CN110055537A - A kind of method for reclaiming of PCB nitric acid spent solder stripper - Google Patents
A kind of method for reclaiming of PCB nitric acid spent solder stripper Download PDFInfo
- Publication number
- CN110055537A CN110055537A CN201910428326.7A CN201910428326A CN110055537A CN 110055537 A CN110055537 A CN 110055537A CN 201910428326 A CN201910428326 A CN 201910428326A CN 110055537 A CN110055537 A CN 110055537A
- Authority
- CN
- China
- Prior art keywords
- tin
- copper
- nitric acid
- pcb
- waste liquor
- 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.)
- Granted
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 46
- 229910017604 nitric acid Inorganic materials 0.000 title claims abstract description 46
- 229910000679 solder Inorganic materials 0.000 title claims abstract description 21
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 147
- 229910052718 tin Inorganic materials 0.000 claims abstract description 145
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000002699 waste material Substances 0.000 claims abstract description 59
- 239000007788 liquid Substances 0.000 claims abstract description 48
- 229910052802 copper Inorganic materials 0.000 claims abstract description 40
- 239000010949 copper Substances 0.000 claims abstract description 40
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000008929 regeneration Effects 0.000 claims abstract description 23
- 238000011069 regeneration method Methods 0.000 claims abstract description 23
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000012528 membrane Substances 0.000 claims abstract description 15
- 239000008139 complexing agent Substances 0.000 claims abstract description 12
- 230000009977 dual effect Effects 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 12
- 238000001556 precipitation Methods 0.000 claims abstract description 11
- 238000000746 purification Methods 0.000 claims abstract description 10
- 238000004090 dissolution Methods 0.000 claims abstract description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 7
- 238000000151 deposition Methods 0.000 claims abstract description 6
- 230000008021 deposition Effects 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 41
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 34
- 229910052742 iron Inorganic materials 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 22
- 239000013049 sediment Substances 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 11
- 239000011814 protection agent Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 8
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 239000003014 ion exchange membrane Substances 0.000 claims description 6
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- YDCFOUBAMGLLKA-UHFFFAOYSA-N 2,6,7-trihydroxy-9-phenylxanthen-3-one Chemical compound C1=2C=C(O)C(O)=CC=2OC2=CC(=O)C(O)=CC2=C1C1=CC=CC=C1 YDCFOUBAMGLLKA-UHFFFAOYSA-N 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 5
- 229960002089 ferrous chloride Drugs 0.000 claims description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 229910001432 tin ion Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 238000005341 cation exchange Methods 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000002659 electrodeposit Substances 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-N iron;hydrochloride Chemical compound Cl.[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- 239000004251 Ammonium lactate Substances 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 229940059265 ammonium lactate Drugs 0.000 claims description 2
- 235000019286 ammonium lactate Nutrition 0.000 claims description 2
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 claims description 2
- 239000003010 cation ion exchange membrane Substances 0.000 claims description 2
- 238000005363 electrowinning Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims 2
- 235000019698 starch Nutrition 0.000 claims 2
- 239000008107 starch Substances 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 17
- 238000004070 electrodeposition Methods 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 4
- 150000001455 metallic ions Chemical class 0.000 abstract description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract description 2
- 239000003223 protective agent Substances 0.000 abstract description 2
- 239000012629 purifying agent Substances 0.000 abstract description 2
- 239000011135 tin Substances 0.000 description 123
- 238000004064 recycling Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 8
- 239000012530 fluid Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- -1 flocculant Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910016874 Fe(NO3) Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010021703 Indifference Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- ORTNWICOMQLICI-UHFFFAOYSA-N [Fe].[Cu].[Sn] Chemical compound [Fe].[Cu].[Sn] ORTNWICOMQLICI-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/10—Halides
-
- 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
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/24—Alloys obtained by cathodic reduction of all their ions
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Electrochemistry (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
A kind of PCB nitric acid spent solder stripper method for reclaiming is separated metal ion with metal ion capturing agent from tin removal waste liquor, the further purification and impurity removal of the tin removal waste liquor of separating metal ions, then nitric acid is added, copper protective agent, tin complexing agent is configured to regeneration tin stripping liquid and is back to use PCB and moves back tin production line, isolated precipitation by metallic ion object is dissolved with hydrochloric acid, then electrolytic deposition is carried out to metal ion solution with electrolyzer with dual membranes and three chambers to recycle to obtain metallic tin, metallic copper, liquor ferri trichloridi, hydrochloric acid solution, hydrochloric acid solution reuse is to precipitation by metallic ion object dissolution process；This method not only isolates metal ion from tin removal waste liquor and obtains metallic tin, copper and ferric chloride purifying agent by method for electrodeposition, but also to the further impurity and purification of tin removal waste liquor, it adds after effective component reuse and moves back tin production line to PCB, realize nitric acid spent solder stripper regeneration, it is not only environmentally friendly, and cost can be greatly reduced.
Description
Technical field
The present invention relates to PCB tin removal waste liquor technical field of regeneration, and in particular, to a kind of PCB nitric acid spent solder stripper
Method for reclaiming.
Background technique
PCB (printed wiring board) is the supporter of electronic product component, is that the most basic hardware of current information-intensive society carries
Body, PCB (printed wiring board) industry are the pillar industry of China's electronics and IT industry, growth rate and electronics and information industry in same
Ratio increases.The PCB production practices of decades, production technology has very big improvement, but draws line map in the circuit board
The method that method still uses chemical medicinal liquid to etch.It is 5-8 μm that a layer thickness, which need to be plated, in patterned surface when outer layer Production of prints
Tin again dissolves the tin on surface layer after etch-forming.Nitric acid type etching agent is the leading dosage form of PCB production at present, generally with nitric acid
It is selection there are also sustained release agents, the effect such as nitric acid stabilizer, nitrogen oxides inhibitor and sulfonate, ferric nitrate for principal component
Dissolves surface layer tin and avoid etch pattern copper face to property.
During moving back tin, after the Theil indices of solution reach a certain concentration (usual high 100g/L), the decline of tin ability is moved back, from
It moves back and is discharged in tin equipment and becomes tin removal waste liquor.Tin removal waste liquor is that a kind of acidity for generating in PCB production process is very high, and contains
There is the dangerous waste liquid of the gas chromatographies such as the metallic compounds such as a large amount of tin, copper, iron and stabilizer, corrosion inhibiter, it is complex in composition, it is comprehensive
Recovery difficult is big.
Current domestic PC B enterprise year generates 50,000 tons or more of tin removal waste liquor according to statistics, currently, processing tin removal waste liquor patent
There are many method, refer to add carbonic acid into tin removal waste liquor in Chinese invention patent ZL101532096A and ZL 102775197A
The method for the method Separation of Tin that sodium, sodium hydroxide, ammonia precipitation process are boiled in conjunction with heating；In ZL101497458A and ZL1569644A
It refers to addition surfactant, flocculant, sodium hydroxide and barium chloride etc. and obtains barium stannate；It is referred in ZL101918133A
Add the method that electrolyte+distillation method obtains sodium stannate and stannic oxide；Addition lime is referred in ZL102086073A
Slurry+evaporating concentrating method separates metal cations, and adds the recycling processing method that additive realizes full recycling and zero-emission；
It is referred in ZL1288075 with+extraction and separation are boiled, ionic adsorption+electronation precipitates+is boiled equal physics+Chemical Decomposition and returned
The method for receiving metal ion, rear end add a certain amount of additive and realize recycling for tin removal waste liquor；ZL202080977,
A kind of adding sodium hydroxide precipitating+plate-type filtering+electrolysis mentions copper+is referred in CN102766883A and ZL202499890 adds one
Determine the method and apparatus that raw material realizes separation metal cation and recycles tin stripper；Patent CN102492860A and
The method by isolated tin mud of chemical substances such as addition electrolyte, flocculants is referred in CN102515259A.
From above processing method it can be found that recycling valuable metal in tin removal waste liquor primarily directed to property, for example add
Add chemical substance such as electrolyte, flocculant, alkali neutralization, the tin in extractant recycling tin removal waste liquor, copper, iron.Tin removal waste liquor nitre
Acid concentration is 4.0-4.5mol/L (being newly 5.5-6.0mol/L with concentration of nitric acid in tin-stripping solution), and traditional processing method is by nitre
Acidification is that nitrate discharges, in tin stripping liquid the utilization rate of nitric acid less than 35%, although have publication introduction by evaporation or
Extracting process recycles nitric acid, but rarely has industrialized report because operating cost is high or the concentration of nitric acid of recycling is too low.CN
103436885 A by tin removal waste liquor add organic acid come so that tin precipitate, then plus after flocculant be separated by solid-liquid separation,
Separating obtained filtrate adds nitric acid etc. and tin removal waste liquor recovery is made to move back tin ability, but from the point of view of practical experience, because because of organic acid, wadding
Solidifying residual of the agent in filtrate will affect move back tin after copper surface quality, while tin stripping liquid is regenerated compared with new tin stripping liquid, in work
A large amount of tin mud can be generated in work and are deposited in cylinder bottom, and blocking moves back tin nozzle, seriously affects PCB production efficiency, can in production application
Row is not high, and the valuable metal in addition recycled from tin removal waste liquor is mixed compound, needs further to divide by pyrometallurgical smelting
From tin, copper, iron, not only cost recovery is high, and the risk of secondary pollution environment is inevitably present in smelting process.
Summary of the invention
To overcome the problems, such as present on, the present invention provides a kind of method for reclaiming of PCB nitric acid spent solder stripper, should
Method is separated metal ion with metal ion capturing agent from tin removal waste liquor, and the tin removal waste liquors of separating metal ions is into one
Purification and impurity removal is walked, nitric acid, copper protective agent, tin complexing agent is then added and is configured to regeneration tin stripping liquid and be back to use PCB and move back tin production line,
Isolated precipitation by metallic ion object is dissolved with hydrochloric acid, electricity then is carried out to metal ion solution with electrolyzer with dual membranes and three chambers
Solution deposition recycling obtains metallic tin, metallic copper, liquor ferri trichloridi, hydrochloric acid solution, hydrochloric acid solution reuse to precipitation by metallic ion
Object dissolution process；This method not only isolated from tin removal waste liquor metal ion and by method for electrodeposition obtain metallic tin,
Copper and ferric chloride purifying agent, but also to the further impurity and purification of tin removal waste liquor add after effective component reuse to PCB and move back tin
Production line realizes nitric acid spent solder stripper regeneration.
In order to achieve the above object, nitric acid spent solder stripper method for reclaiming of the present invention, includes the following steps:
(1) in nitric acid spent solder stripper tin copper metal ion precipitation and separation: by a certain amount of tin removal waste liquor be added react
Slot opens stirring, and metal ion capturing agent is added and makes tin, copper, ferrous ion precipitating, tin copper and iron mixed precipitation is obtained by filtration
Object and filtrate；
In order to enable tin copper is effective to obtain precipitation and separation, metal ion capturing agent described in this step is can be with tin copper in nitric acid body
Lower organic acid, the acylate for forming precipitating of system, including oxalic acid, acetic acid, lactic acid, ammonium oxalate, ammonium acetate, ammonium lactate, in order to make
It obtains the effective precipitation and separation of tin copper and does not influence the quality of tin removal waste liquor regeneration, the additive amount of capturing agent is tin removal waste liquor body
Long-pending 1%-6%, capturing agent are stirred to react -6 hours 2 hours after being added, so that reaction is more abundant, after stopping stirring, stand 12-
It is separated by solid-liquid separation after 24 hours (A-si seasoning effect being played, so that tin copper and iron sediment is easier to carry out being separated by solid-liquid separation), obtains tin
Copper and iron sediment and filtered fluid；
(2) tin removal waste liquor filtrate deep impurity-removing purifies: it is net that cleaner progress deep impurity-removing is added in filtrate obtained by step (1)
Change, belongs to organic matter because remaining the copper-protection agent of failure, tin complexing agent, excessive metal ion capturing agent in tin removal waste liquor, this
Step preferably has the cleaner of suction-operated, including active carbon, sawdust slag, diatomite, the ratio of cleaner addition to organic matter
Example is the 0.5%-2% of filtrate volume, is stirred 2-6 hours after addition, after being then allowed to stand 12-24 hours, after purification is obtained by filtration
Tin removal waste liquor；
(3) allotment nitric acid type moves back tin regenerated liquid: surge-tank is added in tin removal waste liquor after purification obtained by step (2), adds nitre
Acid, promotor, tin complexing agent, copper-protection agent etc. are deployed into regeneration tin stripping liquid,
In order to enable regeneration tin stripping liquid not increment (tin removal waste liquor after regenerating with newly match to move back tin midnight's volume suitable), nitre
The nitric acid that sour preferred mass concentration is 62% or more, in order to which that accelerates regenerated liquid moves back tin speed, the preferred ferric nitrate of promotor or three
Iron chloride needs to be added tin complexing agent in regeneration tin stripping liquid in order to enable moving back the tin stripping liquid after tin does not generate tin mud precipitating, excellent
Select phenylfluorone, additive amount is the 0.005%-0.05% for regenerating tin stripping liquid volume, in order to slow down regeneration tin stripping liquid to moving back copper after tin
The corrosion in face regenerates and needs to add copper-protection agent, the preferred thiocarbamide of copper-protection agent, Ben and San Dan Cuo in tin stripping liquid, and additive amount is that regeneration is moved back
The 0.05%-0.15% of tin liquor volume；
(4) dissolution of tin copper and iron sediment: being first added a certain amount of hydrochloric acid in a kettle, and the additive amount of hydrochloric acid is tin copper
Iron precipitate is completely dissolved 1.1-1.2 times of required stoichiometry, opens stirring, and step (1) resulting tin copper and iron is then added
Mixed sediment is warming up to 90-100 degrees Celsius, so that sediment is completely dissolved, adds pure water and obtains tin ion concentration and maintain
The stannic chloride copper and iron hydrochloric acid solution of 6%-9% concentration；
(5) tin copper is recycled using electrolyzer with dual membranes and three chambers electrolytic deposition: stannic chloride copper and iron solution obtained by step (4) is injected
The hydrochloric acid solution of 0.5%-1% mass concentration, anode chamber's injection are injected in the cathode chamber of electrolyzer with dual membranes and three chambers, intermediate isolating room
The sulfuric acid solution of 0.5%-5% mass concentration, cathode use titanium plate, and anode is using the titanium insoluble anode for being coated with noble metal, in room
Be electrolysed under conditions of temperature, cathode produces successively copper electrowinning, tin metal on plate, the chloride ion that cathode chamber generates by anion from
Proton exchange enters intermediate compartment, and anode generates oxygen and hydrogen ion, and hydrogen ion enters intermediate compartment through cation-exchange membrane,
Electrolysis terminates to extract intermediate compartment hydrochloric acid solution into dissolution process of the reuse to step (4) tin copper and iron sediment, cathode chamber copper and tin out
The mixed solution of iron chloride frerrous chloride is obtained after electrodeposit；
Electrolyzer with dual membranes and three chambers anode chamber and intermediate compartment are separated with cation ion-exchange membrane, intermediate compartment and cathode chamber
Separated with anionic ion exchange membrane；
The electrochemical reaction that this process mainly occurs is:
Anode chamber: 2H2O→4H++O2
Cathode chamber: SnCl4→Sn+4Cl-CuCl2→Cu+2Cl-
Middle compartment: H++Cl-→HCl
(6) ferric trichloride is prepared:
Iron chloride solution of ferrous chloride obtained by step (5) is passed through oxygen caused by step (5) anode chamber and makes ferrous iron
Further oxidation obtains liquor ferri trichloridi, and liquor ferri trichloridi obtained by this step may be used as the flocculant of sewage treatment.
The beneficial effect that the present invention is different from the prior art is:
1, by the deep purifying of the tin removal waste liquor to precipitation and separation tin copper after ferrous, residual failure additive pair is solved
The influence of tin rear surface is moved back, further, deep purifying has also been removed influence of the excessive metal capturing agent to tin effect is moved back, regenerated liquid
Adding tin complexing agent, copper-protection agent etc. makes regenerated liquid move back tin speed, erosion copper speed, move back copper surface and new tin stripping liquid indifference after tin
Not, so that tin removal waste liquor regeneration technology is industrially feasible, the risk of tin removal waste liquor transfer secondary pollution environment is avoided；
2, tin removal waste liquor recycling gained tin copper and iron mixed compound is further processed, and recycling obtains metallic tin copper and tri-chlorination
Silicic acid avoids high energy consumption, the air pollution problems inherent of traditional fire concentrate tin copper and iron.
Detailed description of the invention
The drawings described herein are used to provide a further understanding of the present application, constitutes part of this application, this Shen
Illustrative embodiments and their description please are not constituted an undue limitation on the present application for explaining the application.In the accompanying drawings:
Fig. 1 is the process flow chart of PCB nitric acid spent solder stripper method for reclaiming of the invention；
Fig. 2 is the structural schematic diagram of electrolyzer with dual membranes and three chambers of the invention.
Specific embodiment
Embodiment 1
2000L tin removal waste liquor is added and reacts by certain PCB factory tin removal waste liquor stanniferous 6%, copper 0.5%, nitric acid 4.5mol/L
Kettle opens stirring, is added 20Kg oxalic acid (1% waste liquid volume ratio), is stirred to react 5 hours, stops stirring, it is small to staticly settle 12
When, it is separated by solid-liquid separation, obtains tin copper and iron mixed sediment and filtered fluid；1500L filtered fluid is pumped into reaction kettle, 30Kg (2% is added
Filtrate volume ratio) diatomite stirring 2 hours, 24 hours are stood, purified tin removal waste liquor is obtained by filtration；After 1000L is purified
Tin removal waste liquor is pumped into regeneration tin stripping liquid surge-tank, opens stirring, and the nitric acid that addition mass concentration is 68%, which is deployed to regeneration, moves back tin
Liquid acid concentration is 6mol/L, is added 0.5Kg tin complexing agent phenylfluorone (waste liquid volume ratio 0.05%), three nitrogen of 5Kg copper-protection agent benzo
Cuo, 50 kilograms are moved back tin promotor Fe(NO3)39H2O and are configured to nitric acid regeneration type tin stripping liquid reuse and move back tin production line to PCB；
Embodiment 2
Reaction kettle is added in gained tin removal waste liquor after the nitric acid regeneration type tin stripping liquid reuse production line of 1000L embodiment 1, is opened
Stirring is opened, is added 60Kg ammonium oxalate (2% waste liquid volume ratio), is stirred to react 5 hours, stops stirring, staticly settles 15 hours, Gu
Liquid separation, obtains tin copper and iron mixed sediment and filtered fluid；800L filtered fluid is pumped into reaction kettle, 8Kg (1% filtrate body is added
Product ratio) stirring of sawdust slag 2 hours, 15 hours are stood, purified tin removal waste liquor is obtained by filtration；Tin removal waste liquor after 800L is purified
It is pumped into regeneration tin stripping liquid surge-tank, opens stirring, the nitric acid that mass concentration is 68% is added and deploys to regeneration tin stripping liquid acid concentration
For 6mol/L, it is added 0.08Kg tin complexing agent phenylfluorone (waste liquid volume ratio 0.01%), 8Kg copper-protection agent thiocarbamide, 40 kilograms are moved back tin
Promotor ferric trichloride is configured to nitric acid regeneration type tin stripping liquid reuse and moves back tin production line to PCB；
Embodiment 3
2000L tin removal waste liquor is added and reacts by certain PCB factory tin removal waste liquor stanniferous 8%, copper 0.2%, nitric acid 4.1mol/L
Kettle opens stirring, is added 120Kg oxalic acid (6% waste liquid volume ratio), is stirred to react 5 hours, stops stirring, it is small to staticly settle 24
When, it is separated by solid-liquid separation, obtains tin copper and iron mixed sediment and filtered fluid；1500L filtered fluid is pumped into reaction kettle, 7.5Kg is added
(0.5% filtrate volume ratio) active carbon stirs 2 hours, stands 12 hours, purified tin removal waste liquor is obtained by filtration；By 1000L
Tin removal waste liquor is pumped into regeneration tin stripping liquid surge-tank after purification, opens stirring, and the nitric acid that mass concentration is 68% is added and deploys to again
Raw tin stripping liquid acid concentration is 6mol/L, is added 0.05Kg tin complexing agent phenylfluorone (waste liquid volume ratio 0.005%), 15Kg copper-protection agent
Ben and San Dan Cuo, 30 kilograms are moved back tin promotor Fe(NO3)39H2O, and 20 kilograms of ferric trichlorides are configured to nitric acid regeneration type tin stripping liquid
Reuse moves back tin production line to PCB；
Embodiment 4
Attached drawing 1-2 is please referred to, takes tin copper and iron sediment obtained by a certain amount of embodiment 1-3, stoichiometrically 1.1 extraordinarily
Enter hydrochloric acid, stirring and dissolving under conditions of 90 degrees Celsius adds pure water to be deployed into the stannic chloride copper and iron that tin ion mass concentration is 6%
Hydrochloric acid solution, by the cathode chamber 1 of solution injection electrolyzer with dual membranes and three chambers, intermediate compartment 3 injects 0.5% mass concentration
The sulfuric acid solution of 0.5% mass concentration injects in hydrochloric acid solution, anode chamber 2, and room temperature (25 degrees centigrade) opens electrolytic deposition gold
Belong to copper and tin, the chloride ion that cathode chamber 1 generates enters intermediate compartment 3 by anionic ion exchange membrane 4, and anode generates oxygen and hydrogen
Ion, hydrogen ion enter intermediate compartment 3 through cation-exchange membrane 5, and electrolysis terminates to extract back out the hydrochloric acid solution of intermediate compartment 3
With the dissolution process to tin copper and iron sediment, the mixing that iron chloride frerrous chloride is obtained after cathode chamber copper and tin electrodeposit is molten
Compartment 3 in liquid is enriched with hydrochloric acid, obtains metal copper and tin on cathode plate, and tin copper electrodeposition terminates, and extracts cathode chamber 1 out respectively
Lean electrolyte (solution of ferrous chloride) and 3 hydrochloric acid solution of intermediate compartment are spare；
Embodiment 5
Attached drawing 1-2 is please referred to, takes tin copper and iron sediment obtained by a certain amount of embodiment 1-3, stoichiometrically 1.2 extraordinarily
Enter hydrochloric acid (in addition the preferential hydrochloric acid solution collected using 4 intermediate compartment of embodiment, insufficient section are added) in 100 degrees Celsius of items
Stirring and dissolving under part adds pure water to be deployed into the hydrochloric acid solution for the stannic chloride copper and iron that tin ion mass concentration is 9%, which is infused
Enter in the cathode chamber 1 of electrolyzer with dual membranes and three chambers, intermediate compartment 3 injects the hydrochloric acid solution of 1% mass concentration, the injection of anode chamber 2 1%
The sulfuric acid solution of mass concentration, room temperature (25 degrees centigrade) open electro-deposition of metal copper and tin, the chloride ion that cathode chamber 1 generates
Enter intermediate compartment 3 by anionic ion exchange membrane 4, anode generates oxygen and hydrogen ion, and hydrogen ion is through cation exchange
Film 5 enters intermediate compartment 3, and electrolysis terminates the dissolution work that the hydrochloric acid solution of intermediate compartment 3 is extracted out to reuse to tin copper and iron sediment
Sequence, oxygen are passed through 4 lean electrolyte of embodiment and aoxidize so that solution of ferrous chloride is oxidized to liquor ferri trichloridi, and intermediate compartment 3 is rich
Collect hydrochloric acid, obtain metal copper and tin on cathode plate, tin copper electrodeposition terminates, and extracts 1 lean electrolyte of cathode chamber and centre out respectively
Compartment hydrochloric acid solution is spare；
Embodiment 6
Attached drawing 1-2 is please referred to, takes tin copper and iron sediment obtained by a certain amount of embodiment 1-3, stoichiometrically 1.15 times
Hydrochloric acid (in addition the preferential hydrochloric acid solution using 4 intermediate compartment of embodiment collection 3, insufficient section are added) is added at 95 degrees Celsius
Under the conditions of stirring and dissolving, add pure water be deployed into tin ion mass concentration be 8% stannic chloride copper and iron hydrochloric acid solution, by the solution
It injects in the cathode chamber 1 of electrolyzer with dual membranes and three chambers, intermediate compartment 3 injects the hydrochloric acid solution of 0.8% mass concentration, 2 note of anode chamber
Enter the sulfuric acid solution of 5% mass concentration, room temperature (25 degrees centigrade) opens electro-deposition of metal copper and tin, what cathode chamber 1 generated
Chloride ion enters intermediate compartment 3 by anionic ion exchange membrane 4, and anode generates oxygen and hydrogen ion, hydrogen ion through sun from
Proton exchange 5 enters intermediate compartment 3, and electrolysis terminates to extract out the hydrochloric acid solution of intermediate compartment 3 reuse to tin copper and iron sediment
Dissolution process, the oxygen that anode generates are passed through 4 lean electrolyte of embodiment and aoxidize so that solution of ferrous chloride is oxidized to ferric trichloride
Solution, intermediate compartment 3 are enriched with hydrochloric acid, obtain metal copper and tin on cathode plate, tin copper electrodeposition terminates, and extracts cathode chamber out respectively
1 lean electrolyte and 3 hydrochloric acid solution of intermediate compartment are spare.
In conclusion the invention has the following advantages that
1, the tin copper in tin removal waste liquor is not only efficiently separated out, further to the processing of tin removal waste liquor filtrate, so that moving back tin
Thin stillage recycling has achieved the effect that as new tin stripping liquid；
2, hazardous waste realizes that plant area recycles, and no increment waste liquid outlet is environmentally friendly；
3, the existing etching production method of existing PCB production line is not changed, is easily realized and is promoted；
4, metal copper and tin is recycled by dual membranes and three chambers electrolytic deposition, reduces traditional pyrometallurgical smelting Separation of Tin process for copper pollution
The risk of environment.
The upper only embodiments of the present invention, are not intended to restrict the invention.For those skilled in the art
For, the invention may be variously modified and varied.All any modifications made in spirit and principles of the present invention are equally replaced
It changes, improve, should all be included within scope of the presently claimed invention.
Claims (10)
1. a kind of PCB nitric acid spent solder stripper method for reclaiming, which comprises the following steps:
(1) in nitric acid spent solder stripper tin copper metal ion precipitation and separation: by a certain amount of tin removal waste liquor be added reactive tank, open
Open stirring, metal ion capturing agent be added and makes tin, copper, ferrous ion precipitating, be obtained by filtration tin copper and iron mixed sediment and
Filtrate；
(2) tin removal waste liquor filtrate deep impurity-removing purifies: cleaner is added in filtrate obtained by step (1) and carries out deep impurity-removing purification；
(3) allotment nitric acid type moves back tin regenerated liquid: surge-tank is added in tin removal waste liquor after purification obtained by step (2), nitric acid is added, promotees
Regeneration tin stripping liquid is deployed into agent, tin complexing agent, copper-protection agent；
(4) dissolution of tin copper and iron sediment: being first added a certain amount of hydrochloric acid in a kettle, and the additive amount of hydrochloric acid is heavy for tin copper and iron
Starch is completely dissolved 1.1-1.2 times of required stoichiometry, opens stirring, and step (1) resulting tin copper and iron mixing is then added
Sediment is warming up to 90-100 degrees Celsius, so that sediment is completely dissolved, adds pure water and obtains tin ion concentration and maintain 6%-
The stannic chloride copper and iron hydrochloric acid solution of 9% concentration；
(5) tin copper is recycled using electrolyzer with dual membranes and three chambers electrolytic deposition: stannic chloride copper and iron solution obtained by step (4) is injected into double films
The cathode chamber of three Room electrolytic cells, is electrolysed at room temperature, and cathode produces successively copper electrowinning, tin metal on plate, cathode chamber
The chloride ion of generation enters intermediate compartment by anionic ion exchange membrane, and anode generates oxygen and hydrogen ion, and hydrogen ion penetrates
Cation-exchange membrane enters intermediate compartment, and electrolysis terminates the extraction reuse of intermediate compartment hydrochloric acid solution is heavy to step (4) tin copper and iron
The dissolution process of starch obtains the mixed solution of iron chloride frerrous chloride after cathode chamber copper and tin electrodeposit；
(6) it prepares ferric trichloride: iron chloride solution of ferrous chloride obtained by step (5) is passed through caused by step (5) anode chamber
Oxygen makes ferrous further oxidation obtain liquor ferri trichloridi.
2. PCB nitric acid spent solder stripper method for reclaiming according to claim 1, it is characterised in that: the step 1
Metal ion capturing agent in oxalic acid, acetic acid, lactic acid, ammonium oxalate, ammonium acetate and ammonium lactate any one or it is several
Composition.
3. PCB nitric acid spent solder stripper method for reclaiming according to claim 1 or 2, it is characterised in that: the step
(1) additive amount of metal ion capturing agent be tin removal waste liquor volume 1%-6%, capturing agent be added after be stirred to react 2 hours-
6 hours, so that reaction is more abundant, after stopping stirring, stand 12-24 hours.
4. PCB nitric acid spent solder stripper method for reclaiming according to claim 1, it is characterised in that: the step (2)
Cleaner in active carbon, sawdust slag and diatomite any one or several compositions.
5. PCB nitric acid spent solder stripper method for reclaiming according to claim 4, it is characterised in that:, the cleaner
The ratio of addition is the 0.5%-2% of filtrate volume, stirs 2-6 hours after addition, after being then allowed to stand 12-24 hours, filters
Tin removal waste liquor after to purification.
6. PCB nitric acid spent solder stripper method for reclaiming according to claim 1, it is characterised in that: the step (3)
In nitric acid mass concentration be 62% or more.
7. PCB nitric acid spent solder stripper method for reclaiming according to claim 1, it is characterised in that: the step (3)
In any one or two kind of the promotor in ferric nitrate and ferric trichloride composition.
8. PCB nitric acid spent solder stripper method for reclaiming according to claim 1, it is characterised in that: the step (3)
In tin complexing agent be phenylfluorone, the additive amount of the tin complexing agent be regeneration tin stripping liquid volume 0.005%-0.05%.
9. PCB nitric acid spent solder stripper method for reclaiming according to claim 1, it is characterised in that: the step (3)
In any one or two kind of the copper-protection agent in thiocarbamide and Ben and San Dan Cuo composition, the copper-protection agent additive amount is
Regenerate the 0.05%-0.15% of tin stripping liquid volume.
10. PCB nitric acid spent solder stripper method for reclaiming according to claim 1, it is characterised in that: the step
(5) in, the anode chamber of the electrolyzer with dual membranes and three chambers and intermediate compartment are separated with cation ion-exchange membrane, intermediate compartment and yin
Pole room is separated with anionic ion exchange membrane, and the hydrochloric acid solution of 0.5%-1% mass concentration, anode chamber's note are injected in intermediate isolating room
Enter the sulfuric acid solution of 0.5%-5% mass concentration, cathode uses titanium plate, and anode is using the titanium insoluble anode for being coated with noble metal.
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| PCT/CN2019/123786 WO2020233104A1 (en) | 2019-05-22 | 2019-12-06 | Recycling method for pcb nitric acid tin-stripping waste liquid |
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768742A (en) * | 2009-12-31 | 2010-07-07 | 惠州市雄越保环科技有限公司 | Regenerated acidic etching solution, copper recycling method and special device thereof |
| CN102002729A (en) * | 2009-09-01 | 2011-04-06 | 金益世股份有限公司 | Copper-containing waste etching solution treatment method and etching solution regeneration method |
| CN102775197A (en) * | 2012-08-13 | 2012-11-14 | 深圳市危险废物处理站有限公司 | Method for preparing fertilizer-grade ammonium nitrate concentrated solution by use of mother liquid after immersion tin of tin-stripping waste liquid of circuit board |
| CN102925880A (en) * | 2012-11-16 | 2013-02-13 | 宁波祈禧电器有限公司 | Preparation method of transparent tin antimony oxide electric heating film |
| CN103031437A (en) * | 2011-09-29 | 2013-04-10 | 深圳市格林美高新技术股份有限公司 | Processing method for waste liquid from stripping tin scolding |
| CN103194769A (en) * | 2013-04-22 | 2013-07-10 | 北京工业大学 | Electrolytic device and method for recovering high-purity copper from waste circuit board |
| CN103436885A (en) * | 2013-09-25 | 2013-12-11 | 深圳市瑞世兴科技有限公司 | Method for recycling tin removal waste liquor |
| CN104894599A (en) * | 2015-06-23 | 2015-09-09 | 成都虹华环保科技股份有限公司 | Recycling process of tin-removing waste liquid |
| CN205223353U (en) * | 2015-11-06 | 2016-05-11 | 陶克（苏州）机械设备有限公司 | Tin waste liquid regeneration facility is shelled to nitric acid type |
| CN105723005A (en) * | 2013-07-08 | 2016-06-29 | 阿尔法金属公司 | Metal recovery |
| CN106319519A (en) * | 2016-08-24 | 2017-01-11 | 盛隆资源再生（无锡）有限公司 | Method for cyclically preparing tin stripping solution and electroplated tin by utilizing waste tin stripping solution |
| CN207109135U (en) * | 2017-08-15 | 2018-03-16 | 东莞市同欣表面处理科技有限公司 | The main salt ion electrolytic recovery device of electroplating solution |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014214378A (en) * | 2013-04-30 | 2014-11-17 | 三菱マテリアル株式会社 | METHOD FOR RECOVERING COPPER FROM Sn PLATING STRIPPING WASTE LIQUID |
| CN110055537B (en) * | 2019-05-22 | 2022-03-25 | 惠州市臻鼎环保科技有限公司 | Regeneration and reuse method of nitric acid type tin stripping waste liquid of PCB |
-
2019
- 2019-05-22 CN CN201910428326.7A patent/CN110055537B/en active Active
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Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002729A (en) * | 2009-09-01 | 2011-04-06 | 金益世股份有限公司 | Copper-containing waste etching solution treatment method and etching solution regeneration method |
| CN101768742A (en) * | 2009-12-31 | 2010-07-07 | 惠州市雄越保环科技有限公司 | Regenerated acidic etching solution, copper recycling method and special device thereof |
| CN103031437A (en) * | 2011-09-29 | 2013-04-10 | 深圳市格林美高新技术股份有限公司 | Processing method for waste liquid from stripping tin scolding |
| CN102775197A (en) * | 2012-08-13 | 2012-11-14 | 深圳市危险废物处理站有限公司 | Method for preparing fertilizer-grade ammonium nitrate concentrated solution by use of mother liquid after immersion tin of tin-stripping waste liquid of circuit board |
| CN102925880A (en) * | 2012-11-16 | 2013-02-13 | 宁波祈禧电器有限公司 | Preparation method of transparent tin antimony oxide electric heating film |
| CN103194769A (en) * | 2013-04-22 | 2013-07-10 | 北京工业大学 | Electrolytic device and method for recovering high-purity copper from waste circuit board |
| CN105723005A (en) * | 2013-07-08 | 2016-06-29 | 阿尔法金属公司 | Metal recovery |
| CN103436885A (en) * | 2013-09-25 | 2013-12-11 | 深圳市瑞世兴科技有限公司 | Method for recycling tin removal waste liquor |
| CN104894599A (en) * | 2015-06-23 | 2015-09-09 | 成都虹华环保科技股份有限公司 | Recycling process of tin-removing waste liquid |
| CN205223353U (en) * | 2015-11-06 | 2016-05-11 | 陶克（苏州）机械设备有限公司 | Tin waste liquid regeneration facility is shelled to nitric acid type |
| CN106319519A (en) * | 2016-08-24 | 2017-01-11 | 盛隆资源再生（无锡）有限公司 | Method for cyclically preparing tin stripping solution and electroplated tin by utilizing waste tin stripping solution |
| CN207109135U (en) * | 2017-08-15 | 2018-03-16 | 东莞市同欣表面处理科技有限公司 | The main salt ion electrolytic recovery device of electroplating solution |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020233104A1 (en) * | 2019-05-22 | 2020-11-26 | 惠州市臻鼎环保科技有限公司 | Recycling method for pcb nitric acid tin-stripping waste liquid |
| CN110526445A (en) * | 2019-09-05 | 2019-12-03 | 成都宏明双新科技股份有限公司 | A kind of methane sulfonic acid system tin plating solution treatment process |
| CN112410792A (en) * | 2019-10-08 | 2021-02-26 | 叶涛 | PCB iron-free nitric acid type tin stripping water and regeneration and reuse method thereof |
| CN112410792B (en) * | 2019-10-08 | 2023-03-31 | 叶涛 | PCB iron-free nitric acid type tin stripping water and regeneration and reuse method thereof |
| CN112250208A (en) * | 2020-08-31 | 2021-01-22 | 金禄电子科技股份有限公司 | Tin stripping waste liquid treatment method and device |
| CN112663092A (en) * | 2020-12-10 | 2021-04-16 | 广东臻鼎环境科技有限公司 | Method for treating methanesulfonic acid type tin stripping waste liquid |
| CN112607762A (en) * | 2020-12-29 | 2021-04-06 | 东江环保股份有限公司 | Preparation method of electronic-grade copper chloride dihydrate |
| CN112607762B (en) * | 2020-12-29 | 2022-09-27 | 东江环保股份有限公司 | Preparation method of electronic-grade copper chloride dihydrate |
| CN112813489A (en) * | 2020-12-30 | 2021-05-18 | 广东臻鼎环境科技有限公司 | Preparation method of reagent-grade copper chloride dihydrate crystal |
| CN113213685A (en) * | 2021-04-26 | 2021-08-06 | 萍乡市华星环保工程技术有限公司 | Desulfurization product sulfur recycling treatment process |
| CN114277249A (en) * | 2021-11-26 | 2022-04-05 | 江西瑞亿电子科技有限公司 | Treatment method for recycling tin, copper and waste gas from PCB tin waste liquid in recycling mode |
| CN114317969A (en) * | 2021-11-26 | 2022-04-12 | 江西瑞亿电子科技有限公司 | Method for recycling tin and copper from PCB tin waste liquid in recycling mode |
| CN114368853A (en) * | 2021-12-17 | 2022-04-19 | 广东臻鼎环境科技有限公司 | Method for recycling brown oxidation waste liquid of circuit board |
| CN114232030A (en) * | 2021-12-23 | 2022-03-25 | 广东鑫菱环境科技有限公司 | PCB methanesulfonic acid tin stripping waste liquid recycling method and application thereof |
| CN114369831A (en) * | 2021-12-27 | 2022-04-19 | 广东臻鼎环境科技有限公司 | Recyclable nitric acid type tin-stripping waste liquid additive and application thereof |
| CN114369831B (en) * | 2021-12-27 | 2024-05-07 | 广东臻鼎环境科技有限公司 | Additive for recyclable nitric acid type tin stripping waste liquid and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110055537B (en) | 2022-03-25 |
| WO2020233104A1 (en) | 2020-11-26 |
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