CN112209543B - Composite treatment method of complex copper waste liquid and microetching waste liquid - Google Patents
Composite treatment method of complex copper waste liquid and microetching waste liquid Download PDFInfo
- Publication number
- CN112209543B CN112209543B CN202010915378.XA CN202010915378A CN112209543B CN 112209543 B CN112209543 B CN 112209543B CN 202010915378 A CN202010915378 A CN 202010915378A CN 112209543 B CN112209543 B CN 112209543B
- Authority
- CN
- China
- Prior art keywords
- copper
- waste liquid
- solution
- reaction
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 186
- 239000002699 waste material Substances 0.000 title claims abstract description 136
- 239000010949 copper Substances 0.000 title claims abstract description 123
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 114
- 238000000034 method Methods 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 32
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000005530 etching Methods 0.000 claims abstract description 23
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 21
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims abstract description 13
- 239000013543 active substance Substances 0.000 claims abstract description 12
- 238000005273 aeration Methods 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 63
- 239000011259 mixed solution Substances 0.000 claims description 25
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- 230000008929 regeneration Effects 0.000 claims description 20
- 238000011069 regeneration method Methods 0.000 claims description 20
- 239000000725 suspension Substances 0.000 claims description 20
- 239000005751 Copper oxide Substances 0.000 claims description 19
- 229910000431 copper oxide Inorganic materials 0.000 claims description 19
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 19
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 239000007800 oxidant agent Substances 0.000 claims description 18
- 238000001556 precipitation Methods 0.000 claims description 17
- 238000001179 sorption measurement Methods 0.000 claims description 17
- 230000003472 neutralizing effect Effects 0.000 claims description 16
- 230000001590 oxidative effect Effects 0.000 claims description 15
- 230000002378 acidificating effect Effects 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- 238000005286 illumination Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000011001 backwashing Methods 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003456 ion exchange resin Substances 0.000 claims description 5
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 238000003672 processing method Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 2
- 239000011248 coating agent Substances 0.000 claims 2
- 238000000576 coating method Methods 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 239000011149 active material Substances 0.000 claims 1
- 150000004699 copper complex Chemical class 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 6
- 239000012716 precipitator Substances 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 239000002352 surface water Substances 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000000047 product Substances 0.000 description 15
- 238000011084 recovery Methods 0.000 description 14
- 238000005868 electrolysis reaction Methods 0.000 description 12
- 238000000605 extraction Methods 0.000 description 12
- 238000007747 plating Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 239000002920 hazardous waste Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- -1 Ni and the like Chemical class 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000010812 mixed waste Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 238000005844 autocatalytic reaction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 description 1
- 239000001472 potassium tartrate Substances 0.000 description 1
- 229940111695 potassium tartrate Drugs 0.000 description 1
- 235000011005 potassium tartrates Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000011272 standard treatment Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F7/00—Aeration of stretches of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention relates to the technical field of wastewater treatment, in particular to a composite treatment method of complex copper waste liquid and micro-etching waste liquid. The composite treatment method of the complex copper waste liquid and the microetching waste liquid comprises the steps of firstly carrying out oxidation and decomplexing to remove organic matters, then carrying out solid-phase extraction to recover copper ions for preparing basic copper chloride, finally adding powdery active substances into the extracted water, carrying out electrolytic reaction under the aeration condition, adding a precipitator to generate a wrapping object, realizing the combined treatment of the complex copper waste liquid and the microetching waste liquid by the mode, recovering the copper ions in the waste liquid, filtering the wrapping object to obtain COD, P and NH in the reaction water 3 Indexes such as-N, cu, ni and the like reach IV-type standard discharge of surface water, and the treatment method has the advantages of easily controlled reaction conditions and good treatment effect.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of wastewater treatment, in particular to a composite treatment method of complex copper waste liquid and micro-etching waste liquid.
[ background of the invention ]
The processes of expansion, oil removal, microetching, chemical copper plating, chemical copper deposition and the like are all indispensable procedures in the manufacturing process of circuit boards in the electronic information industry, and a large amount of complex copper waste liquid, microetching and other non-complex copper sulfate waste liquid are generated in the process and respectively belong to HW17 and HW22 in the national hazardous waste records.
The complex copper waste liquid represented by chemical copper plating has the characteristics of alkalinity (pH is more than 11), low copper concentration (20-4000 mg/L), high-concentration organic matter (15000-50000 mg/L) and the like, wherein various organic additives such as EDTA, potassium tartrate, citric acid and the like form a very stable complex with copper, so that the copper cannot be removed by simple precipitation or adsorption, and the organic matter is difficult to be thoroughly oxidized by a conventional method, so the treatment difficulty of the waste liquid is extremely high. The micro-etching waste liquid has the characteristics of strong acidity, high copper concentration (5000-10000 mg/L), hydrogen peroxide, ammonium persulfate and other oxidants, and relatively low organic additive concentration (1000-5000 mg/L).
The characteristic difference between the complex copper waste liquid and the microetching waste liquid is large, the prior research mainly aims at the independent treatment of the complex copper waste liquid and the microetching waste liquid, the recovery of copper resources is emphasized, the treatment method mainly comprises a physical and chemical precipitation method, an adsorption method, an electrolysis method and the like, and correspondingly recovered products comprise copper oxide, copper sulfide, copper sulfate, metal copper and the like.
(1) Method for treating complex copper waste liquid represented by electroless copper plating
CN 105668843B, CN 106219804B, CN 106477807B and CN 108249649A respectively disclose a specific process for recovering copper ions in electroless copper plating wastewater by a precipitation method, and the greatest problems of the precipitation method are that the content of precipitate copper is not high, and the precipitate copper contains impurity elements such as organic matters, phosphorus, nickel and the like, so that the precipitation product has poor quality and low added value and is often sold in a sludge form instead of a product form. Meanwhile, the removal rate of copper by a precipitation method is 70% -97%, the fine filter pressing performance of precipitated product particles is poor, the concentration of copper in precipitated water is still ten to hundreds of mg/L, the precipitated water cannot reach the standard and is discharged, and advanced treatment is required. CN 108793311A discloses a method for oxidizing hypophosphorous in chemical copper plating waste liquid by a photoelectric combination method and synchronously recovering metallic copper by electrodeposition, wherein the copper recovery rate is about 97%, the electrolytic efficiency is rapidly reduced along with the reduction of the copper concentration in the waste water, the quality of metallic copper products is rapidly deteriorated, the Cu concentration of the effluent is still dozens of milligram liters to hundreds of milligram liters, and the effluent cannot be discharged up to the standard. The electrolysis method is more suitable for recovering copper in high-concentration copper solution with simple water quality. CN 110342628A discloses a method for synchronously adsorbing and recovering heavy metal ions by catalyzing hydrogen peroxide to oxidize and complex copper wastewater by using hydrated iron oxide-loaded ion exchange resin, which has the problems that the standard of organic matters cannot be reached due to limited catalytic oxidation effect, the treatment efficiency is low due to the repeated use of a catalyst, and the independent regeneration of copper is difficult to realize due to the simultaneous adsorption of iron oxide and copper by the resin. CN 103224303A proposes a photocatalytic oxidation method for recovering copper phosphate from a chemical copper plating waste liquid, wherein the method needs to strictly control a proper ratio of copper to phosphorus in the waste liquid, and metal salt is additionally added according to needs.
(2) Treatment method of microetching waste liquid
CN 107892322A proposes a method of "ion exchange adsorption-acid washing resin to obtain copper regenerated liquid, evaporating to concentrate copper regenerated liquid, cooling to crystallize and recover copper sulfate" to treat copper-containing wastewater, which does not directly perform ion exchange resin adsorption treatment because the microetching waste liquid has high acidity and contains oxidant, and at the same time, the patent does not disclose how to ensure the purity of copper regenerated liquid. CN 109112312A proposes to recover cathode metal copper from copper microetching solution by adopting a method of reducing oxidant-organic extraction-electrolytic stripping solution by sodium sulfite, wherein the copper in the water treated by the electrolytic method cannot reach the standard and is discharged, and the method lacks an organic matter removal step, the organic matter affects the extraction effect, and the extracted water cannot reach the standard and is discharged. CN 103803744B adopts "elemental copper is obtained by reduction of iron powder-residual copper ion is precipitated by a heavy metal trapping agent-polymeric ferric sulfate is prepared by adding oxidation" to treat the copper-containing microetching waste liquid, the method needs to consume a large amount of acid and oxidant, the cost is high, and the quality of the recovered sponge is poor due to the excessive iron powder.
In conclusion, the existing research on the complex copper waste liquid and the micro-etching waste liquid has the defects that the direction is single, the copper recovery is emphasized, the additional value of the recovered copper product is not high, the condition is difficult to control, the effluent cannot reach the standard, the deep treatment process is lacked, and the like, and the technical system is imperfect, so that the requirements of actual engineering cannot be met. In order to reduce the production cost, improve the treatment efficiency and improve the copper recovery rate and the product purity, the invention develops a novel method for recovering basic copper chloride by carrying out composite treatment on complex copper waste liquid and microetching waste liquid and realizing standard discharge of waste water, and no report and case of any two waste liquid combined treatment processes or report of recovering basic copper chloride from two waste liquids are seen at present.
[ summary of the invention ]
The technical scheme of the invention is as follows: provides a composite treatment method of complex copper waste liquid and microetching waste liquid, which comprises the following steps:
step S1, mixing the complex copper waste liquid and the micro-etching waste liquid, adding a neutralizer to obtain a copper oxide suspension, adding an oxidant to the oxidized suspension, and performing an oxidation reaction under an illumination condition to remove organic matters in the copper oxide suspension to obtain a first reaction liquid;
s2, carrying out solid-liquid separation on the first reaction solution to obtain a copper sulfate solution, carrying out solid-phase extraction on the copper sulfate solution to respectively obtain extracted water and an extractant enriched with copper ions, and carrying out backwashing on the extractant by using a hydrochloric acid solution to obtain a copper chloride regeneration solution;
s3, adding powdery active substances into the extracted water for mixing, and carrying out electrolytic reaction under the aeration condition to obtain second reaction liquid;
and S4, adding a precipitator and a neutralizing agent into the second reaction liquid for precipitation reaction to form a wrapping object taking the powdery active substance as a core, so as to obtain a third reaction liquid, and performing solid-liquid separation on the third reaction liquid to respectively obtain the wrapping object and reaction effluent.
Preferably, the processing method further includes, between step S2 and step S3, the steps of:
s21, mixing the copper chloride regeneration solution with an acidic copper etching solution, adding an alkaline copper etching solution to adjust the pH value to 3-4, stirring and reacting at 40-70 ℃ to obtain a fourth reaction solution, and performing solid-liquid separation on the fourth reaction solution to obtain an alkaline copper chloride solid.
Preferably, in step S1, the step of mixing the complex copper waste liquid and the microetching waste liquid and then adding a neutralizing agent to obtain a copper oxide suspension, includes:
under the condition of stirring, mixing the complex copper waste liquid and the microetching waste liquid to obtain a first mixed liquid;
and adding a neutralizing agent into the first mixed solution to adjust the pH value of the second mixed solution to 2-3, and generating copper oxide precipitate from a small amount of copper to obtain a copper oxide suspension.
Preferably, in the step S1, the volume ratio of the complex copper waste liquid to the microetching waste liquid is 1 (3-6), the concentration of copper ions in the complex copper waste liquid is 10-5000 mg/L, the concentration of COD is 5000-50000mg/L, the concentration of copper ions in the microetching waste liquid is 2000-12000 mg/L, and the concentration of COD is 1000-10000 mg/L.
Preferably, in step S1, the oxidizing agent is a hydrogen peroxide solution with a mass percentage of 20% to 30%, the addition amount of the hydrogen peroxide solution is that the volume ratio of the oxidation suspension is (4 to 8): 100, the illumination condition is 245nm to 285nm ultraviolet irradiation, the temperature of the oxidation reaction is 40 ℃ to 60 ℃, and the time of the oxidation reaction is 0.5 to 2 hours.
Preferably, in step S2, the extractant used in the solid-phase extraction is copper ion adsorption resin, the mass concentration of the hydrochloric acid solution is 10% to 36.5%, and the pH value of the copper sulfate solution is 2 to 3.
Preferably, in step S3, the powdery active substance comprises one or two of activated carbon powder or powdery ion exchange resin, the mass ratio of the powdery active substance to the extracted water is (0.05-0.2): 100, and the current density of the electrolytic reaction is 100-800A/m 2 The electrolysis time is 1-4 h.
Preferably, in step S4, the adding a precipitating agent and a neutralizing agent into the second reaction solution to perform a precipitation reaction includes:
adding a precipitant into the second reaction solution to obtain a second mixed solution;
adding a neutralizing agent into the second mixed solution to adjust the pH value of the second mixed solution to 8-9 to obtain a third mixed solution;
and precipitating or filtering the third mixed solution to perform solid-liquid separation.
Preferably, in step S4, the precipitant includes one or more of polymeric ferric sulfate, polymeric ferric chloride, polymeric aluminum chloride or ferrous sulfate, the neutralizing agent is liquid alkali, and the mass ratio of the precipitant to the second reaction liquid is (0.1-1.0): 100.
Preferably, in step S21, the volume ratio of the copper chloride regeneration liquid to the acidic etching liquid is 1 (1-4), the reaction temperature of the stirring reaction is 40-70 ℃, and the reaction time is 0.5-2 h.
The invention has the beneficial effects that: the invention provides a composite treatment method of complex copper waste liquid and microetching waste liquid, which is a scheme for mixing and jointly treating two waste liquids and recovering copper to prepare basic copper chloride for the first time in the industry, wherein the two waste liquids can be neutralized by acid and alkali, so that the addition amount of a pH regulator is reduced, meanwhile, oxidants such as hydrogen peroxide and the like in the microetching waste liquid can be fully utilized to carry out preliminary pre-oxidation on the complex copper waste liquid, and the purposes of saving chemical agents, reducing cost and removing part of organic matters are achieved; secondly, oxidation and complex breaking are carried out in the process that Cu and CuO in the waste liquid are autocatalyzed by hydrogen peroxide to oxidize organic matters under the illumination condition, and a catalyst is not required to be added to ensure the purity of a subsequent copper product; simultaneously, the characteristics of low copper and high COD of the complex copper waste liquid and high copper and low COD of the micro-etching waste liquid are utilized, and the reasonable compatibility of the components achieves balanced COD and Cu 2+ The concentration of Cu required for achieving better autocatalytic oxidation effect can be ensured 2+ The phenomenon of violent reaction and slow temperature rise due to overhigh concentration of organic matters can be avoided in the process; and thirdly, the solid-phase extraction adopts the ionic resin with a special adsorption function on Cu, which is different from the conventional adsorption requiring neutral conditions, can realize the direct selective adsorption of Cu under acidic conditions without adsorbing metals such as Ni and the like, and avoids the influence of other metal impurities introduced into the regenerated liquid on the product quality. Fourthly, compared with the traditional liquid caustic soda neutralization precipitation method for producing low-value copper oxide, the method provided by the invention has the advantages that the copper chloride regeneration liquid, the acidic etching waste liquid and the alkaline etching waste liquid are simply mixed in a compatible manner, the waste is treated by the waste, the high-cost liquid caustic soda does not need to be additionally added, and the prepared product has the purity and the qualityThe components are all better and have higher value; compared with the traditional method for recovering metal copper by electrolysis or recovering copper sulfate by adsorption, regeneration, evaporation and concentration, the method can be directly embedded into the basic copper chloride production line of the hazardous waste enterprise without additionally arranging electrolysis or evaporation and concentration production facilities. The invention realizes the recovery of copper and the high-standard treatment of waste liquid, is a complete technical system and has obvious beneficial effect.
[ description of the drawings ]
Fig. 1 is a schematic diagram of a composite treatment method of a complex copper waste liquid and a microetching waste liquid according to an embodiment of the present invention.
[ detailed description ] embodiments
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The terms "first", "second" and "third" in the present invention are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first," "second," or "third" may explicitly or implicitly include at least one of the feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless explicitly specified otherwise. Furthermore, the terms "include" and "have," as well as any variations thereof, are intended to cover non-exclusive inclusions.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the invention. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. It is explicitly and implicitly understood by one skilled in the art that the embodiments described herein can be combined with other embodiments.
In order to overcome the defects that the added value of the recovered copper product is not high and the comprehensive standard reaching of the pollution factor cannot be ensured in the prior art system, the invention aims to organically combine the high-valued reclamation and high-standard reaching treatment of the complex copper waste liquid and the microetching waste liquid, and not only develops a new copper reclamation product and a recovery method, but also provides a new advanced treatment method for reaching the standard of the tail end waste water, and the invention is easy to realize industrialized popularization and application.
The embodiment of the invention provides a composite treatment method of complex copper waste liquid and microetching waste liquid, which realizes the advanced treatment of the two waste liquids while preparing basic copper chloride, and as shown in figure 1, the composite treatment method comprises the following steps:
(1) Step of oxidative de-complexation
Mixing the complex copper waste liquid and the microetching waste liquid, adding a neutralizer to obtain a copper oxide suspension, adding an oxidant to the copper oxide suspension, and carrying out an oxidation reaction under the illumination condition to remove organic matters in the copper oxide suspension to obtain a first reaction liquid.
Specifically, the complex copper waste liquid is one or a combination of more of chemical plating (precipitating) copper waste liquid, alkaline degreasing waste water and bulk waste liquid.
In this embodiment, first, the complex copper waste liquid and the microetching waste liquid are mixed under stirring to obtain a first mixed liquid; and then adding a neutralizing agent into the first mixed solution to adjust the pH value of the first mixed solution to 2-3, wherein a small amount of copper in the first mixed solution generates black copper oxide precipitate, and thus the copper oxide suspension is obtained.
Wherein the volume ratio of the complex copper waste liquid to the microetching waste liquid is 1 (3-6), the concentration of copper ions in the first mixed liquid is kept to be 2000-10000 mg/L, and the COD concentration is kept to be 5000-20000 mg/L.
It should be noted that one of the purposes of mixing the complex copper waste liquid and the microetching waste liquid is to balance the copper ion concentration of water quality, and the copper ion concentration of the complex copper waste liquid is increased by high-concentration copper in the microetching waste liquid, so that the copper ion concentration in the mixed waste liquid is kept at a more ideal level, the autocatalysis effect of copper ions is better played, and no catalyst is required to be added.
It should be noted that the second purpose of mixing the complex copper waste liquid and the microetching waste liquid is to balance the concentration of organic matters in water quality, and dilute the high-concentration organic matters in the complex copper waste liquid through the low-concentration organic matters in the microetching waste liquid to keep the concentration of the organic matters in the mixed waste liquid at a more ideal level, thereby avoiding violent and uncontrollable reaction process caused by adding a large amount of oxidants due to overhigh concentration of the organic matters.
It should be noted that the third purpose of mixing the complex copper waste liquid and the microetching waste liquid is to fully utilize the self-contained alkali in the complex copper waste liquid and the self-contained acid in the microetching waste liquid, to realize acid-base neutralization, reduce the dosage of the medicament required for adjusting the pH value of the waste liquid, and reduce the cost.
The fourth purpose of mixing the complex copper waste liquid and the microetching waste liquid is to fully utilize oxidant components such as hydrogen peroxide, ammonium persulfate and the like in the microetching waste liquid, so that the complex copper waste liquid is used for pre-oxidizing the complex copper waste liquid, the using amount of the oxidant is saved, and the cost is reduced.
Then, oxidizing and breaking the complex to remove organic matters in the oxidized suspension, adding an oxidant, and then carrying out an oxidation reaction under the illumination condition, wherein the oxidant is a hydrogen peroxide solution with the mass percent of 20-30%, the adding amount of the hydrogen peroxide solution is that the mass ratio of the oxidized suspension is (4-8): 100, the illumination condition is 245-285 nm ultraviolet irradiation, for example, 40W 254nm ultraviolet lamp can be adopted for irradiation, the temperature of the oxidation reaction is 40-60 ℃, and the time of the oxidation reaction is 0.5-2 h.
(2) Copper enrichment step
And carrying out solid-liquid separation on the first reaction solution to obtain a copper sulfate solution, carrying out solid-phase extraction on the copper sulfate solution to respectively obtain extracted water and an extractant enriched with copper ions, and carrying out backwashing on the extractant by using a hydrochloric acid solution to obtain a copper chloride regeneration solution.
Wherein, the extractant used in the solid phase extraction is copper ion adsorption resin, the mass concentration of the hydrochloric acid solution is 10-36.5%, and the pH value of the copper sulfate solution is 2-3.
Furthermore, the solid phase extracting agent is a chelating resin which has strong selective adsorption effect on copper ions under acidic condition, and the residence time of the extraction reaction is 20-60 min.
It is to be noted that the purpose of the water feeding of the solid phase extraction under acidic conditions is to maintain the copper concentration of the copper sulfate solution as high as possible while well avoiding Ni in the waste solution 2+ 、NH 4 Competitive adsorption of N plasma, thereby further ensuring the purity of the subsequent copper chloride regeneration liquid.
Furthermore, the backwashing retention time in the step two is 5-30 min, the concentration of copper ions in the obtained copper chloride regeneration liquid is 30-60 g/L, and the copper extraction recovery rate is more than 99%.
Furthermore, the solid phase extracting agent is cleaned by industrial water before backwashing, so that a trace amount of waste liquid remained in the extracting agent is discharged.
It should be noted that, besides hydrochloric acid, sulfuric acid can also be used for backwashing of the extracting agent, the invention adopts hydrochloric acid for backwashing, and aims to obtain the copper chloride regenerated liquid, thereby being beneficial to directly embedding into a production line for producing basic copper chloride by recycling copper etching waste liquid in circuit board industry without additionally adding other processes and equipment.
(3) Preparation of basic copper chloride
And mixing the copper chloride regeneration solution with an acidic etching solution, adding an alkaline etching solution to adjust the pH value to 3-4, stirring and reacting at 40-70 ℃ to obtain a fourth reaction solution, and carrying out solid-liquid separation on the fourth reaction solution to obtain basic copper chloride solid.
Wherein the volume ratio of the copper chloride regeneration liquid to the acid etching liquid is 1 (1-4), and the reaction time is 0.5-2 h.
(4) Advanced treatment step
Adding powdery active substances into the extracted water for mixing, and carrying out electrolytic reaction under the aeration condition to obtain a second reaction solution; and adding a precipitator and a neutralizing agent into the second reaction solution for precipitation reaction to form a wrapping object taking the powdery active substance as a core, so as to obtain a third reaction solution, and carrying out solid-liquid separation on the third reaction solution to respectively obtain the wrapping object and reaction effluent.
Wherein, COD, P and NH in the reaction water obtained after the wrappage is filtered 3 Indexes such as-N, cu, ni and the like reach the IV-type standard discharge of surface water.
Wherein the powdery active substance comprises one or two of active carbon powder or powdery ion exchange resin, the mass ratio of the powdery active substance to the extracted water is (0.05-0.2): 100, and the current density of the electrolytic reaction is 100-800A/m 2 The electrolysis time is 1-4 h.
Wherein, the adding the precipitating agent and the neutralizing agent into the second reaction liquid for precipitation reaction comprises the following steps: adding a precipitant into the second reaction solution to obtain a second mixed solution; adding a neutralizing agent into the second mixed solution to adjust the pH value of the second mixed solution to 8-9 to obtain a third mixed solution; and precipitating or filtering the third mixed solution to perform solid-liquid separation. The precipitator comprises one or more of polymeric ferric sulfate, polymeric ferric chloride, polymeric aluminum chloride or ferrous sulfate, the neutralizing agent is liquid alkali, and the mass ratio of the precipitator to the second reaction liquid is (0.1-1.0): 100.
It should be noted that, in the step, organic matters and ammonia nitrogen in the waste liquid can be deeply oxidized at the same time, and pollution factors such as heavy metals and phosphorus are deeply removed through polymerization precipitation, so that comprehensive standard-reaching discharge of multiple pollution factors is realized.
Compared with the prior art, the invention has the following advantages and effects:
the invention carries out combined treatment on the complex copper waste liquid and the microetching waste liquid, and can reduce processes and equipment and improve efficiency compared with the traditional mode that two types of waste liquid are separately treated by two sets of processes.
The invention carries out organic mixed treatment on the alkaline complex copper waste liquid and the acidic microetching waste liquid, can save acid and alkali, and can simultaneously fully utilize oxidants such as hydrogen peroxide and the like in the microetching waste liquid to carry out primary pretreatment on the complex copper waste liquid, thereby achieving the purposes of saving chemical agents, reducing cost and removing partial organic matters.
The oxidation and complex breaking process is an autocatalytic oxidation reaction of metal ions (Cu) and metal oxides (CuO) in the waste liquid under the illumination condition, no additional catalysts such as TiO2, fe2+ and the like are needed, no new impurities are introduced, and the resource recovery of high-value copper in the waste liquid is facilitated; compared with a direct electrolysis recovery or adsorption and extraction recovery method, the method solves the problem that the existence of complex organic matters in the waste liquid causes the ineffective recovery of copper, and ensures high copper recovery rate.
On the basis of oxidation and complex breaking, the method further prepares the basic copper chloride product by solid phase extraction, regeneration of copper chloride solution and high-value recovery of more than 99 percent of copper resources. Compared with the traditional liquid caustic soda neutralization precipitation method for producing low-value copper oxide, the method has the advantages that the copper chloride regeneration liquid, the acidic etching waste liquid and the alkaline etching waste liquid are simply mixed, waste is treated by waste, high-cost liquid caustic soda does not need to be added additionally, and the prepared product is excellent in purity and quality and has high value; compared with the traditional method of adsorbing-regenerating copper sulfate solution-electrolyzing and recovering metal copper or adsorbing-regenerating copper sulfate solution-evaporating, concentrating and crystallizing to recover copper sulfate, the method can be directly embedded into the basic copper chloride production line of a hazardous waste enterprise without additionally arranging an electrolyzing or evaporating and concentrating production facility, and meanwhile, the method adopts solid-phase extraction resin with a special adsorption function on Cu to selectively adsorb Cu under an acidic condition without adsorbing metals such as Ni in the waste liquid, so that the influence of introducing other metal impurities into the regeneration liquid on the product quality is avoided.
According to the invention, a powder active adsorbent is coupled with electrolytic oxidation, the wastewater after copper recovery is subjected to advanced treatment by combining flocculation and precipitation, an oxidation atmosphere is generated by electrolysis, heavy metal adsorption and organic matter enhanced oxidation effects are enhanced by jointly utilizing the large specific surface area, heavy metal complexing adsorption performance, oxidant catalytic performance and the like of the powder active adsorbent, and the active adsorbent continues to play a role in crystal nucleus and encapsulation in the effluent flocculation and precipitation step, so that pollutants are completely removed. Compared with the traditional advanced oxidation method or flocculation method, the method has the advantages of mild and easily-controlled reaction conditions, capability of synchronously realizing deep removal of pollution factors such as ammonia nitrogen, heavy metals, organic matters, phosphorus and the like, excellent precipitation and filtration performance and the like.
Example 1:
laboratory apparatus
An oxidation complex breaking reactor with the diameter of 200mm multiplied by 250mm is internally provided with 2 aeration heads and 2 ultraviolet lamps, and the outside of the oxidation complex breaking reactor is connected with a water pump for internal circulation; a solid phase extraction column, an outer diameter (inner diameter) x height =50 (44) x 500mm chromatography column; the deep flat electrolytic cell is 200mm multiplied by 250mm, an aeration head and 8 flat plate electrode plates are arranged in the deep flat electrolytic cell, and a water pump is connected outside the deep flat electrolytic cell for internal circulation.
The method comprises the following steps: taking 1L of chemical copper plating waste liquid from a circuit board factory to a reaction container, adding 4L of microetching waste liquid, and starting aeration to fully and uniformly mix. Adding 50% liquid caustic soda to adjust the pH value of the mixed solution to 2.5, and generating mixed suspension containing black copper oxide. Starting an ultraviolet lamp source, slowly adding 275ml of oxidizing agent according to the volume ratio of 5.5%, and reacting for 2 hours.
Step two: and (4) leaching reaction effluent, wherein filter residues are copper phosphate precipitates, and 4.95L of filtrate is a copper sulfate solution. The filtrate sequentially passes through four-stage chromatographic columns filled with 400ml of solid phase extracting agent from top to bottom respectively, the flow rate is 15ml/min, the pH value of effluent of each stage is adjusted to 2 by using liquid alkali, and then the effluent enters the next-stage extraction column. Washing the four-stage extraction column with industrial tap water, discharging residual waste liquid, then respectively adding 400ml, 200ml and 200ml of 18% hydrochloric acid solution from the upper part of the four-stage extraction column at the flow rate of 15ml/min, and uniformly collecting after removing residual cleaning liquid in the column to obtain mixed desorption liquid which is copper chloride regeneration liquid.
Step three: and mixing the copper chloride regeneration liquid with the impurity-removed acidic etching liquid according to the volume ratio of 1.
Step four: adding powdered activated carbon into the effluent of the four-stage extraction column, feeding the effluent into an electrolytic cell to start electrolysis, controlling the current density to be 100A/m & lt 2 & gt and the electrolysis time to be 2h, and starting aeration and water pump internal circulation to ensure that the system is in a fully and uniformly mixed state.
Step five: and adding 1% of flocculating agent polymeric ferric sulfate into electrolyzed water, adjusting the pH value to 9 by using 50% of liquid caustic soda of a neutralizing agent, performing suction filtration, and discharging the filtrate after reaching the standard.
TABLE 1 EXAMPLE 1 Combined treatment Effect of electroless copper plating waste liquid and microetching waste liquid
Example 2:
laboratory apparatus
An oxidation complex breaking reactor with the diameter of 200mm multiplied by 250mm is internally provided with 2 aeration heads and 2 ultraviolet lamps, and the outside is connected with a water pump for internal circulation; a solid phase extraction column, an outer diameter (inner diameter) x height =50 (44) x 500mm chromatography column; the deep flat electrolytic cell is 200mm multiplied by 250mm, an aeration head and 8 flat plate electrode plates are arranged in the deep flat electrolytic cell, and a water pump is connected to the outside of the deep flat electrolytic cell for internal circulation.
The method comprises the following steps: taking 1L of chemical copper plating waste liquid from a circuit board factory to a reaction container, adding 6L of microetching waste liquid, and starting aeration to fully and uniformly mix. Adding 50% liquid alkali to adjust the pH value of the mixed solution to 2, and generating mixed suspension containing black copper oxide. Turning on the ultraviolet lamp source, slowly adding 560ml of oxidant according to the volume ratio of 8%, and reacting for 2h.
Step two: and (4) carrying out suction filtration on reaction effluent, wherein filter residues are copper phosphate precipitates, and taking 6.95L of filtrate as a copper sulfate solution. The filtrate sequentially passes through four-stage chromatographic columns filled with 400ml of solid phase extracting agent from top to bottom respectively, the flow rate is 15ml/min, the pH value of effluent of each stage is adjusted to 2 by using liquid alkali, and then the effluent enters the next-stage extraction column. Washing the four-stage extraction column with industrial tap water, discharging residual waste liquid, then respectively adding 400ml, 200ml and 200ml of 18% hydrochloric acid solution from the upper part of the four-stage extraction column at the flow rate of 15ml/min, and uniformly collecting after removing residual cleaning liquid in the column to obtain mixed desorption liquid which is copper chloride regeneration liquid.
Step three: and (3) mixing the copper chloride regenerated solution and the impurity-removed acidic etching solution according to a volume ratio of 1.
Step four: adding powdered activated carbon into the effluent of the four-stage extraction column, entering an electrolytic cell to start electrolysis, controlling the current density to be 100A/m & lt 2 & gt and the electrolysis time to be 2h, and starting aeration and water pump internal circulation to ensure that the system treatment is in a fully and uniformly mixed state.
Step five: and adding 1% of flocculating agent polymeric ferric sulfate into electrolyzed water, adjusting the pH value to 9 by using 50% of liquid caustic soda of a neutralizing agent, performing suction filtration, and discharging the filtrate after reaching the standard.
Table 2 example 2 combined treatment effect of electroless copper plating waste liquid and microetching waste liquid
While the foregoing is directed to embodiments of the present invention, it will be understood by those skilled in the art that various changes may be made without departing from the spirit and scope of the invention.
Claims (9)
1. A composite treatment method of complex copper waste liquid and microetching waste liquid is characterized by comprising the following steps:
step S1, mixing the complex copper waste liquid and the micro-etching waste liquid, adding a neutralizer to obtain a copper oxide suspension, adding an oxidant to the copper oxide suspension, and carrying out an oxidation reaction under the illumination condition to remove organic matters in the copper oxide suspension to obtain a first reaction liquid;
s2, carrying out solid-liquid separation on the first reaction solution to obtain a copper sulfate solution, carrying out solid-phase extraction on the copper sulfate solution to respectively obtain extracted water and an extractant enriched with copper ions, and carrying out backwashing on the extractant by using a hydrochloric acid solution to obtain a copper chloride regeneration solution;
s3, adding powdery active substances into the extracted water for mixing, and carrying out electrolytic reaction under the aeration condition to obtain a second reaction solution, wherein the powdery active substances comprise one or two of active carbon powder or powdery ion exchange resin;
s4, adding a precipitant and a neutralizer into the second reaction solution to perform precipitation reaction to form a coating with the powdery active substance as a core to obtain a third reaction solution, and performing solid-liquid separation on the third reaction solution to obtain the coating and reaction effluent respectively;
in step S1, the step of mixing the copper complex waste liquid and the microetching waste liquid and then adding a neutralizing agent to obtain a copper oxide suspension includes:
under the condition of stirring, mixing the complex copper waste liquid and the microetching waste liquid to obtain a first mixed liquid;
and adding a neutralizing agent into the first mixed solution to adjust the pH value of the first mixed solution to 2-3, and generating copper oxide precipitate from a small amount of copper in the first mixed solution to obtain a copper oxide suspension.
2. The composite processing method according to claim 1, characterized in that the processing method further comprises, between step S2 and step S3, the steps of:
s21, mixing the copper chloride regeneration solution with an acidic etching solution, adding an alkaline etching solution to adjust the pH value to 3-4, stirring and reacting at 40-70 ℃ to obtain a fourth reaction solution, and performing solid-liquid separation on the fourth reaction solution to obtain basic copper chloride solid.
3. The composite treatment method according to claim 1, wherein in step S1, the volume ratio of the complex copper waste liquid to the microetching waste liquid is 1 (3-6), the copper ion concentration of the complex copper waste liquid is 10-5000 mg/L, the COD concentration is 5000-50000mg/L, the copper ion concentration of the microetching waste liquid is 2000-12000 mg/L, and the COD concentration is 1000-10000 mg/L.
4. The composite treatment method according to claim 1, wherein in step S1, the oxidizing agent is a hydrogen peroxide solution with a mass percent of 20% to 30%, the amount of the hydrogen peroxide solution added is that the volume ratio of the copper oxide suspension is (4 to 8): 100, the illumination condition is ultraviolet light irradiation at 245nm to 285nm, the temperature of the oxidation reaction is 40 ℃ to 60 ℃, and the time of the oxidation reaction is 0.5 to 2 hours.
5. The composite treatment method according to claim 1, wherein in step S2, the extractant used for solid phase extraction is a copper ion adsorption resin, the mass concentration of the hydrochloric acid solution is 10% to 36.5%, and the pH value of the copper sulfate solution is 2 to 3.
6. The composite treatment method according to claim 1, wherein in step S3, the mass ratio of the powdery active material to the extract water is (0.05 to 0.2): 100, the current density of the electrolytic reaction is 100A/m2 to 800A/m2, and the electrolytic time is 1 to 4 hours.
7. The composite treatment method according to claim 1, wherein in step S4, the adding a precipitant and a neutralizer to the second reaction solution to perform a precipitation reaction comprises:
adding a precipitant into the second reaction solution under the condition of stirring to obtain a second mixed solution;
adding a neutralizing agent into the second mixed solution to adjust the pH value of the second mixed solution to 8-9 to obtain a third mixed solution;
and precipitating or filtering the third mixed solution to perform solid-liquid separation.
8. The composite treatment method according to claim 7, wherein in step S4, the precipitant comprises one or more of polyferric sulfate, polyferric chloride, polyaluminum chloride or ferrous sulfate, the neutralizer is a liquid alkali, and the mass ratio of the precipitant to the second reaction solution is (0.1-1.0): 100.
9. The composite treatment method according to claim 2, wherein in step S21, the volume ratio of the copper chloride regeneration liquid to the acidic etching liquid is 1 (1-4), and the reaction time is 0.5-2 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010915378.XA CN112209543B (en) | 2020-09-03 | 2020-09-03 | Composite treatment method of complex copper waste liquid and microetching waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010915378.XA CN112209543B (en) | 2020-09-03 | 2020-09-03 | Composite treatment method of complex copper waste liquid and microetching waste liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112209543A CN112209543A (en) | 2021-01-12 |
| CN112209543B true CN112209543B (en) | 2022-12-20 |
Family
ID=74049080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010915378.XA Active CN112209543B (en) | 2020-09-03 | 2020-09-03 | Composite treatment method of complex copper waste liquid and microetching waste liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112209543B (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007297662A (en) * | 2006-04-28 | 2007-11-15 | Nittetsu Mining Co Ltd | Method for producing high purity electrolytic copper from ammonia-based copper etching waste liquid |
| CN101391800B (en) * | 2007-09-20 | 2011-06-15 | 深圳市东江环保股份有限公司 | Method for producing basic copper chloride, cupric sulfate pentahydrate from copper-containing etching waste liquid |
| JP5307478B2 (en) * | 2008-08-21 | 2013-10-02 | 水ｉｎｇ株式会社 | Method and apparatus for recovering copper-containing solid from copper-containing acidic waste liquid |
| JP5808132B2 (en) * | 2011-04-19 | 2015-11-10 | 水ｉｎｇ株式会社 | Treatment and recovery method for copper-containing acidic waste liquid and equipment therefor |
| CN102303917B (en) * | 2011-08-25 | 2014-01-01 | 石祥阁 | Method for mixed treatment of waste liquid from acid etching and micro etching of printed circuit boards |
| CN108249649B (en) * | 2016-12-29 | 2021-05-04 | 南京源泉环保科技股份有限公司 | Chemical copper plating waste liquid resource utilization method |
| CN108862365A (en) * | 2017-05-09 | 2018-11-23 | 广东省博罗县湘澧精细化工有限公司 | A kind of circuit board acidic and alkaline waste etching solution recovery processing technique |
-
2020
- 2020-09-03 CN CN202010915378.XA patent/CN112209543B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112209543A (en) | 2021-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105858987B (en) | The recycling treatment process of pure water pure nickel is reclaimed from electronickelling poaching wastewater | |
| CN109678196B (en) | Method for fully recycling anions and cations in microetching waste liquid | |
| CN106927547B (en) | Method for removing complex heavy metal by reducing and breaking complexing of magnetic iron-based material | |
| CN109868476B (en) | Method for recycling etching liquid containing copper ions and nitrate radicals | |
| JP6990348B1 (en) | How to recover and reuse nickel and phosphorus resources in electroless nickel plating waste liquid | |
| CN105565533A (en) | Zero-discharge on-line treatment process for preparing deionized water from copper sulphate electroplating waste water | |
| CN101284692A (en) | Treating method of washes of copper deposition in production process of printed circuit board | |
| WO2016029613A1 (en) | Method and apparatus for purifying desulfurization lead plaster filtrate | |
| CN106542670A (en) | A kind of wet desulphurization waste water zero discharge treatment process | |
| WO2024113796A1 (en) | Membrane-method treatment process for tin-containing wastewater generated during pcb production process | |
| WO2024113798A1 (en) | Membrane treatment technology for copper-containing wastewater generated in pcb production process | |
| CN112708885A (en) | Recycling method and system for copper-etching waste nitric acid | |
| CN108249649B (en) | Chemical copper plating waste liquid resource utilization method | |
| CN110616327A (en) | Method and device for recovering elemental nickel from nickel-containing wastewater | |
| CN112209543B (en) | Composite treatment method of complex copper waste liquid and microetching waste liquid | |
| CN102531257B (en) | Recycling device of inorganic wastewater and the recycling method of inorganic wastewater using the solar heat | |
| CN112813268A (en) | PCB (printed circuit board) copper electroplating and acid etching copper resource recycling method | |
| CN110790427A (en) | Treatment and recovery process of alkaline etching wastewater | |
| CN112777774A (en) | Nickel-containing wastewater treatment device and nickel-containing wastewater treatment method | |
| CN111333152A (en) | Method for treating high-concentration nickel-phosphorus-containing organic waste liquid through electrolytic oxidation | |
| CN102942274B (en) | Treatment method of saline and alkaline wastewater in copper oxide production process | |
| CN106396164A (en) | Industrial acidic wastewater treatment process | |
| CN111500872A (en) | Recovery treatment method of low-concentration palladium-containing waste liquid | |
| CN115652114A (en) | Recycling process of thallium in thallium-containing solution | |
| CN211255522U (en) | Nickel-containing wastewater treatment device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 518000 building a, No.18 Industrial Avenue, No.3 Industrial Zone, Bitou community, Songgang street, Bao'an District, Shenzhen City, Guangdong Province Applicant after: Shenzhen Environmental Protection Technology Group Co.,Ltd. Address before: No. 181, Longwei Road, Futian District, Shenzhen, Guangdong 518000 Applicant before: Shenzhen Environmental Protection Technology Group Co.,Ltd. Address after: No. 181, Longwei Road, Futian District, Shenzhen, Guangdong 518000 Applicant after: Shenzhen Environmental Protection Technology Group Co.,Ltd. Address before: No. 181, Longwei Road, Futian District, Shenzhen, Guangdong 518000 Applicant before: SHENZHEN SHENTOU ENVIRONMENT TECHNOLOGY Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |