CN101643243A - Method for recovering copper, nickel, chromium, zinc and iron from electroplating sludge - Google Patents
Method for recovering copper, nickel, chromium, zinc and iron from electroplating sludge Download PDFInfo
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- CN101643243A CN101643243A CN200910184773A CN200910184773A CN101643243A CN 101643243 A CN101643243 A CN 101643243A CN 200910184773 A CN200910184773 A CN 200910184773A CN 200910184773 A CN200910184773 A CN 200910184773A CN 101643243 A CN101643243 A CN 101643243A
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- iron
- zinc
- chromium
- nickel
- copper
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 186
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 92
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 81
- 239000011651 chromium Substances 0.000 title claims abstract description 81
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 75
- 239000011701 zinc Substances 0.000 title claims abstract description 75
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 59
- 239000010949 copper Substances 0.000 title claims abstract description 59
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000009713 electroplating Methods 0.000 title claims abstract description 40
- 239000010802 sludge Substances 0.000 title claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 238000000605 extraction Methods 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 57
- 239000002893 slag Substances 0.000 claims description 55
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 46
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000005987 sulfurization reaction Methods 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000000926 separation method Methods 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 238000007254 oxidation reaction Methods 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 23
- 238000002386 leaching Methods 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 20
- 230000003647 oxidation Effects 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 18
- 238000007731 hot pressing Methods 0.000 claims description 17
- 238000000746 purification Methods 0.000 claims description 16
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 14
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 12
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 10
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 10
- 235000017550 sodium carbonate Nutrition 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 239000000284 extract Substances 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 210000002966 serum Anatomy 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- WQSRXNAKUYIVET-UHFFFAOYSA-N sulfuric acid;zinc Chemical compound [Zn].OS(O)(=O)=O WQSRXNAKUYIVET-UHFFFAOYSA-N 0.000 claims description 7
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 6
- 239000003350 kerosene Substances 0.000 claims description 6
- 238000007127 saponification reaction Methods 0.000 claims description 6
- 239000011133 lead Substances 0.000 claims description 5
- 235000010265 sodium sulphite Nutrition 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 7
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000001784 detoxification Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 28
- 238000011084 recovery Methods 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 12
- 238000012797 qualification Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 5
- KOMIMHZRQFFCOR-UHFFFAOYSA-N [Ni].[Cu].[Zn] Chemical compound [Ni].[Cu].[Zn] KOMIMHZRQFFCOR-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- 239000010440 gypsum Substances 0.000 description 4
- 229910052602 gypsum Inorganic materials 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 description 4
- 229960001763 zinc sulfate Drugs 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 229910000570 Cupronickel Inorganic materials 0.000 description 2
- 239000003978 infusion fluid Substances 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical class Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- GCPRNIZDNTXQIX-NBPLQZBRSA-N 1-chloro-2-(2-chloroethylsulfanyl)ethane;dichloro-[(e)-3-chloroprop-2-enyl]arsane Chemical compound ClCCSCCCl.Cl\C=C\C[As](Cl)Cl GCPRNIZDNTXQIX-NBPLQZBRSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910000604 Ferrochrome Inorganic materials 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- -1 and greater than 60% Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
A method for recovering copper, nickel, chromium, zinc and iron from electroplating sludge belongs to the technical field of metallurgy and chemical industry. The method has strong adaptability to different types of electroplating sludge, and has the remarkable advantages of high utilization rate of metal resources, high added value of products, small amount of process waste residues, thorough detoxification and the like.
Description
Technical field
The present invention relates to the chemical metallurgy technical field, particularly from electroplating sludge, reclaim the technology of metal.
Background technology
Electroplating sludge is the solid waste of the waste water of processing industries such as electronics, plating, PCB surface processing through neutralizing treatment, is classified as Hazardous wastes by country.Electroplating sludge water ratio height; Particle is thinner, is thin mud shape; The composition complexity contains various heavy element such as copper, zinc, nickel, chromium etc.; The many tax with states such as oxyhydroxide, oxide compound, carbonate of metal deposited, and the metal content fluctuation range is big, brings sizable difficulty therefore for the comprehensive utilization of electroplating sludge.Therefore, the method for disposal that electroplating sludge is commonly used is to store up landfill, burning curing etc., some direct air storage at present.Owing to there is leaching toxicity, easily surface water or underground water polluted.
In order to reduce pollution, also there is pair electroplating sludge to carry out the research of the utilization of resources, method has fire reduction melting and wet chemistry Separation and Recovery etc., but the general technical level is not high, there is following defective: (1) small scale, it is imperfect that technology is disposed chain, and comprehensive utilization ratio is lower, produce waste residue, waste water such as improper conducting oneself well and put, cause secondary pollution easily.(2) treatment process is simple, and is poor to adaptability to raw material, can only select cupric, higher being reclaimed of nickel.(3) majority can only be produced thick product, and is low in economic efficiency.
The fire reduction smelting technique is handled to reclaim copper nickel cupric nickel electroplating sludge at present, and its main products is for containing cupronickel, low nickel matte, matte etc.Promptly then carry out retailoring by sintering or briquetting.Be limited to state of the art, can only intermittently produce, metal recovery rate is not high.Bigger to cupric, raw material intractability that nickel is lower, generally this part raw material is not dealt with, the production process energy consumption is big, and is seriously polluted, and resource utilization is not high, and iron, chromium etc. can't obtain to utilize.Belong to the technology that country progressively eliminates.
The wet separation technology reclaims heavy metal, as leaching---segmentation fractionation, leaching---extraction separation method etc., product is a copper, and nickel and other salt etc. exist the problem poor to the raw material adaptation, that resource utilization is low equally, and still contain heavy metal in the secondary residue, also deal with improperly and can cause secondary pollution, the more important thing is that wet processing can only select cupric, high the handling of nickel, resources such as chromium, zinc, iron are not well utilized.
Common electroplating sludge can be copper-contained electroplating sludge, nickeliferous electroplating sludge, chromium containing electroplating mud etc. according to content what or the simple classification of recovery target.With regard to the character characteristics of electroplating sludge, reach comparatively ideal comprehensive utilization effect and should solve following problems emphatically: (1) is to the adaptability problem of raw material.Because electroplating sludge is from different producers, complicated component, major metal and foreign matter content fluctuation range are big, bring bigger difficulty to process choice.(2) the not high problem of metals resources comprehensive utilization ratio.Be limited to technical factor, some available resources are not fully used, and do not lose in waste or waste water because of metal recovery rate is high, very easily cause secondary pollution.(3) economy problems: wet processing is often because of long flow path, and metal recovery rate is high and make production cost higher.Therefore should select a kind of adaptable Technology, when improving resource utilization, should produce high-valued product as much as possible and thoroughly solve the secondary pollution problem, accomplish the efficient utilization of resources, be only the crucial outlet that solves harmlessness disposing.
Summary of the invention
The objective of the invention is to propose a kind of utilization of resources method of electroplating sludge, from electroplating sludge, reclaim copper, nickel, zinc, chromium, iron.It is few that this method has a metals resources utilization ratio height, added value of product height, process waste residue amount, and detoxifcation thoroughly waits remarkable advantage.
The present invention is gone out, is vulcanized processes such as separation and concentration, hot pressing leaching, purification by liquid extraction, chromium hot-pressure oxidation, extraction chromic salts, extraction iron(ic) chloride and forms by acidleach, step is as follows:
1) acidleach goes out: the pH value of reaction system is under 0.5～1.0 the condition, and electroplating sludge and sulfuric acid stirring reaction after 2.5～3.0 hours, are separated reacted dope filtration, gets leach liquor;
2) sulfuration separation and concentration: the pH value of leach liquor is adjusted to 2.0～2.5, and with the reaction of leach liquor and vulcanizing agent, the sulfide of generation copper, nickel, zinc also separates with iron, chromium, after filtration, gets respectively and vulcanizes slag and chromium solution in stirred reactor;
3) hot pressing is leached: will vulcanize slag and sulfuric acid stirring reaction 2.5 hours under 130～145 ℃ of temperature, oxygen partial pressure 0.3～0.4MPa and 4: 1 condition of liquid-solid ratio, filtering separation obtains iron oxide red slag and leach liquor then;
4) purification by liquid extraction: extracting and separating zinc, iron, copper from leach liquor, through back extraction, washed metal, step such as concentrate, obtain crystalline sulfuric acid zinc, cupric sulfate crystals and acid chlorization ferrous solution respectively; Adopt the nickelous carbonate adjustment through extracting pH value to 6.0～6.2 of the nickel solution that obtains behind zinc, iron, the copper, under 40～50 ℃ of temperature condition, the mixed solution of forming with yellow soda ash and sodium bicarbonate carries out neutralization precipitation, obtains basic nickel carbonate; The mass ratio of yellow soda ash and sodium bicarbonate is 3: 1 in the described mixed solution;
5) chromium hot-pressure oxidation: with step 2) chromium solution of obtaining mixes the formation mixed serum with chromium containing electroplating mud, add chromic acid or chromic salt again, stir the back and add sodium hydroxide, hot-pressure oxidation reacted 2.5～3.0 hours under the condition of 140～145 ℃ of oxidizing temperatures, oxygen partial pressure 0.3～0.4Mpa in oxygen is pressed reactor, after filtration, obtain chromium solution and iron oxide red slag respectively;
6) chromium solution purification: with sour set-up procedure 5) the chromium solution pH value that obtains makes zinc, aluminium, lead, silicon precipitate and separate to 7.5-8.0;
7) produce iron(ic) chloride: under 70～80 ℃ of reaction conditionss, the iron oxide red slag that step 3) and step 5) are obtained, the acidic ferric chloride solution acidolysis after-filtration of obtaining with step 4), get ferric chloride Solution, ferric chloride Solution is concentrated into ferric chloride concn to 350～400g/l, be cooled to then below 10 ℃, crystallization obtains iron(ic) chloride.
Key issue at the electroplating sludge processing, the present invention uses sulfuration enrichment, hot pressing leaching, extraction and separation technology and chromium hot-pressure oxidation, produces wet process technology such as chromic salts technology, metals resources such as copper in the electroplating sludge, nickel, chromium, zinc, iron are all got the efficient use, product is fine chemical products such as copper sulfate, basic nickel carbonate, chromic salts, zinc sulfate, iron chloride salt, it is few to have metals resources utilization ratio height, added value of product height, process waste residue amount, and detoxifcation thoroughly waits remarkable advantage.
The concrete scheme of the present invention is:
1, acidleach goes out:
Cupric, nickel electroplating sludge enter in the reactor, add sulfuric acid stirring reaction hierarchy of control pH, can suitably add hydrogen peroxide for promoting reaction, react the rear slurry that finishes and send filtering separation, obtain metal leach liquor and gypsum tailings.Because the molten material of sulfuric acid is an exothermic process, so do not need heating also can react completely.The leaching yield of copper, nickel, zinc, chromium, iron is greater than 98%.PH is between 0.5～1.0 for the maintenance system, and main purpose has two: the one, copper, nickel, chromium, zinc, iron etc. are leached as much as possible fully, to improve resource utilization; The 2nd, reach abundant detoxifcation, make the gypsum tailings washing after the separation leach the requirement of toxicity conformance with standard, can be directly used in the production building material product.
The technical qualification that acidleach goes out:
Leaching agent: sulfuric acid; The stirring reaction time: 2.5～3.0 hours, terminal point Ph:0.5～1.0 additives: hydrogen peroxide consumption: 15kg/t mud.
2, sulfuration separation and concentration:
The main purpose of sulfuration separation and concentration is copper nickel zinc to be separated with siderochrome and be enriched in to vulcanize in the slag.
Utilize difference selective precipitation copper, nickel, the zinc of the solubility product of metallic sulfide, and iron and chromium are retained in the solution, thereby reach the purpose of separation and concentration, improve the efficient that later separation is handled simultaneously.Leach liquor is regulated acidity with alkaline matter, to pH2.0～2.5, then in stirred reactor, slowly add vulcanizing agent (Iron sulfuret slag, sodium sulphite etc.), reaction end pH is controlled at 3.2～3.5, copper, nickel, zinc all form sulfide and separate with iron, chromium at this moment, obtain vulcanizing slag and chromium solution after filtration.The sulfide precipitation rate of copper, nickel, zinc is greater than 98%.
For reducing the content of iron in the sulfuration slag, the sulfuration slag of press filtration can be added heated and stirred in the leach liquor that pH is 1.5～2.0 left and right sides cuprics, nickel, zinc, copper in Iron sulfuret and the solution, nickel, zinc carry out vulcanization reaction, can obtain the sulfuration slag of higher metal grade once more after the press filtration.The sulfuration slag contains heavy metal greater than 60%, and iron content is less than 5%.Secondary filtrate can generate the Iron sulfuret slag and return use as main vulcanizing agent directly with the sodium sulphite sulfuration.
Sulfuration separation and concentration technical qualification:
Vulcanizing agent: sodium sulphite, Iron sulfuret slag etc., consumption: in the vulcanizing agent in sulphur and the leach liquor the total mol ratio of copper, nickel and zinc be 3.5～5.0: 1; Initial pH2.0～2.5, terminal point pH3.5～3.8, reaction times: 1.5～3.0h, temperature: 40～60 ℃.
3, hot pressing is leached: adopt hot pressing leaching mode to handle the sulfuration slag, its objective is that copper, nickel, zinc all are converted into vitriol to be entered solution and separate with iron.The sulfuration slag is the sulfide of nascent state, thereby has higher reactive behavior, can be because of S
0Parcel and hinder reaction and carry out, therefore must not add tensio-active agent.Under the condition of control, mainly finish S
2--S
0-SO
4 2-Conversion, promptly vulcanize the sulphur vitriolic source the most in the slag, the vitriol that copper, nickel, zinc are formed separately enters solution, thereby initial only the need keep lower acidity get final product, leaches the end of a period sulfuric acid concentration and changes not quite.Meanwhile, iron is oxidized to trivalent and at high temperature goes into slag with the form of rhombohedral iron ore.
Carry out sulfuric acid hot pressing in the sulfuration slag adding reactor and leach, control certain acidity, temperature, oxygen partial pressure and liquid-solid ratio, stirring reaction can reach satisfied leaching effect after for some time.Because adopt hot pressing leaching mode, the leaching of copper nickel zinc is complete and quick, and iron rule is because also at high temperature gone into slag with the rhombohedral iron ore form by abundant oxidation.Obtain iron oxide red slag and leach liquor after separating after filtration.The leaching yield of copper, nickel, zinc is greater than 98%, and the leach liquor iron content is less than 1g/l.
Hot pressing leaching-out technique condition: initial sulfuric acid consumption (mass ratio): sulfuric acid: sulfuration slag=12～15: 100,130～145 ℃ of temperature, oxygen partial pressure 0.3～0.4MPa, liquid-solid ratio 4: 1; Reaction times 2.5h.
4, purification by liquid extraction: the purpose of purification by liquid extraction is separating copper, nickel, zinc and extracts corresponding metal-salt product.
Cupric, nickel, zinc lixiviating solution are carried out the extracting and separating and the product salt of purifying metals.Iron concentration is lower in the isolating infusion solution after hot pressing is leached, and can directly carry out extracting and separating.Traditional extraction process requires the solution iron content lower, and is main because of iron back extraction difficulty, and the hydrochloric acid consumption of washing usefulness is big, and therefore solution need pass through degree of depth deironing before the extraction, causes the loss of main metal unavoidably.And at first be that zinc, iron are together extracted in this technology, produce crystalline sulfuric acid zinc behind the back extraction zinc, the iron content organic phase is regenerated with 8N salt acid elution iron, and the acid chlorization ferrous solution then can return and leach the iron oxide red slag, thereby reaches the purpose that makes full use of.Behind extracting and separating zinc, the iron, extracting copper again, condensing crystal is produced copper sulfate after the back extraction.Solution obtains purifying and has obtained cleaner nickel solution behind extracting and separating iron, zinc, copper, be adjusted to pH6.0～6.2 with nickelous carbonate after, directly obtain the basic nickel carbonate product with yellow soda ash+sodium bicarbonate neutralization precipitation.Crystalline sulfuric acid zinc, cupric sulfate crystals, basic nickel carbonate product meet the technical grade standard, and the comprehensive recovery of copper, nickel, zinc product is greater than 96%.
The purification by liquid extraction technical qualification are:
(1) extracting zinc: extraction agent: 30% di(2-ethylhexyl)phosphate isooctyl+kerosene, saponification deg 65%, collection zinc pH1.0～1.5,4 grades of extraction progression; Back extraction zinc: sulfuric acid circulation back extraction, 2 grades of back extraction zinc progression; Washed metal: concentration of hydrochloric acid: 8N, agitated pool circulation washed metal.
(2) extracting copper: extraction agent: 30%P204+ kerosene, saponification deg 65%, collection copper pH2.5～3.0,4 grades of extraction progression; Back extraction copper: sulfuric acid circulation back extraction, 2 grades of back extraction progression.
(3) coprecipitated nickel hydroxide: nickelous carbonate is transferred pH to 6.0～6.2 removal of impurities; Precipitation agent: the mixed solution of sodium bicarbonate and yellow soda ash, concentration 20～30%, the mass ratio of yellow soda ash and sodium bicarbonate is 3: 1; 40～50 ℃ of heavy nickel temperature, terminal point pH.8.0～8.5.
(4) the zinc sulfate crystallization routinely crystallisation step carry out, the zinc sulfate quality meets the technical grade standard.Cupric sulphate crystal crystallisation step routinely carries out, and the copper sulfate quality meets the technical grade standard.
5, chromium hot-pressure oxidation: the main purpose of hot-pressure oxidation is to separate siderochrome.
Utilize chromium under alkaline condition, easily to be oxidized to chromic characteristics, adopt the hot-pressure oxidation technology to strengthen the chromium oxidation reaction process, make chromium be oxidized to CrO
4 2-Enter solution, and iron is oxidized to the a-Fe of rhombohedral iron ore form
2O
3Go into slag, thereby realize effectively separating of chromium and iron, replace traditional alkali roasting method with this.
The chromium solution that step 2 is obtained mixes with chromium containing electroplating mud and forms mixed serum, adds chromic acid or chromic salt again, stirs the back and adds sodium hydroxide, then delivers to oxygen and presses and carry out the hot-pressure oxidation reaction in the reactor, and the chromium conversion rate of oxidation is greater than 98%.Obtain chromium solution and iron oxide red slag after filtration, send production iron(ic) chloride after iron oxide red wash heat is washed.
Chromium hot-pressure oxidation technical qualification:
130～145 ℃ of temperature, oxygen partial pressure 0.3～0.4MPa; Alkali is than (mol ratio): the mol ratio of chromium is 1.2～1.3: 1 in the sodium hydroxide of adding and the mixing sludge; The mol ratio of iron was respectively 0.5: 1 in chromic acid or chromic salt and the described mixed serum; Hot-pressure oxidation leached 2.5～3.0 hours.
6, chromium solution purifies:
Contain alkali-soluble metal impurity such as zinc, aluminium, lead in the chromium solution, adjust pH with acid and make precipitation such as zinc, aluminium, lead and separate, make that foreign matter content meets the chromium salt production requirement in the solution.Chromium solution after the purification can extract chromic salts products such as chrome tanning agent or lead-chrome yellow, and the chromic salts product recovery rate is greater than 98%.
The purification techniques condition:
Neutralizing agent: sulfuric acid, terminal point pH7.5～8.0.
7, extract iron(ic) chloride:
The raw material that is used to produce iron(ic) chloride comprises the iron oxide red slag that the iron oxide red slag of sulfuration slag treating processes, the reaction of chromium solution hot-pressure oxidation obtain, iron oxide red slag iron content is greater than 55%, washed metal liquid with the zinc extraction process directly carries out acidolysis, separate through the acidolysis after-filtration, ferric chloride Solution concentrates, then be cooled in water cooler below 10 ℃, crystallization obtains the iron(ic) chloride product, and comprehensive recovery is greater than 90%.
Extract the iron(ic) chloride technical qualification:
Acidolysis: liquid-solid ratio 3: 1, time 2.0～2.5h, 70～80 ℃ of temperature; Concentrate: ferric chloride concn is concentrated into 350～400g/l; Crystallization: Tc＜10 ℃.
The present invention has following advantage:
1, multiple metal ions such as the leach liquor cupric of electroplating sludge after leaching, nickel, zinc, chromium, iron, aluminium, conventional separation method exist metal recovery rate on the low side, separate thoroughly, problem that production cost is high.Adopt the advantage of sulfuration separation and concentration to be: (1) makes copper, nickel, zinc change into sulfide and obtain enrichment, thereby convenient follow-up processing, because the sulfide of copper, nickel, zinc all has less solubility product, can from solution, obtain separating more completely, thereby the metal recovery rate height.(2) because the solubility product of Iron sulfuret less than the sulfide solubility product of copper, nickel, zinc, therefore can be selected separation of iron under the technical qualification of control; Chromium does not form sulfide under acidic conditions, therefore can realize the good separation of chromium and copper, nickel, zinc.(3) sulfuration slag of Sheng Chenging and leach liquor heated and stirred reaction can utilize Iron sulfuret and the copper in the solution, nickel, zine ion in the sulfuration slag to react, thereby reduces the content of iron in the sulfuration slag, improves metal content.
2, the advantage that adopts the hot pressing leaching method to handle the sulfuration slag is: (1) metal leaching rate height, leaching velocity are fast, and the sulfuration slag needs strong oxidizer to leach or calcination process under the normal condition; (2) leaching process is directly realized the separation of iron, and obtains the very high iron oxide red slag of iron content, can directly utilize and produce the iron(ic) chloride product.
3, the sulfuration slag after hot pressing is leached in the isolating infusion solution iron concentration lower, can directly carry out extracting and separating.Adopt the advantage of extraction process to be: metal separation is effective, metal recovery rate is high, can obtain the metal-salt product of high added value; The leaching agent that while washed metal hydrochloric acid can be used as production crystallization iron chloride salt is used.
4, utilize chromium easily to be oxidized to chromic characteristics under alkaline condition, adopt the hot-pressure oxidation technology to strengthen the chromium oxidation reaction process, under the condition of control, chromium is oxidized to CrO
4 2-Enter solution, and iron is oxidized to a-Fe
2O
3Go into slag, thereby realize effectively separating of chromium and iron.Compare present technique with conventional separation method and have that but ferrochrome separates thoroughly, chromium recovery ratio is high, the advantage of the iron utilization of resources.
5, the present invention is strong to different types of electroplating sludge adaptability, metals resources utilization ratio height, and the rate of recovery of copper, nickel, zinc, chromium is greater than 90%.
6, added value of product height of the present invention, product meet zinc sulfate, copper sulfate, basic nickel carbonate, chromic salts, the iron(ic) chloride product of technical grade.
7, process waste residue of the present invention is few, and detoxifcation is thorough, and the harmlessness disposing effect is obvious.
Embodiment
As shown in Figure 1, operation steps of the present invention has: acidleach goes out, vulcanizes separation and concentration, hot pressing leaching, purification by liquid extraction, chromium hot-pressure oxidation, chromium solution purification, extracts iron(ic) chloride.
1, acidleach goes out: the electroplating sludge of cupric, nickel is pumped in the reactor, add sulfuric acid, stirring reaction hierarchy of control pH0.5～1.0, for promoting reaction, press 15kg/t mud and add hydrogen peroxide, react 2.5～3.0 hours rear slurries and send filtering separation, obtain metal leach liquor and gypsum tailings.Copper, nickel, chromium, zinc, iron leaching yield are greater than 98%.
The requirement of toxicity conformance with standard is leached in gypsum tailings washing back, can do the general industry waste residue and handle.
2, sulfuration separation and concentration: leach liquor is regulated acidity to pH2.0～2.5 with alkaline matter, then in stirred reactor, by copper, nickel and zinc total mass ratio in sulphur in the vulcanizing agent and the leach liquor is 3.5～5.0: 1, slowly add vulcanizing agent (as Iron sulfuret slag, sodium sulphite etc.), reaction end pH is controlled at 3.2～3.5, reaction times 1.5-2.0h, copper, nickel, zinc all form sulfide and separate with iron, chromium at this moment, obtain vulcanizing slag and chromium solution after filtration.
The sulfide precipitation rate of copper, nickel, zinc is greater than 98%.The sulfuration slag contains heavy metal (copper nickel zinc), and greater than 60%, iron content is less than 5%.
3, hot pressing is leached: the sulfuration slag adds and carries out hot pressing in the reactor and leach, and control initial sulfuric acid amount and be: sulfuric acid is 12～15: 100 with the mass ratio that the sulfuration slag feeds intake; At 140～145 ℃ of temperature, oxygen partial pressure 0.3～0.4MPa, 4: 1 condition of liquid-solid ratio, stirring reaction was promptly finished leaching process in 2.5 hours.Copper, nickel, zinc enter solution with the vitriol form, and iron rule is because also at high temperature gone into slag with the rhombohedral iron ore form by abundant oxidation.Obtain iron oxide red slag and leach liquor after separating after filtration.
The leaching yield of copper, nickel, zinc is greater than 99%, and the leach liquor iron content is less than 1g/l.
4, purification by liquid extraction: the sulfuration slag separates the leach liquor that obtains and carries out purification by liquid extraction after hot pressing is leached, extracting and separating zinc, iron, copper from leach liquor, through back extraction, washed metal, step such as concentrate, obtain crystalline sulfuric acid zinc, cupric sulfate crystals and acid chlorization ferrous solution respectively; The nickel solution that obtains behind extracting and separating zinc, iron, copper adopts nickelous carbonate to adjust pH value to 6.0～6.2, under 40～50 ℃ of temperature condition, with concentration is that the mixed solution that 15～20% yellow soda ash and sodium bicarbonate are formed carries out neutralization precipitation, heavy nickel terminal point pH is 8.0～8.5, and filtering separation obtains basic nickel carbonate.
The quality product of crystalline sulfuric acid zinc, cupric sulfate crystals, basic nickel carbonate reaches the technical grade standard respectively.The washed metal acid solution is as the leaching agent of producing iron(ic) chloride.The rate of recovery of copper, nickel, zinc is greater than 97%.
The technical qualification of purification by liquid extraction are:
(1) extracting zinc: extraction agent: by volume fraction is that 30%P204 (di(2-ethylhexyl)phosphate isooctyl) and kerosene mixing are formed, saponification deg 65%, collection zinc pH1.0～1.5,4 grades of extraction progression; Back extraction zinc: sulfuric acid circulation back extraction, 2 grades of back extraction zinc progression, washed metal: concentration of hydrochloric acid: 8N, agitated pool circulation washed metal.
(2) extracting copper: extraction agent: by volume fraction is that 30%P204 (di(2-ethylhexyl)phosphate isooctyl) and kerosene mixing are formed, saponification deg 65%, collection copper pH2.5～3.0,4 grades of extraction progression; Back extraction copper: sulfuric acid circulation back extraction, 2 grades of back extraction progression.
(3) coprecipitated nickel hydroxide: nickelous carbonate is transferred pH to 6.0～6.2 removal of impurities, precipitation agent: the mixed solution of sodium bicarbonate and yellow soda ash, concentration 20～30%, the mass ratio of yellow soda ash and sodium bicarbonate 3: 1,40～50 ℃ of temperature, terminal point pH8.0～8.5.
(4) crystalline sulfuric acid zinc, cupric sulfate crystals technical qualification and step routinely carried out.
5, chromium hot-pressure oxidation: the chromium solution behind the sulfuration separating copper nickel zinc mixes the formation mixed serum with chromium-bearing sludge, add chromic acid solution or chromic salt again, stir the back and add sodium hydroxide, then in pressing reactor, oxygen carries out the hot-pressure oxidation reaction, the condition of control is: the chromic acid add-on: the mol ratio of iron is 0.5: 1 in chromium and the mixed serum, alkali number: alkali is 1.2～1.3: 1 with the mol ratio of total chromium; 130～145 ℃ of oxidizing temperatures, oxygen partial pressure 0.3-0.4MPa,, 2.5～3.0 hours reaction times.The chromium conversion rate of oxidation is greater than 99%.Obtain chromium solution and iron oxide red slag after filtration.
6, chromium solution purifies: adjust chromium solution pH to 7.5～8.0 with acid, make precipitation such as zinc, aluminium, lead, silicon and separate.Zinc, aluminium, plumbous clearance are greater than 98%, and the chromium solution after the purification can extract chromic salts products such as chrome tanning agent, but while by-product sodium sulfate.Chromium recovery ratio is greater than 98%.
7, produce iron(ic) chloride: the raw material that is used to produce iron(ic) chloride comprises the iron oxide red slag that step 3 and step 5 are obtained, iron oxide red slag iron content is all greater than 55%, washed metal liquid with the zinc extraction process directly carries out acidolysis, control liquid-solid ratio 3: 1,70～80 ℃ of temperature of reaction, acidolysis time 2.0～2.5h, separate through the acidolysis after-filtration, ferric chloride Solution is concentrated into ferric chloride concn and reaches 350～400g/l, then is cooled in water cooler below 10 ℃, and crystallization obtains the iron(ic) chloride product.
Claims (8)
1, from electroplating sludge, reclaims the method for copper, nickel, chromium, zinc, iron, it is characterized in that comprising that acidleach goes out, vulcanizes separation and concentration, hot pressing leaching, purification by liquid extraction, chromium hot-pressure oxidation, extracts chromic salts, extracts the iron(ic) chloride process;
1) acidleach goes out: the pH value of reaction system is under 0.5～1.0 the condition, and electroplating sludge and sulfuric acid stirring reaction after 2.5～3.0 hours, are separated reacted dope filtration, gets leach liquor;
2) sulfuration separation and concentration: the pH value of leach liquor is adjusted to 2.0～2.5, and with the reaction of leach liquor and vulcanizing agent, the sulfide of generation copper, nickel, zinc also separates with iron, chromium, after filtration, gets respectively and vulcanizes slag and chromium solution in stirred reactor;
3) hot pressing is leached: will vulcanize slag and sulfuric acid stirring reaction 2.5 hours under 130～145 ℃ of temperature, oxygen partial pressure 0.3～0.4MPa and 4: 1 condition of liquid-solid ratio, filtering separation obtains iron oxide red slag and leach liquor then;
4) purification by liquid extraction: extracting and separating zinc, iron, copper from leach liquor, through back extraction, washed metal, concentrated, obtain crystalline sulfuric acid zinc, cupric sulfate crystals and acid chlorization ferrous solution respectively; Adopt the nickelous carbonate adjustment through extracting pH value to 6.0～6.2 of the nickel solution that obtains behind zinc, iron, the copper, under 40～50 ℃ of temperature condition, the mixed solution of forming with yellow soda ash and sodium bicarbonate carries out neutralization precipitation, obtains basic nickel carbonate; The mass ratio of yellow soda ash and sodium bicarbonate is 3: 1 in the described mixed solution;
5) chromium hot-pressure oxidation: with step 2) chromium solution of obtaining mixes the formation mixed serum with chromium containing electroplating mud, add chromic acid or chromic salt again, stir the back and add sodium hydroxide, hot-pressure oxidation reacted 2.5～3.0 hours under the condition of 140～145 ℃ of oxidizing temperatures, oxygen partial pressure 0.3～0.4Mpa in oxygen is pressed reactor, after filtration, obtain chromium solution and iron oxide red slag respectively;
6) chromium solution pH value to 7.5～8.0 of obtaining extraction chromic salts: with sour set-up procedure 5) make zinc, aluminium, lead, silicon precipitate and separate;
7) produce iron(ic) chloride: the iron oxide red slag that step 3) and step 5) are obtained, the acidic ferric chloride solution acidolysis after-filtration of under 70～80 ℃ of temperature of reaction conditions, obtaining with step 4), get ferric chloride Solution, ferric chloride Solution is concentrated into ferric chloride concn to 350～400g/l, be cooled to then below 10 ℃, crystallization obtains iron(ic) chloride.
2, according to the described method that from electroplating sludge, reclaims copper, nickel, chromium, zinc, iron of claim 1, it is characterized in that in the described step 1), add hydrogen peroxide in the reaction system of being made up of electroplating sludge and sulfuric acid, the mass ratio of described hydrogen peroxide and electroplating sludge is 15: 1000.
3, according to the described method that from electroplating sludge, reclaims copper, nickel, chromium, zinc, iron of claim 1, it is characterized in that described step 2) in, described vulcanizing agent is Iron sulfuret slag or sodium sulphite; In the vulcanizing agent in sulphur and the leach liquor total mol ratio of copper, nickel and zinc be 1.2～1.5: 1.
4, according to the described method that from electroplating sludge, reclaims copper, nickel, chromium, zinc, iron of claim 1, it is characterized in that described step 2) in, the pH value of reaction end is 3.5～3.8.
According to the described method that from electroplating sludge, reclaims copper, nickel, chromium, zinc, iron of claim 1, it is characterized in that in the described step 3) that 5, sulfuric acid is 12～15: 100 with the mass ratio that the sulfuration slag feeds intake.
6, according to the described method that from electroplating sludge, reclaims copper, nickel, chromium, zinc, iron of claim 1, it is characterized in that in the described step 4), the extraction agent in zinc when extraction is that 30% di(2-ethylhexyl)phosphate isooctyl and kerosene are formed by volume fraction, saponification deg is 65%, the pH value of control solution is 1.0～1.5 in the extracting zinc process, and extraction progression is 4 grades; With sulfuric acid circulation back extraction zinc, 2 grades of back extraction zinc progression; Adopting concentration is the hydrochloric acid washed metal of 8N.
7, according to the described method that from electroplating sludge, reclaims copper, nickel, chromium, zinc, iron of claim 1, it is characterized in that in the described step 4), during the copper extraction, the extraction agent that adopts is that 30% di(2-ethylhexyl)phosphate isooctyl and kerosene are formed by volume fraction, saponification deg is 65%, the pH value of control solution is 2.5～3.0 in the extracting copper process, and extraction progression is 4 grades; With sulfuric acid circulation back extraction, 2 grades of back extraction progression.
According to the described method that from electroplating sludge, reclaims copper, nickel, chromium, zinc, iron of claim 1, it is characterized in that in the described step 5) that 8, the mol ratio of iron was respectively 0.5: 1 in described chromic acid or chromic salt and the described mixed serum; The mol ratio of chromium is 1.2～1.3: 1 in sodium hydroxide that adds and the mixing sludge.
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