complete oxidation
For Fe3+, then press filtration, obtained filter cake is rough redingtonite, and filtrate enters copper, zinc, nickel, cobalt, manganese separation circuit；
（4）Preparing phosphoric acid iron：By the H of rough redingtonite filter cake and water slurrying, thereto addition 98%2SO4Regulation pH to 0.5 makes
Iron, chromium are entered in solution, then press filtration, and Fe is supplemented into filtrate3+, make Fe in filtrate3+Concentration ratio phosphate radical concentration it is high
2 ~ 3 g/L, the sodium hydroxide solution for being slowly added to 10% adjusts pH to 2.0, obtains light yellow FePO4Precipitation, pressure filtration washing, filter
Cake is finished product ferric phosphate, and filtrate enters next step process；
（5）Reduction：Iron filings, and the H for Jia 98% are added into filtrate2SO4PH to 1.0 ~ 1.5 is kept, by Fe3+It is reduced to Fe2+, also
Original is filtered after finishing；
（6）Heavy chromium：The CaCO of addition 10% into filtrate3Slurries adjust pH to 5.5 precipitate C r3+, the filter cake after press filtration is Cr
(OH)3；
（7）Heavy iron：Fe will be contained2+Filtrate return to rough redingtonite process, and thereto supplement iron or directly further plus
Alkali lye is precipitated, and oxidation in atmosphere obtains Fe (OH)3。
4. the method according to claim 1-3 any one, it is characterised in that：The metallic element includes but is not limited to
Iron, chromium, copper, zinc, nickel, cobalt, manganese.
5. the method according to claim 1-3 any one, it is characterised in that step（1）In the comprehensive sludge dispensing,
The mol ratio of total iron and total chromium is 2.5 ~ 3.5:1；The sludge is with water with mass ratio 1:1 ~ 5 carries out slurrying.
6. the method according to claim 1-3 any one, it is characterised in that step（4）The slurrying is by rough iron
Chrome alum filter cake is with water with 1:1 ~ 3 prepares.
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| CN115928108A (en) * | 2022-12-23 | 2023-04-07 | 中国科学院青海盐湖研究所 | Method for preparing trivalent chromium compound directly by electrochemical oxidation of ferrochrome |
| WO2024130917A1 (en) * | 2022-12-23 | 2024-06-27 | 中国科学院青海盐湖研究所 | Method for directly preparing trivalent chromium compound by means of electrochemical oxidation of ferrochromium |
| US12281399B1 (en) | 2022-12-23 | 2025-04-22 | Qinghai Institute Of Salt Lakes, Chinese Academy Of Sciences | Method for directly preparing trivalent chromium compound by electrochemical oxidation of ferrochrome |
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