CN114752766A - Method for selectively separating zinc, chromium and iron and recovering multiple metals in electroplating sludge - Google Patents
Method for selectively separating zinc, chromium and iron and recovering multiple metals in electroplating sludge Download PDFInfo
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- CN114752766A CN114752766A CN202110868684.7A CN202110868684A CN114752766A CN 114752766 A CN114752766 A CN 114752766A CN 202110868684 A CN202110868684 A CN 202110868684A CN 114752766 A CN114752766 A CN 114752766A
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- chromium
- iron
- zinc
- phosphate
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000011651 chromium Substances 0.000 title claims abstract description 65
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 58
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 52
- 239000011701 zinc Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 48
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 46
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000009713 electroplating Methods 0.000 title claims abstract description 27
- 239000010802 sludge Substances 0.000 title claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 title abstract description 20
- 239000002184 metal Substances 0.000 title abstract description 20
- 150000002739 metals Chemical class 0.000 title abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000001556 precipitation Methods 0.000 claims abstract description 35
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 34
- 239000010452 phosphate Substances 0.000 claims abstract description 32
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 31
- 239000000706 filtrate Substances 0.000 claims abstract description 26
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- 239000010949 copper Substances 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 21
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 claims abstract description 20
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 238000002386 leaching Methods 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002244 precipitate Substances 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 claims abstract description 11
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- 230000001376 precipitating effect Effects 0.000 claims abstract description 6
- 238000004064 recycling Methods 0.000 claims abstract description 6
- 230000009466 transformation Effects 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 238000000605 extraction Methods 0.000 claims description 23
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 9
- 229910000604 Ferrochrome Inorganic materials 0.000 claims description 8
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 7
- 229910001430 chromium ion Inorganic materials 0.000 claims description 7
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 claims description 7
- 235000010265 sodium sulphite Nutrition 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- -1 iron ions Chemical class 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 229960004887 ferric hydroxide Drugs 0.000 claims description 3
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 238000007127 saponification reaction Methods 0.000 claims description 3
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 8
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 5
- 239000002920 hazardous waste Substances 0.000 abstract description 2
- 239000012716 precipitator Substances 0.000 abstract description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 9
- 229910001385 heavy metal Inorganic materials 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000002893 slag Substances 0.000 description 7
- 238000005070 sampling Methods 0.000 description 6
- 239000001488 sodium phosphate Substances 0.000 description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 229910001463 metal phosphate Inorganic materials 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GXTNDOSGOPRCEO-UHFFFAOYSA-N [Cr].[Fe].[Zn] Chemical compound [Cr].[Fe].[Zn] GXTNDOSGOPRCEO-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- CDHFNBTXTGGTQI-UHFFFAOYSA-J sodium chromium(3+) tetrahydroxide Chemical compound [OH-].[Na+].[Cr+3].[OH-].[OH-].[OH-] CDHFNBTXTGGTQI-UHFFFAOYSA-J 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ASTWEMOBIXQPPV-UHFFFAOYSA-K trisodium;phosphate;dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[O-]P([O-])([O-])=O ASTWEMOBIXQPPV-UHFFFAOYSA-K 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
Abstract
The invention discloses a method for selectively separating zinc, chromium and iron and recovering multiple metals in electroplating sludge, wherein in a leaching solution, copper is selectively extracted by sequentially adopting a special-effect extracting agent; selectively extracting nickel by using a specific extracting agent; reducing ferric iron into ferrous iron by using a reducing agent, and selectively precipitating chromium by using a specific precipitator; extracting zinc by using a conventional acidic extracting agent; washing the chromium precipitate with dilute acid to remove entrained iron; leaching the washed chromium precipitate with concentrated alkali at a certain temperature to realize the transformation of the chromium phosphate precipitate to chromium hydroxide, and allowing phosphorus to enter the solution to be evaporated, concentrated and cooled with excess liquid alkali to realize the recycling of phosphate and excess alkali; cooling the recovered leachate to room temperature to separate out a large amount of hydrous phosphate crystals, filtering, returning the phosphate crystals to selective precipitation for recovering chromium, and adding a small amount of solid alkali into the filtrate to return to leaching conversion type chromium phosphate precipitation. The whole process of the invention has no wastewater discharge, and the output of secondary hazardous waste is eliminated.
Description
Technical Field
The invention relates to the technical field of metal separation, in particular to a method for selectively separating zinc, chromium and iron and a method for recovering multiple metals in electroplating sludge.
Background
Electroplating is a common metal and plastic surface treatment technology, and can improve wear resistance, corrosion resistance and decorative beauty. However, the electroplating industry generates large amounts of heavy metal wastewater during pretreatment and washing. In general, most of the wastewater is precipitated by neutralization to form electroplating sludge. The electroplating sludge contains 60-80% of water and considerable amount of heavy metals, such as Cu (1-2%), Ni (0.5-1%), Zn (1-2%), Cr (2-3%) and the like. These heavy metals pose fatal potential threats to human health through underground water systems and food chains, so that the electroplating sludge is classified as dangerous solid waste, and about 1000 million tons of electroplating sludge are produced each year in China alone. In the past, most of electroplating sludge is solidified in a refuse landfill, which brings long-term environmental problems and refuse landfill space problems, and in addition, along with the consumption of ore resources, the exhaustion of ores such as nickel, cobalt, copper, chromium and the like is another important problem facing the sustainable development of society. In recent years, with the development of increasingly strict and sustainable environmental regulations, the resource utilization and harmless treatment of electroplating sludge are receiving more and more attention.
Recovery of single or multiple valuable metals from electroplating sludge can be achieved by pyrometallurgical and hydrometallurgical processes. The pyrometallurgical recovery of metals as alloy materials, generally mixed metal ingots, and the preparation of residues as building materials, has low resource utilization efficiency and low added value. Compared with the conventional metallurgy route, the hydrometallurgy realizes the extraction and separation of single metal in a single process, and shows good adaptability to the recycling of electroplating sludge containing various heavy metals.
At present, the heavy metal recovery in the electroplating sludge is mainly copper, nickel, zinc and chromium in the industry, wherein the copper can be recovered with high selectivity by adopting LIX984 or M5640 (an extracting agent), most other metals adopt a precipitation method, because the pH of the combined precipitation of nickel, zinc, chromium and iron is close, the precipitation products are seriously carried with each other and incompletely precipitated, and the chromium is used as ferrochromium slag carrying a large amount of zinc and nickel to be stockpiled or disposed outside as secondary dangerous waste, so the purity of the product is not high. The whole resource utilization rate (or single metal recovery rate) is low, the added value of the product is not high, and a large amount of secondary hazardous waste is generated.
The Xuxiong university Xushifeng proposes a process for precipitating chromium by phosphate and converting the chromium into chromium hydroxide by using sodium hydroxide, but the process has the defects that the phosphate and the sodium hydroxide cannot be recycled and sodium salt wastewater containing chromium is generated; meanwhile, other metals are used for producing crude products by (except copper) precipitation method, and the same problems as the traditional process exist.
Disclosure of Invention
The invention aims to provide a method for selectively separating ferrochrome and a method for recovering multiple metals in electroplating sludge, and aims to overcome the defects that valuable metals in the existing electroplating sludge are difficult to effectively recover and waste water is easy to generate.
In order to achieve the purpose, the method for selectively separating the zinc, the chromium and the iron, provided by the invention, comprises the following steps of:
(1) adding a reducing agent into the solution containing zinc and chromium iron for pretreatment and adjusting the pH value of the solution;
(2) adding soluble phosphate into the solution obtained in the step (1), stirring, and carrying out selective chromium precipitation reaction;
(3) filtering and separating to obtain chromium phosphate filter residue and iron and zinc containing filtrate, and washing the filter residue with dilute acid to wash away entrained iron and chromium hydroxide;
(4) leaching the washed filter residue with concentrated alkali at high temperature to obtain chromium hydroxide solid and leaching solution;
(5) and (3) cooling the leaching solution to obtain soluble phosphate precipitate, filtering, returning phosphate crystals to the step (2) for selective chromium precipitation, and concentrating the filtrate, and returning the filtrate to the step (4) for a chromium phosphate precipitation transformation process.
Preferably, in the solution containing ferrochrome, the content of chromium ions is 0.1-30g/L, the content of iron ions is 0.1-20g/L, and the content of zinc ions is 0.1-10 g/L.
Preferably, the pretreatment process by adding the reducing agent is a reduction pretreatment by adding at least one of sodium thiosulfate or sodium sulfite or Fe powder, so that chromium ions and iron ions in the solution are respectively kept in Cr3+、Fe2+Status.
Preferably, in the step (1), the pH value of the solution is in the range of 0.5-2.5.
Preferably, the amount of the soluble phosphate added in the step (2) is 0.8 to 1.5 in terms of phosphate, and the molar ratio of phosphate to chromium ions is 0.8; the chromium deposition reaction temperature is 60-90 ℃, and the reaction time is 30-120 min.
Preferably, the step (2) is to add a chromium phosphate solid into the solution treated in the step (1), add a soluble phosphate, stir, and perform a selective chromium precipitation reaction.
Preferably, the pH of the dilute acid in the step (3) is in the range of 0.5-2; the reaction temperature of the dilute acid washing is controlled to be 60-90 ℃, the reaction time is 30-120min, and the liquid-solid ratio is 1:1-5: 1.
Preferably, the concentrated alkali in the step (4) is NaOH solution, and the concentration of NaOH is 100g/L-250 g/L; in the process of leaching the washed filter residue by concentrated alkali, the temperature is controlled to be 60-90 ℃, the time is 30-120min, and the liquid-solid ratio is 2:1-10: 1.
In order to achieve the purpose, the method for recycling the polymetallic such as copper, nickel, chromium, zinc and iron in the electroplating sludge comprises the following steps:
a. Leaching the electroplating sludge by using dilute sulfuric acid to obtain calcium sulfate solid and leachate containing nickel, zinc, copper, chromium and iron;
b. b, extracting, washing and back-extracting the copper in the leaching solution in the step a by using a specific extracting agent to obtain a copper sulfate solution and a raffinate containing nickel, zinc, chromium and iron, wherein the specific extracting agent comprises LIX984 or M5640;
c. b, saponifying, extracting, washing and back-extracting the nickel in the raffinate in the step b by using a specific extractant HBL110 to obtain a nickel sulfate solution and a raffinate containing zinc, chromium and iron;
d. treating a raffinate containing zinc, chromium and iron by a process as claimed in any one of claims 1 to 8;
e. d, extracting zinc from the iron-containing filtrate obtained by the treatment in the step d by using an acidic phosphorus extractant, and performing saponification, extraction, washing and step-by-step back extraction to obtain a zinc sulfate enriched solution and a ferrous sulfate raffinate;
f. and e, neutralizing and precipitating the ferrous sulfate raffinate obtained in the step e by using sodium hydroxide to obtain ferric hydroxide precipitate and sodium sulfate mother liquor.
Preferably, step-by-step back extraction in the step e is performed by: and (3) performing back extraction on zinc by using dilute sulfuric acid of more than 0.5mol/L and performing back extraction on a small amount of co-extracted iron by using hydrochloric acid of 6 mol/L.
The technical concept of the ferrochrome separation in the invention is as follows:
First, use Cr3+、Fe2+The selective precipitation separation of chromium and iron is realized by the solubility difference of the phosphate. With increasing pH, the order of hydrolysis of the metal is Fe (III)>Cu(II)≈Cr(III)>Zn(II)≈Fe(II)>Ni (II) indicates that iron (III) is preferentially hydrolyzed compared with other metal ions and can be separated from Cr (III). However, in practice, about 30% of Cr (III) is co-precipitated with Fe (III) during the hydrolysis of iron (III), resulting in an undesirable separation of Fe (III) from Cr (III). The research shows that the precipitation sequence of the metal phosphate is Cr (III) in the pH value range of 1.0-5.0>Fe(III)>Fe(II)>Ni(II)>Cu(II)>Zn (ii), further pH increase will result in conversion of the metal phosphate to the corresponding hydroxyl group. The transition pH values of Fe (III), (Cu (II), (Zn (II), (Ni (II), (III)) and Fe (II) are 5.0, 8.0, 9.5, 10.0, 10.2 and 10.5, respectively. This shows that nickel, zinc, copper and iron and chromium can be separated from the leachate by using a phosphate precipitation method. The chromium phosphate precipitate can be decomposed by sodium hydroxide to form chromium hydroxide, and the phosphate precipitate can be recycled.
Compared with the prior art, the invention has the beneficial technical effects that:
1. the method adopts the independently synthesized nickel specific extractant HBL-110 (refer to CN103421952A specifically) and the independently developed new direct nickel extraction process, realizes the selective extraction and enrichment of nickel and the deep separation of iron, chromium and zinc under the acidic condition, and provides guarantee for the whole process;
2. The closed cycle of sodium phosphate and sodium hydroxide is realized by adopting phosphate precipitation chromium-sodium hydroxide transformation-sodium phosphate low-temperature precipitation-alkali circulation, the chromium heavy metal wastewater is eliminated, the reagent consumption is greatly reduced, and no heavy metal wastewater is generated in the whole process;
3. the zinc and iron are separated by adopting potential reduction and selective zinc extraction-step back extraction, so that the high-selectivity recovery of zinc is realized;
4. the whole process realizes the productization high-value utilization of valuable metals such as copper, nickel, chromium and zinc in the electroplating sludge, greatly reduces the amount of waste residues and realizes near zero emission of wastewater compared with the traditional treatment process of the electroplating sludge, and is a typical low-cost clean high-efficiency energy-saving emission-reduction production process.
Drawings
FIG. 1 is a flow chart of an embodiment of a method for selective separation of zinc, chromium and iron provided by the present invention;
fig. 2 is a flowchart of an embodiment of a method for recycling the polymetallic of copper, nickel, chromium, zinc and iron in the electroplating sludge according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by those skilled in the art without any creative work based on the embodiments of the present invention belong to the protection scope of the present invention.
Example 1
Referring to fig. 1, the feed liquid is a laboratory prepared iron, chromium, zinc sulfate solution: the feed liquid contains Cr4.9g/L, Fe 2.0g/L and Zn 1.6 g/L. The reducing agent is sodium sulfite, the sodium sulfite is added according to 1.5 times of the theoretical amount of reaction required by complete reduction of iron and chromium, the pH value is adjusted to 2.0 by sulfuric acid, sodium phosphate is added according to the molar ratio of phosphate radical to chromium ion of 1.1, the mixture is stirred at 90 ℃ for 60min under heat preservation, coarse chromium phosphate precipitate is obtained by filtration, the concentrations of chromium, iron and zinc in the filtrate are respectively 0.07g/L, 1.67g/L and 1.57g/L, the chromium precipitation rate is 98.59%, the iron precipitation rate is 19.21% and the zinc precipitation rate is 1.21%. The filter residue is the chromium-removing residue, and the filtrate is the solution after chromium removal.
Taking 5g of fresh chromium-removed slag, washing the fresh chromium-removed slag by using sulfuric acid washing water with the pH value of 1, wherein the liquid-solid ratio is 2:1, adding 1g of sodium sulfite into the filtrate, keeping the temperature and stirring the mixture for 60min at the temperature of 90 ℃, filtering the mixture, returning the filtrate to the step of depositing chromium by using phosphate, and respectively containing 0.47g/L, 0.48g/L and 0.1g/L of chromium, iron and zinc in the filtrate. The filter residue is chromium phosphate washing residue.
Taking 5g of washing slag, using 200g/L NaOH solution according to a liquid-solid ratio of 5:1, keeping the temperature at 90 ℃, stirring for 60min, filtering, wherein the iron, chromium, zinc and phosphorus in the filtrate are respectively 0.02g/L, 0.03g/L, 0.1g/L and 1.5g/L, the alkalinity is 3.65mol/L, the filter residue is chromium hydroxide transformation slag, cooling the filtrate to the normal temperature, separating out a large amount of sodium phosphate crystals which can be returned as a chromium removal precipitator, and the filtrate can be returned to transform the chromium phosphate washing slag into the chromium hydroxide slag after supplementing consumed alkali.
Example 2
Solution preparation:
preparation of Cr under acidic condition3+/Fe2+/Zn2+Mixed solution ([ Cr ]3+]Initial＝5.00g/L，[Fe2+]Initial＝3.15g/L，[Zn2+]Initial＝2.78g/L)；
Preparing a sodium phosphate dodecahydrate solution with a certain volume; a certain volume of sodium hydroxide solution (4.5mol/L) is prepared.
Pre-treating a ferrochrome zinc solution:
adding a small amount of sodium sulfite to reduce and pretreat the chromium-iron-zinc solution so as to ensure that the iron in the solution is completely Fe2+The form exists.
Precipitation experiment (atmospheric pressure):
measuring 0.5L of ferrochrome mixed solution by a measuring cylinder, dripping one or two drops of the mixed solution into 5 percent potassium thiocyanate solution, and detecting whether Fe exists or not3+If the red color exists, a small amount of sodium sulfite is added for reduction, and if the red color does not exist, sulfuric acid is added dropwise to adjust the pH of the solution to be 2.0 (measured by a pH meter); taking a liquid sample before experiment, and sealing the cup mouth of the beaker by adopting a preservative film; heating in water bath to 80 deg.C (using mercury thermometer for calibration) without magnetic stirring; starting magnetic stirring, setting the rotating speed at 500rpm according to PO4 3-/Cr3+Slowly dropping sodium phosphate solution according to the molar ratio of 1.1; dropwise adding a small amount of sulfuric acid in the sample adding process to control the pH value of the solution to be less than 3.0, and reacting for 30min after the sample adding process is finished; stopping stirring, and keeping the temperature for 30 min; vacuum filtering, adding a small amount of acid water (pH 2.0) into the filter cake for rinsing, measuring the volume of the mixed filtrate, uniformly mixing, measuring the pH of the filtrate and sampling; washing the precipitate with appropriate amount of acid water (pH 1.0) under magnetic stirring (500rpm) at room temperature for 1 h; filtering, adding a small amount of acid water (pH is 2.0) into a filter cake for rinsing, measuring the volume of the mixed filtrate, uniformly mixing, measuring the pH of the filtrate and sampling; and (4) putting the filter cake into an oven for drying, weighing, sampling, decomposing and then sending to ICP for detection.
Precipitation control experiment (addition of chromium phosphate seed):
other parts were identical to the procedure of the precipitation experiment, with the following changes: according to PO4 3-/Cr3+Calculated according to the molar ratio of 1.1, 5 percent (the amount of the chromium phosphate generated theoretically) of chromium phosphate solid is added first, and then equivalent weight of the chromium phosphate solid is droppedSodium phosphate solution. Table 1 shows the effect of seeding or not on the phosphate precipitation ferrochrome experiments.
Decomposition experiment:
preparing a certain amount of acid-washed chromium phosphate solid (dry basis), and adding a certain amount of sodium hydroxide solution (4.5mol/L) according to the ratio of L/S to 5: 1; the water bath was warmed to 80 ℃ (calibrated with an alcohol thermometer); starting magnetic stirring (500rpm) and reacting for 60 min; vacuum filtering, adding a proper amount of pure water for rinsing, calculating the volume of the mixed filtrate, and sampling after uniformly mixing; adding a proper amount of pure water into the transformed precipitate, and stirring and washing for 30min at the temperature of 80 ℃; filtering, calculating the volume of filtrate, adding a proper amount of pure water for rinsing, calculating the volume of mixed filtrate, and sampling after uniform mixing; and drying and weighing the filter cake, sampling, decomposing and sending to ICP for detection. Table 2 shows the metal precipitation rate and the alkali-conversion element leaching rate.
In a phosphate precipitation experiment, the precipitation rate of iron can be reduced by adding the chromium phosphate seed crystal, and the precipitation rate of chromium is increased, namely the chromium content in the solution after precipitation is reduced.
TABLE 1
In a phosphate precipitation experiment, the precipitation rate of chromium can reach more than 98.0% by controlling the pH value in the reaction process, and the precipitation rate of iron is controlled within 5.0% at the same time. In the phosphate transformation experiment, the leaching rate of phosphorus can reach more than 90.0 percent by controlling the liquid-solid ratio of liquid alkali and precipitate, and chromium is hardly leached.
TABLE 2
Example 3
Referring to fig. 2, the electroplating sludge is dissolved by sulfuric acid to obtain calcium sulfate solid and leachate, wherein the leachate is a mixed acid solution of Cu, Cr, Ni, Zn and Fe ([ Cu ] Fe [)2+]Initial＝1.03g/L，[Ni2+]Initial＝2.04g/L，[Cr3+]Initial＝5.00g/L，[Fe2+]Initial＝3.15g/L，[Zn2+]Initial＝2.78g/L))。
In the leaching solution, an extractant LIX984 is adopted to selectively extract copper, and the organic phase after copper extraction is subjected to back extraction by adopting sulfuric acid to obtain copper sulfate.
And selectively extracting nickel by using an extracting agent HBL110 in a raffinate phase after copper extraction, and back-extracting an organic phase after nickel extraction by using sulfuric acid to obtain nickel sulfate.
Adding sodium phosphate into the raffinate phase after nickel extraction, stirring, filtering and separating to obtain chromium phosphate filter residue and iron-containing filtrate, and washing the filter residue with dilute acid to wash away entrained iron and chromium hydroxide. And leaching the washed filter residue by using concentrated alkali at high temperature to obtain chromium hydroxide solid and leaching solution. And cooling the leaching solution to obtain soluble phosphate precipitate, filtering, circularly using the phosphate precipitate for selectively precipitating chromium, and circularly using the filtrate after concentration for a chromium phosphate precipitation transformation process.
Selectively extracting zinc from the iron-containing filtrate by using an extractant D2EHPA, and performing saponification, extraction, washing and fractional back extraction to obtain a zinc sulfate enriched solution and a ferrous sulfate raffinate, wherein the fractional back extraction adopts the following steps: and (3) back-extracting zinc by using 0.6mol/L sulfuric acid and back-extracting a small amount of co-extracted iron by using 6mol/L hydrochloric acid.
Neutralizing and precipitating the ferrous sulfate raffinate with sodium hydroxide to obtain ferric hydroxide precipitate and sodium sulfate mother liquor, evaporating the sodium sulfate mother liquor to obtain sodium sulfate crystals and condensed water, and using the condensed water to prepare sulfuric acid to dissolve electroplating sludge.
TABLE 3
Note: the extraction/precipitation rate of each process is calculated by dividing the metal content of the product of that process by the total metal content of the feed solution
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited to the above-described examples. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.
Claims (10)
1. A method for selectively separating zinc, chromium and iron is characterized by comprising the following steps:
(1) adding a reducing agent into the solution containing zinc and chromium iron for pretreatment and adjusting the pH value of the solution;
(2) Adding soluble phosphate into the solution obtained in the step (1), stirring, and carrying out selective chromium precipitation reaction;
(3) filtering and separating to obtain chromium phosphate filter residue and iron and zinc containing filtrate, and washing the filter residue with dilute acid to wash away entrained iron and chromium hydroxide;
(4) leaching the washed filter residue by using concentrated alkali at high temperature to obtain chromium hydroxide solid and leachate;
(5) and (3) cooling the leachate to obtain soluble phosphate precipitate, filtering, returning phosphate crystals to the step (2) for selective chromium precipitation, and concentrating the filtrate and returning to the step (4) for a chromium phosphate precipitation transformation process.
2. The method of claim 1, wherein: in the solution containing the zinc and the ferrochrome, the content of chromium ions is 0.1-30g/L, the content of iron ions is 0.1-20g/L, and the content of zinc ions is 0.1-10 g/L.
3. The method of claim 1, wherein: the pretreatment process by adding the reducing agent is to add at least one of sodium thiosulfate or sodium sulfite or Fe powder for reduction pretreatment, so that chromium ions and iron ions in the solution are respectively kept in Cr3+、Fe2+Status.
4. The method of claim 1, wherein: in the step (1), the pH value range of the solution is 0.5-2.5.
5. The method of claim 1, wherein: the amount of the soluble phosphate added in the step (2) is calculated as phosphate, and the molar ratio of the phosphate to the chromium ions is 0.8-1.5; the chromium deposition reaction temperature is 60-90 ℃, and the reaction time is 30-120 min.
6. The method of claim 1, wherein: and (2) adding a chromium phosphate solid into the solution treated in the step (1), adding a soluble phosphate, stirring, and performing a selective chromium precipitation reaction.
7. The method of claim 1, wherein: the pH range of the dilute acid in the step (3) is 0.5-2; the reaction temperature of the dilute acid washing is controlled to be 60-90 ℃, the reaction time is 30-120min, and the liquid-solid ratio is 1:1-5: 1.
8. The method of claim 1, wherein: the concentrated alkali in the step (4) is NaOH solution, and the concentration of NaOH is 100g/L-250 g/L; in the process of leaching the washed filter residue by concentrated alkali, the temperature is controlled to be 60-90 ℃, the time is 30-120min, and the liquid-solid ratio is 2:1-10: 1.
9. A method for recycling polymetallic such as copper, nickel, chromium, zinc and iron in electroplating sludge is characterized by comprising the following steps:
a. leaching the electroplating sludge by using dilute sulfuric acid to obtain calcium sulfate solid and leachate containing nickel, zinc, copper, chromium and iron;
b. B, extracting, washing and back-extracting the copper in the leaching solution in the step a by using a specific extracting agent to obtain a copper sulfate solution and a raffinate containing nickel, zinc, chromium and iron, wherein the specific extracting agent comprises LIX984 or M5640;
c. b, saponifying, extracting, washing and back-extracting the nickel in the raffinate in the step b by using a specific extractant HBL110 to obtain a nickel sulfate solution and a raffinate containing zinc, chromium and iron;
d. treating a raffinate containing zinc, chromium and iron by a process as claimed in any one of claims 1 to 8;
e. d, extracting zinc from the iron-containing filtrate obtained by the treatment in the step d by using an acidic phosphorus extractant, and performing saponification, extraction, washing and step-by-step back extraction to obtain a zinc sulfate enriched solution and a ferrous sulfate raffinate;
f. and e, neutralizing and precipitating the ferrous sulfate raffinate obtained in the step e by using sodium hydroxide to obtain ferric hydroxide precipitate and sodium sulfate mother liquor.
10. The method for recycling the polymetallic such as copper, nickel, chromium, zinc and iron in the electroplating sludge according to claim 9, wherein the step-by-step back extraction in the step e comprises the following steps: and (3) performing back extraction on zinc by using dilute sulfuric acid of more than 0.5mol/L and performing back extraction on a small amount of co-extracted iron by using hydrochloric acid of 6 mol/L.
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